KR102194062B1 - Thermoplastic resin composition and article including same - Google Patents

Abstract

(A) 60% to 85% by weight of a polycarbonate resin having a terminal hydroxyl group content of 15% to 50% by mole, (B) 6% to 25% by weight of an acrylic graft copolymer, and (C) (D) 0.1 to 0.7 parts by weight of a modifier containing an epoxy group, and (E) crosslinked aromatic vinyl with respect to 100 parts by weight of the base resin containing 5 to 20% by weight of an aromatic vinyl-cyanide copolymer -It provides a thermoplastic resin composition comprising 1 to 5 parts by weight of a vinyl cyanide copolymer and a molded article comprising the same.

Description

Thermoplastic resin composition and molded article containing the same {THERMOPLASTIC RESIN COMPOSITION AND ARTICLE INCLUDING SAME}

It relates to a thermoplastic resin composition and a molded article comprising the same.

Acrylate-Styrene-Acrylonitrile (ASA) resin has excellent weather resistance and is widely used in outdoor building materials and automotive exterior materials. However, in order to apply the ASA resin to applications that require high impact strength due to poor impact resistance, etc., the content of the acrylic rubber polymer in the ASA resin must be increased. However, if the content of the acrylic rubber polymer is increased, the heat resistance, etc. There is a limit to application to applications requiring high heat resistance, such as.

As an alternative to this, a method of supplementing heat resistance and impact resistance by alloying ASA resin and polycarbonate (PC) resin having excellent heat resistance has been proposed. Such PC/ASA resins are used as interior/exterior materials for various vehicles. Can be applied to

As a representative method for producing a polycarbonate (PC) resin, two methods are known: an interfacial polymerization method (also called a solvent method or a phosgene method) and a melt polymerization method. Among them, the phosgene gas used in the interfacial polymerization method has serious toxicity, and a problem has been raised in terms of environmental safety.

On the other hand, the melt polymerization method is a method of producing a polycarbonate resin by using a transesterification reaction without using a phosgene gas, so it is more eco-friendly than the above-described interfacial polymerization method. In addition, the melt polymerization method is excellent in terms of mass productivity because the reaction device is simple and there is no need to use a separate solvent.

However, the polycarbonate resin prepared by the melt polymerization method has a lot of hydroxyl groups at the ends of the polycarbonate polymer chain compared to the polycarbonate resin prepared by the interfacial polymerization method, so when a polycarbonate resin prepared by the melt polymerization method is used, During product molding or use, the polycarbonate resin is likely to undergo an unintended hydrolysis reaction due to external heat or ultraviolet rays, and as a result, there is a possibility that unintended deterioration of physical properties may occur.

Even if a polycarbonate resin prepared by melt polymerization is used, a thermoplastic resin composition having excellent low light resistance, light resistance, and mechanical properties is provided.

Another embodiment provides a molded article comprising the thermoplastic resin composition.

According to one embodiment, (A) 60% to 85% by weight of a polycarbonate resin having a terminal hydroxyl group content of 15 mol% to 50 mol%; (B) 6% to 25% by weight of an acrylic graft copolymer; And (C) an aromatic vinyl-vinyl cyanide copolymer 5% to 20% by weight; (D) 0.1 to 0.7 parts by weight of an epoxy group-containing modifier based on 100 parts by weight of the base resin; And (E) 1 to 5 parts by weight of a crosslinked aromatic vinyl-cyanide copolymer, a thermoplastic resin composition is provided.

The (D) epoxy group-containing modifier may be a compound represented by the following formula (1).

[Formula 1]

In Formula 1, R ¹ to R ³ are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or Any one selected from an unsubstituted C4 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkylcarbonyl group, and L is a single bond, a substituted or An unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C4 to C30 cycloalkylene group, an ether group, or a combination thereof.

The (D) epoxy group-containing modifier may be a compound represented by the following formula (2).

[Formula 2]

In Formula 2, R ¹ to R ³ are each independently selected from a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C4 to C30 cycloalkyl group, and a substituted or unsubstituted C1 to C30 alkoxy group. One, and L ^a and L ^b are each independently selected from a substituted or unsubstituted C1 to C30 alkylene group, and a substituted or unsubstituted C4 to C30 cycloalkylene group.

