Thermoplastic resin composition

Abstract

The present invention relates to a thermoplastic resin composition comprising: a diene-based graft polymer; a first polymer comprising vinyl aromatic monomer units and vinyl cyanide monomer units; a second polymer comprising vinyl aromatic monomer units, maleimide monomer units and maleic acid monomer units; a third polymer comprising two or more different olefin oxide monomer units; and a mixture comprising a fluoropolymer comprising tetrafluoroethylene monomer units and a vinyl polymer comprising vinyl aromatic monomer units and vinyl cyanide monomer units.

Description

Technology Field

[0001] The present invention relates to a thermoplastic resin composition, and more specifically, provides a thermoplastic resin composition having excellent processability, heat resistance, impact resistance, and heat fusion properties. Background Technology

[0003] Diene-based graft polymers are graft polymers comprising diene rubbery polymers grafted with vinyl aromatic monomer units and vinyl cyanide monomer units. Compared to conventional high-strength polystyrene, diene-based graft polymers exhibit superior high impact resistance, chemical resistance, thermal stability, colorability, fatigue resistance, stiffness, and processability. Due to these characteristics, thermoplastic resin molded articles made from diene-based graft polymers are used as components for automotive interior and exterior materials, office equipment, and various electrical and electronic products.

[0004] Meanwhile, a diene-based thermoplastic resin composition containing a diene-based graft polymer can be used as a material for the rear lamp housing among automotive parts. Although the rear lamp is an exterior component, the rear lamp housing is directly connected to the interior of the vehicle; therefore, in terms of safety—specifically protecting the user—it must possess excellent impact resistance to minimize damage during assembly or storage of parts. Furthermore, since the design of the rear lamp housing changes depending on various options even for the same car model, it must be possible to injection mold it into various shapes.

[0005] Meanwhile, the injection-molded taillight housing is manufactured by bonding it with a lens. Furthermore, to accommodate the diverse taillight sizes and shapes depending on the vehicle model, changes in internal structure due to options, and the trend toward increasing or decreasing size, there is a need for a thermoplastic resin composition for taillight housing that possesses high fluidity for smooth processing as well as excellent heat resistance. However, while excellent processability facilitates the production of parts via injection, it leads to the problem of heat sealing during the bonding process with the lens.

[0006] Therefore, there is a need to develop thermoplastic resin compositions that not only improve processability, heat resistance, and impact resistance but also minimize the occurrence of heat-fused seals. Prior art literature

[0008] KR1679254B The problem to be solved

[0009] The problem that the present invention aims to solve is to provide a thermoplastic resin composition having excellent processability, heat resistance, impact resistance, and thermal fusion properties. means of solving the problem

[0011] 1) The present invention provides a thermoplastic resin composition comprising: a diene-based graft polymer; a first polymer comprising vinyl aromatic monomer units and vinyl cyanide monomer units; a second polymer comprising vinyl aromatic monomer units, maleimide monomer units and maleic acid monomer units; a third polymer comprising two or more different olefin oxide monomer units; and a mixture comprising a fluoropolymer comprising tetrafluoroethylene monomer units and a vinyl polymer comprising vinyl aromatic monomer units and vinyl cyanide monomer units.

[0012] 2) The present invention provides a thermoplastic resin composition according to 1), wherein the thermoplastic resin composition comprises 18.00 to 30.00 wt% of the diene-based graft polymer; 55.00 to 65.00 wt% of the first polymer; 10.00 to 25.00 wt% of the second polymer; 0.01 to 1.50 wt% of the third polymer; and 0.01 to 0.25 wt% of the mixture.

[0013] 3) The present invention provides a thermoplastic resin composition according to 1) or 2), wherein the diene-based graft polymer comprises a diene-based rubbery polymer grafted with vinyl aromatic monomer units and vinyl cyanide monomer units.

[0014] 4) The present invention provides a thermoplastic resin composition in any one of 1) to 3), wherein the first polymer has a weight-average molecular weight of 100,000 to 160,000 g / mol.

[0015] 5) The present invention provides a thermoplastic resin composition in which, in any one of 1) to 4), the first polymer is one or more selected from the group consisting of styrene / acrylonitrile polymer, α-methyl styrene / acrylonitrile polymer, and α-methyl styrene / styrene / acrylonitrile polymer.

[0016] 6) The present invention provides a thermoplastic resin composition in which, in any one of 1) to 5), the second polymer has a glass transition temperature of 180 to 190 ℃.

[0017] 7) The present invention provides a thermoplastic resin composition in which, in any one of 1) to 6), the second polymer has a weight-average molecular weight of 100,000 to 160,000 g / mol.

