WO2014119827A9 - Polycarbonate-based thermoplastic resin composition and molded article - Google Patents

Abstract

A polycarbonate-based thermoplastic composition according to the present invention comprises (A) a polycarbonate resin, (B) a rubber-modified acryl-based graft copolymer resin, and (C) a silicon-based compound containing copolymer. The polycarbonate-based thermoplastic composition has excellent flowability without deteriorations in impact strength and heat resistance by introducing the silicon-based containing copolymer into the polycarbonate resin.

Description

Polycarbonate Thermoplastic Compositions and Molded Articles

The present invention relates to a polycarbonate-based thermoplastic resin composition. More specifically, the present invention relates to a polycarbonate-based thermoplastic resin composition excellent in fluidity without impairing impact strength and heat resistance.

Thermoplastic resins have a lower specific gravity than glass or metal, and have excellent physical properties such as moldability and impact resistance. Recently, due to the trend of low cost, large size, and light weight of electric and electronic products, plastic products are rapidly replacing the existing glass or metal areas, thereby expanding the use area from electric and electronic products to automobile parts. Accordingly, the function and appearance performance of the exterior material is important, and the demand for external impact and workability is also increasing.

Among the thermoplastic resins, polycarbonate-based thermoplastic resins have high impact strength, high heat resistance, and high transparency, and thus are used in various engineering devices.

However, polycarbonate-based thermoplastic resins have a relatively poor fluidity. Therefore, in order to improve the fluidity of the polycarbonate-based thermoplastic resin, one or more polymers and additives are mixed and used.

Conventionally, attempts have been made to improve the fluidity of polycarbonate-based thermoplastic resins by using low molecular weight styrene-acrylonitrile (SAN) resins. However, these attempts have succeeded in improving the fluidity, but the impact strength and heat resistance are deteriorated. Have

In addition, g-ABS is used as an impact modifier in the existing PC / SAN alloy technology. Because g-ABS has a high affinity with SAN, it exists inside the SAN during PC / SAN alloy, and when the external shock is applied, the impact reinforcement effect is lowered mainly because the destruction occurs first at the interface between the PC and the SAN. Therefore, when g-ABS is used as the impact reinforcing material, when an external impact is applied, there is a problem that destruction occurs mainly at the interface between the PC and the SAN.

The present inventors intend to improve the impact reinforcement effect by using a rubber-modified acrylic graft copolymer resin similar in affinity with both PC and SAN. In addition, it is intended to develop a polycarbonate-based thermoplastic resin composition having excellent fluidity and improved moldability and processability without deteriorating mechanical properties such as impact strength and heat resistance.

An object of the present invention is to provide a polycarbonate-based thermoplastic resin composition having excellent fluidity.

Another object of the present invention is to provide a polycarbonate-based thermoplastic resin composition having excellent impact strength and heat resistance.

Another object of the present invention is to provide a polycarbonate-based thermoplastic resin composition having excellent moldability.

Still another object of the present invention is to provide a molded article manufactured using the polycarbonate-based thermoplastic resin composition.

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

The polycarbonate-based thermoplastic resin composition according to the present invention includes a copolymer resin containing (A) a polycarbonate resin, (B) a rubber-modified acrylic graft copolymer resin, and (C) a silicone-based compound.

Polycarbonate-based thermoplastic resin composition of the present invention is a copolymer resin containing 40 to 80% by weight of polycarbonate resin (A), 1 to 30% by weight of the rubber-modified acrylic graft copolymer resin (B) and the silicone-based compound ( C) 10 to 30% by weight.

In another embodiment, the polycarbonate-based thermoplastic resin composition of the present invention is an impact reinforcing material located at the interface between the first resin in the continuous phase, the second resin in the dispersed phase and the first resin in the continuous phase and the second resin in the dispersed phase. It may include.

The polycarbonate-based thermoplastic resin composition of the present invention may include 40 to 80% by weight of the first resin in the continuous phase, 10 to 30% by weight of the second resin in the dispersed phase, and 1 to 30% by weight of the impact modifier.

The first resin in the continuous phase is a polycarbonate resin (A), the second resin in the dispersed phase is a copolymer resin (C) containing a silicone compound, and the impact modifier may be a rubber-modified acrylic graft copolymer resin (B). .

The rubber-modified acrylic graft copolymer resin (B) may include 40 to 98% by weight of rubber (b1), 1 to 30% by weight of alkyl methacrylate (b2) and 1 to 40% by weight of vinyl aromatic monomer (b3). Can be.

Alkyl methacrylate (b2) may have 1 to 20 carbon atoms.

The copolymer resin (C) including the silicone compound may be a branched vinyl copolymer resin.

Copolymer (C) comprising a silicone-based compound is 10 to 80% by weight aromatic vinyl monomer (c1), 10 to 80% by weight unsaturated nitrile monomer (c2), 1 to 30% by weight (meth) acrylic monomer (c3) And it may be a copolymer prepared by copolymerizing 0.1 to 25% by weight of the silicon-based compound (c4) having two or more unsaturated reactors.

The weight average molecular weight of the copolymer resin (C) including the silicone compound may be 30,000 to 800,000 g / mol.

The aromatic vinyl monomer (c1) may be selected from the group consisting of styrene, p-methylstyrene, α-methylstyrene, halogen substituted styrene, alkyl substituted styrene, and mixtures thereof.

The unsaturated nitrile monomer (c2) may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile and mixtures thereof.

