KR102337560B1 - Thermoplastic resin composition and article including same - Google Patents

Abstract

(A) 40% to 80% by weight of a polycarbonate resin; (B) 5% to 35% by weight of an acrylic graft copolymer; And (C) with respect to 100 parts by weight of the base resin comprising 10% to 40% by weight of the aromatic vinyl-vinyl cyanide copolymer, (D) an epoxide group-containing reactive additive, and (E) a weight average molecular weight A thermoplastic comprising an aromatic vinyl-vinyl cyanide copolymer of 4,000,000 g/mol or more, wherein the weight ratio of (E) an aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 4,000,000 g/mol or more to (D) reactive additive is 1 to 12; A resin composition and a molded article including the same are provided.

Description

Thermoplastic resin composition and molded article including 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 automobile interior/exterior materials. However, since ASA resin has poor impact resistance, etc., in order to apply it to a use requiring high impact strength, the acrylic rubber polymer content of the ASA resin must be increased. / There is a limit to its application to applications requiring high heat resistance, such as exterior materials.

As an alternative to this, a method of supplementing heat resistance and impact resistance by alloying an ASA resin and a polycarbonate (PC) resin with excellent heat resistance has been proposed. can be applied to

In this way, when PC/ASA resin is applied to interior/exterior materials for vehicles, heat resistance and low light properties may be required depending on the parts to be applied. In general, a method of adding a separate matting agent or the like is being considered in order to impart low light properties to the PC/ASA resin.

However, there is a concern that other physical properties of the PC/ASA resin such as impact resistance and heat resistance may be greatly reduced even if low light properties are secured by the addition of the matting agent. Accordingly, there is a need for a method capable of improving low light properties without degrading the basic physical properties of the PC/ASA resin.

Provided is a thermoplastic resin composition with significantly improved low light properties while maintaining excellent heat resistance and impact resistance.

Another embodiment provides a molded article including the thermoplastic resin.

According to one embodiment, (A) 40% by weight to 80% by weight of a polycarbonate resin; (B) 5% to 35% by weight of an acrylic graft copolymer; And (C) with respect to 100 parts by weight of the base resin comprising 10% to 40% by weight of the aromatic vinyl-vinyl cyanide copolymer, (D) an epoxide group-containing reactive additive, and (E) a weight average molecular weight Including an aromatic vinyl-vinyl cyanide copolymer of 4,000,000 g/mol or more, wherein the weight ratio of the (E) aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 4,000,000 g/mol or more to the (D) reactive additive is 1 to 12 A phosphorus thermoplastic resin composition is provided.

The polycarbonate resin (A) may have a hydroxyl group content of 10 mol% to 50 mol% at the terminal.

The (A) polycarbonate resin may be prepared by melt polymerization.

Based on 100 parts by weight of the base resin, 0.1 parts by weight to 5 parts by weight of the reactive additive (D) is included, and 0.5 parts by weight of the (E) aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 4,000,000 g/mol or more to 10 parts by weight may be included.

The (D) reactive additive may include a compound represented by the following formula (1).

[Formula 1]

(Q)m - L - (R)n

In Formula 1,

Q and R are each independently at least one selected from the moieties represented by the following formulas A to C,

L is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, at least one selected from a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C1 to C20 heteroarylene group,

m and n are each 0 or 1, but at least one of m and n is 1,

[Formula A]

[Formula B]

[Formula C]

In Formulas A to C, t is an integer from 1 to 10, and * represents a connection site.

The compound represented by Formula 1 may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

L is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, at least one selected from a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C1 to C20 heteroarylene group,

m and n are each an integer of 0 or 1, but at least one of m and n is an integer of 1.

L is a substituted or unsubstituted C1 to C20 heteroalkylene group containing 1 to 3 heteroatoms selected from N, O, S, and Si, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted It may be any one selected from a cyclic C1 to C20 heteroarylene group.

