KR102705483B1 - Thermoplastic resin composition and article manufactured using the same - Google Patents

Abstract

The present invention provides a thermoplastic resin composition comprising (A) 75 to 85 wt% of a polycarbonate resin; (B) 7 to 15 wt% of an acrylic rubber-modified aromatic vinyl graft copolymer; and (C) 7 to 13 wt% of an aromatic vinyl-cyanide vinyl copolymer, relative to 100 wt% of a base resin, (D) 0.7 to 5 wt% of zinc oxide (ZnO); and (E) 0.2 to 0.6 wt% of a phosphorus compound represented by the following chemical formula 1, and a molded article manufactured therefrom.
[Chemical Formula 1]
(RO) _n P(=O)(OH) _3-n
In chemical formula 1,
n is an integer from 1 to 3,
R is selected from a substituted or unsubstituted C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted C3 to C30 heteroaryl group.

Description

Thermoplastic resin composition and molded article manufactured therefrom {THERMOPLASTIC RESIN COMPOSITION AND ARTICLE MANUFACTURED USING THE SAME}

The present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom.

Polycarbonate (PC) resin is one of the engineering plastics and is a widely used material in the plastics industry.

Polycarbonate resin has a glass transition temperature (Tg) of approximately 150℃ due to its bulky molecular structure, similar to bisphenol-A, and exhibits high heat resistance. It is also an amorphous polymer with excellent transparency.

In addition, although it has excellent impact resistance and compatibility with other resins, polycarbonate resin has the disadvantage of low fluidity, so it is widely used in the form of an alloy with various resins to improve formability and post-processing properties.

Acrylonitrile-styrene-acrylate (ASA) resin has excellent weather resistance and light resistance, and is widely used in outdoor building materials, automobile interior/exterior materials, etc. However, ASA resin has poor impact resistance, etc., so in order to apply it to applications requiring high impact strength, the acrylic rubber component content of the ASA resin must be increased. However, if the acrylic rubber component content is increased, the heat resistance, etc. decreases, and therefore, there is a limit to its application to applications requiring high heat resistance, such as automobile interior/exterior materials.

Accordingly, a method for securing excellent heat resistance, impact resistance, weather resistance, and light resistance by using PC/ASA resin, which is an alloy of the aforementioned PC resin and ASA resin, is proposed, and such PC/ASA resin can be applied not only to interior materials but also to exterior materials of various automobiles.

However, despite its excellent weather resistance and light resistance, PC/ASA resins may exhibit yellowing over time and there is also a concern that various molds and bacteria may grow on the surface of molded products. In order to further enhance the weather resistance and light resistance of PC/ASA resins and improve antibacterial properties, it is possible to consider introducing additives such as antibacterial agents and weather stabilizers into PC/ASA resins. However, if appropriate additives are not used in appropriate amounts, compatibility, impact resistance, etc. may deteriorate and a large amount of gas may be generated due to decomposition of the resin during injection molding.

Therefore, there is a need to develop a thermoplastic resin composition with excellent antibacterial properties, weather resistance, light resistance, impact resistance, and heat resistance.

Provided is a thermoplastic resin composition having excellent antibacterial properties, weather resistance, light resistance, impact resistance, heat resistance, etc.

Another embodiment provides a molded article manufactured from the thermoplastic resin composition.

According to one embodiment, a thermoplastic resin composition is provided, comprising: (A) 75 to 85 wt% of a polycarbonate resin; (B) 7 to 15 wt% of an acrylic rubber-modified aromatic vinyl graft copolymer; and (C) 7 to 13 wt% of an aromatic vinyl-cyanide vinyl copolymer; relative to 100 wt% of a base resin, (D) 0.7 to 5 wt% of zinc oxide (ZnO); and (E) 0.2 to 0.6 wt% of a phosphorus compound represented by the following chemical formula 1.

[Chemical Formula 1]

(RO) _n P(=O)(OH) _3-n

In chemical formula 1,

n is an integer from 1 to 3,

R is selected from a substituted or unsubstituted C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted C3 to C30 heteroaryl group.

The average particle diameter (D50) of the above (D) zinc oxide may be 0.5 to 3 ㎛.

The BET surface area of the above (D) zinc oxide can be 1 to 10 m ² /g.

The above (D) zinc oxide may have a peak position 2θ value of 35 to 37° in X-ray diffraction (XRD) analysis, and a crystallite size value of 1,000 to 2,000 Å according to the following equation 1.

[Formula 1]

Microcrystal size (D) =

In the above equation 1, k is the shape factor and λ is the X-ray wavelength.

wavelength), β is the FWHM value (degree) of the X-ray diffraction peak, and θ is the peak position value (peak position degree).

The above (D) zinc oxide may have a size ratio (B/A) of peak A in the range of 370 to 390 nm and peak B in the range of 450 to 600 nm in photoluminescence measurement of 0.01 to 1.

The above (A) polycarbonate resin may have a melt flow index of 5 to 40 g/10 min as measured under conditions of 250°C and 10 kg load according to ASTM D1238.

The above (B) acrylic rubber-modified aromatic vinyl graft copolymer may have an average particle diameter of 100 to 500 nm of the acrylic rubber polymer.

The above (B) acrylic rubber-modified aromatic vinyl graft copolymer may be a copolymer obtained by graft polymerizing a monomer mixture containing an aromatic vinyl compound and a cyanide vinyl compound to 40 to 60 wt% of an acrylic rubber polymer.

The above (B) acrylic rubber-modified aromatic vinyl graft copolymer may be an acrylonitrile-styrene-acrylate graft copolymer.

