KR20160083584A - Silicon-containing vinyl-based copolymer, method for preparing the same and thermoplastic resin composition comprising the same - Google Patents

Abstract

The present invention relates to a silicon-containing vinyl-based copolymer, which is a polymer of a monomer mixture comprising: 10-20 wt% of an acrylic monomer; 50-80 wt% of an aromatic vinyl monomer; 5-30 wt% of a vinyl cyanide monomer; and 0.05-5 wt% of a silane compound represented by chemical formula 1. A thermoplastic resin composition comprising the silicon-containing vinyl-based copolymer has excellent impact resistance, flowability and heat resistance, and a good balance thereof. In chemical formula 1, R_1 is H or a methyl group; each of R_2, R_3 and R_4 independently represents a C1-C10 alkoxy group, a C6-C10 aryloxy group, or *-O-R_5-O-R_6 (wherein R_5 is a C1-C3 alkylene group, R_6 is a C1-C10 alkyl group or a C6-C10 aryl group, and * represents a binding site); m is an integer of zero to 10; and n is zero or one.

Description

TECHNICAL FIELD [0001] The present invention relates to a silicone-containing vinyl copolymer, a process for producing the same, and a thermoplastic resin composition containing the same. BACKGROUND ART [0002] Silicone-containing vinyl copolymers,

TECHNICAL FIELD The present invention relates to a silicone-containing vinyl copolymer, a method for producing the same, and a thermoplastic resin composition containing the same. More specifically, the present invention relates to a novel silicone-containing vinyl-based copolymer, a process for producing the same, and a thermoplastic resin composition having excellent impact resistance, flowability, heat resistance and balance of physical properties thereof.

Polycarbonate resin is an engineering plastic excellent in mechanical strength, heat resistance and transparency. The polycarbonate resin is used in various fields such as office automation equipment, electric / electronic parts, and building materials. Particularly, when a rubber-modified aromatic vinyl copolymer resin such as acrylonitrile-butadiene-styrene (ABS) is mixed with the above polycarbonate resin, the polycarbonate resin can be produced without degrading the impact resistance, heat resistance, Can be improved. As such, the blend of the polycarbonate resin and the rubber-modified aromatic vinyl copolymer resin as the thermoplastic resin can provide excellent physical properties as compared with the rubber-modified aromatic vinyl copolymer resin, and the cost can be reduced compared to the polycarbonate resin So that it is utilized for various purposes.

Such a resin composition (blend) comprising a polycarbonate resin and a rubber-modified aromatic vinyl copolymer resin is representative of a PC / ABS alloy (U.S. Patent No. 3,130,177, etc.). The PC / ABS alloy is a blend of a polycarbonate resin and an ABS resin and is used for interior / exterior materials such as electric / electronic products which require high gloss, high flow and high impact. However, reinforcing materials (thermoplastic resin compositions) reinforced by an inorganic filler, a flame retardant, or the like have been developed because PC / ABS alone has poor modulus and flame retardancy.

Generally, when an inorganic filler such as glass fiber is blended with a thermoplastic resin, mechanical properties such as tensile strength, flexural strength and flexural modulus of the resin can be improved owing to the intrinsic properties of the inorganic filler, and excellent heat resistance is exhibited, It is suitable for parts that are to receive or withstand constant heat. In particular, it is widely used for interior / exterior materials of automobiles, electric and electronic products which require flame retardancy, impact resistance and mechanical properties by adding flame retardant.

However, since the inorganic filler usually has poor compatibility and adhesiveness with the thermoplastic resin, there is a possibility that when added to the resin composition, the impact resistance and the fluidity (moldability) are greatly lowered.

Furthermore, in order to form a thin film of a thermoplastic resin composition containing a polycarbonate resin and a rubber-modified aromatic vinyl copolymer resin in accordance with the trend of weight reduction and thinning of the product, to be.

Therefore, development of a thermoplastic resin composition excellent in impact resistance, fluidity, heat resistance, and balance of physical properties such as impact strength and the like is required for application of an inorganic filler.

It is an object of the present invention to provide a novel silicone-containing vinyl-based copolymer and a process for producing the same.

Another object of the present invention is to provide a thermoplastic resin composition which is excellent in impact resistance, flowability, heat resistance and balance of physical properties by applying the silicone-containing vinyl-based copolymer.

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

One aspect of the present invention relates to a silicon-containing vinyl-based copolymer. Wherein the silicon-containing vinyl copolymer comprises 10 to 20 wt% of an acrylic monomer, 50 to 80 wt% of an aromatic vinyl monomer, 5 to 30 wt% of a vinyl cyan monomer, and 0.05 to 5 wt% of a silane- ≪ / RTI > is a polymer of a monomer mixture comprising:

[Chemical Formula 1]

(여기서, R₅는 탄소수 1 내지 3의 알킬렌기이고, R₆는 탄소수 1 내지 10의 알킬기 또는 탄소수 6 내지 10의 아릴기이며, *는 결합 부위를 나타냄)이며, m은 0 내지 10의 정수이고, n은 0 또는 1이다.Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ , R ₃ and R ₄ are each independently an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms,

(Wherein R ₅ is an alkylene group having 1 to 3 carbon atoms, R ₆ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, * indicates a bonding site), and m is an integer of 0 to 10 And n is 0 or 1.