The (A) polycarbonate resin may be manufactured by a melt polymerization method.

The (B) acrylic graft copolymer may have an average particle diameter of an acrylic rubber polymer of 300 nm to 400 nm.

The (B) acrylic graft copolymer may be obtained by graft polymerization of 40% to 60% by weight of an acrylic rubber polymer and 40% to 60% by weight of a mixture of an aromatic vinyl compound and a vinyl cyanide compound.

The (B) acrylic graft copolymer may be an acrylonitrile-styrene-acrylate graft copolymer.

The (C) aromatic vinyl-vinyl cyanide copolymer may be a copolymer of a monomer mixture including 60% to 80% by weight of an aromatic vinyl compound and 20% to 40% by weight of a vinyl cyanide compound.

The weight average molecular weight of the (C) aromatic vinyl-cyanide vinyl copolymer may be 80,000 g/mol to 200,000 g/mol.

The (E) crosslinked aromatic vinyl-vinyl cyanide copolymer may have a glass transition temperature (Tg) of 100°C to 150°C.

The (E) crosslinked aromatic vinyl-vinyl cyanide copolymer may be a crosslinked styrene-acrylonitrile copolymer.

The thermoplastic resin composition is at least one additive selected from flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, release agents, thermal stabilizers, antioxidants, inorganic additives, ultraviolet stabilizers, antistatic agents, pigments, and dyes It may further include.

Meanwhile, according to another embodiment, a molded article using the above-described thermoplastic resin composition may be provided.

Even if a polycarbonate resin prepared by a melt polymerization method is used, a thermoplastic resin composition having excellent low light resistance, light resistance, and mechanical properties can be provided.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

In the present specification, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

In the present specification, unless otherwise specified, the average particle diameter means a Z-average mean particle diameter measured using a dynamic light scattering analyzer.

In the present specification, "substitution" means a substituent selected from the group consisting of a halogen group, a C1 to C30 alkyl group, a C1 to C30 haloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, and combinations thereof It means substituted with, and "unsubstituted" means that a hydrogen atom remains as a hydrogen atom without being substituted with another substituent.

The thermoplastic resin composition of the present invention comprises (A) 60% to 85% by weight of a polycarbonate resin having a terminal hydroxyl group content of 15% to 50% by mole; (B) 6% to 25% by weight of an acrylic graft copolymer; And (C) with respect to 100 parts by weight of the base resin containing 5 to 20% by weight of the aromatic vinyl-vinyl cyanide copolymer, (D) 0.1 to 0.7 parts by weight of a modifier containing an epoxy group; And (E) 1 to 5 parts by weight of a crosslinked aromatic vinyl-vinyl cyanide copolymer.

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

(A) Polycarbonate resin

In the thermoplastic resin composition, the polycarbonate is a polyester having a carbonate bond.

The polycarbonate resin (A) may be prepared using an interfacial polymerization method and a melt polymerization method. In one embodiment, the polycarbonate resin (A) may be prepared using a melt polymerization method.

When preparing a polycarbonate resin through a melt polymerization method, for example, the process of synthesizing a polycarbonate by separating phenol using a transesterification reaction of an aromatic diol compound and a diaryl carbonate compound may be included.

Examples of the aromatic diol compound include 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1, 1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane , 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, etc. are mentioned. Preferably 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4 -Hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and the like, more preferably 2,2-bis-(4-hydroxyphenyl) called "bisphenol A" Propane is mentioned.

Examples of the diaryl carbonate include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, and the like, but these may be used alone or as 2 More than one species may be used, and for example, diphenyl carbonate may be used.

The polycarbonate resin (A) may be used having a weight average molecular weight of 5,000 　 to 200,000 　g/mol, and specifically 5,000 　 to 40,000 　g/mol for mechanical properties and moldability. When the weight average molecular weight of the polycarbonate resin (A) is within the above range, excellent impact resistance and fluidity can be obtained. In addition, in order to satisfy the desired fluidity, two or more types of polycarbonate resins having different weight average molecular weight ranges may be mixed and used.