The above (C) aromatic vinyl-vinyl cyanide copolymer may be a copolymer of a monomer mixture comprising 60 to 85 wt% of an aromatic vinyl compound and 15 to 40 wt% of a vinyl cyanide compound.

The above (C) aromatic vinyl-vinyl cyanide copolymer may have a melt flow index of 1 to 10 g/10 min as measured at 200°C under a load of 5 kg according to ASTM D1238.

The above (C) aromatic vinyl-cyanide vinyl copolymer may be a styrene-acrylonitrile copolymer.

The thermoplastic resin composition may further include at least one additive selected from a flame retardant, a nucleating agent, a coupling agent, a filler, a plasticizer, an impact modifier, a lubricant, a release agent, a heat stabilizer, an antioxidant, an inorganic additive, an ultraviolet stabilizer, an antistatic agent, a pigment, and a dye.

Meanwhile, according to another embodiment, a molded product manufactured from the thermoplastic resin composition is provided.

The above molded article can have a notched Izod impact strength of 30 to 100 kgf cm/cm for a 1/8" thick specimen according to ASTM D256.

The above molded product may have an antibacterial activity value of 2 to 7, respectively, when inoculated with Staphylococcus aureus and Escherichia coli on a specimen according to the JIS Z 2801 antibacterial evaluation method and cultured for 24 hours under conditions of 35°C and 90% RH.

The above molded product was tested under the conditions of 89℃, RH 50%, 84 MJ/ ^m2 , and lamp wavelength 300 to 400 nm by the xenon arc test method specified in SAE J 1885 for the color difference change of the specimen. E) can be greater than 0 and less than 0.4.

The above molded product may have a heat deflection temperature (HDT) of a specimen measured under a load of 18.56 kg according to ASTM D648 of 110 to 200°C.

A thermoplastic resin composition having excellent antibacterial properties, weather resistance, light resistance, impact resistance, heat resistance, etc., and a molded product manufactured therefrom can be provided.

Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples, and the present invention is not limited thereby, and the present invention is defined only by the scope of the claims that follow.

In this specification, “copolymerization” means block copolymerization or random copolymerization, and “copolymer” means block copolymer or random copolymer.

In the present invention, unless otherwise specified, the average particle diameter of a rubber polymer is a volume average diameter and means the Z-average particle diameter measured using a dynamic light scattering analyzer.

Unless otherwise specified in the present invention, the average particle size of zinc oxide means the particle size (D50) corresponding to 50% of the weight percentage in the particle size distribution curve of single particles (particles do not agglomerate to form secondary particles) measured using a particle size analyzer (Laser Diffraction Particle Size Analyzer LS I3 320 equipment of Beckman Coulter).

Unless otherwise specifically stated in the present invention, the weight average molecular weight is measured by dissolving a powder sample in a solvent and using Agilent Technologies' 1200 series gel permeation chromatography (GPC) (using Shodex LF-804 as the column and Shodex polystyrene as the standard sample).

Unless otherwise specifically stated in the present invention, the specific surface area is measured using a nitrogen gas adsorption method with a BET analysis device (Surface Area and Porosity Analyzer ASAP 2020 device from Micromeritics).

According to one embodiment, a thermoplastic resin composition comprises 100 parts by weight of a base resin including (A) 75 to 85 wt% of a polycarbonate resin; (B) 7 to 15 wt% of an acrylic rubber-modified aromatic vinyl graft copolymer; and (C) 7 to 13 wt% of an aromatic vinyl-cyanide vinyl copolymer; (D) 0.7 to 5 wt% of zinc oxide (ZnO); and (E) 0.2 to 0.6 wt% of a phosphorus compound represented by the following chemical formula 1.

[Chemical Formula 1]

(RO) _n P(=O)(OH) _3-n

In chemical formula 1,

n is an integer from 1 to 3,

R is selected from a substituted or unsubstituted C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted C3 to C30 heteroaryl group.

Hereinafter, each component included in the thermoplastic resin composition will be described in detail.

(A) polycarbonate resin

Polycarbonate resin is a polyester having a repeating structure of carbonate units, and its type is not particularly limited, and any polycarbonate resin available in the field of resin compositions can be used.

For example, it can be produced by reacting a diphenol compound represented by the following chemical formula K with a compound selected from the group consisting of phosgene, halogen acid ester, carbonic ester, and combinations thereof.

[Chemical formula K]

In the above chemical formula K,

A is a linking group selected from the group consisting of a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C2 to C5 alkenylene group, a substituted or unsubstituted C2 to C5 alkylidene group, a substituted or unsubstituted C1 to C30 haloalkylene group, a substituted or unsubstituted C5 to C6 cycloalkylene group, a substituted or unsubstituted C5 to C6 cycloalkenylene group, a substituted or unsubstituted C5 to C10 cycloalkylidene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C20 alkoxylene group, a halogen acid ester group, a carbonic ester group, -Si(-R ¹¹ )(-R ¹² ), -O-, -S-, and -S(=O) ₂ -, and R ¹ , R ² , R ¹¹ , and R ¹² are each independently a substituted or unsubstituted C1 is a C30 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, and n1 and n2 are each independently an integer from 0 to 4.

Two or more diphenol compounds represented by the above chemical formula K may be combined to form a repeating unit of a polycarbonate resin.