L is -(CH ₂ ) ₂ - C2 to C20 alkylene group having a unit structure, C6 to C20 cycloalkylene group, C6 to C20 arylene group,

The -(CH ₂ ) ₂ - unit structure may be substituted with an ester group.

The (B) acrylic graft copolymer may have an average particle diameter of the acrylic rubber polymer of 100 nm to 300 nm.

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

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 comprising 60 wt% to 85 wt% of an aromatic vinyl compound and 15 wt% to 40 wt% of a vinyl cyanide compound.

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

The (E) aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 4,000,000 g/mol or more may be a styrene-acrylonitrile copolymer having a weight average molecular weight of 4,000,000 g/mol or more.

The thermoplastic resin composition may 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, an antibacterial agent, a mold release agent, a heat stabilizer, an antioxidant, an inorganic additive, an ultraviolet stabilizer, an antistatic agent, a pigment, and a dye. may further include.

On the other hand, according to another embodiment, a molded article using the above-described thermoplastic resin composition is provided.

It is possible to provide a thermoplastic resin composition with significantly improved low light properties while maintaining excellent heat resistance and impact resistance.

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

As used herein, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymerization or random copolymerization.

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

Unless otherwise defined herein, 'substituted' means that a hydrogen atom in a compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amino group Dino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, vinyl group, C1 to C20 alkyl group, C2 to C20 alke Nyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C6 to C30 allyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group , means substituted with a substituent selected from a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C3 to C30 heterocycloalkyl group, and combinations thereof.

In addition, "unsubstituted" means that a hydrogen atom remains as a hydrogen atom without being substituted with another substituent.

In addition, unless otherwise defined herein, 'hetero' means containing 1 to 3 heteroatoms selected from N, O, S, P, and Si.

One embodiment provides a thermoplastic resin composition with significantly improved low light properties while maintaining excellent both heat resistance and impact resistance.

The thermoplastic resin composition comprises (A) 40 wt% to 80 wt% of a polycarbonate resin; (B) 5% to 35% by weight of an acrylic graft copolymer; and (C) 10 wt% to 40 wt% of the aromatic vinyl-vinyl cyanide copolymer; based on 100 parts by weight of the base resin comprising, (D) an epoxide group-containing reactive additive, and (E) a weight average molecular weight Including this 4,000,000 g/mol or more of the aromatic vinyl-vinyl cyanide copolymer, the weight ratio of the (E) weight average molecular weight of the aromatic vinyl-vinyl cyanide copolymer of 4,000,000 g/mol or more to the (D) reactive additive is 1 to 12 is satisfied.

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 two methods: an interfacial polymerization method (also called a solvent method or a phosgene method) and a melt polymerization method. In one embodiment, the polycarbonate resin (A) may include one prepared by a melt polymerization method. Meanwhile, in one embodiment, the polycarbonate resin (A) may be prepared by a melt polymerization method.

When the polycarbonate resin is prepared through melt polymerization, a process of synthesizing polycarbonate by separating phenol using, for example, a transesterification reaction between 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, and the like. 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, etc., More preferably 2,2-bis-(4-hydroxyphenyl) called "bisphenol A" and propane.

Examples of the diaryl carbonate include diphenyl carbonate, ditoryl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, etc., but these are single or two More than one species may be used, for example, diphenyl carbonate may be used.

The polycarbonate resin (A) may have a weight average molecular weight of 5,000 g/mol to 200,000 g/mol, and specifically, 5,000 g/mol 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 general, among the two methods of manufacturing a polycarbonate resin, the phosgene gas used in the interfacial polymerization method has a serious toxicity, which raises a problem in terms of environmental safety.

On the other hand, since the melt polymerization method is a method of producing a polycarbonate resin by separating phenol in the transesterification reaction without using phosgene gas, it is more environmentally friendly than the above-described interfacial polymerization method.