In one embodiment, the polycarbonate resin (A) may have a terminal hydroxyl group content of 15 mol% or more, for example, 20 mol% or more, and, for example, 50 mol% or less, such as 40 mol% It may be less than or equal to, for example, 15 mol% to 50 mol%, for example, 20 mol% to 40 mol%.

When the polycarbonate resin (A) according to an embodiment is manufactured using a melt polymerization method, a hydroxyl group at the end of the polymer chain may be contained within the above-described range. That is, the polycarbonate resin (A) may contain more hydroxyl groups than other polycarbonate resins that can be prepared using an interfacial polymerization method.

When the hydroxyl group contained in the polycarbonate resin receives external heat or ultraviolet rays during various processing processes (eg, injection molding processes) of a thermoplastic resin composition containing the polycarbonate resin or during use of a molded product using the thermoplastic resin composition Unintended hydrolysis reactions may occur.

However, the thermoplastic resin composition according to an embodiment may deactivate the hydroxyl groups in the polycarbonate resin (A) by using the modifier (D) containing an epoxy group, and as a result, external heat during various processing or use of the thermoplastic resin composition , It is possible to prevent the occurrence of an unintended hydrolysis reaction in the polycarbonate resin (A) due to ultraviolet rays. The structure and function of the epoxy group-containing modifier (D) will be described later.

The polycarbonate resin (A) may be contained at least 60% by weight or more, for example 70% by weight or more, for example 80% by weight or more, based on 100% by weight of the base resin, for example 90% by weight Below, for example, it may contain 85% by weight or less.

When the content of the polycarbonate resin (A) in the base resin is less than 60% by weight, there is a concern that the heat resistance of the thermoplastic resin composition is deteriorated. On the other hand, if the polycarbonate resin (A) content in the base resin exceeds 90% by weight, impact resistance may be lowered, and it becomes difficult to deactivate the terminal hydroxyl groups contained in the polycarbonate resin to the desired level, so the molding of the thermoplastic resin composition In the process, there is a risk of deterioration of properties due to hydrolysis.

(B) Acrylic graft copolymer

In one embodiment, the acrylic graft copolymer (B) performs a function of enhancing the weather resistance and impact resistance of the thermoplastic resin composition by alloying with the polycarbonate resin (A).

In one embodiment, the acrylic graft copolymer (B) may be prepared by graft polymerization of a monomer mixture including an aromatic vinyl compound and a vinyl cyanide compound on an acrylic rubber polymer.

The acrylic graft copolymer (B) may be prepared according to any method known to a person skilled in the art.

As the production method, conventional polymerization methods, for example, emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization may be used. As a non-limiting example, an acrylic rubber polymer is prepared, and a monomer mixture including an aromatic vinyl compound and a vinyl cyanide compound is graft-polymerized on a core formed of one or more layers of the acrylic rubber polymer to form one or more shell layers. It can be manufactured by a method.

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

The acrylic monomer may be copolymerized with one or more radically polymerizable other monomers. When copolymerized, the amount of the one or more radically polymerizable other monomers may be 5% to 30% by weight, specifically 10% to 20% by weight, based on the total weight of the acrylic rubber polymer.

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

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

Based on 100% by weight of the total acrylic graft copolymer (B), the acrylic rubber polymer may be 30% to 70% by weight, for example, 40% to 60% by weight.

Meanwhile, the monomer mixture including the aromatic vinyl compound and the vinyl cyanide compound graft-polymerized to the acrylic rubber polymer may be 30% to 70% by weight, for example, 40% to 60% by weight.

In a shell layer formed by graft polymerization of a monomer mixture including the aromatic vinyl compound and the vinyl cyanide compound to the acrylic rubber polymer, the aromatic vinyl compound is 50% to 80% by weight based on the total weight of the shell layer, Specifically, it is 60% by weight to 70% by weight, and the vinyl cyanide compound may be 20% by weight to 50% by weight, specifically 30% by weight to 40% by weight, based on the total weight of the shell layer.