Specific examples of the above diphenol compounds include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (also called 'bisphenol-A'), 2,4-bis(4-hydroxyphenyl)-2-methylbutane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, Bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ether, etc. can be mentioned. Among the above diphenol compounds, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, or 1,1-bis(4-hydroxyphenyl)cyclohexane can be preferably used. 2,2-bis(4-hydroxyphenyl)propane can be more preferably used.

The above polycarbonate resin may be a mixture of copolymers prepared from two or more diphenol compounds.

In addition, the polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, a polycarbonate-polysiloxane copolymer resin, a polyester-polycarbonate copolymer resin, etc.

Specific examples of the linear polycarbonate resin include bisphenol-A polycarbonate resins. Specific examples of the branched polycarbonate resin include resins produced by reacting a polyfunctional aromatic compound such as trimellitic anhydride, trimellitic acid, etc. with a diphenol compound and a carbonate. The polycarbonate-polysiloxane copolymer resin includes resins produced by reacting a siloxane compound including a terminal hydroxyl group with a diphenol compound and phosgene, halogen formate, carbonic diester, etc.

The above polyester-polycarbonate copolymer resin can be produced by reacting a difunctional carboxylic acid with a diphenol compound and a carbonate, wherein the carbonate used can be a diaryl carbonate such as diphenyl carbonate or ethylene carbonate.

The above polycarbonate resin can be manufactured using a method such as interfacial polymerization (also called solvent polymerization or phosgene method), melt polymerization, etc.

When the polycarbonate resin is produced by a melt polymerization method, the ester interchange reaction can be performed at a temperature of 150 to 300°C, for example, 160 to 280°C, specifically 190 to 260°C, under a reduced pressure condition of 100 torr or less, for example, 75 torr or less, specifically 30 torr or less, more specifically 1 torr or less, for at least 10 minutes, for example, 15 minutes to 24 hours, specifically 15 minutes to 12 hours. Proceeding within the above range is preferable in terms of reaction speed and reduction of side reactions, and can reduce gel formation.

The above reaction can be carried out in the presence of a catalyst. As the catalyst, a catalyst used in a typical ester interchange reaction can be used, and for example, an alkali metal catalyst, an alkaline earth metal catalyst, etc. can be used. Examples of the alkali metal catalyst include, but are not limited to, LiOH, NaOH, KOH, etc. These can be used alone or in combination of two or more. The content of the catalyst can be used in the range of 1×10 ^-8 to 1×10 ^-3 mol, for example, 1×10 ^-7 to 1×10 ^-4 mol per 1 mol of the diphenol compound. In the above range, sufficient reactivity can be obtained, and the generation of by-products due to side reactions can be minimized, so that the effects of improving thermal stability and color stability can be exhibited.

When the polycarbonate resin is formed by an interfacial polymerization method, the detailed reaction conditions can be variously controlled, but for example, a method may be exemplified in which a reactant of a diphenol compound is dissolved or dispersed in caustic soda or potash in water, the resulting mixture is added to a water-immiscible solvent, and the reactant is brought into contact with a carbonate in the presence of triethylamine or a phase transfer catalyst under controlled pH conditions, such as about 8 to about 10.

Examples of solvents that do not mix with water include methylene chloride, 1,2-dichloroethane, chlorobenzene, and toluene.

Examples of carbonate precursors include carbonyl halides, such as carbonyl bromide or carbonyl chloride, or haloformates, such as the bishaloformates of dihydric phenols (e.g., bischloroformates such as bisphenol A, hydroquinone, etc.), or haloformates, such as the bishaloformates of glycols (e.g., bishaloformates such as ethylene glycol, neopentyl glycol, polyethylene glycol, etc.).

Examples of phase transfer catalysts include [CH ₃ (CH ₂ ) ₃ ] ₄ NX, [CH ₃ (CH ₂ ) ₃ ] ₄ PX, [CH ₃ (CH ₂ ) ₅ ] ₄ NX, [CH ₃ (CH ₂ ) ₆ ] ₄ NX, [CH ₃ (CH ₂ ) ₄ ] ₄ NX, CH ₃ [CH ₃ (CH ₂ ) ₃ ] ₃ NX, and CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NX (wherein X is selected from halogen, a C1 to C8 alkoxy group, and a C6 to C188 aryloxy group).

It is preferable to use the polycarbonate resin having a weight average molecular weight of 10,000 to 200,000 g/mol, for example, 10,000 to 90,000 g/mol, for example, 14,000 to 90,000 g/mol, for example, 14,000 to 80,000 g/mol, for example, 14,000 to 70,000 g/mol, for example, 14,000 to 60,000 g/mol, for example, 14,000 to 50,000 g/mol, for example, 14,000 to 40,000 g/mol. When the weight average molecular weight of the polycarbonate resin is within the above range, a molded article manufactured therefrom can obtain excellent impact resistance and fluidity.

The above polycarbonate resin may have a melt flow index measured under conditions of 250° C. and 10 kg load according to ASTM D1238 of, for example, 5 to 40 g/10 min, for example, 8 to 40 g/10 min, for example, 8 to 35 g/10 min, for example, 10 to 35 g/10 min, for example, 10 to 33 g/10 min. When a polycarbonate resin having a melt flow index within the above range is used, a molded product manufactured therefrom may obtain excellent impact resistance and fluidity.

The above polycarbonate resin may be used by mixing two or more types of polycarbonate resins having different weight average molecular weights or melt flow indices. By mixing and using polycarbonate resins having different weight average molecular weights or melt flow indices, it is easy to control the thermoplastic resin composition to have a desired fluidity and/or weight average molecular weight.