In an embodiment, the acrylic monomer may be an alkyl (meth) acrylate having 1 to 10 carbon atoms.

In an embodiment, the aromatic vinyl monomer is selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, And vinyl naphthalene.

In an embodiment, the vinyl cyanide monomer may include at least one of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and fumaronitrile.

In an embodiment, the silicon-containing vinyl-based copolymer may have a glass transition temperature of 60 to 90 캜.

In embodiments, the silicon-containing vinyl-based copolymer may have a weight average molecular weight of 50,000 to 200,000 g / mol.

Another aspect of the present invention relates to a method for producing the silicon-containing vinyl copolymer. The above-mentioned production method is characterized by comprising a step of preparing a monomer composition comprising 10 to 20 wt% of an acrylic monomer, 50 to 80 wt% of an aromatic vinyl monomer, 5 to 30 wt% of a vinyl cyan monomer, and 0.05 to 5 wt% And polymerizing the mixture.

In an embodiment, the polymerization can be carried out at 70 to 120 < 0 > C.

Another aspect of the present invention relates to a thermoplastic resin composition. Wherein the thermoplastic resin composition is a base resin comprising a polycarbonate resin and a rubber-modified aromatic vinyl-based copolymer resin; Inorganic fillers; And the silicon-containing vinyl-based copolymer.

In an embodiment, the content of the polycarbonate resin is 50 to 99% by weight of the entire base resin, the content of the rubber-modified aromatic vinyl copolymer resin is 1 to 50% by weight of the entire base resin, the content of the inorganic filler Is 5 to 100 parts by weight based on 100 parts by weight of the base resin, and the content of the silicon-containing vinyl copolymer is 0.1 to 40 parts by weight based on 100 parts by weight of the base resin.

In an embodiment, the rubber-modified aromatic vinyl-based copolymer resin comprises 10 to 100% by weight of a graft copolymer resin obtained by graft copolymerizing an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer in a rubbery polymer; And 0 to 90% by weight of an aromatic vinyl-based copolymer resin in which an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer are copolymerized.

In an embodiment, the inorganic filler may include at least one of talc, wollastonite, glass fiber, whisker, silica, mica, and basalt fiber.

In an embodiment, the thermoplastic resin composition may further include at least one of a flame retardant, a surfactant, an antioxidant, a drip inhibitor, a releasing agent, a nucleating agent, an antistatic agent, a heat stabilizer, a light stabilizer, a pigment and a dye.

In the specific examples, the thermoplastic resin composition had an Izod impact strength of 6 to 20 kgf · cm / cm measured in accordance with ASTM D256 and measured at 220 ° C. and 10 kgf according to ASTM D1238 A melt index (MI) of 40 to 70 g / 10 min, and a heat distortion temperature (HDT) measured according to ASTM D648 of 75 to 120 캜.

The present invention relates to a novel silicone-containing vinyl-based copolymer, a process for producing the same, and the silicon-containing vinyl-based copolymer so as to provide the thermoplastic resin composition excellent in impact resistance, flowability, heat resistance and balance of physical properties thereof I have.

Hereinafter, the present invention will be described in detail.

The silicon-containing vinyl copolymer according to the present invention is a polymer of a monomer mixture containing an aromatic vinyl monomer, a vinyl cyanide monomer and a silane compound represented by the following formula (1) in an acrylic monomer.

[Chemical Formula 1]

(여기서, R₅는 탄소수 1 내지 3의 알킬렌기이고, R₆는 탄소수 1 내지 10, 예를 들면 탄소수 1 내지 4의 알킬기 또는 탄소수 6 내지 10, 예를 들면 탄소수 6 내지 8의 아릴기이며, *는 결합 부위를 나타냄)이며, m은 0 내지 10의 정수이고, n은 0 또는 1이다.Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ , R ₃ and R ₄ are each independently an alkoxy group having 1 to 10 carbon atoms, for example, 1 to 4 carbon atoms, 6 to 10 carbon atoms, for example, An aryloxy group having 6 to 8 carbon atoms, or

(Wherein R ₅ is an alkylene group having 1 to 3 carbon atoms and R ₆ is an alkyl group having 1 to 10 carbon atoms, for example, 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, for example, 6 to 8 carbon atoms, * Represents a bonding site, m is an integer of 0 to 10, and n is 0 or 1.

In an embodiment, typical (meth) acrylate may be used as the acrylic monomer. For example, alkyl (meth) acrylates having 1 to 10 carbon atoms, specifically, butyl (meth) acrylate can be used, but the present invention is not limited thereto. These may be used alone or in combination of two or more.

In an embodiment, the content of the acrylic monomer may be 10 to 20 wt%, for example 13 to 17 wt%, of 100 wt% of the total monomer mixture. When the silicone-containing vinyl-based copolymer is polymerized in the above-mentioned range, it is easy to handle, and the silicone-containing vinyl-based copolymer can have excellent impact resistance and fluidity.