In one embodiment, the acrylic graft copolymer (B) may be an acrylate-styrene-acrylonitrile graft copolymer.

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

In one embodiment, the acrylic graft copolymer (B) has an average particle diameter of the acrylic rubber polymer of 250 nm or more, such as 300 nm or more, for example, 400 nm or less, such as 350 nm or less, For example, it may be 300 nm to 400 nm, for example 300 nm to 350 nm.

When the average particle diameter of the acrylic rubber polymer in the acrylic graft copolymer (B) is less than 250 nm, there is a concern that overall mechanical properties such as impact resistance and tensile strength of the thermoplastic resin composition including the same may be deteriorated.

On the other hand, when the average particle diameter of the acrylic rubber polymer in the acrylic graft copolymer (B) exceeds 400 nm, the fluidity and processability of the thermoplastic resin composition containing the same decreases, and the dispersibility of the acrylic graft copolymer in the resin composition There is a risk of deterioration.

The acrylic graft copolymer (B) may contain more than 5% by weight, for example 6% by weight or more, for example 7% by weight or more, based on 100% by weight of the base resin, for example 25% by weight % Or less, for example 20% by weight or less, for example, 15% by weight or less.

If the content of the acrylic graft copolymer (B) in the base resin is 5% by weight or less, the impact resistance of the thermoplastic resin composition may be reduced, and the content of the acrylic graft copolymer (B) in the base resin may exceed 25% by weight. In this case, there is a concern that the mechanical rigidity and colorability of the thermoplastic resin composition may be deteriorated.

(C) Aromatic vinyl-vinyl cyanide copolymer

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer (C) performs a function of maintaining compatibility between components of the thermoplastic resin composition at a certain level.

In one embodiment, the aromatic vinyl-cyanide vinyl copolymer (C) may be a copolymer of an aromatic vinyl compound and a vinyl cyanide compound. The aromatic vinyl-vinyl cyanide copolymer (C) has a weight average molecular weight of 80,000 g/mol or more, such as 85,000 g/mol or more, such as 90,000 g/mol or more, for example 200,000 g/mol or less, For example, it is 150,000 g/mol or less, for example, 80,000 g/mol to 200,000 g/mol, for example, 80,000 g/mol to 150,000 g/mol may be used.

In the present invention, the weight average molecular weight is measured by dissolving a powder sample in tetrahydrofuran (THF), and then using Agilent Technologies' 1200 series Gel Permeation Chromatography (GPC) (column is Shodex LF-804, The standard sample is Shodex's polystyrene).

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

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer (C) may be a styrene-acrylonitrile copolymer (SAN) having a weight average molecular weight of 80,000 g/mol to 200,000 g/mol.

In one embodiment, based on 100% by weight of the aromatic vinyl-vinyl cyanide copolymer (C), 10% by weight or more of the vinyl cyanide compound, such as 15% by weight or more, for example, 20% by weight or more may be included. May be, for example, 50% by weight or less, for example, 40% by weight or less, may be included, for example, 10% by weight to 50% by weight, for example, 20% by weight to 40% by weight may be included .

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer (C) may contain 5% by weight or more, for example 7% by weight or more, based on 100% by weight of the base resin, for example, 20% by weight or less, for example 15% by weight or less, for example, 10% by weight or less may be included, for example, 5% by weight to 20% by weight, for example, 5% by weight to 10% by weight may be included.

If the content of the aromatic vinyl-vinyl cyanide copolymer (C) is less than 5% by weight, the mechanical rigidity and heat resistance of the thermoplastic resin composition may be lowered, and if it exceeds 20% by weight, the impact resistance and weather resistance of the thermoplastic resin composition There is a risk of deterioration.

(D) Epoxy group-containing modifier

In one embodiment, the epoxy group-containing modifier (D) deactivates a hydroxyl group in the polycarbonate resin (A) as described above, thereby various processing of the thermoplastic resin composition including the polycarbonate resin (A) or the thermoplastic resin composition. In the process of using the used molded product, it functions to prevent unintended hydrolysis reaction from occurring in the polycarbonate resin (A) due to external heat, ultraviolet rays, etc., especially external ultraviolet rays.