The polycarbonate resin may be included in an amount of 75 to 85 wt% based on 100 wt% of the base resin, for example, 78 to 85 wt%, for example, 78 to 82 wt%. When the polycarbonate resin is included in an amount of less than 75 wt%, the mechanical strength and heat resistance of the thermoplastic resin composition and the molded article manufactured therefrom are poor, and when it exceeds 85 wt%, the moldability of the thermoplastic resin composition and the molded article manufactured therefrom may be reduced.

(B) Acrylic rubber-modified aromatic vinyl graft copolymer

The acrylic rubber-modified aromatic vinyl graft copolymer performs the function of enhancing the light resistance, weather resistance and impact resistance of the thermoplastic resin composition.

In one embodiment, the acrylic rubber-modified aromatic vinyl graft copolymer can be prepared by graft polymerizing a monomer mixture comprising an aromatic vinyl compound and a cyanide vinyl compound onto an acrylic rubbery polymer.

The above acrylic rubber-modified aromatic vinyl graft copolymer can be produced by any production method known to those skilled in the art.

The above manufacturing method may utilize a conventional polymerization method, for example, emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization. As a non-limiting example, the method may include manufacturing an acrylic rubber polymer, and graft polymerizing a monomer mixture including an aromatic vinyl compound and a cyanide vinyl compound onto a core formed of one or more layers of the acrylic rubber polymer to form one or more shell layers.

The above acrylic rubber polymer can be produced using an acrylic monomer as a main monomer. The acrylic monomer may be at least one selected from the group consisting of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and hexyl acrylate, but is not limited thereto.

The above acrylic monomer can be copolymerized with one or more other radically polymerizable monomers. When copolymerized, the amount of the one or more other radically polymerizable monomers can be 1 to 30 wt%, specifically 1 to 20 wt%, based on the total weight of the acrylic rubber polymer.

The aromatic vinyl compound included in the shell layer may be at least one selected from styrene, α-methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, and vinylnaphthalene, but is not limited thereto.

The cyanide vinyl compound included in the shell layer may be at least one selected from acrylonitrile, methacrylonitrile, and fumaronitrile, but is not limited thereto.

The acrylic rubber polymer may be present in an amount of 40 to 60 wt%, for example, 45 to 55 wt%, based on 100 wt% of the total acrylic rubber-modified aromatic vinyl graft copolymer.

In the shell layer formed by graft polymerizing a monomer mixture including the aromatic vinyl compound and the cyanide vinyl compound onto the acrylic rubber polymer, the aromatic vinyl compound may be present in an amount of 50 to 80 wt%, specifically, 60 to 75 wt%, based on the total weight of the shell layer, and the cyanide vinyl compound may be present in an amount of 20 to 50 wt%, specifically, 25 to 40 wt%, based on the total weight of the shell layer.

In one embodiment, the acrylic rubber modified aromatic vinyl graft copolymer can include an acrylonitrile-styrene-acrylate graft copolymer (g-ASA). For example, the acrylic rubber modified aromatic vinyl graft copolymer can be an acrylonitrile-styrene-acrylate graft copolymer.

As a non-limiting example, the acrylonitrile-styrene-acrylate graft copolymer may be a core-shell type acrylonitrile-styrene-acrylate graft copolymer prepared by graft polymerizing a mixture of acrylonitrile and styrene through emulsion polymerization onto a butyl acrylate rubbery polymer core of two or more layers including an inner core in which butyl acrylate and styrene are copolymerized and an outer core composed of a butyl acrylate polymer.

In one embodiment, the acrylic rubber-modified aromatic vinyl graft copolymer has an average particle diameter of the acrylic rubber polymer of 100 nm or more, for example, 150 nm or more, for example, 200 nm or more, and 500 nm or less, for example, 450 nm or less, for example, 400 nm or less, and may be, for example, 100 to 500 nm, for example, 150 to 450 nm, for example, 200 to 400 nm.

When the average particle size of the acrylic rubber polymer in the acrylic rubber-modified aromatic vinyl graft copolymer is less than 100 nm, there is a concern that the mechanical properties, such as impact resistance and tensile strength, of the thermoplastic resin composition containing it may deteriorate.

Meanwhile, if the average particle size of the acrylic rubber polymer in the acrylic rubber-modified aromatic vinyl graft copolymer exceeds 500 nm, there is a concern that the fluidity and processability of the thermoplastic resin composition containing it may deteriorate.

The above acrylic rubber-modified aromatic vinyl graft copolymer may be included in an amount of 7 wt% or more, for example 8 wt% or more, based on 100 wt% of the base resin, and may be included in an amount of 15 wt% or less, for example 13 wt% or less, and may be included in an amount of 7 to 15 wt%, for example 8 to 13 wt%.

When the content of the acrylic rubber-modified aromatic vinyl graft copolymer in the base resin is less than 7 wt%, there is a concern that the impact resistance of the thermoplastic resin composition and the molded article manufactured therefrom may be reduced, and when it exceeds 13 wt%, there is a concern that the mechanical strength and colorability of the thermoplastic resin composition and the molded article manufactured therefrom may be reduced.

(C) Aromatic vinyl-cyanide vinyl copolymer

Aromatic vinyl-vinyl cyanide copolymers perform the function of improving the fluidity of thermoplastic resin compositions and maintaining compatibility between components at a certain level.

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer can be a copolymer of a monomer mixture comprising an aromatic vinyl compound and a vinyl cyanide compound. The aromatic vinyl-vinyl cyanide copolymer has a weight average molecular weight of at least 80,000 g/mol, for example at least 85,000 g/mol, for example at least 90,000 g/mol, and at most 200,000 g/mol, for example at most 150,000 g/mol, for example from 80,000 to 200,000 g/mol, for example from 80,000 to 150,000 g/mol.