In an embodiment, the aromatic vinyl monomer is at least one monomer selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dibromostyrene , Vinyl naphthalene, mixtures thereof, and the like, but are not limited thereto. These may be used alone or in combination of two or more.

In an embodiment, the content of the aromatic vinyl monomer may be 50 to 80 wt%, for example 55 to 75 wt%, of 100 wt% of the total monomer mixture. Within the above range, the silicone-containing vinyl-based copolymer can have excellent processability, impact resistance, fluidity, and the like.

In the specific examples, examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, fumaronitrile, and mixtures thereof , But is not limited thereto. These may be used alone or in combination of two or more.

In an embodiment, the content of the vinyl cyanide monomer may be from 5 to 30% by weight, for example from 10 to 25% by weight, based on 100% by weight of the total monomer mixture. In the above range, compatibility of the silicon-containing vinyl copolymer and polycarbonate resin can be excellent.

The silane-based compound represented by the above formula (1) can obtain an effect of improving impact resistance and the like without lowering the heat resistance and the like of the silicon-containing vinyl copolymer. Examples of the silane-based compound include, but are not limited to, compounds represented by the following formulas (1a), (1b) and (1c). These may be used alone or in combination of two or more.

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

In an embodiment, the content of the silane-based compound represented by Formula 1 may be 0.05 to 5% by weight, for example, 0.1 to 3% by weight, based on 100% by weight of the total monomer mixture. In the above range, the silicone-containing vinyl-based copolymer may have excellent impact resistance.

In embodiments, the silicon-containing vinyl-based copolymer may have a glass transition temperature of 60 to 90 캜, such as 75 to 85 캜.

In embodiments, the silicon-containing vinyl-based copolymer may have a weight average molecular weight of 50,000 to 200,000 g / mol, such as 100,000 to 180,000 g / mol.

The silicon-containing vinyl-based copolymer of the present invention can be obtained by subjecting a reaction mixture containing the above-mentioned contents of an acrylate monomer, an aromatic vinyl monomer, a vinyl cyanide monomer and a silane compound represented by the above formula 1 to suspension polymerization, emulsion polymerization, But the present invention is not limited thereto. For example, suspension polymerization may be used. Specifically, the reaction mixture, the polymerization initiator, the dispersant, the suspension stabilizer (dispersion auxiliary agent), water and the like may be added to the reactor to homogenize the suspension, and the suspension may be polymerized in a nitrogen atmosphere. At this time, the polymerization temperature and the polymerization time can be appropriately controlled. For example, at a polymerization temperature of 65 to 125 ° C, specifically 70 to 120 ° C, for 1 to 8 hours.

In the specific examples, as the polymerization initiator, a conventional radical polymerization initiator can be used. Examples of the polymerization initiator include 1,1-di (tert-butylperoxy) cyclohexane, octanoyl peroxide, decanoyl peroxide, (2,4-dimethyl) benzoyl peroxide, monochlorobenzoyl peroxide, dichlorobenzoyl peroxide, p-methyl benzoyl peroxide, tert-butyl perbenzoate, azobisisobutyronitrile and azobis- - valeronitrile, and the like may be used, but the present invention is not limited thereto. These polymerization initiators may be used alone or in combination of two or more. The polymerization initiator may be included in an amount of 0.01 to 10 parts by weight, for example, 0.03 to 5 parts by weight, based on 100 parts by weight of the reaction mixture, but is not limited thereto.

In the specific examples, polyoxyethylene alkyl ether phosphate and the like may be used as the dispersing agent, but the present invention is not limited thereto. The dispersant may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the reaction mixture, but is not limited thereto.

In an embodiment, the suspension stabilizer includes an inorganic suspension stabilizer including tricalcium phosphate and the like; A homopolymer or copolymer of acrylic acid or methacrylic acid, an organic suspension stabilizer including polyalkyl acrylate-acrylic acid, polyolefin-maleic acid, polyvinyl alcohol, cellulose and the like; Mixtures thereof, and the like may be used, but are not limited thereto. The suspension stabilizer may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the reaction mixture, but is not limited thereto.

In the specific example, additives such as a chain transfer agent, a suspension stabilizing auxiliary agent, and an antioxidant may be further added, if necessary, at the time of the polymerization. The additive may be included in an amount of 0.001 to 20 parts by weight based on 100 parts by weight of the reaction mixture, but is not limited thereto.

In a specific example, a bead-type silicon-containing vinyl-based copolymer can be obtained through usual cooling, washing, dehydration and drying processes after the polymerization is completed.

The thermoplastic resin composition according to the present invention comprises (A) a base resin comprising (A1) a polycarbonate resin and (A2) a rubber-modified aromatic vinyl-based copolymer resin; (B) an inorganic filler; And (C) the silicon-containing vinyl-based copolymer.