Specifically, the epoxy group-containing modifier (D) includes an epoxy group, and the epoxy group may form a chemical bond with a hydroxyl group at the end of the polymer chain of the polycarbonate resin.

In one embodiment, the epoxy group in the epoxy group-containing modifier (D) may cause a reaction to open a ring by a hydroxyl group included in the polycarbonate resin. In this case, one of the two carbon atoms constituting the epoxy group together with the oxygen atom may form an ether bond with a hydroxyl group included in the polycarbonate resin.

That is, in one embodiment, the epoxy group-containing modifier (D) may be deactivated by capping a highly reactive hydroxyl group contained in the polycarbonate resin with an epoxy group. Accordingly, it is possible to provide a thermoplastic resin composition having excellent light resistance by effectively inactivating the hydroxyl groups contained in the polycarbonate resin (A) with the epoxy group-containing modifier (D).

In one embodiment, the epoxy group-containing modifier (D) may be a compound represented by Formula 1 below.

[Formula 1]

In Formula 1, R ¹ to R ³ are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or Any one selected from an unsubstituted C4 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkylcarbonyl group, and L is a single bond, a substituted or It may include an unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C4 to C30 cycloalkylene group, an ether group, or a combination thereof.

Specifically, the epoxy group-containing modifier (D) may be a compound represented by Formula 2 below.

[Formula 2]

In Formula 2, R ¹ to R ³ are each independently selected from a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C4 to C30 cycloalkyl group, and a substituted or unsubstituted C1 to C30 alkoxy group. One, and L ^a and L ^b may each independently be any one selected from a substituted or unsubstituted C1 to C30 alkylene group, and a substituted or unsubstituted C4 to C30 cycloalkylene group.

In one embodiment, based on 100 parts by weight of the base resin, the epoxy group-containing modifier (D) may be more than 0, for example, 0.1 parts by weight or more, and less than 1 part by weight, for example, 0.9 parts by weight or less, for example For example, 0.8 parts by weight or less, for example 0.7 parts by weight or less, for example 0.6 parts by weight or less, for example, 0.5 parts by weight or less, may be included, for example, 0.1 parts by weight to 0.7 parts by weight, for example 0.1 parts by weight To 0.5 parts by weight, for example, 0.2 to 0.5 parts by weight.

When the thermoplastic resin composition according to an embodiment does not contain an epoxy group-containing modifier (D), it is difficult to inactivate the terminal hydroxyl groups in the polycarbonate resin (A), and thus there is a risk of unintended deterioration in physical properties during molding or use. . On the other hand, when the thermoplastic resin composition contains 1 part by weight or more of the epoxy group-containing modifier (D), there is a concern that the epoxy group-containing modifier (D) deteriorates the impact resistance function inherent in the polycarbonate resin.

(E) crosslinked aromatic vinyl-vinyl cyanide copolymer

In one embodiment, the cross-linked aromatic vinyl-vinyl cyanide copolymer (E) may be a material having an ultra-high molecular weight by forming a cross-linking bond with some of the polymer chains of the aromatic vinyl-cyanide vinyl copolymer. The crosslinked aromatic vinyl-vinyl cyanide copolymer (E) can provide a natural matting effect while maintaining excellent appearance on the surface of the molded article by forming fine-sized irregularities on the surface of the molded article when molding a thermoplastic resin composition containing the same. As a result, the crosslinked aromatic vinyl-vinyl cyanide copolymer (E) can enhance the low light characteristics and appearance characteristics of the thermoplastic resin.

In the crosslinked aromatic vinyl-cyanide vinyl copolymer (E), the aromatic vinyl compound is from styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, and vinylnaphthalene. It may be one or more selected.

In the crosslinked aromatic vinyl-cyanide vinyl copolymer (E), the vinyl cyanide compound may be at least one selected from acrylonitrile, methacrylonitrile, and fumaronitrile.