However, in the case of a polycarbonate resin prepared by melt polymerization, an unintended hydrolysis reaction of the polycarbonate resin is likely to occur due to external light or heat during molding or use, and as a result, unintended deterioration of physical properties may occur. There is a possibility. In addition, if the content of the polycarbonate resin is reduced in order to solve this problem, there is a risk that the mechanical properties of the thermoplastic resin composition including the same may be deteriorated.

However, the polycarbonate resin (A) according to an embodiment may include one prepared by the melt polymerization method as described above, or may be prepared by the melt polymerization method. That is, since the polycarbonate resin (A) according to one embodiment contains at least the polycarbonate resin prepared by the melt polymerization method, the content of hydroxyl groups at the ends of the polycarbonate polymer chains is polycarbonate produced by the interfacial polymerization method. It may be slightly higher than resin.

For example, the polycarbonate resin (A) may have a terminal hydroxyl group content of 15 mol% or more, for example, 20 mol% or more, for example, 25 mol% or more, for example, 50 mol% or less. , for example 45 mol% or less, for example 40 mol% or less, for example 15 mol% to 50 mol%, for example 20 mol% to 40 mol%.

When the hydroxyl group contained in the polycarbonate resin receives external heat, ultraviolet light, etc. during various processing processes (eg, injection molding process) of the thermoplastic composition containing the polycarbonate resin or the use of a printed article using the thermoplastic resin composition Unintentional hydrolysis reactions may occur.

However, in the thermoplastic composition according to an embodiment, the hydroxyl group in the polycarbonate resin (A) can be deactivated by using the epoxide group-containing reactive additive (D), and as a result, external heat during various processing or use of the thermoplastic composition , it is possible to prevent an unintentional hydrolysis reaction from occurring in the polycarbonate resin (A) by ultraviolet rays or the like. The specific configuration and function of the epoxide group-containing reactive additive (D) will be described later.

The polycarbonate resin (A) may contain at least 40% by weight or more, for example, 50% by weight or more, for example, 60% by weight or more, based on 100% by weight of the base resin, for example, 80% by weight. Below, for example, 70% by weight or less may be contained, for example, 40% to 80% by weight, for example 50% to 80% by weight, for example 50% to 70% by weight can

When the content of the polycarbonate resin (A) in the base resin is less than 40% by weight, there is a fear that the heat resistance of the thermoplastic resin composition may be lowered. On the other hand, when the content of the polycarbonate resin (A) in the base resin exceeds 80% by weight, there is a risk that the impact resistance may be lowered, and since it becomes difficult to deactivate the terminal hydroxyl groups contained in the polycarbonate resin to a desired level, the molding process of the thermoplastic composition There is a risk of deterioration of physical properties due to hydrolysis.

(B) Acrylic graft copolymer

In one embodiment, the acrylic graft copolymer (B) performs a function of strengthening 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 to an acrylic rubber polymer.

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

As the preparation method, conventional polymerization methods, for example, emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization, may be used. As a non-limiting example, preparing an acrylic rubber polymer, graft polymerization of a monomer mixture including an aromatic vinyl compound and a vinyl cyanide compound to 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 rubbery polymer may be prepared 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 acrylic monomer may be copolymerized with one or more other radically polymerizable monomers. In the case of copolymerization, the amount of the one or more radically polymerizable other monomers may be 5 wt% to 30 wt%, specifically 10 wt% to 20 wt%, based on the total weight of the acrylic rubbery polymer.

The aromatic vinyl compound included 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. , but 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 wt% of the total acrylic graft copolymer (B), the acrylic rubbery polymer may be 30 wt% to 70 wt%, for example 40 wt% to 60 wt%.

On the other hand, the monomer mixture comprising the aromatic vinyl compound and the vinyl cyanide compound graft-polymerized to the acrylic rubber polymer may be 30 wt% to 70 wt%, for example, 40 wt% to 60 wt%.

In the 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 wt% to 70 wt%, and the vinyl cyanide compound may be 20 wt% to 50 wt%, specifically 30 wt% to 40 wt%, 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 has two or more layers of butyl acrylate rubbery polymer comprising an inner core of copolymerized butyl acrylate and styrene and an outer core of 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 emulsion polymerization.