(A) Base resin

(A1) Polycarbonate resin

As the polycarbonate resin to be used in the present invention, a usual thermoplastic polycarbonate resin can be used without limitation. For example, an aromatic polycarbonate resin prepared by reacting at least one diphenol (aromatic dihydroxy compound) with a carbonate precursor such as phosgene, halogen formate, or carbonic acid diester can be used.

Specific examples of the diphenols include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) Propane, mixtures thereof, and the like, but are not limited thereto. Examples of the above diphenols include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 1,1- -Hydroxyphenyl) cyclohexane, and specifically 2,2-bis (4-hydroxyphenyl) propane, also referred to as bisphenol-A, can be used.

The polycarbonate resin may be used in the form of a branched chain. For example, 0.05 to 2 mol% of a trifunctional or more polyfunctional compound, for example, trivalent or more, And further adding a compound having a phenol group. The polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin or a blend thereof. The polycarbonate resin may be partially or wholly substituted with an aromatic polyester-carbonate resin obtained by polymerization reaction in the presence of an ester precursor such as a bifunctional carboxylic acid.

In embodiments, the weight average molecular weight (Mw) of the polycarbonate resin may be 10,000 to 50,000 g / mol, such as, but not limited to, 15,000 to 40,000 g / mol.

In an embodiment, the polycarbonate resin may comprise 50 to 99 wt%, for example 60 to 95 wt%, of 100 wt% of the total base resin. Within the above range, the thermoplastic resin composition may have excellent impact resistance, mechanical properties, heat resistance, and the like.

(A2) Rubber-modified aromatic vinyl-based copolymer resin

The rubber-modified aromatic vinyl-based copolymer resin used in the present invention is a rubber-modified aromatic vinyl-based copolymer resin in which 10 to 100% by weight of (a1) graft copolymer resin in which an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer are graft- And 0 to 90% by weight of an aromatic vinyl-based copolymer resin (a2) in which an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer are copolymerized. That is, in the rubber-modified aromatic vinyl copolymer resin of the present invention, the graft copolymer resin (a1) may be used alone or in the form of a mixture of the graft copolymer resin (a1) and the aromatic vinyl copolymer resin (a2) .

In an embodiment, the graft copolymer resin (a1) can be polymerized by adding an aromatic vinyl monomer, a monomer copolymerizable with the aromatic vinyl monomer, and the like to the rubbery polymer, and the aromatic vinyl copolymer resin (a2) Can be polymerized by adding an aromatic vinyl monomer, a monomer copolymerizable with the aromatic vinyl monomer, and the like. The polymerization can be carried out by a known polymerization method such as emulsion polymerization, suspension polymerization and bulk polymerization. In the case of the above-mentioned bulk polymerization, the graft copolymer resin (a1) can be produced by a single step reaction process without separately preparing the graft copolymer resin (a1) and the aromatic vinyl copolymer resin (a2) A rubber-modified aromatic vinyl-based copolymer resin in a form dispersed in the coalescing resin (a2) can be produced.

In a specific example, the content of the rubber (rubbery polymer) in the final rubber-modified aromatic vinyl-based copolymer resin component is preferably 5 to 50% by weight. In addition, the particle size of the rubber may be 0.05 to 6.0 탆 in Z-average. The properties such as impact resistance can be excellent in the above range.

Hereinafter, the graft copolymer resin (a1) and the aromatic vinyl copolymer resin (a2) will be described in more detail as follows.

(a1) graft copolymer resin

The graft copolymer resin can be obtained by graft copolymerizing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer to a rubbery polymer, and may further include a monomer which imparts processability and heat resistance, if necessary .

Specific examples of the rubbery polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene) and saturated rubbers hydrogenated with the diene rubbers, isoprene rubber, polybutylacrylic acid Acrylic rubber, ethylene-propylene-diene monomer terpolymer (EPDM), and the like. These may be used alone or in combination of two or more.

 For example, a diene rubber can be used, and specifically, a butadiene rubber can be used. The content of the rubbery polymer may be 5 to 65% by weight, for example, 10 to 60% by weight, specifically 20 to 50% by weight, based on the total weight of the graft copolymer resin (a1). It is possible to obtain a good balance of impact strength and mechanical properties in the above range. The average particle size (Z-average) of the rubbery polymer (rubber particles) may be 0.05 to 6 탆, for example, 0.15 to 4 탆, specifically 0.25 to 3.5 탆. The impact strength and appearance can be excellent in the above range.

The aromatic vinyl-based monomer may be graft-copolymerized with the rubbery copolymer. Examples of the aromatic vinyl monomer include styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, , Monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like, but the present invention is not limited thereto. These may be used alone or in combination of two or more. The content of the aromatic vinyl monomer may be 15 to 94% by weight, for example, 20 to 80% by weight, specifically 30 to 60% by weight, based on the total weight of the graft copolymer resin (a1). It is possible to obtain a good balance of impact strength and mechanical properties in the above range.