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

The glass transition temperature (Tg) measured by Differential Scanning Calorimetry (DSC) of the crosslinked aromatic vinyl-vinyl cyanide copolymer (E) is, for example, 100°C to 150°C, for example 110°C to It may be 150 ℃, for example 100 ℃ to 140 ℃, for example 110 ℃ to 140 ℃.

When the range of the glass transition temperature (Tg) of the crosslinked aromatic vinyl-vinyl cyanide copolymer (E) is out of the above range, there is a concern that the moldability of the thermoplastic resin composition including the same or appearance characteristics may decrease.

The crosslinked aromatic vinyl-vinyl cyanide copolymer (E) may be included in an amount of, for example, 10 parts by weight or less, for example, 8 parts by weight or less, for example, 5 parts by weight or less, based on 100 parts by weight of the base resin. , For example, more than 0, for example, 1 part by weight or more, for example, 2 parts by weight or more, may be included, for example, more than 0 and 10 parts by weight or less, for example, 1 part by weight to 5 parts by weight There may be.

When the content of the crosslinked styrene-acrylonitrile copolymer (E) satisfies the above range, low light characteristics and appearance characteristics of a thermoplastic resin composition including the same can be greatly improved.

(F) additive

In addition to the components (A) to (E), the thermoplastic resin composition according to an embodiment prevents degradation of physical properties due to hydrolysis of the polycarbonate resin during processing or use, and maintains excellent low light resistance, light resistance and mechanical strength. It may further include one or more additives necessary to balance the physical properties under conditions or according to the final use of the thermoplastic resin composition.

Specifically, as the additive, a flame retardant, a nucleating agent, a coupling agent, a filler, a plasticizer, an impact modifier, a lubricant, an antibacterial agent, a release agent, a heat stabilizer, an antioxidant, an inorganic additive, an ultraviolet stabilizer, an antistatic agent, a pigment, a dye 　, etc. can be used. These may be used alone or in combination of two or more.

These additives may be appropriately included within a range that does not impair the physical properties of the thermoplastic resin composition, and specifically, may be included in 20 parts by weight or less based on 100 parts by weight of the total amount of components (A) to (E). It is not limited.

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

On the other hand, another embodiment provides a molded article including the thermoplastic resin composition according to the embodiment. The molded article may be manufactured by various methods known in the art such as injection molding and extrusion molding using the thermoplastic resin composition.

The molded article has excellent mechanical properties such as impact resistance and heat resistance, as well as excellent light resistance, and greatly improved colorability, so that it can be advantageously used for various electric and electronic parts, building materials, sports goods, and automobile parts used outdoors. Specifically, the molded products may be used for satellite antennas, automobile door panels, automobile radiator grills, automobile side mirror housings, etc., but are not limited thereto.

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

Example

Hereinafter, the present invention will be described in more detail through examples and comparative examples, but the following examples and comparative examples are for the purpose of description and are not intended to limit the present invention.

Examples 1 to 4

Each of the components shown in Table 1 was mixed in the amount shown in Table 1 below, melted and extruded to prepare a thermoplastic resin composition in a pellet form. The extrusion was performed using a twin-screw extruder having L/D=44 and a diameter of 35 mm, and the barrel temperature was set to 260°C.

Comparative Examples 1 to 8

A thermoplastic resin composition in the form of pellets was prepared in the same manner as in Example 1, except for using the components and amounts shown in Table 1 below.

ingredient unit Example Comparative example One 2 3 4 One 2 3 4 5 6 7 8 Basic balance (A) weight% 80 80 85 85 80 80 80 80 80 80 91 91 (B) weight% 10 10 7 7 10 10 10 10 10 10 5 5 (C) weight% 10 10 8 8 10 10 10 10 10 10 4 4 (D) Parts by weight 0.2 0.5 0.2 0.5 - One - One 0.5 - 0.2 0.5 (E) Parts by weight 2 2 2 2 2 2 - - - 7 2 2