[0018] 8) The present invention provides a thermoplastic resin composition in which, in any one of 1) to 7), the second polymer is a styrene / N-phenyl maleimide / maleic anhydride polymer.

[0019] 9) The present invention provides a thermoplastic resin composition in which, in any one of 1) to 8), the third polymer is a block polymer comprising different olefin-based oxide monomer units.

[0020] 10) The present invention provides a thermoplastic resin composition in which, in any one of 1) to 9), the third polymer is a propylene oxide / ethylene oxide block polymer.

[0021] 11) The present invention provides a thermoplastic resin composition in which, in any one of 1) to 10), the mixture comprises polytetrafluoroethylene and a styrene / acrylonitrile polymer. Effects of the invention

[0023] The thermoplastic resin composition according to the present invention has improved processability, heat resistance, impact resistance, and heat fusion properties. Accordingly, the thermoplastic resin composition according to the present invention can be used as a material for automobile taillight housings having various designs and thin thicknesses. Specific details for implementing the invention

[0026] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0027] Terms and words used in this specification and claims shall not be interpreted as being limited to their ordinary or dictionary meanings, but shall be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0029] In the present invention, the 'weight-average molecular weight' can be measured by gel permeation chromatography using polystyrene as a standard material.

[0031] In the present invention, the 'glass transition temperature' can be measured by differential scanning calorimetry.

[0033] In the present invention, the 'average particle size' can be measured using the dynamic light scattering method, and specifically using the Nicomp 380 instrument of Particle Sizing Systems. In the present invention, the average particle size may refer to the arithmetic mean particle size in the particle size distribution measured by the dynamic light scattering method, that is, the average particle size of the scattering intensity distribution.

[0035] In the present invention, the 'diene-based rubbery polymer' is prepared by polymerizing a diene-based monomer, and the diene-based monomer may be one or more selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and piperylene, among which 1,3-butadiene is preferred.

[0037] In the present invention, the 'vinyl aromatic monomer unit' may be a unit derived from a vinyl aromatic monomer. The vinyl aromatic monomer may be one or more selected from the group consisting of styrene, 4-fluorostyrene, 4-chlorostyrene, 4-bromostyrene, α-methylstyrene, α-ethylstyrene, and p-methylstyrene, among which styrene is preferred in terms of processability.

[0039] In the present invention, the 'vinyl cyanide-based monomer unit' may be a unit derived from a vinyl cyanide-based monomer. The vinyl cyanide-based monomer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, among which acrylonitrile is preferred.

[0041] In the present invention, the 'maleimide-based monomer unit' may be a unit derived from a maleimide-based monomer. The above maleimide monomer may be one or more selected from the group consisting of maleimide, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-isobutyl maleimide, Nt-butyl maleimide, N-lauryl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N-(4-chlorophenyl) maleimide, 2-methyl-N-phenyl maleimide, N-(4-bromophenyl) maleimide, N-(4-nitrophenyl) maleimide, N-(4-hydroxyphenyl) maleimide, N-(4-methoxyphenyl) maleimide, N-(4-carboxyphenyl) maleimide, and N-benzyl maleimide, among which N-phenyl maleimide is preferred.

[0043] In the present invention, the 'maleic acid-based monomer unit' may be a unit derived from a maleic acid-based monomer. The maleic acid-based monomer may be one or more selected from the group consisting of maleic anhydride, maleic acid, maleic monoester, and maleic diester, among which maleic anhydride is preferred.

[0045] In the present invention, 'olefin' may be one or more selected from the group consisting of ethylene, propylene, and butene.

[0047] In the present invention, 'C1 to C 10The alkyl group of is a methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, It may be one or more selected from the group consisting of 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group, and 5-methylhexyl group.

[0049] In the present invention, 'C1 to C 10 The alkylene group of is C1 to C 10 It can mean that there are two bonding positions in the alkyl group, that is, a divalent group.

[0051] Thermoplastic resin composition

[0053] A thermoplastic resin composition according to one embodiment of the present invention comprises: 1) a diene-based graft polymer; 2) a first polymer comprising vinyl aromatic monomer units and vinyl cyanide monomer units; 3) a second polymer comprising vinyl aromatic monomer units, maleimide monomer units and maleic acid monomer units; 4) a third polymer comprising two or more different olefin oxide monomer units; and 5) a mixture comprising a fluoropolymer comprising tetrafluoroethylene monomer units and a vinyl polymer comprising vinyl aromatic monomer units and vinyl cyanide monomer units.

[0055] Hereinafter, a thermoplastic resin composition according to one embodiment of the present invention will be described in detail.