 The (meth) acrylic monomer (c3) is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylates and mixtures thereof.

The silicone compound (c4) having two or more unsaturated reactors may include a silicone compound having a structure represented by the following Chemical Formula 4 alone or in a mixture of two or more thereof:

[Formula 4]

(In Formula 4, l, m and n are integers of 0 to 100 (wherein l, m and n are not 0 at the same time), R ₁ to R ₈ are each independently a hydrogen atom, linear or branched C An alkyl group of ₁ -C ₅ , a cycloalkyl group of C ₄ -C ₆ , an unsaturated alkyl group of C ₂ -C ₁₂ , a C ₆ -C ₁₀ aryl group, a hydroxyl group, an alkoxy group of C ₁ -C ₅ , an acetoxy group, an amino group, An amide group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group, and a mercapto group, wherein at least two of R ₁ to R ₈ have a polymerizable unsaturated reactor.)

 The silicone-based compound (c4) having two or more unsaturated reactors may have a viscosity of 5000 cPs or less and a vinyl content of 0.05 to 10 mmol / g.

Silicone-based compounds (c4) having two or more unsaturated reactors are 2,4,6,8-tetramethyl tetravinyl cyclotetrasiloxane, 1,3,5-trivinyl-1,1,3,5,5-pentamethyl Trisiloxane, 2,4,6-trivinyl-1,3,5-trimethylcyclosilazane, α, ω-divinylpolydimethylsiloxane, polyvinylmethylsilazane, 1,3-divinyl-1,1, 3,3-tetramethyldisiloxane and mixtures thereof.

In addition, the molded article produced from the polycarbonate-based thermoplastic resin composition of the present invention.

Hereinafter, specific contents of the present invention will be described in detail below.

The polycarbonate-based thermoplastic resin composition according to the present invention is excellent in fluidity, impact strength and heat resistance, and improves moldability.

The polycarbonate-based thermoplastic resin composition according to the present invention is excellent in fluidity, impact strength and heat resistance, and improves moldability.

The polycarbonate-based thermoplastic resin composition of the present invention includes a copolymer resin containing (A) a polycarbonate resin, (B) a rubber-modified acrylic graft copolymer resin, and (C) a silicone compound. Each component is demonstrated concretely below.

In addition, the polycarbonate-based thermoplastic resin composition of the present invention is located at the interface between (A) the first resin in the continuous phase, (C) the second resin in the dispersed phase and (B) the first resin in the continuous phase and the second resin in the dispersed phase. Impact modifiers. Each component is demonstrated concretely below.

Polycarbonate Thermoplastic Resin Composition

Polycarbonate-based thermoplastic resin composition according to the present invention is a copolymer comprising (A) 40 to 80% by weight of polycarbonate resin, (B) 1 to 30% by weight of rubber-modified acrylic graft copolymer resin and (C) silicone compound It may include 10 to 30% by weight of the resin.

In addition, the polycarbonate-based thermoplastic resin composition of the present invention (A) 40 to 80% by weight of the first resin in the continuous phase, (C) 10 to 30% by weight of the second resin in the dispersed phase and the first resin and the dispersed phase of the continuous phase 1 to 30% by weight of the impact modifier (B) located at the interface of the two resins. Each component is demonstrated concretely below.

(A) polycarbonate resin

In the present invention, the polycarbonate resin (A) is not particularly limited. For example, an aliphatic polycarbonate resin, an aromatic polycarbonate resin, a copolycarbonate thereof, a copolycarbonate carbonate resin, a polycarbonate-polysiloxane copolymer or a mixture thereof may be used as the polycarbonate resin. In addition, the polycarbonate resin may have a linear or branched structure.

In the present invention, the polycarbonate resin is a continuous phase in the polycarbonate-based thermoplastic resin composition.

In the present invention, the polycarbonate resin (A) can be prepared by reacting a compound selected from the group consisting of diphenols represented by the following formula (1) with phosgene, halogen formate, carbonate, and combinations thereof.

[Formula 1]

In Formula 1, A is a single bond, a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 5 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 6 carbon atoms , A substituted or unsubstituted cycloalkylidene group having 5 to 10 carbon atoms, CO, S, and SO _{2 It} is a linking group selected from the group, each R ₁ and R ₂ are each independently substituted or unsubstituted carbon 1 It is a substituent selected from the group consisting of an alkyl group of 30 to 30, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, n ₁ and n ₂ are each independently an integer of 0 to 4, the "substituted" is a hydrogen atom And a substituent selected from the group consisting of a halogen group, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a combination thereof. It means the.

The diphenols represented by the formula (1) may combine two or more kinds to form a repeating unit of the polycarbonate resin. Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane (also called 'bisphenol-A'), 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydrate Hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, etc. are mentioned. 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, or 1,1-bis- in the said diphenols (4-hydroxyphenyl) -cyclohexane can be preferably used. Also, 2,2-bis- (4-hydroxyphenyl) -propane can be used more preferably.

The polycarbonate resin (A) is preferably a weight average molecular weight of 10,000 to 200,000 g / mol, more preferably 15,000 to 80,000 g / mol, it is possible to ensure excellent impact strength in the molecular weight range, moderate fluidity It is possible to obtain excellent workability.