In one embodiment, in the acrylic graft copolymer (B), the average particle diameter of the acrylic rubber polymer is 100 nm or more, for example, 150 nm or more, for example 300 nm or less, for example 250 nm or less, For example, it may be 100 nm to 300 nm, for example 150 nm to 250 nm.

When the average particle diameter of the acrylic rubber polymer in the acrylic graft copolymer (B) is less than 100 nm, overall mechanical properties such as impact resistance and tensile strength of the thermoplastic resin composition including the same may be reduced.

On the other hand, when the average particle diameter of the acrylic rubber polymer in the acrylic graft copolymer (B) exceeds 300 nm, there is a fear that the fluidity and processability of the thermoplastic resin composition including the same may be reduced.

The acrylic graft copolymer (B) may contain 5% by weight or more, for example, 10% by weight or more, for example, 15% by weight or more, based on 100% by weight of the base resin, for example, 35% by weight or more. % or less, for example, 30% by weight or less, for example, 25% by weight or less.

If the content of the acrylic graft copolymer (B) in the base resin is less than 5% by weight, there is a risk that the impact resistance of the thermoplastic resin composition may decrease, and the content of the acrylic graft copolymer (B) in the base resin exceeds 35% by weight. In this case, there is a fear that the mechanical rigidity and colorability of the thermoplastic resin composition may be reduced.

(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-vinyl cyanide 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, for example 85,000 g/mol or more, for example 90,000 g/mol or more, for example 200,000 g/mol or less, For example, 150,000 g/mol, 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 (GP) (column is Shodex's LF-804, The standard sample was made using 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, for example, 15% by weight or more, for example, 20% by weight or more. may be included, for example, 50% by weight or less, for example 40% by weight or less, for example, 10% to 50% by weight, for example 15% to 40% by weight, for example 20 It may be included in an amount of 40% by weight to 40% by weight.

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer (C) may be included in 10 wt% or more, for example 15 wt% or more, for example 20 wt% or more, based on 100 wt% of the base resin, for example, 40% by weight or less, for example 35% by weight or less, for example 30% by weight or less, for example 10% to 40% by weight, for example 20% to 40% by weight, for example 20% by weight Weight % to 30% by weight may be included.

If the content of the aromatic vinyl-vinyl cyanide copolymer (C) is less than 10% by weight, there is a fear that the mechanical rigidity and heat resistance of the thermoplastic resin composition may decrease, and if it exceeds 40% by weight, the impact resistance and weather resistance of the thermoplastic resin composition There is a risk of deterioration.

(D) Reactive additive containing an epoxide group

In one embodiment, the reactive additive containing an epoxide group inactivates the hydroxyl group in the polycarbonate resin (A) as described above, thereby preventing an unintentional hydrolysis reaction in the polycarbonate resin (A) from occurring perform the function However, the epoxide group-containing reactive additive according to an embodiment may perform a function of improving low-light properties of the thermoplastic resin composition in addition to the above-described function.

First, as a specific method of inactivating the hydroxyl group in the polycarbonate resin (A), the epoxide group in the reactive additive (D) may form a chemical bond with the hydroxyl group at the end of the polymer chain of the polycarbonate resin.

In one embodiment, the epoxy group in the reactive additive (D) may undergo a ring-opening reaction by a hydroxyl group included in the polycarbonate resin. In this case, any one of the two carbon atoms constituting the epoxide group together with the oxygen atom may form an ether bond with the hydroxyl group included in the polycarbonate resin.

That is, in one embodiment, the reactive additive (D) may be inactivated by capping a highly reactive hydroxyl group included in the polycarbonate resin with an epoxide group. Accordingly, by effectively deactivating the hydroxyl group included in the polycarbonate resin (A) with the reactive additive (D), it is possible to provide a thermoplastic resin composition excellent in both light resistance and low light properties.