[0057] 1) Diene-based graft polymer

[0059] Diene-based graft polymers are components that improve the impact resistance of thermoplastic resin compositions.

[0060] The above-mentioned diene-based graft polymer may include a diene-based rubbery polymer grafted with vinyl aromatic monomer units and vinyl cyanide monomer units, and may include vinyl aromatic monomer units and vinyl cyanide monomer units that are not grafted onto the diene-based rubbery polymer.

[0062] The above-described diene-based rubbery polymer may have an average particle size of 200 to 400 nm, preferably 250 to 350 nm. If the above conditions are satisfied, the impact resistance at room temperature and low temperature can be further improved.

[0064] The content of the diene-based rubbery polymer in the above-mentioned diene-based graft polymer may be 50 to 70 weight%, preferably 55 to 65 weight%. If the above-mentioned conditions are satisfied, a diene-based graft polymer with excellent impact resistance at room temperature and low temperature can be produced.

[0065] The content of vinyl aromatic monomer units in the above-mentioned diene-based graft polymer may be 20 to 40 weight%, preferably 25 to 35 weight%. If the above-mentioned conditions are satisfied, a diene-based graft polymer with excellent moldability can be produced.

[0066] The content of vinyl cyanide monomer units in the above-mentioned diene-based graft polymer may be 1 to 20 weight%, preferably 5 to 15 weight%. If the above-mentioned conditions are satisfied, a diene-based graft polymer with excellent chemical resistance can be produced.

[0068] The above-mentioned diene-based graft polymer may be an acrylonitrile / butadiene / styrene graft polymer comprising a butadiene rubbery polymer in which acrylonitrile monomer units and styrene units are monomer-grafted.

[0070] The content of the above-mentioned diene-based graft polymer may be 18.00 to 30.00 weight%, preferably 20.00 to 24.00 weight%, and more preferably 21.00 to 23.00 weight%. If the above conditions are satisfied, the impact resistance of the thermoplastic resin composition can be improved and the heat fusion strength can be improved.

[0072] 2) First polymer

[0074] The first polymer is a component that improves the processability and surface properties of the thermoplastic resin.

[0075] The first polymer above is a non-graft polymer comprising vinyl aromatic monomer units and vinyl cyanide monomer units.

[0077] The first polymer may have a weight-average molecular weight of 100,000 to 160,000 g / mol, preferably 120,000 to 140,000 g / mol. If the above conditions are satisfied, a thermoplastic resin composition with excellent heat fusion properties, impact resistance, tensile strength, and flexural strength can be produced.

[0079] The first polymer above may contain vinyl aromatic monomer units and vinyl cyanide monomer units in a weight ratio of 25:75 to 35:65, preferably 25:75 to 30:65. If the above conditions are satisfied, a thermoplastic resin composition with excellent impact resistance, tensile resistance, flexural resistance, heat resistance, and heat fusion properties can be produced.

[0081] The first polymer may be one or more selected from the group consisting of styrene / acrylonitrile polymer, α-methyl styrene / acrylonitrile polymer, and α-methyl styrene / styrene / acrylonitrile polymer, and among these, a styrene / acrylonitrile polymer with excellent processability is preferred.

[0083] The content of the first polymer may be 55.00 to 65.00 weight%, preferably 58.00 to 62.00 weight%, and more preferably 59.00 to 61.00 weight%. If the above conditions are satisfied, a thermoplastic resin composition with excellent processability and heat fusion properties can be produced.

[0085] 3) Second polymer

[0087] The second polymer is a component that improves the heat resistance of the thermoplastic resin composition.

[0088] The second polymer is a non-graft polymer comprising vinyl aromatic monomer units, maleimide monomer units, and maleic acid monomer units.

[0090] The second polymer may comprise 45.0 to 59.0 wt% of vinyl aromatic monomer units, 40.0 to 54.0 wt% of maleimide monomer units, and 0.1 to 3.0 wt% of maleic acid monomer units, and preferably may comprise 48.0 to 56.0 wt% of vinyl aromatic monomer units, 43.0 to 51.0 wt% of maleimide monomer units, and 0.5 to 2.0 wt% of maleic acid monomer units. If the above conditions are satisfied, a thermoplastic resin composition with improved heat resistance and mechanical properties such as tensile strength and flexural strength can be produced.

[0092] The second polymer may have a glass transition temperature of 180 to 190 ℃, preferably 183 to 187 ℃. If the above conditions are satisfied, a thermoplastic resin composition with excellent heat resistance can be produced.