The polycarbonate resin (A) may be a mixture of copolymers prepared from two or more kinds of diphenols. In addition, as the polycarbonate resin (A), a linear polycarbonate resin, a branched polycarbonate resin, a polyester carbonate copolymer resin, or the like can be used. Bisphenol-A type | system | group polycarbonate resin etc. are mentioned as linear polycarbonate resin. Examples of the branched polycarbonate resin include those produced by reacting polyfunctional aromatic compounds such as trimellitic anhydride, trimellitic acid, and the like with diphenols and carbonates. It is preferable that a polyfunctional aromatic compound is contained in 0.05-2 mol% with respect to the branched polycarbonate resin total amount. As polyester carbonate copolymer resin, what was manufactured by making bifunctional carboxylic acid react with diphenols and a carbonate is mentioned. In this case, as the carbonate, a diaryl carbonate such as diphenyl carbonate, cyclic ethylene carbonate, or the like may be used.

The polycarbonate resin (A) is based on 100% by weight of the total resin composition containing the polycarbonate resin (A), the rubber-modified acrylic graft copolymer resin (B) and the copolymer resin (C) containing the silicone compound. To 80% by weight. Preferably it may be included in 60 to 80% by weight.

When the polycarbonate resin (A) is less than 40% by weight, impact resistance, tensile properties and heat resistance are lowered, and when it is more than 80% by weight, fluidity is lowered.

(B) Rubber Modified Acrylic Graft Copolymer Resin

In the present invention, the rubber-modified acrylic graft copolymer resin (B) is a copolymer obtained by grafting rubber (b1), alkyl methacrylate (b2) and vinyl-based aromatic monomer (b3) as impact modifiers. The rubber-modified acrylic graft copolymer resin (B) may include 40 to 98% by weight of rubber (b1), 1 to 30% by weight of alkyl methacrylate (b2) and 1 to 40% by weight of vinyl aromatic monomer (b3). Can be.

Non-limiting examples of the rubber (b1) include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), saturated rubbers in which hydrogen is added to the diene-based rubber, isoprene rubber, and chlorochloroprene rubber. And acrylic rubber such as butyl polyacrylate, ethylene-propylene rubber, and ethylene-propylene-diene terpolymer (EPDM). The rubber (b1) may be used alone or in combination of two or more thereof. Among these, the diene diene rubber is preferable, and butadiene rubber is more preferable. The content of the rubber (b1) is appropriately 40 to 98% by weight of the total weight of the rubber-modified acrylic graft copolymer resin (B). When the content of the rubber (b1) is less than 40% by weight, the impact resistance is lowered, and when it is more than 98% by weight, the heat resistance is lowered. Preferably 60 to 80% by weight. The average particle size of the rubber (b1) is preferably 0.1 to 0.7 μm in consideration of the impact strength and appearance.

In the present invention, the rubber-modified acrylic graft copolymer resin (B) is used as an impact reinforcing material, and is used at the interface between a polycarbonate resin (first resin) in a continuous phase and a copolymer resin (second resin) containing a silicone compound in a dispersed phase. Located.

In the existing polycarbonate resin composition (eg, PC / SAN alloy), g-ABS resin was used as an impact reinforcing material. Since g-ABS resin has a high affinity with SAN, it exists inside SAN, and when the external shock is applied, the impact reinforcing effect is inferior because the destruction occurs first at the interface between PC and SAN.

However, the rubber-modified acrylic graft copolymer resin (B) used as the impact reinforcing material in the present invention has similar affinity with the copolymer resin (C) containing a polycarbonate (A) and a silicone-based compound. That is, the affinity of the polycarbonate (A) and the rubber modified acrylic graft copolymer resin (B) and the affinity of the rubber modified acrylic graft copolymer resin (B) and the copolymer resin (C) containing a silicone compound are similar. . Therefore, the rubber-modified acrylic graft copolymer resin (B) is located at the interface between the continuous polycarbonate resin (first resin) and the copolymer resin (second resin) containing the disperse phase silicone-based compound, so that external impact is applied. At this time, no destruction occurs at the interface. Therefore, the polycarbonate-based resin composition according to the present invention is excellent in impact reinforcing effect.

As the alkyl methacrylate (b2), alkyl methacrylate having 1 to 20 carbon atoms may be used.

Examples of the alkyl methacrylate include, but are not limited to, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. These may be used alone or in mixture of two or more thereof. Most preferred is methyl methacrylate. The content of the alkyl methacrylate may be applied in 1 to 30% by weight, preferably 5 to 15% by weight of the total weight of the rubber-modified acrylic graft copolymer resin (B). If the content of the alkyl methacrylate is less than 1% by weight, the dispersibility may be lowered, and if it is more than 30% by weight, impact resistance may be lowered.

The vinyl aromatic monomer (b3) may use styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, halogen or alkyl substituted styrene, or a mixture thereof, preferably styrene. This is not restrictive. Vinyl-based aromatic monomer (b3) may be included in 1 to 40% by weight, preferably 10 to 30% by weight of the total weight of the rubber-modified acrylic graft copolymer resin (B). When the content of the vinyl aromatic monomer (b3) is less than 1% by weight, the polymerizability may be lowered, and when it is more than 40% by weight, the glossiness may be lowered.

The rubber-modified acrylic graft copolymer resin (B) is a total weight of 100 resin compositions comprising a polycarbonate resin (A), a rubber-modified acrylic graft copolymer resin (B) and a copolymer resin (C) containing a silicone compound. With respect to%, it may be included in 1 to 30% by weight. Preferably it may be included in 5 to 15% by weight.