Examples of the monomer copolymerizable with the aromatic vinyl monomer include vinyl cyanide compounds such as acrylonitrile and unsaturated nitrile compounds such as ethacrylonitrile and methacrylonitrile. Or more. The content of the monomer copolymerizable with the aromatic vinyl monomer may be 1 to 50% by weight, for example, 5 to 45% by weight, specifically 10 to 30% by weight, based on the total weight of the graft copolymer resin. It is possible to obtain a good balance of impact strength and mechanical properties in the above range.

Examples of the monomer for imparting the above processability and heat resistance include, but are not limited to, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide and the like. These may be used alone or in combination of two or more. The content of the monomer for imparting the above processability and heat resistance may be 0 to 15% by weight, for example, 0.1 to 10% by weight, based on the total weight of the graft copolymer resin. The workability and heat resistance can be imparted without deteriorating the other properties within the above range.

(a2) an aromatic vinyl-based copolymer resin

The aromatic vinyl-based copolymer resin used in the present invention can be produced by using a monomer mixture excluding the rubber (rubbery polymer) among the components of the graft copolymer resin (a1), and the ratio of the monomers varies depending on the compatibility and the like . For example, the aromatic vinyl-based copolymer resin can be obtained by copolymerizing the aromatic vinyl-based monomer and the monomer copolymerizable with the aromatic vinyl-based monomer.

Examples of the aromatic vinyl monomers include aromatic vinyl monomers such as styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromo Styrene, vinylnaphthalene, and the like, but is not limited thereto. These may be used alone or in combination of two or more.

Examples of the monomer copolymerizable with the aromatic vinyl monomer include vinyl cyanide compounds such as acrylonitrile and unsaturated nitrile compounds such as ethacrylonitrile and methacrylonitrile. Two or more of them may be used in combination.

The aromatic vinyl-based copolymer resin may further contain a monomer which imparts the above processability and heat resistance, if necessary. Examples of the monomer for imparting the above processability and heat resistance include, but are not limited to, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide and the like. These may be used alone or in combination of two or more.

In the aromatic vinyl-based copolymer resin, the content of the aromatic vinyl-based monomer is 50 to 95% by weight, for example, 60 to 90% by weight, specifically 70 to 80% by weight, based on the total weight of the aromatic vinyl- . It is possible to obtain a good balance of impact strength and mechanical properties in the above range.

The content of the copolymerizable monomer with the aromatic vinyl-based monomer may be 5 to 50% by weight, for example, 10 to 40% by weight, specifically 20 to 30% by weight, based on the total weight of the aromatic vinyl-based copolymer resin. It is possible to obtain a good balance of impact strength and mechanical properties in the above range.

The content of the monomer for imparting workability and heat resistance may be from 0 to 30% by weight, for example, from 0.1 to 20% by weight, based on the total weight of the aromatic vinyl-based copolymer resin. The workability and heat resistance can be imparted without deteriorating the other properties within the above range.

The weight average molecular weight of the aromatic vinyl-based copolymer resin may be 50,000 to 500,000 g / mol, but is not limited thereto.

Non-limiting examples of the rubber-modified aromatic vinyl copolymer resin (A2) of the present invention include copolymers of styrene monomer, which is an aromatic vinyl compound, and acrylonitrile monomer, which is an unsaturated nitrile compound, grafted to a center butadiene rubber- Butadiene-styrene copolymer resin (ABS resin), acrylonitrile-ethylene-propylene rubber-styrene copolymer resin (AES resin (a-1) (A1) such as acrylonitrile-acrylic rubber-styrene copolymer resin (AAS resin), acrylonitrile-acrylic rubber-styrene copolymer resin (AAS resin) and the like. Here, the ABS resin may be one in which the g-ABS is dispersed in the styrene-acrylonitrile copolymer resin (SAN resin) as the aromatic vinyl copolymer resin (a2) as the graft copolymer resin (a1) have.

In a specific example, the rubber-modified aromatic vinyl-based copolymer resin may be contained in an amount of 1 to 50% by weight, for example, 5 to 40% by weight, based on 100% by weight of the total base resin. The impact resistance and mechanical properties of the thermoplastic resin composition may be excellent in the above range.

(B) inorganic filler

The inorganic filler used in the present invention can improve the rigidity, heat resistance and the like of the thermoplastic resin composition. As the inorganic filler, a conventional inorganic filler may be used without limitation. For example, talc, wollastonite, glass fiber, whisker, silica, mica, basalt fiber, mixtures thereof and the like can be used, and talc and the like can be used specifically.

In embodiments, the average particle size of the inorganic filler may be, for example, 50 nm to 100 탆, but is not limited thereto.

In an embodiment, the content of the inorganic filler may be 5 to 100 parts by weight, for example, 10 to 30 parts by weight, based on 100 parts by weight of the base resin. Within the above range, a thermoplastic resin composition having excellent impact resistance, fluidity, heat resistance, rigidity and the like can be obtained.

(C) a silicone-containing vinyl copolymer

The silicone-containing vinyl-based copolymer used in the present invention can improve the impact resistance, fluidity, heat resistance and balance of physical properties of the thermoplastic resin composition by improving the compatibility of the base resin and the inorganic filler.