[0094] The second polymer may have a weight-average molecular weight of 100,000 to 160,000 g / mol, preferably 120,000 to 140,000 g / mol. If the above conditions are satisfied, a thermoplastic resin composition with excellent processability can be produced.

[0096] The second polymer above may be a styrene / N-phenyl maleimide / maleic anhydride polymer.

[0098] The content of the second polymer may be 10.00 to 25.00 weight%, preferably 15.00 to 19.00 weight%, and more preferably 16.00 to 18.00 weight%. If the above conditions are satisfied, a thermoplastic resin composition with improved heat resistance and impact resistance can be produced without degrading the basic physical properties and processability required for taillights.

[0100] 4) Third polymer

[0102] The third polymer is a polymer comprising two or more different olefin-based oxide monomer units and is a component that modifies the surface of the thermoplastic resin composition. Through synergy with the mixture described below, it can improve the heat fusion characteristics of the thermoplastic resin composition, specifically the surface characteristics and heat fusion strength during heat fusion, suppress thread formation, and minimize the generation of heat plate residue.

[0104] The third polymer may be a block polymer comprising different olefinic oxide monomer units, and may be a block copolymer represented by the following chemical formula 1:

[0105] <Chemical Formula 1>

[0106]

[0107] In the above chemical formula 1,

[0108] L1 and L2 each independently C1 to C 10 It is an alkylene group, and L1 and L2 are different from each other,

[0109] a is 30 to 50, and

[0110] b is 10 to 50, and

[0111] c is 30 to 50.

[0113] The third polymer may be a propylene oxide / ethylene oxide block polymer. Specifically, it may be a block polymer represented by the following chemical formula 1-2.

[0114] <Chemical Formula 1-2>

[0115]

[0116] The block polymer represented by the above chemical formula 1-2 is a hydrophobic propylene oxide monomer unit ( ) and hydrophilic ethylene oxide monomer units ( Since it includes all of the above, the thermoplastic resin composition can be surface modified to have low affinity with the fluorine film. Specifically, since the thermoplastic resin composition can be structurally modified to have low affinity with the fluorine film of the heating plate used when molding the thermoplastic resin composition, adhesion between the thermoplastic resin composition and the fluorine film of the heating plate can be suppressed to the maximum extent.

[0118] The block polymer represented by the above chemical formula 1-2 may contain ethylene oxide monomer units in an amount of 70 to 90 mol%, preferably 75 to 85 mol%. If the above conditions are satisfied, adhesion with fluorinated polymers on the surface can be suppressed, thereby improving thermal fusion properties.

[0119] The molar mass of the propylene oxide monomer unit in the block polymer represented by the above chemical formula 1-2 is 1,000 to 2,500 g / mol, and preferably 1,250 to 2,250 g / mol. If the above range is satisfied, the third polymer can be uniformly dispersed within the thermoplastic resin composition during extrusion processing.

[0121] The content of the third polymer may be 0.01 to 1.50 weight%, preferably 0.50 to 1.20 weight%, and more preferably 0.90 to 1.00 weight%. If the above conditions are satisfied, a thermoplastic resin composition can be produced that has excellent heat fusion characteristics, that is, excellent surface condition during heat fusion, suppresses the occurrence of threads and heat plate residues, and has excellent heat fusion strength.

[0123] 5) Mixture

[0125] Since the mixture contains a fluoropolymer, it is a component that improves the viscosity of the thermoplastic resin composition at low shear stress, thereby providing resistance to thermal deformation.

[0126] Meanwhile, since thermal fusion is a process that proceeds at a low speed, low shear stress is generated. Accordingly, the above mixture improves the viscosity of the thermoplastic resin composition to provide resistance to thermal deformation, and through synergy with the aforementioned third polymer, it can improve the thermal fusion characteristics of the thermoplastic resin composition—specifically, surface characteristics and thermal fusion strength during thermal fusion—and suppress thread formation and minimize the generation of heat plate residue.

[0128] The above polymer includes a fluoropolymer containing tetrafluoroethylene monomer units, and a vinyl polymer containing vinyl aromatic monomer units and vinyl cyanide monomer units.

[0129] The above fluoropolymers have strong interactions with each other, so if the fluoropolymers are used alone, it is difficult to disperse them uniformly within the thermoplastic resin composition. However, if the fluoropolymers are included in the thermoplastic resin composition in a mixed state with the vinyl polymers, the vinyl polymers act as dispersants for the fluoropolymers, allowing the fluoropolymers to be uniformly dispersed within the thermoplastic resin composition.