The above aromatic vinyl compound may be at least one selected from styrene, α-methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, and vinylnaphthalene.

The above cyanide vinyl compound may be at least one selected from acrylonitrile, methacrylonitrile, and fumaronitrile.

In one embodiment, the aromatic vinyl-cyanide vinyl copolymer can be a styrene-acrylonitrile copolymer (SAN).

In one embodiment, based on 100 wt% of the aromatic vinyl-vinyl cyanide copolymer, the aromatic vinyl compound-derived component may be contained in an amount of 60 wt% or more, for example, 65 wt% or more, for example, 70 wt% or more, for example, 85 wt% or less, for example, 80 wt% or less, and for example, 60 to 85 wt%, for example, 60 to 80 wt%.

In one embodiment, based on 100 wt% of the aromatic vinyl-cyanide vinyl copolymer, the cyanide vinyl compound derived component may be contained in an amount of 15 wt% or more, for example, 20 wt% or more, for example, 40 wt% or less, for example, 35 wt% or less, for example, 30 wt% or less, and for example, 15 to 40 wt%, for example, 20 to 40 wt%.

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer can have a melt flow index measured under the condition of 200° C., 5 kg load according to ASTM D1238 of 1 g/10 min or more, 1.5 g/10 min or more, 2 g/10 min or more, 10 g/10 min or less, 9 g/10 min or less, 8 g/10 min or less, 7 g/10 min or less, 6 g/10 min or less, 5 g/10 min or less, for example, 1 to 10 g/10 min, for example, 1 to 9 g/10 min, for example, 1 to 8 g/10 min, for example, 1 to 7 g/10 min, for example, 1 to 6 g/10 min, for example, 1 to 5 g/10 min, for example, 1.5 to 5 g/10 min.

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer can be present in an amount of at least 7 wt%, for example at least 8 wt%, based on 100 wt% of the base resin, and can be present in an amount of at most 13 wt%, for example at most 12 wt%, and can be present in an amount of from 7 to 13 wt%, for example from 8 to 12 wt%.

If the content of the aromatic vinyl-cyanide vinyl copolymer is less than 7 wt%, there is a concern that the mechanical rigidity and fluidity of the thermoplastic resin composition and the molded article manufactured therefrom may deteriorate, and if it exceeds 13 wt%, there is a concern that the impact resistance of the thermoplastic resin composition and the molded article manufactured therefrom may deteriorate.

(D) Zinc oxide

Zinc oxide performs the function of improving the antibacterial properties, light resistance, and weather resistance of a thermoplastic resin composition and a molded article manufactured therefrom.

In one embodiment, the average particle size (D50) of the zinc oxide can be 0.5 ㎛ or more, for example 0.8 ㎛ or more, for example 1 ㎛ or more, for example 5 ㎛ or less, for example 4 ㎛ or less, for example 3 ㎛ or less, for example 0.5 to 5 ㎛, for example 0.5 to 4 ㎛, for example 0.5 to 3 ㎛, for example 0.8 to 3 ㎛.

In one embodiment, the BET surface area of the zinc oxide can be at least 1 m ² /g, for example, at most 10 m ² /g, for example, at most 9 m ² /g, for example, at most 8 m ² /g, for example, at most 7 m ² /g, for example, from 1 to 10 m ² /g, for example, from 1 to 7 m ² /g.

If the average particle size and/or BET specific surface area of the zinc oxide are outside the above-mentioned range, there is a concern that the light resistance, weather resistance, antibacterial properties, etc. of the thermoplastic resin composition containing it and the molded article manufactured therefrom may deteriorate.

In one embodiment, the purity of the zinc oxide, as measured from the weight remaining at a temperature of 800° C. using TGA thermal analysis, can be greater than or equal to 99%.

In one embodiment, the zinc oxide may have a peak position 2θ value of 35 to 37° in the range of X-ray diffraction (XRD) analysis, and a crystallite size value calculated by applying Scherrer's equation (Equation 1 below) based on the measured FWHM value (Full width at Half Maximum of a diffraction peak) may be 1,000 to 2,000 Å, for example, 1,200 to 1,800 Å.

Specifically, the above crystallite size can be measured using a high resolution X-ray diffractometer (manufacturer: X'pert, device name: PRO-MRD), and can be measured regardless of the specimen type (e.g., powder form, injection molded specimen). Meanwhile, when an injection molded specimen is used, for more accurate analysis, the residual polymer is removed by heat treatment at 600°C in air for 2 hours, and then XRD analysis is performed.

If the peak position of the zinc oxide and/or the size of the crystallites are outside the above range, there is a concern that the light resistance, weather resistance, antibacterial properties, etc. of the thermoplastic resin composition containing the same and the molded article manufactured therefrom may deteriorate.

[Formula 1]

Microcrystal size (D) =

In the above equation 1, k is the shape factor and λ is the X-ray wavelength.

wavelength), β is the FWHM value (degree) of the X-ray diffraction peak, and θ is the peak position value (peak position degree).

In one embodiment, the zinc oxide can have various shapes, including, for example, spherical, plate-shaped, rod-shaped, and combinations thereof.

In one embodiment, the zinc oxide may have a size ratio of peak A in a region of 370 to 390 nm and peak B in a region of 450 to 600 nm (PL size ratio, B/A) in a photoluminescence measurement of 0.01 to 1, for example, 0.1 to 1, and specifically 0.1 to 0.5.