In an embodiment, the content of the silicon-containing vinyl-based copolymer may be 0.1 to 40 parts by weight, for example, 1 to 20 parts by weight, based on 100 parts by weight of the base resin. Within the above range, a thermoplastic resin composition having excellent impact resistance, fluidity, heat resistance, physical properties and the like can be obtained.

In an embodiment, the content of the silicon-containing vinyl copolymer may be less than or equal to that of the inorganic filler. In this case, a thermoplastic resin composition having better impact resistance, fluidity, heat resistance, balance of physical properties and the like can be obtained.

The thermoplastic resin composition according to an embodiment of the present invention may further contain additives such as a flame retardant, a surfactant, an antioxidant, an antistatic agent, a releasing agent, a nucleating agent, an antistatic agent, a heat stabilizer, a light stabilizer, a pigment, a dye, .

In a specific example, a conventional phosphorus flame retardant used in the flame retardant thermoplastic resin composition may be used as the flame retardant. For example, phosphorous compounds such as phosphates, phosphonate compounds, phosphinate compounds, phosphine oxide compounds, phosphazene compounds, metal salts of these compounds, Flame retardants may be used. The phosphorus-based flame retardant may be used alone or in combination of two or more. Specific examples include diaryl phosphates such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, triazylenyl phosphate, tri (2,6-dimethylphenyl) phosphate, tri (2,4,6-trimethylphenyl) Tri (2, 6-dimethylphenyl) phosphate, bisphenol-A bis (diphenylphosphate), resorcinol bis (diphenylphosphate), resorcinol bis [bis (2,4-ditertiary butylphenyl) phosphate], hydroquinone bis [bis (2,6-dimethylphenyl) phosphate], hydroquinone bis [ Bis (2,4-ditertiary butylphenyl) phosphate], a mixture of these compounds, and the like can be used. The flame retardant is contained in an amount of 1 to 40 parts by weight, for example, 5 to 30 parts by weight based on 100 parts by weight of the base resin, the inorganic filler and the silicon-containing vinyl copolymer ((A) + (B) + . Within the above range, flame retardancy can be improved without deteriorating other physical properties of the thermoplastic resin composition.

In a specific example, a conventional surfactant used in the thermoplastic resin composition may be used as the surfactant. Examples of the surfactant include anionic surfactants such as sodium dodecylbezene sulfonate (SDBS) and sodium lauryl sulfate, polyoxyethylene alkyl ether, polyethylene oxide Non-ionic surfactants such as tri-block copolymers, and mixtures thereof, but are not limited thereto. The surfactant is used in an amount of 0.1 to 10 parts by weight, for example, 0.2 to 3 parts by weight per 100 parts by weight of the base resin, the inorganic filler and the silicon-containing vinyl copolymer ((A) + (B) + . The inorganic filler can be easily dispersed in the above range.

In the specific examples, the content of the additive excluding the flame retardant and the surfactant when used is 0.01 (parts by weight) to 100 parts by weight of the base resin, the inorganic filler and the silicon-containing vinyl copolymer ((A) + But it is not limited thereto.

The thermoplastic resin composition according to one embodiment of the present invention is excellent in impact resistance, fluidity, heat resistance, and physical properties thereof. The 1/4 inch thick specimen measured according to ASTM D256 has an Izod impact strength of 6 to 20 kgf cm / cm, for example 6.5 to 15 kgf / cm / cm.

The thermoplastic resin composition may have a melt index (MI) of 40 to 70 g / 10 minutes, for example, 45 to 65 g / 10 minutes, measured at 220 DEG C and 10 kgf according to ASTM D1238.

The thermoplastic resin composition may have a heat distortion temperature (HDT) of 75 to 120 ° C, for example, 76 to 95 ° C as measured according to ASTM D648.

The thermoplastic resin composition according to one embodiment of the present invention can be produced by a known method for producing a thermoplastic resin composition. For example, after mixing the above components and other additives as necessary, they may be melt-extruded in an extruder to produce pellets. The produced pellets can be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those of ordinary skill in the art to which the present invention pertains. The molded article is excellent in impact resistance, fluidity, heat resistance, physical properties, and the like, and therefore is useful as parts for automobiles, electric and electronic products, interior / exterior materials, daily necessities and the like.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Example

Examples 1 to 5: Preparation of silicon-containing vinyl-based copolymer

After adding a reaction mixture containing butyl acrylate, styrene, acrylonitrile and silane compounds represented by the following formulas (1a), (1b) and (1c) to a 100 L batch reactor according to the composition and content of the following Table 1, 0.5 part by weight of 1,1-di (tert-butylperoxy) cyclohexane, 0.003 part by weight of polyoxyethylene alkyl ether phosphate, 0.5 part by weight of tricalcium phosphate and 90 parts by weight of water were added to 100 parts by weight of the mixture, Respectively. Next, in order to remove dissolved oxygen in the reactor, a nitrogen atmosphere was maintained for 1 hour, and then the temperature was raised to 90 DEG C to polymerize. After the polymerization was completed, cooling, washing, dehydration and drying were carried out to obtain a bead-shaped silicon-containing vinyl copolymer.