When the rubber-modified acrylic graft copolymer resin (B) is less than 1% by weight, impact resistance and flexural strength are lowered, and when it is more than 30% by weight, fluidity and heat resistance are lowered.

(C) Copolymer Resin Containing Silicone Compound

As the copolymer resin (C) including the silicone compound of the present invention, a flexible branched vinyl copolymer resin may be used.

In the present invention, the copolymer resin containing the silicone compound is a dispersed phase in the polycarbonate thermoplastic resin composition.

In the present invention, the copolymer resin (C) including the silicone-based compound includes (c1) an aromatic vinyl monomer, (c2) an unsaturated nitrile monomer, (c3) a (meth) acrylic monomer, and (c4) two or more unsaturated reactors. The copolymer prepared by copolymerizing the silicone-based compound or a mixture of these copolymers can be used.

In the present invention, the copolymer resin (C) including the silicone compound is 10 to 80 wt% of the aromatic vinyl monomer (c1), 10 to 80 wt% of the unsaturated nitrile monomer (c2), and (meth) acrylic monomer (c3) Copolymers prepared by copolymerizing 1 to 30% by weight and 0.1 to 25% by weight of the silicone-based compound (c4) having two or more unsaturated reactors or a mixture of these copolymers may be used.

Copolymer resin (C) containing such a silicone-based compound can be prepared using conventional polymerization methods known in the art, for example, bulk polymerization, emulsion polymerization, suspension polymerization and the like.

Copolymer resin (C) containing a silicone-based compound has an advantage of having low stability because of its low impurity content and low manufacturing cost because it is manufactured by a simple suspension polymerization process.

Copolymer resin (C) comprising the silicone compound of the present invention is characterized in that it is made of a branched structure that can improve the fluidity at the same time as the silicone-based compound having a high molecular weight during copolymerization can improve the impact of the resin.

Copolymer resins (C) comprising silicone-based compounds are readily dissolved and mixed with other engineering plastics due to materials having a low glass transition temperature (Tg) (eg, butyl acrylate and silicone crosslinkers). This contributes to improving physical properties such as the flowability of the result.

The aromatic vinyl monomer (c1) may use styrene, p-methylstyrene, α-methylstyrene, halogen or alkyl substituted styrene, or a mixture thereof, preferably styrene, but is not limited thereto. The aromatic vinyl monomer (c1) is preferably contained in 10 to 80% by weight, more preferably 50 to 70% by weight based on 100% by weight of the copolymer resin (C) containing a silicone-based compound.

The unsaturated nitrile monomer (c2) may be acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile, α-chloroacrylonitrile, or a mixture thereof, and preferably acrylonitrile. This is not restrictive. The unsaturated nitrile monomer (c2) is preferably contained in 10 to 80% by weight, more preferably 20 to 50% by weight based on 100% by weight of the copolymer resin (C) containing a silicone-based compound.

The (meth) acrylic monomer (c3) may preferably include an aromatic or aliphatic methacrylate having a structure represented by the following formulas (2) and (3).

[Formula 2]

In Formula 2, m is an integer of 0 to 20, X is hydrogen or methyl, Y is methyl, cyclohexyl, phenyl, benzyl, methylphenyl, methylethylphenyl, methoxyphenyl, cyclohexylphenyl, chlorophenyl group , Bromophenyl group, phenylphenyl group and benzylphenyl group.

[Formula 3]

In Formula 3, m is an integer of 0 to 20, X is hydrogen or a methyl group, Z is oxygen (O) or sulfur (S), Ar is a phenyl group, methylphenyl group, methylethylphenyl group, methoxyphenyl group, cyclohexyl It may be selected from the group consisting of phenyl group, chlorophenyl group, bromophenyl group, phenylphenyl group and benzylphenyl group.

Examples of the aromatic or aliphatic methacrylate including the structures of Formulas 2 and 3 include cyclohexyl methacrylate, phenoxy methacrylate, phenoxy ethyl methacrylate, 2-ethylphenoxy methacrylate, 2- Ethylthiophenyl methacrylate, 2-ethylaminophenyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate, 3-phenylpropyl methacrylate, 4-phenylbutyl methacrylate, 2-2-methylphenylethyl methacrylate, 2-3-methylphenylethyl methacrylate, 2-4-methylphenylethyl methacrylate, 2- (4-propylphenyl) ethyl methacrylate, 2- (4- (1 -Methylethyl) phenyl) ethyl methacrylate, 2- (4-methoxyphenyl) ethyl methacrylate, 2- (4-cyclohexylphenyl) ethyl methacrylate, 2- (2-chlorophenyl) ethyl methacrylate Rate, 2- (3-chlorophenyl) ethyl methacrylate , 2- (4-chlorophenyl) ethyl methacrylate, 2- (4-bromophenyl) ethyl methacrylate, 2- (3-phenylphenyl) ethyl methacrylate, 2- (4-benzylphenyl) Ethyl methacrylate and the like.

Further, as another specific example of the (meth) acrylic monomer (c3), methacrylic acid esters, acrylic acid esters, unsaturated carboxylic acids, acid anhydrides, esters containing hydroxy groups, etc. may be used, and these may be used alone or in combination. It may be used by mixing more than one species. Specifically, methacrylic acid esters including methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, and benzyl methacrylate; Acrylic esters including methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate; Unsaturated carboxylic acids including acrylic acid and methacrylic acid; Acid anhydrides including maleic anhydride; Esters containing hydroxy groups, including 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and monoglycerol acrylate; Or mixtures thereof.