The above photoluminescence measurement is performed by placing zinc oxide powder into a 6 mm diameter pelletizer and pressing it to produce a flat measurement specimen, and then irradiating the measurement specimen with a He-Cd laser (KIMMON, 30 mW) having a wavelength of 325 nm at room temperature, and detecting the emitted spectrum using a CCD detector. The temperature of the CCD detector is set to be maintained at -70°C.

When the PL size ratio of the zinc oxide is within the above range, a thermoplastic resin composition containing the same and a molded article manufactured therefrom can exhibit excellent light resistance, weather resistance, and antibacterial properties.

In one embodiment, the zinc oxide can be manufactured by melting zinc in a metallic form, heating it to 850 to 1,000°C, for example, 900 to 950°C, vaporizing it, injecting oxygen gas, cooling it to 20 to 30°C, and then heating it at 400 to 900°C, for example, 500 to 800°C, for 30 to 150 minutes, for example, 60 to 120 minutes.

In one embodiment, the zinc oxide may be included in an amount of 0.7 to 5 parts by weight, for example, 0.8 to 5 parts by weight, for example, 0.8 to 4.5 parts by weight, for example, 1 to 4.5 parts by weight, for example, 1 to 4 parts by weight, based on 100 parts by weight of the base resin.

When the amount of the zinc oxide is less than 0.7 parts by weight, there is a concern that the light resistance, weather resistance, antibacterial properties, etc. of the thermoplastic resin composition containing it and the molded article manufactured from it may deteriorate, and when it exceeds 5 parts by weight, there is a concern that the weather resistance, light resistance, heat resistance, heat stability, etc. of the thermoplastic resin composition containing it and the molded article manufactured from it may deteriorate.

(E) A phosphorus compound represented by chemical formula 1

A thermoplastic resin composition according to one embodiment comprises a predetermined phosphorus compound. The predetermined phosphorus compound can be represented by the following chemical formula 1.

[Chemical Formula 1]

(RO) _n P(=O)(OH) _3-n

In chemical formula 1,

n is an integer from 1 to 3,

R is selected from a substituted or unsubstituted C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted C3 to C30 heteroaryl group.

In one embodiment, the phosphorus compound represented by the chemical formula 1 may be exemplified by trimethyl phosphate, triethyl phosphate, triphenyl phosphate, stearyl phosphate, etc., and these may be used alone or in combination of two or more.

The phosphorus compound represented by the chemical formula 1 above can prevent deterioration of the thermoplastic resin composition (e.g., decomposition of polycarbonate resin, etc.) that may occur due to the addition of the zinc oxide described above. That is, the thermoplastic resin composition according to one embodiment exhibits excellent light resistance, weather resistance, and antibacterial properties by using the phosphorus compound represented by the chemical formula 1 together with the zinc oxide described above, and can excellently maintain a balance of other properties such as heat resistance, impact resistance, and thermal stability.

The phosphorus compound represented by the above chemical formula 1 may be included in an amount of 0.2 parts by weight or more, for example, 0.25 parts by weight or more, for example, 0.3 parts by weight or more, with respect to 100 parts by weight of the base resin, and may be included in an amount of, for example, 0.6 parts by weight or less, for example, 0.55 parts by weight or less, for example, 0.5 parts by weight or less, and may be included in an amount of, for example, 0.2 to 0.6 parts by weight, for example, 0.25 to 0.55 parts by weight, for example, 0.3 to 0.5 parts by weight.

If the phosphorus compound represented by the chemical formula 1 above is outside the above-mentioned range, there is a concern that the physical property balance of the thermoplastic resin composition containing it and the molded article manufactured therefrom may deteriorate, and in particular, there is a concern that the impact resistance, weather resistance, light resistance, etc. may be significantly reduced.

(F) Additive

A thermoplastic resin composition according to one embodiment may further include, in addition to the components (A) to (E), one or more additives necessary to balance the properties of the thermoplastic resin composition under conditions that minimize deterioration of the properties of the thermoplastic resin composition during processing or use, or depending on the final use of the thermoplastic resin composition.

Specifically, as the additives, flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, release agents, heat stabilizers, antioxidants, inorganic additives, ultraviolet stabilizers, antistatic agents, pigments, dyes, etc. can be used, and these can be used alone or in combination of two or more.

These additives may be appropriately included within a range that does not impair the properties of the thermoplastic resin composition, and specifically, may be included in an amount of 20 parts by weight or less relative to 100 parts by weight of the base resin, but is not limited thereto.

Meanwhile, the thermoplastic resin composition according to one embodiment can also be mixed and used together with other resins or other rubber components.

Meanwhile, another embodiment provides a molded article manufactured using a thermoplastic resin composition according to one embodiment. The molded article can be manufactured using the thermoplastic resin composition by various methods known in the art, such as injection molding and extrusion molding.

The above molded article may have a notched Izod impact strength of a 1/8" thick specimen according to ASTM D256 of 30 kgf cm/cm or more, for example, 31 kgf cm/cm or more, for example, 32 kgf cm/cm or more, for example, 33 kgf cm/cm or more, for example, 34 kgf cm/cm or more, for example, 35 kgf cm/cm or more, for example, 36 kgf cm/cm or more, for example, 37 kgf cm/cm or more, for example, 38 kgf cm/cm or more, for example, 39 kgf cm/cm or more, for example, 40 kgf cm/cm or more, and may have a strength of 100 kgf cm/cm or less, for example, 90 kgf cm/cm or less, for example, 80 kgf cm/cm or less, for example, 70 kgf cm/cm or less, for example, 30 to 100 kgf·cm/cm, for example, 35 to 100 kgf·cm/cm, for example, 40 to 100 kgf·cm/cm.