In one embodiment, the reactive additive (D) may include a compound represented by the following formula (1).

[Formula 1]

(Q)m - L - (R)n

In Formula 1,

Q and R are each independently at least one selected from the moieties represented by the following formulas A to C,

L is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, at least one selected from a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C1 to C20 heteroarylene group,

m and n are each 0 or 1, but at least one of m and n is 1,

[Formula A]

[Formula B]

[Formula C]

In Formulas A to C, t is an integer from 1 to 10, and * represents a connection site.

In Formula 1, Q and R may be selected from the same moiety or different moieties from each other.

The compound represented by Formula 1 may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

L is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, at least one selected from a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C1 to C20 heteroarylene group,

m and n are each 0 or 1, but at least one of m and n is 1.

In one embodiment, L is a substituted or unsubstituted C1 to C20 heteroalkylene group containing 1 to 3 heteroatoms selected from N, O, S, and Si, a substituted or unsubstituted C2 to C20 heterocycloalkyl It may be any one selected from a ene group, a substituted or unsubstituted C1 to C20 heteroarylene group.

Meanwhile, L is -(CH ₂ ) ₂ -C2 to C20 alkylene group having a unit structure, C6 to C20 cycloalkylene group, and C6 to C20 arylene group, wherein the -(CH ₂ ) ₂ - unit structure is It may be substituted with an ester group.

The reactive additive (D) may be composed of one type of compound satisfying Formula 1, or may be composed of a mixture of two or more compounds satisfying Formula 1 above.

In one embodiment, based on 100 parts by weight of the base resin, the reactive additive (D) may be included in more than 0, for example, 0.1 parts by weight or more, for example, 0.2 parts by weight or more, and less than 5 parts by weight, for example, For example, 4 parts by weight or less, for example 3 parts by weight or less, for example 2 parts by weight or less, may be included, for example, 0.1 parts by weight to 5 parts by weight, for example 0.1 parts by weight to 3 parts by weight, for example 0.1 parts by weight to 2 parts by weight may be included.

When the thermoplastic resin composition according to an embodiment does not contain the reactive additive (D), deactivation of hydroxyl groups in the polycarbonate resin (A) and the low-light properties of the thermoplastic resin composition cannot be properly controlled, so the intention in the molding or use process There is a possibility that an unintended deterioration of physical properties may occur, and it may be difficult to express low-light characteristics. On the other hand, when the thermoplastic resin composition contains more than 5 parts by weight of the reactive additive (D), there is a fear that the reactive additive (D) reduces the inherent impact resistance function of the polycarbonate resin.

(E) an aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 4,000,000 g/mol or more

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer (E) having a weight average molecular weight of 4,000,000 g/mol or more functions to impart low-light properties of the thermoplastic resin composition.

The aromatic vinyl-vinyl cyanide copolymer (E) having a weight average molecular weight of 4,000,000 g/mol or more according to an embodiment has a weight average molecular weight of at least 4,000,000 g/mol or more, for example 5,000,000 g/mol or more, for example 5,000,000 g /mol to 10,000,000 g/mol, for example from 5,000,000 g/mol to 9,000,000 g/mol, for example from 5,000,000 g/mol to 8,000,000 g/mol, for example from 6,000,000 g/mol to 8,000,000 g/mol - means a vinyl cyanide copolymer.

In the aromatic vinyl-vinyl cyanide copolymer (E) having a weight average molecular weight of 4,000,000 g/mol or more, the aromatic vinyl compound is styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene , and may be at least one selected from vinyltoluene and vinylnaphthalene.

In the aromatic vinyl-vinyl cyanide copolymer (E) having a weight average molecular weight of 4,000,000 g/mol or more, the vinyl cyanide compound may be at least one selected from acrylonitrile, methacrylonitrile, and fumaronitrile.

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer (E) having a weight average molecular weight of 4,000,000 g/mol or more may be a styrene-acrylonitrile copolymer (SAN) having a weight average molecular weight of 4,000,000 g/mol or more.