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

Example 1 Example 2 Example 3 Example 4 Example 5 Butyl acrylate (% by weight) 15 10 20 15 15 Styrene (wt%) 60 65 55 60 60 Acrylonitrile (% by weight) 23 23 23 23 23 Silane compound Formula 1a 2 2 2 - - 1b - - - 2 - Formula 1c - - - - 2 Glass transition temperature 75 83 72 76 77 Weight average molecular weight 150k 156k 147k 152k 153k

Comparative Examples 1 to 3: Preparation of Vinyl Copolymer

A bead-type vinyl copolymer was prepared in the same manner as in Example 1, except that the compositions and contents of butyl acrylate, styrene, acrylonitrile and silane compounds were changed according to the following Table 2, .

Comparative Example 1 Comparative Example 2 Comparative Example 3 Butyl acrylate (% by weight) 15 5 25 Styrene (wt%) 60 70 50 Acrylonitrile (% by weight) 23 23 23 Silane compound Formula 1a - 2 2 Glass transition temperature 75 87 67 Weight average molecular weight 158k 161k 145k

Property evaluation method

(1) Glass transition temperature (Tg, unit: 占 폚): Measured by a differential scanning calorimeter. The equipment used for the differential scanning calorimeter was DSC Q100 (TA INSTRUMENTS KOREA), which was heated from 30 ° C to 300 ° C in a nitrogen atmosphere at a rate of 10 ° C / min.

(2) Weight average molecular weight (unit: g / mol): Measured by gel permeation chromatography (GPC).

The specifications of each component used in the following examples and comparative examples are as follows:

(A) Base resin

(A1) Polycarbonate resin

Bisphenol-A polycarbonate resin (manufacturer: Samsung SDI, product name: SC-1190) was used.

(A2) Rubber-modified aromatic vinyl-based copolymer resin

Modified ABS resin (ABS resin) prepared by kneading 16.7 wt% of the following graft copolymer resin (g-ABS) and 83.3 wt% of the following SAN resin was used.

Grafted copolymer resin (g-ABS): 52 wt% styrene monomer and acrylonitrile (SM / AN: 73 / g) were added to polybutadiene rubber (PBR) having a Z- 27) were graft-copolymerized with g-ABS.

* SAN resin: styrene-acrylonitrile copolymer (SM / AN weight ratio: 76/24, weight average molecular weight: 150,000 g / mol) was used.

(B) inorganic filler

Talc (manufacturer: HAYASHI, product name: UPN HS-T 0.5) was used.

(C) a silicone-containing vinyl copolymer

(C1) The silicon-containing vinyl copolymer produced in Example 1 was used.

(C2) The silicon-containing vinyl copolymer produced in Example 2 was used.

(C3) The silicon-containing vinyl copolymer produced in Example 3 was used.

(C4) The silicon-containing vinyl copolymer produced in Example 4 was used.

(C5) The silicon-containing vinyl copolymer produced in Example 5 was used.

(C6) The vinyl copolymer produced in Comparative Example 1 was used.

(C7) The vinyl copolymer produced in Comparative Example 2 was used.

(C8) The vinyl copolymer produced in Comparative Example 3 was used.

Examples 6 to 10 and Comparative Examples 4 to 6

19 parts by weight of a phosphorus flame retardant (bisphenol-A bis (diphenylphosphate) (BDP)) and 20 parts by weight of a surfactant (sodium dodecylbenzene (BDP)) were added to 100 parts by weight of the above components and components, (SDBS)) was added to a twin screw type extruder having an L / D ratio of 44 and a diameter of 45 mm. The mixture was melted at 250 DEG C and a stirring speed of 250 rpm, And extruded to produce pellets. The prepared pellets were dried at 80 DEG C for 5 hours or more, and then ejected from a screw extruder (150 tons single injector) at 240 to 280 DEG C to prepare specimens. The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 1 below.

How to measure property

(1) Heat resistance evaluation: The heat distortion temperature (HDT, unit: 占 폚) was measured according to ASTM D648.

(2) Melt Index (MI, unit: g / 10 min): Measured at 220 캜 and 10 kgf according to the evaluation method specified in ASTM D1238.

(3) IZOD Impact Strength (Unit: kgf · cm / cm): Based on the evaluation method described in ASTM D256, a notch was formed on a 1/8 "thick Izod sample to evaluate it.