The above molded product may have an antibacterial activity value of 2 or more, for example 2.5 or more, for example 3 or more, for example 3.5 or more, for example 4 or more, when inoculated with Staphylococcus aureus and Escherichia coli according to JIS Z 2801 antibacterial evaluation method and cultured for 24 hours under conditions of 35°C and 90% RH, respectively; and may be 7 or less, for example 6.5 or less, for example 2 to 7, for example 3 to 7, for example 4 to 7.

The above molded product may have a color difference change (△E) of more than 0 and less than 0.4, for example, more than 0 and 0.35 or less, for example, more than 0 and 0.3 or less, as measured under the conditions of 89℃, RH 50%, 84 MJ/ ^m2 , and a lamp wavelength of 300 to 400 nm by the xenon arc test method specified in SAE J 1885.

The above molded article may have a heat deflection temperature (HDT) of a specimen measured under a load of 18.56 kg according to ASTM D648 of 110 to 200°C, for example, 115 to 200°C.

In this way, the molded article can be advantageously used in various electrical and electronic components, building materials, sporting goods, and interior/exterior parts of automobiles because it has excellent impact resistance, antibacterial properties, light resistance, and heat resistance. Specifically, the molded article can be used in automobile interior materials that require high heat resistance, light resistance, and impact resistance, and additionally antibacterial properties, such as automobile overhead consoles, but is not limited thereto.

Hereinafter, preferred embodiments of the present invention will be described. However, the following embodiments are only preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.

Examples 1 to 4 and Comparative Examples 1 to 6

The thermoplastic resin compositions of Examples 1 to 4 and Comparative Examples 1 to 6 were prepared according to the component content ratios described in Table 1 below.

In Table 1, (A), (B), and (C) are included in the base resin and are expressed in weight % based on the total weight of the base resin, and (D) and (E) are added to the base resin and are expressed in weight parts per 100 weight parts of the base resin.

The components described in Table 1 were dry mixed and quantitatively and continuously fed into the feed section (barrel temperature: approximately 260°C) of a twin-screw extruder (L/D=44, φ=35 mm) to be melted/kneaded. Then, the pelletized thermoplastic resin composition was dried at approximately 80°C for approximately 4 hours through the twin-screw extruder, and then specimens for property evaluation were manufactured using a 6 oz injection molding machine having a cylinder temperature of approximately 280°C and a mold temperature of approximately 80°C.

ingredient unit Example Comparative example 1 2 3 4 1 2 3 4 5 6 Basic balance (A) weight% 80 80 80 80 80 80 80 80 80 80 (B) weight% 10 10 10 10 10 10 10 10 10 10 (C) weight% 10 10 10 10 10 10 10 10 10 10 (D) Weight part 1 2 2 4 0 0.5 1 2 6 6 (E) Weight part 0.2 0.2 0.4 0.4 0 0 0 0.1 0.2 0.4

(A) Polycarbonate resin

Polycarbonate resin having a weight average molecular weight of 20,000 to 30,000 g/mol and a melt flow index of 11 to 15 g/10 min measured under 250℃ and 10 kg load conditions according to ASTM D1238 (Lotte Advanced Materials Co., Ltd.)

(B) Acrylic rubber-modified aromatic vinyl graft copolymer

Acrylonitrile-styrene-acrylate graft copolymer (Lotte Advanced Materials Co., Ltd.) prepared by graft polymerizing 50 parts by weight of an acrylic rubber polymer having an average particle size of about 320 nm manufactured using butyl acrylate as a main monomer and a mixture of styrene and acrylonitrile

(C) Aromatic vinyl-cyanide vinyl copolymer

A styrene-acrylonitrile copolymer (Lotte Advanced Materials) having a melt flow index of approximately 2.4 g/10 min measured under conditions of 200°C and 5 kg load according to ASTM D1238 and containing approximately 24 wt% of acrylonitrile-derived components

(D) Zinc oxide

Specific gravity 5.47 to 5.64 g/cm ³ , pH 6.95 to 7.37, (absolute) refractive index Zinc oxide (Hanil Chemical Co., KS-1) having an average particle size (D50) of about 1.2 ㎛, a BET surface area of about 4 m ² /g, a purity of about 99%, a PL size ratio (B/A) of about 0.28, and a crystallite size of about 1,417 Å

(E) A phosphorus compound represented by chemical formula 1

Stearyl phosphate (ADEKA) as a phosphorus compound satisfying the chemical formula 1 described above, having a melting point of 68 to 75°C

Property Evaluation

For the physical property evaluation specimens manufactured in Examples 1 to 4 and Comparative Examples 1 to 6, the antibacterial properties, impact resistance, light resistance, and heat resistance were measured as follows, and the results are summarized in Table 2.

(1) Antibacterial activity: Staphylococcus aureus and Escherichia coli were inoculated onto the specimen according to the JIS Z 2801 antibacterial evaluation method, and the antibacterial activity was measured after culturing for 24 hours under conditions of 35°C and RH 90%.

(2) Impact strength (unit: kgf cm/cm): The notched Izod impact strength was measured on 1/8" thick specimens according to ASTM D256.

(3) Light resistance: The color difference change (△E) of the specimen was measured under the conditions of 89℃, RH 50%, 84 MJ/ ^m2 , and lamp wavelength 300 to 400 nm by the xenon arc test method specified in SAE J 1885.