[0131] The above fluoropolymer may be polytetrafluoroethylene, and the mixture may contain the fluoropolymer in an amount of 45 to 60 weight%, preferably 49 to 54 weight%. If the above conditions are satisfied, the viscosity of the thermoplastic resin composition can be improved at low shear stress, thereby suppressing the occurrence of heat-fusion threads and heat-fusion residues.

[0133] The vinyl polymer above may be the same as or different from the first polymer, and in detail may be a styrene / acrylonitrile polymer.

[0135] The above mixture may include polytetrafluoroethylene and a styrene / acrylonitrile polymer, and more specifically, polytetrafluoroethylene may be dispersed in a styrene / acrylonitrile polymer.

[0137] The content of the above mixture may be 0.01 to 0.25 weight%, preferably 0.05 to 0.20 weight%, and more preferably 0.08 to 0.15 weight%. If the above conditions are satisfied, the extrusion of the thermoplastic resin composition can be easily performed, and a thermoplastic resin composition can be manufactured that has excellent heat fusion characteristics, specifically surface characteristics and strength during heat fusion, and minimizes the occurrence of threads and heat plate residues.

[0139] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0141] Examples and Comparative Examples

[0142] The description of the components used in the following examples and comparative examples is as follows.

[0144] 1) Diene-based rubbery polymer: LG Chem’s DP271 (graft polymer obtained by graft polymerization of styrene and acrylonitrile onto a butadiene rubbery polymer with an average particle size of 300 nm)

[0145] 2) First polymer: LG Chem’s 92RF (styrene / acrylonitrile polymer with a weight-average molecular weight of 130,000 g / mol)

[0146] 3) Second polymer: MSNI from DENKA (styrene / N-phenyl maleimide / maleic anhydride polymer with a glass transition temperature of 185 °C and a weight-average molecular weight of 130,000 g / mol)

[0147] 4) Tertiary Polymer: BASF’s Pluronic Pe6800 (Propylene Oxide / Ethylene Oxide Block Polymer, Molar mass of propylene oxide monomer units in propylene oxide / ethylene oxide block polymer: 1,750 g / mol, Content of ethylene oxide monomer units in propylene oxide / ethylene oxide block polymer: 80 mol%)

[0148] 5) Mixture: POCERA's XFLON-G (polytetrafluoroethylene dispersed in a styrene / acrylonitrile polymer)

[0150] A thermoplastic resin composition was prepared by mixing and stirring the above-described components according to the amounts listed in Tables 1 to 3 below.

[0152] Experimental Example 1

[0153] The thermoplastic resin compositions of the examples and comparative examples were extruded to produce pellets, the pellets were evaluated by the method described below, and the results are listed in Tables 1 to 3 below.

[0155] (1) Melt Flow Index (g / 10 min): Measured according to ASTM D1238 under conditions of 220 ℃ and 10 kg.

[0157] Experimental Example 2

[0158] Specimens were prepared by extruding and injecting the thermoplastic resin compositions of the examples and comparative examples, and the specimens were evaluated by the method described below, and the results are listed in Tables 1 to 3 below.

[0160] (1) Izod impact strength (kg·cm / cm, 1 / 4 In, 1 / 8 In): Measured at 23 ℃ according to ASTM D256.

[0161] (2) Tensile strength (kg / cm²) and tensile elongation (%): Measured at 23 ℃ in accordance with ASTM D638. For the tensile strength measurement, the specimen dimensions were 216 mm (W) × 19 mm (D) × 3.2 mm (H), and the crosshead speed was 50 mm / min. For the tensile elongation measurement, the specimen dimensions were 216 mm (W) × 19 mm (D) × 3.2 mm (H), and the strain rate was 7.5 × 10⁻⁶ -3 sec -1 It was.

[0162] (3) Flexural strength (kg / cm²): Measured at 23 ℃ according to ASTM D790. The specimen dimensions were 100 mm (W) × 3.2 mm (D) × 25.4 mm (H), and the strain rate was 1.6 × 10⁻⁶ -3 sec -1 It was.

[0163] (4) Heat distortion temperature ( H eat D eflection T Temperature, °C): Measured under unanealed conditions in accordance with ASTM D648.

[0164] (5) Softening temperature ( V icat S oftening T Temperature, °C): Measured under unanealed conditions in accordance with ASTM D1525.

[0166] Experimental Example 3

[0167] A specimen of 10 cm x 10 cm was prepared by extruding and injecting the thermoplastic resin compositions of the examples and comparative examples. Under conditions of a relative humidity of 55 RH%, the specimen was brought into contact with a hot plate with a surface temperature of 240 ℃ for 10 seconds using a heat fusion device and then removed. Subsequently, the surface condition of the specimen, the degree of thread formation, and the residue on the hot plate were measured, and the results are listed in Tables 1 to 3 below.