The aromatic vinyl-vinyl cyanide copolymer (E) having a weight average molecular weight of 4,000,000 g/mol or more according to an embodiment is greater than 0, for example, 0.5 parts by weight or more, for example 1 part by weight based on 100 parts by weight of the base resin. or more may be contained, for example, 10 parts by weight or less, for example, 8 parts by weight or less, for example, 6 parts by weight or less, for example, 5 parts by weight or less, for example, 0.5 to 10 parts by weight or less. , for example, may be contained in 0.5 to 5 parts by weight.

If the copolymer (E) is not included or is too little, the effect of improving the low-light properties of the thermoplastic resin composition is not expressed, and when the copolymer (E) is too much at a level exceeding 10 parts by weight, there is a risk that the moldability and heat resistance of the thermoplastic resin composition may be lowered. have.

On the other hand, in one embodiment, the weight ratio of the aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 4,000,000 g/mol or more to the (D) reactive additive included in the thermoplastic resin composition is 1 or more, for example For example 2 or more, for example 3 or more, for example less than 15, for example 12 or less, for example 10 or less, for example 1 to 12, for example 2 to 12, for example 3 to 10 days.

(D) When the weight ratio of the copolymer (E) to the reactive additive is out of the above range, the low-light property improvement effect of the thermoplastic resin composition is not expressed, or other physical properties (for example, heat resistance) , impact resistance, fluidity, etc.) is not preferable because there is a possibility that it may greatly decrease.

(F) additives

In addition to the components (A) to (E), the thermoplastic resin composition according to an embodiment does not deteriorate other physical properties while being able to express excellent low-light properties, In order to balance the respective physical properties under conditions that can also prevent deterioration of physical properties, or according to the end use of the thermoplastic resin composition, one or more additives may be further included.

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 mold release agent, a heat stabilizer, an antioxidant, an inorganic additive, an ultraviolet stabilizer, an antistatic agent, a pigment, a dye, etc. may 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 an amount of 20 parts by weight or less relative to 100 parts by weight of the total amount of the 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 to be 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 can be advantageously used in various electrical and electronic parts used outdoors, building materials, sporting goods, and interior/exterior parts of automobiles by greatly improving low-light properties while maintaining excellent mechanical properties such as impact resistance and heat resistance. Specifically, the molded articles may be used in satellite antennas, door panels, automobile radiator grilles, side mirror housings, etc., but is 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 thereto.

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 illustrative purposes and are not intended to limit the present invention.

Examples 1 to 7

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

Comparative Examples 1 to 8

A thermoplastic resin composition in pellet form was prepared in the same manner as in Example 1 except for using the components and amounts shown in Table 2 below.

ingredient unit Example One 2 3 4 5 6 7 basic resin (A) weight% 55 55 55 55 55 75 55 (B) weight% 20 20 20 20 20 10 20 (C) weight% 25 25 25 25 25 15 25 (D) Type-I parts by weight 0.3 0.5 1.0 0 0 0.3 0.5 Type-II parts by weight 0 0 0 0.5 1.0 0 0.5 (E) parts by weight 3 3 3 3 3 3 3 E/D weight ratio - 10 6 3 6 3 10 3

Parts by weight: parts by weight based on 100 parts by weight of the base resin ((A)+(B)+(C))

ingredient division comparative example One 2 3 4 5 6 7 8 basic resin (A) weight% 55 55 55 55 55 90 20 55 (B) weight% 20 20 20 20 20 5 40 20 (C) weight% 25 25 25 25 25 5 40 25 (D) Type-I parts by weight 0 One 0 10 One One One 3 Type-II parts by weight 0 0 One 0 0 0 0 3 (E) parts by weight 3 0 0 3 15 3 3 3 E/D weight ratio - N/A 0 0 0.3 15 3 3 0.5

Parts by weight: parts by weight based on 100 parts by weight of the base resin ((A)+(B)+(C))