(4) Heat resistance (unit: ℃): Heat deflection temperature (HDT) was measured under a load of 18.56 kg according to ASTM D648.

Physical properties Example Comparative example 1 2 3 4 1 2 3 4 5 6 Antibacterial activity Staphylococcus aureus 4.6 4.6 4.6 4.6 0 0 4.6 4.6 4.6 4.6 Escherichia coli 6.2 6.2 6.2 4.2 0.4 0.4 3.2 6.2 6.2 6.2 Izod impact strength 43 42 45 43 42 20 20 22 37 35 Color difference change 0.22 0.25 0.21 0.23 0.21 0.4 0.45 0.41 0.5 0.45 Heat deflection temperature 116 118 117 117 117 117 115 116 115 115

From Tables 1 and 2, it can be confirmed that the thermoplastic resin compositions of the examples are all excellent in antibacterial properties, impact resistance, light resistance, and heat resistance.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the appended claims also fall within the scope of the present invention.

Claims (18)

(A) 75 to 85 wt% of polycarbonate resin;
(B) 7 to 15 wt% of an acrylic rubber-modified aromatic vinyl graft copolymer; and
(C) 7 to 13 wt% of aromatic vinyl-cyanide vinyl copolymer
For 100 parts by weight of base resin containing
(D) 0.7 to 5 parts by weight of zinc oxide (ZnO); and
(E) 0.2 to 0.6 parts by weight of a phosphorus compound represented by the following chemical formula 1
Including,
The above (A) polycarbonate resin is a thermoplastic resin composition having a melt flow index of 5 to 40 g/10 min as measured under conditions of 250°C and 10 kg load according to ASTM D1238:
[Chemical Formula 1]
(RO) _n P(=O)(OH) _3-n
In chemical formula 1,
n is an integer from 1 to 3,
R is selected from a substituted or unsubstituted C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted C3 to C30 heteroaryl group. In paragraph 1,
A thermoplastic resin composition having an average particle size (D50) of the zinc oxide (D) of 0.5 to 3 ㎛. In paragraph 1,
A thermoplastic resin composition having a BET surface area of the zinc oxide (D) of 1 to 10 m ² /g. In paragraph 1,
The above (D) zinc oxide is a thermoplastic resin composition having a peak position 2θ value of 35 to 37° in X-ray diffraction (XRD) analysis and a crystallite size value of 1,000 to 2,000 Å according to the following formula 1:
[Formula 1]
Microcrystal size (D) =
In the above equation 1, k is the shape factor and λ is the X-ray wavelength.
wavelength), β is the FWHM value (degree) of the X-ray diffraction peak, and θ is the peak position value (peak position degree). In paragraph 1,
The above (D) zinc oxide is a thermoplastic resin composition in which, when measuring photoluminescence, the size ratio (B/A) of peak A in the range of 370 to 390 nm and peak B in the range of 450 to 600 nm is 0.01 to 1. delete In paragraph 1,
The above (B) acrylic rubber-modified aromatic vinyl graft copolymer is a thermoplastic resin composition having an average particle diameter of the acrylic rubber polymer of 100 to 500 nm. In paragraph 1,
The above (B) acrylic rubber-modified aromatic vinyl graft copolymer is a thermoplastic resin composition in which a monomer mixture containing an aromatic vinyl compound and a cyanide vinyl compound is graft-polymerized into 40 to 60 wt% of an acrylic rubber polymer. In paragraph 1,
The above (B) acrylic rubber-modified aromatic vinyl graft copolymer is a thermoplastic resin composition which is an acrylonitrile-styrene-acrylate graft copolymer. In paragraph 1,
A thermoplastic resin composition wherein the above (C) aromatic vinyl-vinyl cyanide copolymer is a copolymer of a monomer mixture containing 60 to 85 wt% of an aromatic vinyl compound and 15 to 40 wt% of a vinyl cyanide compound. In paragraph 1,
The above (C) aromatic vinyl-vinyl cyanide copolymer is a thermoplastic resin composition having a melt flow index of 1 to 10 g/10 min measured under conditions of 200°C and 5 kg load according to ASTM D1238. In paragraph 1,
A thermoplastic resin composition wherein the above (C) aromatic vinyl-cyanide vinyl copolymer is a styrene-acrylonitrile copolymer. In the first paragraph,
A thermoplastic resin composition further comprising at least one additive selected from flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, release agents, heat stabilizers, antioxidants, inorganic additives, ultraviolet stabilizers, antistatic agents, pigments, and dyes. A molded product manufactured from a thermoplastic resin composition according to any one of claims 1 to 5 and claims 7 to 13. In Article 14,
The above molded product is a molded product having a notched Izod impact strength of 30 to 100 kgf cm/cm for a 1/8" thick specimen according to ASTM D256. In Article 14,
The above molded product is a molded product having an antibacterial activity value of 2 to 7, respectively, when inoculated with Staphylococcus aureus and Escherichia coli on a specimen according to the JIS Z 2801 antibacterial evaluation method and cultured for 24 hours under conditions of 35°C and 90% RH. In Article 14,
The above molded product is a molded product in which the color difference change (△E) of the specimen is greater than 0 and less than 0.4, as measured under the conditions of 89℃, RH 50%, 84 MJ/m ² , and a lamp wavelength of 300 to 400 nm by the xenon arc test method specified in SAE J 1885. In Article 14,
The above molded product is a molded product having a heat deflection temperature (HDT) of 110 to 200°C when measured under a load of 18.56 kg according to ASTM D648.