The (meth) acrylic monomer (c3) is preferably contained in an amount of 1 to 30% by weight, more preferably 5 to 20% by weight, based on 100% by weight of the copolymer resin (C) containing the silicone compound.

If the content range of the (meth) acrylic monomer (c3) is less than 1% by weight, the effect of improving fluidity is slight, and if it exceeds 30% by weight, there is a problem of lowering the heat resistance of the resin.

The silicon compound (c4) having two or more unsaturated reactors may include a silicon compound having a structure represented by the following Chemical Formula 4 in the form of one kind or a mixture of two or more kinds. In the present invention, the silicone compound serves as a crosslinking agent in the copolymer resin.

[Formula 4]

In Formula 4, l, m and n are integers of 0 to 100 (wherein l, m and n are not simultaneously 0), R ₁ to R ₈ are each independently a hydrogen atom, linear or branched C ₁ -C ₅ alkyl group, C ₄ -C ₆ cycloalkyl group, C ₂ -C ₁₂ unsaturated alkyl group, C ₆ -C ₁₀ aryl group, hydroxyl group, C ₁ -C ₅ alkoxy group, acetoxy group, amino group, amide Group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group and a mercapto group, wherein at least two or more of R ₁ to R ₈ have a polymerizable unsaturated reactor.

Specific examples of the silicone-based compound (c4) having two or more unsaturated reactors include dimethoxymethylvinylsilane, diethoxymethylvinylsilane, diacetoxy methylvinylsilane, 1,1,1,3,5,5,5,- Heptamethyl-3-vinyltrisiloxane, 2,4,6,8-tetramethyl tetravinyl cyclotetrasiloxane, α, ω-divinyl polydimethylsiloxane and vinyl modified dimethylsiloxane, 1,3,5-trivinyl-1 , 1,3,5,5-pentamethyltrisiloxane, 2,4,6-trivinyl-1,3,5-trimethylcyclosilazane, polyvinylmethylsilazane, 1,3-divinyl-1,1 , 3,3-tetramethyldisiloxane and the like are possible, but are not limited thereto, and these may be used alone or in combination.

The silicone compound (c4) having two or more unsaturated reactors serves as a cross-linker agent, and has a vinyl content of 0.05 to 10 mmol / g.

The silicone compound (c4) having two or more unsaturated reactors is preferably included in an amount of 0.1 to 25% by weight, more preferably 1 to 10% by weight, based on 100% by weight of the copolymer resin (C) containing the silicon-based compound. to be.

When the content range of the silicone compound (c4) having two or more unsaturated reactors is 1 to 25% by weight, it has the advantage of simultaneously expressing impact resistance and fluidity improving effect.

In addition, the silicone compound (c4) having two or more unsaturated reactors has a viscosity of 5,000 cPs or less, specifically 0.001 to 5,000 cPs, and preferably a vinyl content of 0.05 to 10 mmol / g, more preferably 0.5 To 3,000 cPs and vinyl content of 0.1 to 5 mmol / g.

Copolymer resin (C) comprising the silicone compound of the present invention is 10 to 80% by weight aromatic vinyl monomer (c1), 10 to 80% by weight unsaturated nitrile monomer (c2), (meth) acrylic monomer (c3) 1 When prepared in a composition of 0.1 to 25% by weight of the silicone-based compound (c4) having from 30 to 30% by weight and two or more unsaturated reactors, it is possible to simultaneously improve impact resistance and fluidity without compromising the heat resistance of the polycarbonate resin. There is this.

It is preferable that the weight average molecular weight of copolymer resin (C) containing a silicone type compound is 30,000-800,000 g / mol. When the copolymer resin (C) containing the silicone-based compound has such a molecular weight range, it is possible to simultaneously increase the fluidity and impact resistance of the thermoplastic resin while maintaining the existing excellent physical properties.

Copolymer resin (C) comprising a silicone compound is 100% by weight of the total resin composition comprising (A) a polycarbonate resin, (B) a rubber-modified acrylic graft copolymer resin, and (C) a copolymer resin containing a silicone compound. With respect to%, it may be included in 10 to 30% by weight.

If the content of the copolymer resin (C) containing a silicon-based compound is less than 10% by weight, it is impossible to obtain a sufficient impact and fluidity improvement effect, and if more than 30% by weight, impact and fluidity may be lowered.

In particular, the polycarbonate-based thermoplastic resin composition of the present invention is added to the blend of the polycarbonate resin (A) and the rubber-modified acrylic graft copolymer resin (g-ASA) by adding a copolymer resin containing a silicone compound to the impact strength and fluidity. At the same time, the characteristics are improved.

(D) additive

The polycarbonate-based thermoplastic resin composition of the present invention may further include an additive (D) according to each use. The polycarbonate-based thermoplastic resin composition includes surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, thermal stabilizers, antioxidants, light stabilizers, compatibilizers, inorganic additives, colorants, stabilizers, lubricants, and static electricity. An inhibitor, a pigment, a dye, a flame retardant, or a mixture thereof may further be included as an additive (D), but is not necessarily limited thereto.

The polycarbonate-based thermoplastic resin composition according to the present invention can be produced by a known method for producing a resin composition. For example, the components of the present invention and other additives may be mixed at the same time and then melt-extruded in an extruder to produce pellets or chips.