(A) polycarbonate resin: a polycarbonate resin prepared by melt polymerization, having a weight average molecular weight of about 28,000 g/mol as measured by gel permeation chromatography (GPC), and a terminal hydroxyl group content of about 30 mol% (manufacturer: Lotte Advanced Materials)

(B) acrylic graft copolymer: styrene and acrylonitrile 50 parts by weight to 50 parts by weight of a butyl acrylate rubbery polymer having an average particle diameter of 180 nm by graft copolymerization of an acrylonitrile-styrene-acrylate graft copolymer (manufacturer) : Lotte Advanced Materials)

(C) Aromatic vinyl-vinyl cyanide copolymer: a styrene-acrylonitrile copolymer having a weight average molecular weight of about 110,000 g/mol and an acrylonitrile content of about 24% by weight as measured by gel permeation chromatography (GPC) ( Manufacturer: Lotte Advanced Materials)

(D) reactive additives

Type-I: an epoxide group-containing reactive additive represented by the above-mentioned Chemical Formula 2 (provided that m = 0, n = 1 in Chemical Formula 2) (Manufacturer: Momentive Performance materials)

Type-II: Reactive additive containing an epoxide group represented by the above-mentioned Formula 2 (provided that m=n=1 in Formula 2) (Manufacturer: Daicel Corp.)

(E) Aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 4,000,000 g/mol or more: A styrene-acrylonitrile copolymer having a weight average molecular weight of about 5,000,000 g/mol (Manufacturer: Zibo Huaxing Additives)

Physical property evaluation

After drying the pellets prepared in Examples 1 to 7 and Comparative Examples 1 to 8 at 80 ° C. for 6 hours, using a 6 oz injection molding machine, under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C. of the specimen, after measuring glossiness, impact resistance, and fluidity as follows, the results are summarized in Table 3 (Examples 1 to 7) and Table 4 (Comparative Examples 1 to 8), respectively.

(1) Impact resistance (unit: kgf·cm/cm): Notched Izod impact strength was measured for each of 3.2 mm and 6.4 mm thick specimens according to ASTM D256.

(2) Flowability (unit: g/10min): Melt flow index (MI) was measured at 220°C and 10 kg load condition according to ASTM D1238.

(3) Glossiness (unit: GU): Measurement angles of 20°, 45°, 60°, 75° and 85° were respectively measured using a VG7000 glossmeter manufactured by Nippon Denshoku in accordance with JIS Z 8741.

Properties Example One 2 3 4 5 6 7 impact strength
(kgf cm/cm) 3.2mm 43.5 42.2 41.3 48.1 40.1 69.1 41.8 6.4mm 18.1 14.8 13.7 15.4 14.1 34.5 13.9 flow index
(g/10min) 22.0 19.2 14.0 17.2 16.1 9.8 14.8 glossiness
(GU) 20° 4.3 4.6 4.4 5.7 4.4 4.1 4.6 45° 21.0 22.5 23.9 25.3 21.8 20.8 23.1 60° 25.0 27.8 31.3 31.3 27.1 23.9 31.6 75° 55.8 59.5 66.6 62.8 58.9 51.4 67.0 85° 81.2 84.4 88.5 85.6 84.6 79.6 88.7

Properties comparative example One 2 3 4 5 6 7 8 impact strength
(kgf cm/cm) 3.2mm 42.7 44.5 42.0 24.4 35.2 75.4 21.3 25.6 6.4mm 18.6 16.2 14.6 6.5 10.2 48.5 10.5 8.1 flow index
(g/10min) 29.2 35.9 33.8 6.7 4.5 0.8 45.2 7.7 glossiness
(GU) 20° 98.1 97.5 98.5 4.8 4.3 7.8 6.3 4.4 45° 99.0 99.0 98.7 26.5 21.5 31.0 29.2 22.5 60° 99.8 99.4 99 30.2 31.5 44.5 38.6 30.1 75° 99.4 99.1 99.1 57.4 67.5 71.6 69.8 54.3 85° 99.2 99.0 99.6 83.2 87.4 89.7 88.5 81.9

From Tables 1 to 4, it can be seen that, in the case of the specimens made of the thermoplastic resin compositions of Examples, it is possible to maintain excellent low-light properties while maintaining excellent impact resistance and fluidity. Although described in detail, 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 also fall within the scope of the present invention.