Parts by weight: parts by weight based on 100 parts by weight of base resin ((A) + (B) + (C)) (A) Polycarbonate resin: prepared by melt polymerization, and measured by gel permeation chromatography (GPC) Polycarbonate resin with an average molecular weight of about 28,000 g/mol and a terminal hydroxyl group content of about 30 mol% (manufacturer: Lotte Advanced Materials)

(B) Acrylic graft copolymer: An acrylonitrile-styrene-acrylate graft copolymer in which 50 parts by weight of styrene and acrylonitrile are graft-copolymerized to 50 parts by weight of a butyl acrylate rubber polymer having an average particle diameter of 320 nm (manufacturer : Lotte Advanced Materials)

(C) Aromatic vinyl-vinyl cyanide copolymer: A styrene-acrylonitrile copolymer having a weight average molecular weight of about 150,000 g/mol and an acrylonitrile content of about 24% by weight measured by gel permeation chromatography (GPC) ( Manufacturer: Lotte Advanced Materials)

(D) Epoxy group-containing modifier: Epoxy group-containing silane compound represented by the following formula (3) (manufacturer: Momentive Performance materials)

[Formula 3]

(E) Cross-linked aromatic vinyl-vinyl cyanide copolymer: Cross-linked styrene-acrylonitrile copolymer having a glass transition temperature (Tg) of about 122°C measured by differential scanning calorimeter (DSC) (manufacturer: Galata Chemicals)

Property evaluation

After drying the pellets prepared in Examples 1 to 4 and Comparative Examples 1 to 8 at 80°C for 6 hours, a 6 oz injection molding machine was used to prepare specimens for physical properties testing under conditions of cylinder temperature of 240°C and mold temperature of 60°C, respectively. For the specimen of, after measuring or observing the light resistance, glossiness, impact resistance, mechanical strength, and appearance as follows, the results are summarized in Table 2.

E)를 코니카-미놀타 CM-2500C spectrophotometer를 이용하여 측정하였다.(1) Light resistance: 84 MJ/m ² (300 nm ~ 400) using Atlas Ci4000 Weather-Ometer equipment according to the light resistance test method using a Xenon-Arc lamp specified in MS 210-05 of Hyundai Motor Company. nm) Color difference of the specimen before/after exposure evaluation (

E) was measured using a Konica-Minolta CM-2500C spectrophotometer.

(2) Glossiness (unit: GU): according to JIS Z 8741 It was measured at a measurement angle of 60° using a VG7000 gloss meter of Nippon Denshoku.

(3) Impact resistance (unit: kgf·cm/cm): Notched Izod impact strength was measured for a 3.2mm thick specimen according to ASTM D256.

(4) Mechanical strength (unit: kgf/cm ² ): Tensile strength at the yield point was measured for a 3.2 mm thick specimen according to ASTM D 638.

(5) Appearance: For specimens injection-molded in a size of 50 mm x 200 mm x 2 mm using a pinpoint gate structure, the degree of flow mark occurrence of each specimen can be visually determined. Observed. Depending on the degree of flow mark occurrence, it was divided into ○ (occurring, appearing clearly), △ (occurring, appearing slightly blurred), and X (not occurring).

Properties Example Comparative example One 2 3 4 One 2 3 4 5 6 7 8 Color difference
1.3 1.2 1.2 1.1 2.9 1.2 3.0 1.1 1.2 3.3 2.1 1.8 Glossiness (GU) 25 23 26 26 35 21 92 93 93 12 24 21 Impact strength (kgf·cm/cm) 30 25 35 28 45 18 55 22 50 7 24 19 The tensile strength
(kgf/cm ² ) 590 610 615 620 600 615 580 615 550 670 620 635 Exterior △ △ △ △ ○ △ X X X ○ △ △

From Tables 1 to 2, it can be seen that in the case of the specimens made of the thermoplastic resin compositions of Examples 1 to 4, while having excellent light resistance and low light characteristics, impact resistance and mechanical strength can also be maintained at an excellent level.

On the other hand, when it contains too much polycarbonate resin (A) (Comparative Example 7, Comparative Example 8), it can be confirmed that the light resistance is lowered, and when the epoxy group-containing modifier (D) is not included (Comparative Example 1, Comparative Example 8) In Example 3 and Comparative Example 6), it can be seen that the light resistance is greatly reduced.