The polycarbonate-based thermoplastic resin composition of the present invention may be prepared in the form of a resin molded article according to a known resin production method. For example, the components of the present invention and other additives may be mixed at the same time and then melt extruded in an extruder to produce pellet form. And such pellets can be used to manufacture plastic injection or compression molded articles. There is no particular limitation on the molding method, and for example, extrusion molding, injection molding, calender molding, vacuum molding, or the like may be applied.

By molding the polycarbonate-based thermoplastic resin composition of the present invention can be usefully used in various products. In particular, it is widely applicable including exterior materials, components or parts of automobiles, lenses, windows, etc. that require heat resistance and impact resistance at the same time, for example, televisions, washing machines, cassettes including automotive parts or exterior materials It can be used to manufacture housings of electrical and electronic products such as players, MP3, DMB, navigation, mobile phones, telephones, game machines, audio players, computers, printers, copiers and the like.

Molded article

The present invention also provides a molded article prepared from the polycarbonate-based thermoplastic resin composition. There is no particular limitation on the method of molding the molded article, and an extrusion, injection or casting molding method may be applied. Such molding can be easily carried out by those skilled in the art.

The molded article of the present invention has an Izod impact strength of 23.00 to 90.00 kgf · cm / cm for 1/8 ″ thick specimens measured according to ASTM D256. For example, molded articles may have an Izod notch impact strength of 23.02 kgf · cm / cm, 34.10 kgf · cm / cm, 57.68 kgf · cm / cm, or 58.0 kgf · cm of a 1/8 ″ thick specimen measured according to ASTM D256. / cm, 64.53 kgf cm / cm, 65.17 kgf cm / cm.

The molded article of the present invention has a melt flow index (MI) of 34.00 to 80.00 g / 10min, measured under a temperature of 220 ° C. and a load of 10 kg according to ASTM D1238. For example, molded articles have a melt flow index (MI) of 55.8 g / 10min, 45.6 g / 10min, 40.2 g / 10min, 38.4 g / 10min, 35.4, measured under a temperature of 220 ° C. and a load of 10 kg, in accordance with ASTM D1238. g / 10 min, 34.2 g / 10 min.

The molded article of the present invention has a bending strength of 810 to 840 kgf / cm 2 of 1/4 ″ thick specimen measured according to ASTM D790. For example, molded articles may have a flexural strength of 816 kgf / cm2, 828 kgf / cm2, 814 kgf / cm2, 836 kgf / cm2, 823 kgf / cm2, 835 kgf / Cm 2.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Examples and Comparative Examples

Each component used in the Example and the comparative example is as follows.

(A) polycarbonate resin

Cheil Industries used a 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol-A) having a weight average molecular weight of 30,000 g / mol based on linear carbonate.

(B) Rubber Modified Acrylic Graft Copolymer Resin

Mitsubishi Rayon Corporate, metable C-223A was used.

(C) Copolymer Resin Containing Silicone Compound

(C1) Copolymer Resin Containing Silicone Compound

[Correction under Article 91 of the Rule 27.02.2014]
58.22 wt% styrene, 23.78 wt% acrylonitrile, 15 wt% butyl acrylate, using conventional suspension polymerization, using 3 wt% of a vinyl-modified dimethylsiloxane compound having a viscosity of 100 cPs and a vinyl content of 0.5 mmol / g. A copolymer resin containing a silicone compound having a weight average molecular weight of 90,000 g / mol was used.

(C2) Copolymer Resin Containing Silicone Compound

A copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 110,000 g / mol.

(C3) Copolymer Resin Containing Silicone Compound

A copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 150,000 g / mol.

(C4) Copolymer Resin Containing Silicone Compound

A copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 190,000 g / mol.

(C5) Copolymer Resin Containing Silicone Compound

A copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 250,000 g / mol.

(C6) Copolymer Resin Containing Silicone Compound

A copolymer resin containing the same silicone compound as (C1) was used except that the weight average molecular weight was 335,000 g / mol.

(C7) linear aromatic vinyl copolymer resin

Using styrene-acrylonitrile copolymer resin (SAN resin) having a weight average molecular weight of 90,000 g / mol prepared by conventional suspension polymerization at 75 ° C. using 75% by weight of styrene and 25% by weight of acrylonitrile. It was.

(C8) linear aromatic vinyl copolymer resin

Using styrene-acrylonitrile copolymer resin (SAN resin) having a weight average molecular weight of 115,000 g / mol prepared by conventional suspension polymerization at 75 ° C. using 71% by weight of styrene and 29% by weight of acrylonitrile. It was.

(C9) linear aromatic vinyl copolymer resin

Using 60.35% styrene and 24.65% acrylonitrile and 15% butyl acrylate, a copolymer resin having a weight average molecular weight of 90,000 g / mol prepared by conventional suspension polymerization at 75 ° C. for 5 hours was used.

(C10) Branched Aromatic Vinyl Copolymer Resin

[Correction under Article 91 of the Rule 27.02.2014]
A weight average molecular weight of 90,000 prepared by conventional suspension polymerization using 68.87% styrene and 28.13% acrylonitrile using 3% by weight of a vinyl-modified dimethylsiloxane compound having a viscosity of 100 cPs and a vinyl content of 0.5 mmol / g A branched vinyl copolymer resin of g / mol was used.

Example 1-6 and Comparative Example 1-4

Each component was added to the composition shown in Table 1, followed by melting and kneading to prepare a pellet. At this time, the extrusion was used L / D = 29, 45 mm diameter twin-screw extruder, and the prepared pellet was dried for 6 hours at 70 ℃ and injected in a 6 oz injection machine to prepare a specimen for evaluation of physical properties.