Example Comparative Example 6 7 8 9 10 4 5 6 (A1) (% by weight) 89.74 89.74 89.74 89.74 89.74 89.74 89.74 89.74 (A2) (% by weight) 10.26 10.26 10.26 10.26 10.26 10.26 10.26 10.26 (B) (parts by weight) 25.64 25.64 25.64 25.64 25.64 25.64 25.64 25.64 (C1) (parts by weight) 2.56 - - - - - - - (C2) (parts by weight) - 2.56 - - - - - - (C3) (parts by weight) - - 2.56 - - - - - (C4) (parts by weight) - - - 2.56 - - - - (C5) (parts by weight) - - - - 2.56 - - - (C6) (parts by weight) - - - - - 2.56 - - (C7) (parts by weight) - - - - - - 2.56 - (C8) (parts by weight) - - - - - - - 2.56 HDT 82.6 84.3 79.9 79.1 80.2 82.6 86.1 76.4 MI 50.0 48.0 62.8 58.3 60.5 42.3 22.0 71.3 Izod impact strength 7.2 6.9 9.0 9.2 8.7 5.5 3.2 11.7

From the above results, it can be seen that the thermoplastic resin composition according to the present invention has excellent impact resistance (Izod impact strength), fluidity and heat resistance.

On the other hand, in the case of Comparative Example 4, the impact resistance was lowered as compared with the Examples. In Comparative Example 5, both the impact resistance and the fluidity were reduced as compared with the Examples. In Comparative Example 6, .

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (14)

A polymer of a monomer mixture comprising 10 to 20% by weight of an acrylic monomer, 50 to 80% by weight of an aromatic vinyl monomer, 5 to 30% by weight of a vinyl cyan monomer, and 0.05 to 5% by weight of a silane- Wherein the silicon-containing vinyl-based copolymer comprises:
[Chemical Formula 1]

Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ , R ₃ and R ₄ are each independently an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms,

(Wherein R ₅ is an alkylene group having 1 to 3 carbon atoms, R ₆ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, * indicates a bonding site), and m is an integer of 0 to 10 And n is 0 or 1.
The silicone-containing vinyl copolymer as claimed in claim 1, wherein the acrylic monomer is an alkyl (meth) acrylate having 1 to 10 carbon atoms.
The aromatic vinyl monomer as claimed in claim 1, wherein the aromatic vinyl monomer is at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, Styrene, and vinylnaphthalene. The vinyl-based copolymer according to claim 1,
The method according to claim 1, wherein the vinyl cyanide monomer is at least one of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and fumaronitrile Based copolymer.
The silicone-containing vinyl-based copolymer according to claim 1, wherein the silicon-containing vinyl-based copolymer has a glass transition temperature of 60 to 90 占 폚.
The silicone-containing vinyl-based copolymer according to claim 1, wherein the silicon-containing vinyl-based copolymer has a weight-average molecular weight of 50,000 to 200,000 g / mol.
A monomer mixture comprising 10 to 20% by weight of an acrylic monomer, 50 to 80% by weight of an aromatic vinyl monomer, 5 to 30% by weight of a vinyl cyan monomer and 0.05 to 5% by weight of a silane compound represented by the following formula Containing vinyl-based copolymer.
[Chemical Formula 1]

Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ , R ₃ and R ₄ are each independently an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms,

(Wherein R ₅ is an alkylene group having 1 to 3 carbon atoms, R ₆ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, * indicates a bonding site), and m is an integer of 0 to 10 And n is 0 or 1.
The process for producing a silicon-containing vinyl copolymer according to claim 7, wherein the polymerization is carried out at 70 to 120 캜.
A base resin comprising a polycarbonate resin and a rubber-modified aromatic vinyl copolymer resin;
Inorganic fillers; And
A thermoplastic resin composition comprising the silicon-containing vinyl copolymer according to any one of claims 1 to 6.
The rubber-modified aromatic vinyl-based copolymer resin according to claim 9, wherein the content of the polycarbonate resin is 50 to 99% by weight of the entire base resin, the content of the rubber-modified aromatic vinyl-based copolymer resin is 1 to 50% Is contained in an amount of 5 to 100 parts by weight based on 100 parts by weight of the base resin, and the content of the silicon-containing vinyl-based copolymer is 0.1 to 40 parts by weight based on 100 parts by weight of the base resin. .
The rubber-modified aromatic vinyl-based copolymer resin according to claim 9, wherein the rubber-modified aromatic vinyl-based copolymer resin comprises 10 to 100% by weight of a graft copolymer resin obtained by graft copolymerizing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer in a rubbery polymer; And 0 to 90% by weight of an aromatic vinyl-based copolymer resin in which an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer are copolymerized.
The thermoplastic resin composition according to claim 9, wherein the inorganic filler comprises at least one of talc, wollastonite, glass fiber, whisker, silica, mica, and basalt fiber.
The thermoplastic resin composition according to claim 9, wherein the thermoplastic resin composition further comprises at least one of a flame retardant, a surfactant, an antioxidant, an antistatic agent, a releasing agent, a nucleating agent, an antistatic agent, a heat stabilizer, a light stabilizer, Thermoplastic resin composition.
The thermoplastic resin composition according to claim 9, wherein the thermoplastic resin composition has an Izod impact strength of 6 to 20 kgf / cm / cm measured in accordance with ASTM D256 at a temperature of 220 DEG C and 10 kgf according to ASTM D1238 (MI) of 40 to 70 g / 10 min and a heat distortion temperature (HDT) of 75 to 120 DEG C measured according to ASTM D648.