[0169] <Surface condition of the specimen (degree of gas generation)>

[0170] ◎: 20 or fewer 1 mm bubble marks, ○: 21 to 50 1 mm bubble marks, △: 5 or fewer 3 mm bubble marks, ×: 6 or more 3 mm bubble marks

[0171] <Actual Occurrence>

[0172] ◎: No threading, ○: Threading 0.5 mm or less, △: Threading exceeding 0.5 mm and up to 1 cm, ×: Threading exceeding 1 cm

[0174] Experimental Example 4

[0175] A specimen of 10 cm x 10 cm was prepared by extruding and injecting the thermoplastic resin compositions of the examples and comparative examples. Under conditions of a relative humidity of 55 RH%, the specimen was brought into contact with a hot plate with a surface temperature of 250 ℃ for 10 seconds using a heat fusion device and then removed. Subsequently, the surface condition of the specimen, the degree of thread formation, and the residue on the hot plate were measured, and the results are listed in Tables 1 to 3 below.

[0177] <Surface condition of the specimen (degree of gas generation)>

[0178] ◎: 20 or fewer 1 mm bubble marks, ○: 21 to 50 1 mm bubble marks, △: 5 or fewer 3 mm bubble marks, ×: 6 or more 3 mm bubble marks

[0179] <Actual Occurrence>

[0180] ◎: No threading, ○: Threading 0.5 mm or less, △: Threading exceeding 0.5 mm and up to 1 cm, ×: Threading exceeding 1 cm

[0182] Experimental Example 5

[0183] A specimen of 10 cm × 10 cm was prepared by extruding and injecting the thermoplastic resin compositions of the examples and comparative examples. For thermal fusion bonding, a specimen of 10 cm × 10 cm was additionally prepared by injecting polymethyl methacrylate. After leaving the prepared specimens at 23°C and 55 RH% for 24 hours, each specimen was bonded using a thermal fusion device by contacting it with a hot plate having a surface temperature of 240°C for 30 seconds and then contacting the specimen for 10 seconds. Since the specimen prepared by the above method consisted of a 10 cm × 10 cm specimen of the thermoplastic resin composition and a 10 cm × 10 cm specimen of polymethyl methacrylate, the total size was 20 cm × 10 cm, and the bonding surface was located in the center.

[0185] (1) Surface condition of the cut surface: After measuring the tensile strength and tensile elongation at 23°C according to ASTM D638, the surface condition of the cut surface was evaluated based on the amount of polymethyl methacrylate residue remaining on the cut surface. The more polymethyl methacrylate residue remains on the surface of the specimen, the better the bonding.

[0186] ◎: 75% or more, ○: 50% or more, △: Less than 50%, ×: No residue

[0187] (2) Tensile strength (kg / cm²) and tensile elongation (%): Measured at 23 ℃ in accordance with ASTM D638. For the tensile strength measurement, the specimen dimensions were 100 mm (W) × 197 mm (D) × 3 mm (H), and the crosshead speed was 50 mm / min. For the tensile elongation measurement, the specimen dimensions were 100 mm (W) × 197 mm (D) × 3 mm (H), and the strain rate was 7.5 × 10⁻⁶ -3sec -1 It was.

[0189] division Example 1 Example 2 Example 3 Example 4 Example 5 diene-based graft polymer (parts by weight) 22.00 24.00 22.00 20.00 22.00 First polymer (parts by weight) 60.10 58.10 58.10 62.10 62.10 Second polymer (parts by weight) 17.00 17.00 19.00 17.00 15.00 Third polymer (parts by weight) 0.80 0.80 0.80 0.80 0.80 Mixture (parts by weight) 0.10 0.10 0.10 0.10 0.10 Liquidity index (g / 10 min) 9.8 9.3 9.5 10.3 10.2 Izod impact strength (kg·cm / cm) 1 / 4 In 12.6 13.4 11.2 11.4 12.9 1 / 8 In 17.6 19.1 16.5 17.0 18.1 Tensile strength (kg / cm²) 493.5 476.2 500.2 498.7 488.6 Tensile elongation (%) 46.1 42.1 38.3 43.1 41.6 Flexural strength (kg / cm²) 691.4 671.0 685.8 696.3 685.1 Heat distortion temperature (°C) 101.6 100.5 101.9 101.8 100.5 Softening temperature (°C) 109.8 109.1 110.0 110.1 109.1 Thermal fusion (240 ℃, 55 RH%) Specimen surface condition ◎ ◎ ◎ ◎ ◎ Actual occurrence ◎ ◎ ◎ ◎ ◎ Hot plate residue (%) 0 0 0 0 0 Thermal fusion (250 ℃, 55 RH%) Specimen surface condition ◎ ◎ ◎ ◎ ◎ Actual occurrence ◎ ◎ ◎ ◎ ◎ Hot plate residue (%) 0 0 0 0 0 Heat fusion strength (240 ℃ bonding, 55 RH%) Surface condition of the cut surface (PMMA residue) ◎ ◎ ◎ ◎ ◎ Tensile strength (kg / cm²) 300.3 283.2 281.1 294.3 298.2 Tensile elongation (%) 2.57 2.21 2.16 2.23 2.31