In the following [Table 1], the mixing ratios of (A), (B) and (C) are expressed in weight% based on 100% by weight of the total of (A), (B) and (C).

Table 1

The physical properties of the prepared specimens were measured by the following method, and the results are shown in Table 2.

(1) Impact strength (kgf · cm / cm): Notch was evaluated by making a notch on 1/8 ″ Izod specimens according to the evaluation method specified in ASTM D256.

(2) Flow index (g / 10minute): measured at 220 ℃, 10 kg conditions by the evaluation method specified in ASTM D1238.

(3) Flexural strength: Measured by a 1/4 "thickness specimen by the evaluation method specified in ASTM D790.

(4) Heat resistance (HDT): Measured according to ASTM D648 (1/4 inch, 18.6 kgf / cm 2, 120 ° C./hr).

TABLE 2

As shown in Table 2, in Examples 1-6, the impact strength was improved by the increased molecular weight and the silicone-based compound, and the flexible butyl acrylate monomer having a branched structure and a low glass transition temperature (Tg) was used. As a result, the fluidity was improved, and the moldability was improved.

In Examples 1-2, the molecular weight of the copolymer (C) is reduced, and the use of monomers (butyl acrylate and silicone-based compounds) with a flexible, low glass transition temperature (Tg) shows excellent fluidity. However, the impact strength was slightly reduced.

In Example 3-4, impact strength and fluidity were improved by using an appropriate molecular weight of the flexible branched vinyl copolymer.

In Examples 5-6, the use of high molecular weight branched copolymers showed excellent impact strength and relatively high flowability.

In Comparative Example 2, the impact strength was improved by using a high molecular weight SAN resin having a high acrylonitrile content, but it was confirmed that the fluidity and the flexural properties were sharply decreased.

Comparative Example 3 shows that the butyl acrylate monomer having a low glass transition temperature (Tg) is used instead of the silicon-based compound (c4) having two or more unsaturated reactors, thereby improving fluidity but decreasing impact strength.

Comparative Example 4 shows that the impact strength is improved by using a silicone-based compound having two or more unsaturated reactors as a crosslinking agent, but the fluidity is lowered because no (meth) acrylic monomer (c3) is used.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (23)

1. (A) polycarbonate resin;

   (B) rubber modified acrylic graft copolymer resin; And

   (C) a copolymer resin containing a silicone compound;

   Polycarbonate-based thermoplastic resin composition comprising a.
2. The copolymer resin (C) according to claim 1, comprising 40 to 80 wt% of the polycarbonate resin (A), 1 to 30 wt% of the rubber-modified acrylic graft copolymer resin (B) and the silicone compound. To 30% by weight of polycarbonate-based thermoplastic resin composition.
3. According to claim 1, wherein the rubber-modified acrylic graft copolymer resin (B) is 40 to 98% by weight of rubber (b1), 1 to 30% by weight of alkyl methacrylate (b2) and vinyl aromatic monomer (b3) 1 Polycarbonate-based thermoplastic resin composition comprising from 40% by weight.
4. The polycarbonate-based thermoplastic resin composition according to claim 3, wherein the alkyl methacrylate (b2) has 1 to 20 carbon atoms.
5. The polycarbonate-based thermoplastic resin composition according to claim 1, wherein the copolymer resin (C) containing the silicone compound is a branched vinyl copolymer resin.
6. The copolymer resin (C) of claim 1, wherein the copolymer resin (C) including the silicone compound is 10 to 80 wt% of an aromatic vinyl monomer (c1), 10 to 80 wt% of an unsaturated nitrile monomer (c2), and a (meth) acrylic monomer. (c3) Polycarbonate-based thermoplastic resin composition, characterized in that the copolymer prepared by copolymerizing 1 to 30% by weight and 0.1 to 25% by weight of the silicone-based compound (c4) having two or more unsaturated reactors.
7. The polycarbonate-based thermoplastic resin composition according to claim 1, wherein the weight average molecular weight of the copolymer resin (C) containing the silicone compound is 30,000 to 800,000 g / mol.
8. The method of claim 6, wherein the aromatic vinyl monomer (c1) is selected from the group consisting of styrene, p-methylstyrene, α-methylstyrene, halogen substituted styrene, alkyl substituted styrene, and mixtures thereof,

   The unsaturated nitrile monomer (c2) is selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile and mixtures thereof,

   The (meth) acrylic monomer (c3) is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( Aliphatic (meth) acrylates, including those selected from the group consisting of meth) acrylates and mixtures thereof,

    The silicone-based compound (c4) having two or more unsaturated reactors is a polycarbonate-based thermoplastic resin composition comprising a silicon-based compound having a structure represented by the following formula (4) alone or in mixture of two or more thereof:

   [Formula 4]

   