Claims (16)

(A) 40% to 80% by weight of a polycarbonate resin;
(B) 5% to 35% by weight of an acrylonitrile-styrene-acrylate graft copolymer; and
(C) 10% to 40% by weight of an aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 80,000 g/mol to 200,000 g/mol;
With respect to 100 parts by weight of the base resin comprising,
(D) 0.1 parts by weight to 5 parts by weight of a reactive additive containing an epoxide group, and
(E) containing 0.5 to 10 parts by weight of an aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 4,000,000 g/mol or more,
The weight ratio of the (E) aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 4,000,000 g/mol or more to the (D) reactive additive is 3 to 6, the thermoplastic resin composition. In claim 1,
The (A) polycarbonate resin has a terminal hydroxyl group content of 10 mol% to 50 mol%, a thermoplastic resin composition. In claim 1,
Wherein (A) the polycarbonate resin is prepared by melt polymerization (Melt Polymerization), the thermoplastic resin composition. delete In claim 1,
The (D) reactive additive is a thermoplastic resin composition comprising a compound represented by the following formula (1):
[Formula 1]
(Q)m - L - (R)n
In Formula 1,
Q and R are each independently at least one selected from moieties represented by the following formulas A to C,
L is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, at least one selected from a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C1 to C20 heteroarylene group,
m and n are each 1,
[Formula A]

[Formula B]

[Formula C]

In Formulas A to C, t is an integer of 1 to 10, and * represents a connection site. In claim 5,
The compound represented by the formula (1) is represented by the following formula (2), a thermoplastic resin composition:
[Formula 2]

In Formula 2,
L is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, at least one selected from a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C1 to C20 heteroarylene group,
m and n are each 1. In claim 5,
L is a substituted or unsubstituted C1 to C20 heteroalkylene group containing 1 to 3 heteroatoms selected from N, O, S, and Si, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted Any one selected from a cyclic C1 to C20 heteroarylene group, the thermoplastic resin composition. In claim 5,
L is -(CH ₂ ) ₂ - C2 to C20 alkylene group having a unit structure, C6 to C20 cycloalkylene group, C6 to C20 arylene group,
The -(CH ₂ ) ₂ - unit structure is substituted with an ester group, the thermoplastic resin composition. In claim 1,
The (B) acrylonitrile-styrene-acrylate graft copolymer has an average particle diameter of the acrylic rubber polymer of 100 nm to 300 nm, a thermoplastic resin composition. In claim 1,
The (B) acrylonitrile-styrene-acrylate graft copolymer is a mixture of styrene and acrylonitrile in 40 wt% to 60 wt% of an acrylic rubber polymer in an amount of 40 wt% to 60 wt% , a thermoplastic resin composition. delete In claim 1,
The (C) aromatic vinyl-vinyl cyanide copolymer is a copolymer of a monomer mixture comprising 60 wt% to 85 wt% of an aromatic vinyl compound and 15 wt% to 40 wt% of a vinyl cyanide compound, a thermoplastic resin composition. delete In claim 1,
The (E) aromatic vinyl-vinyl cyanide copolymer having a weight average molecular weight of 4,000,000 g/mol or more is a styrene-acrylonitrile copolymer having a weight average molecular weight of 4,000,000 g/mol or more, a thermoplastic resin composition. According to claim 1,
Thermoplastic comprising at least one additive selected from flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, heat stabilizers, antioxidants, inorganic additives, UV stabilizers, antistatic agents, pigments, and dyes resin composition. A molded article prepared from the thermoplastic resin composition according to any one of claims 1 to 3, and claims 5 to 10, 12, 14, and 15.