[0190] division Example 6 Example 7 Example 8 Example 9 diene-based graft polymer (parts by weight) 22.00 22.00 22.00 22.00 First polymer (parts by weight) 59.70 60.40 60.00 60.15 Second polymer (parts by weight) 17.00 17.00 17.00 17.00 Third polymer (parts by weight) 1.20 0.50 0.80 0.80 Mixture (parts by weight) 0.10 0.10 0.20 0.05 Liquidity index (g / 10 min) 10.8 10.2 10.2 10.2 Izod impact strength (kg·cm / cm) 1 / 4 In 13.1 12.3 12.8 12.4 1 / 8 In 17.5 17.2 17.7 17.3 Tensile strength (kg / cm²) 510.2 491.5 484.7 495.6 Tensile elongation (%) 42.3 40.9 38.6 43.2 Flexural strength (kg / cm²) 676.2 688.2 700.2 693.5 Heat distortion temperature (°C) 100.7 101.1 101.5 101.4 Softening temperature (°C) 109.3 109.6 109.8 109.7 Thermal fusion (240 ℃, 55 RH%) Specimen surface condition ○ ◎ ◎ ○ Actual occurrence ◎ ◎ ◎ ○ Hot plate residue (%) 0 10 0 0 Thermal fusion (250 ℃, 55 RH%) Specimen surface condition ○ ◎ ◎ ○ Actual occurrence ◎ ○ ◎ ○ Hot plate residue (%) 0 10 0 0 Heat fusion strength (240 ℃ bonding, 55 RH%) Cut surface condition (PMMA residue) ◎ ◎ ○ ◎ Tensile strength (kg / cm²) 274.3 286.2 273.4 287.5 Tensile elongation (%) 2.41 2.15 2.08 2.32

[0191] division Comparative Example 1 Comparative Example 2 Comparative Example 3 diene-based graft polymer (parts by weight) 22.00 22.00 22.00 First polymer (parts by weight) 61.00 60.90 60.20 Second polymer (parts by weight) 17.00 17.00 17.00 Third polymer (parts by weight) 0.00 0.00 0.80 Mixture (parts by weight) 0.00 0.10 0.00 Liquidity index (g / 10 min) 8.8 8.9 9.6 Izod impact strength (kg·cm / cm) 1 / 4 In 13.8 12.8 12.3 1 / 8 In 18.1 17.9 17.2 Tensile strength (kg / cm²) 483.6 485.6 491.2 Tensile elongation (%) 40.1 42.6 41.1 Flexural strength (kg / cm²) 696.3 693.7 685.9 Heat distortion temperature (°C) 102.1 102.2 101.1 Softening temperature (°C) 110.3 109.9 109.7 Thermal fusion (240 ℃, 55 RH%) Specimen surface condition × × ◎ Actual occurrence × △ × Hot plate residue (%) 50 40 5 Thermal fusion (250 ℃, 55 RH%) Specimen surface condition × × ◎ Actual occurrence × △ × Hot plate residue (%) 50 40 5 Heat fusion strength (240 ℃ bonding, 55 RH%) Surface condition of the cut surface (PMMA residue) ◎ ○ ◎ Tensile strength (kg / cm²) 295.4 276.6 275.5 Tensile elongation (%) 2.31 2.24 2.13

[0192] When comparing Example 1, Example 3, and Example 5 with reference to Tables 1 to 3 above, Example 5, which had the lowest content of the second polymer, exhibited superior impact resistance compared to Examples 1 and 5, even though the content of the diene-based graft polymer, the third polymer, and the mixture were the same. Furthermore, it was found that Example 1, with a content of 17 parts by weight of the second polymer, had the best thermal fusion strength compared to Example 3, with a content of 19 parts by weight of the second polymer, and Example 5, with a content of 15 parts by weight of the second polymer. From these results, it was found that the second polymer affects the impact resistance of the thermoplastic resin composition, and that the thermal fusion strength is best when the second polymer is included in an appropriate amount.