   (In Formula 4, l, m and n are integers of 0 to 100 (wherein l, m and n are not 0 at the same time), R ₁ to R ₈ are each independently a hydrogen atom, linear or branched C An alkyl group of ₁ -C ₅ , a cycloalkyl group of C ₄ -C ₆ , an unsaturated alkyl group of C ₂ -C ₁₂ , a C ₆ -C ₁₀ aryl group, a hydroxyl group, an alkoxy group of C ₁ -C ₅ , an acetoxy group, an amino group, An amide group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group, and a mercapto group, wherein at least two of R ₁ to R ₈ have a polymerizable unsaturated reactor.)
9. The polycarbonate-based thermoplastic resin composition of claim 6, wherein the silicone-based compound (c4) having two or more unsaturated reactors has a viscosity of 5,000 cPs or less and a vinyl content of 0.05 to 10 mmol / g.
10. The method of claim 6, wherein the silicon-based compound (c4) having two or more unsaturated reactors is 2,4,6,8-tetramethyl tetravinyl cyclotetrasiloxane, 1,3,5-trivinyl-1,1,3 , 5,5-pentamethyltrisiloxane, 2,4,6-trivinyl-1,3,5-trimethylcyclosilazane, α, ω-divinylpolydimethylsiloxane, polyvinylmethylsilazane, 1,3- A polycarbonate-based thermoplastic resin composition selected from the group consisting of divinyl-1,1,3,3-tetramethyldisiloxane and mixtures thereof.
11. A molded article prepared from the polycarbonate-based thermoplastic resin composition according to any one of claims 1 to 10.
12. A first resin in continuous phase;

    Second resin which is a dispersed phase; And

    An impact reinforcing material located at an interface between the first resin in the continuous phase and the second resin in the dispersed phase;

    Polycarbonate-based thermoplastic resin composition comprising a.
13. The polycarbonate-based thermoplastic according to claim 12, comprising 40 to 80 wt% of the first resin in the continuous phase, 10 to 30 wt% of the second resin in the dispersed phase, and 1 to 30 wt% of the impact modifier. Resin composition.
14. The method of claim 12, wherein the first resin in the continuous phase is a polycarbonate resin (A), the second resin in the dispersed phase is a copolymer resin (C) containing a silicone-based compound, the impact modifier is a rubber-modified acrylic graft It is a copolymer resin (B), The polycarbonate type thermoplastic resin composition characterized by the above-mentioned.
15. The rubber-modified acrylic graft copolymer resin (B) is 40 to 98% by weight of rubber (b1), 1 to 30% by weight of alkyl methacrylate (b2) and vinyl aromatic monomer (b3) 1 Polycarbonate-based thermoplastic resin composition comprising from 40% by weight.
16. The polycarbonate-based thermoplastic resin composition according to claim 15, wherein the alkyl methacrylate (b2) has 1 to 20 carbon atoms.
17. The polycarbonate-based thermoplastic resin composition according to claim 14, wherein the copolymer resin (C) containing the silicone compound is a branched vinyl copolymer resin.
18. The copolymer resin (C) comprising the silicone-based compound is 10 to 80% by weight of the aromatic vinyl monomer (c1), 10 to 80% by weight of the unsaturated nitrile monomer (c2), (meth) acrylic monomer (c3) Polycarbonate-based thermoplastic resin composition, characterized in that the copolymer prepared by copolymerizing 1 to 30% by weight and 0.1 to 25% by weight of the silicone-based compound (c4) having two or more unsaturated reactors.
19. The polycarbonate-based thermoplastic resin composition according to claim 14, wherein the weight average molecular weight of the copolymer resin (C) containing the silicone compound is 30,000 to 800,000 g / mol.
20. 19. The method of claim 18, wherein the aromatic vinyl monomer (c1) is selected from the group consisting of styrene, p-methylstyrene, α-methylstyrene, halogen substituted styrene, alkyl substituted styrene, and mixtures thereof,

    The unsaturated nitrile monomer (c2) is selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile and mixtures thereof,

    The (meth) acrylic monomer (c3) is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( Aliphatic (meth) acrylates, including those selected from the group consisting of meth) acrylates and mixtures thereof,

    The silicone-based compound (c4) having two or more unsaturated reactors is a polycarbonate-based thermoplastic resin composition comprising a silicon-based compound having a structure represented by the following formula (4) alone or in mixture of two or more thereof:

    [Formula 4]

    

    (In Formula 4, l, m and n are integers of 0 to 100 (wherein l, m and n are not 0 at the same time), R ₁ to R ₈ are each independently a hydrogen atom, linear or branched C An alkyl group of ₁ -C ₅ , a cycloalkyl group of C ₄ -C ₆ , an unsaturated alkyl group of C ₂ -C ₁₂ , a C ₆ -C ₁₀ aryl group, a hydroxyl group, an alkoxy group of C ₁ -C ₅ , an acetoxy group, an amino group, An amide group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group, and a mercapto group, wherein at least two of R ₁ to R ₈ have a polymerizable unsaturated reactor.)
21. The polycarbonate-based thermoplastic resin composition of claim 18, wherein the silicone-based compound (c4) having two or more unsaturated reactors has a viscosity of 5,000 cPs or less and a vinyl content of 0.05 to 10 mmol / g.
22. 19. The method of claim 18, wherein the silicone-based compound (c4) having two or more unsaturated reactors is 2,4,6,8-tetramethyl tetravinyl cyclotetrasiloxane, 1,3,5-trivinyl-1,1,3 , 5,5-pentamethyltrisiloxane, 2,4,6-trivinyl-1,3,5-trimethylcyclosilazane, α, ω-divinylpolydimethylsiloxane, polyvinylmethylsilazane, 1,3- A polycarbonate-based thermoplastic resin composition selected from the group consisting of divinyl-1,1,3,3-tetramethyldisiloxane and mixtures thereof.
23. A molded article produced from the polycarbonate-based thermoplastic resin composition according to any one of claims 12 to 22.