On the other hand, when it does not contain the crosslinked aromatic vinyl-vinyl cyanide copolymer (E) (Comparative Examples 3 to 5), it can be confirmed that the low-light properties are significantly reduced, and the crosslinked aromatic vinyl-vinyl cyanide copolymer (E) When containing an excessive amount (Comparative Example 6), it can be seen that the impact resistance is lowered.

In addition, in the case of the specimens made of the thermoplastic resin composition of Examples 1 to 4, compared to Comparative Examples 1 and 6, it can be seen that a distinct flow mark does not occur, and thus has excellent appearance characteristics.

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 by those skilled in the art using the basic concept of the present invention defined in the appended claims are also present. It belongs to the scope of the invention.

Claims (13)

(A) 60% to 85% by weight of a polycarbonate resin having a terminal hydroxyl group content of 15 mol% to 50 mol%;
(B) 6% to 25% by weight of an acrylic graft copolymer; And
(C) 5 to 20% by weight of an aromatic vinyl-cyanide vinyl copolymer;
Based on 100 parts by weight of the basic resin containing,
(D) 0.1 parts by weight to 0.7 parts by weight of an epoxy group-containing modifier; And
(E) 1 to 5 parts by weight of a crosslinked aromatic vinyl-vinyl cyanide copolymer;
Including,
The (D) epoxy group-containing modifier is a compound represented by the following formula (1), a thermoplastic resin composition:
[Formula 1]

In Formula 1,
R ¹ to R ³ are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C4 To C30 cycloalkyl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkylcarbonyl group,
L includes a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C4 to C30 cycloalkylene group, an ether group, or a combination thereof. delete In claim 1,
The (D) epoxy group-containing modifier is a compound represented by the following formula (2), a thermoplastic resin composition:
[Formula 2]

In formula 2,
R ¹ to R ³ are each independently selected from a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C4 to C30 cycloalkyl group, and a substituted or unsubstituted C1 to C30 alkoxy group,
L ^a and L ^b are each independently selected from a substituted or unsubstituted C1 to C30 alkylene group and a substituted or unsubstituted C4 to C30 cycloalkylene group. In claim 1,
The (A) polycarbonate resin is manufactured by a melt polymerization method (Melt Polymerization), a thermoplastic resin composition. In claim 1,
The (B) acrylic graft copolymer has an average particle diameter of an acrylic rubber polymer of 300 nm to 400 nm, a thermoplastic resin composition. In claim 1,
The (B) acrylic graft copolymer is a mixture of an aromatic vinyl compound and a vinyl cyanide compound 40% by weight to 60% by weight of the acrylic rubber polymer 40% to 60% by weight graft polymerization. In claim 1,
The (B) acrylic graft copolymer is an acrylonitrile-styrene-acrylate graft copolymer, a thermoplastic resin composition. In claim 1,
The (C) aromatic vinyl-vinyl cyanide copolymer is a copolymer of a monomer mixture comprising 60% to 80% by weight of an aromatic vinyl compound and 20% to 40% by weight of a vinyl cyanide compound, a thermoplastic resin composition. In claim 1,
The weight average molecular weight of the (C) aromatic vinyl-vinyl cyanide copolymer is 80,000 g/mol to 200,000 g/mol, a thermoplastic resin composition. In claim 1,
The (E) crosslinked aromatic vinyl-vinyl cyanide copolymer has a glass transition temperature (Tg) of 100°C to 150°C. In claim 1,
The (E) crosslinked aromatic vinyl-vinyl cyanide copolymer is a crosslinked styrene-acrylonitrile copolymer, a thermoplastic resin composition. In claim 1,
Thermoplastic further comprising at least one additive selected from flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, release agents, heat stabilizers, antioxidants, inorganic additives, ultraviolet stabilizers, antistatic agents, pigments, and dyes Resin composition. A molded article manufactured from the thermoplastic resin composition according to any one of claims 1 and 3 to 12.