[0193] When comparing Examples 1, 2, and 4, Example 4, which had the lowest content of diene-based graft polymer, exhibited the best heat resistance despite having the same content of the second polymer, third polymer, and mixture. Additionally, Example 1, with a diene-based graft polymer content of 22.00 parts by weight, showed the best heat fusion strength compared to Example 2, with a diene-based graft polymer content of 24.00 parts by weight, and Example 4, with a diene-based graft polymer content of 20.00 parts by weight. From these results, it was found that the diene-based graft polymer affects heat resistance, and that the heat fusion strength is best when the diene-based graft polymer is included in an appropriate amount.

[0194] When comparing Examples 1, 6, and 7, even though the content of the diene graft polymer, the second polymer, and the mixture were the same, Example 1, with a content of 0.80 parts by weight of the third polymer, exhibited superior heat resistance compared to Example 6, with a content of 1.20 parts by weight of the third polymer, and Example 7, with a content of 0.50 parts by weight of the third polymer. Additionally, Example 7, with the lowest content of the third polymer, showed the most deterioration in thermal fusion surface properties compared to Examples 1 and 6. Furthermore, Example 1, with a content of 0.80 parts by weight of the third polymer, exhibited the best thermal fusion strength compared to Examples 6 and 7. From these results, it was found that the third polymer affects heat resistance, and that the thermal fusion strength is best when the third polymer is included in an appropriate amount.

[0195] When comparing Example 1, Example 8, and Example 9, even though the content of the diene-based graft polymer, the second polymer, and the third polymer were the same, Example 1, with a mixture content of 0.10 parts by weight, showed the best thermal fusion strength compared to Example 8, with a mixture content of 0.20 parts by weight, and Example 9, with a mixture content of 0.05 parts by weight. From these results, it was found that the thermal fusion strength was best when the mixture was included in an appropriate amount.

[0196] Meanwhile, Comparative Example 1, which does not contain both the third polymer and the mixture, showed a significantly deteriorated thermal fusion surface condition compared to Examples 1 to 9.

[0197] Comparative Example 2, which does not contain the third polymer, showed a significantly deteriorated thermal fusion surface condition compared to Examples 1 to 9.

[0198] Comparative Example 3, which does not contain a mixture, showed a significantly deteriorated thermal fusion surface condition compared to Examples 1 to 9.

Claims

Claim 1 A thermoplastic resin composition comprising: a diene-based graft polymer; a first polymer comprising vinyl aromatic monomer units and vinyl cyanide monomer units; a second polymer comprising vinyl aromatic monomer units, maleimide monomer units and maleic acid monomer units; a third polymer comprising two or more different olefin oxide monomer units; and a mixture comprising a fluoropolymer comprising tetrafluoroethylene monomer units and a vinyl polymer comprising vinyl aromatic monomer units and vinyl cyanide monomer units; wherein the content of the third polymer is 0.50 to 1.20 weight%. Claim 2 A thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises 18.00 to 30.00 weight% of the diene-based graft polymer; 55.00 to 65.00 weight% of the first polymer; 10.00 to 25.00 weight% of the second polymer; and 0.01 to 0.25 weight% of the mixture. Claim 3 A thermoplastic resin composition according to claim 1, wherein the diene-based graft polymer comprises a diene-based rubbery polymer grafted with vinyl aromatic monomer units and vinyl cyanide monomer units. Claim 4 A thermoplastic resin composition according to claim 1, wherein the first polymer has a weight-average molecular weight of 100,000 to 160,000 g / mol. Claim 5 A thermoplastic resin composition according to claim 1, wherein the first polymer is one or more selected from the group consisting of styrene / acrylonitrile polymer, α-methyl styrene / acrylonitrile polymer, and α-methyl styrene / styrene / acrylonitrile polymer. Claim 6 A thermoplastic resin composition according to claim 1, wherein the second polymer has a glass transition temperature of 180 to 190 ℃. Claim 7 A thermoplastic resin composition according to claim 1, wherein the second polymer has a weight-average molecular weight of 100,000 to 160,000 g / mol. Claim 8 A thermoplastic resin composition according to claim 1, wherein the second polymer is a styrene / N-phenyl maleimide / maleic anhydride polymer. Claim 9 A thermoplastic resin composition according to claim 1, wherein the third polymer is a block polymer comprising different olefinic oxide monomer units. Claim 10 A thermoplastic resin composition according to claim 1, wherein the third polymer is a propylene oxide / ethylene oxide block polymer. Claim 11 A thermoplastic resin composition according to claim 1, wherein the mixture comprises polytetrafluoroethylene and a styrene / acrylonitrile polymer.

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