KR101781677B1 - Styrenic thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a styrenic thermoplastic resin composition. More specifically, the present invention relates to a styrenic thermoplastic resin composition capable of realizing a synergistic effect of impact resistance and heat resistance as well as low light properties by using a styrenic copolymer containing a compound having two or more unsaturated reactive groups.

Description

TECHNICAL FIELD The present invention relates to a styrenic thermoplastic resin composition,

The present invention relates to a styrenic thermoplastic resin composition. More specifically, the present invention relates to a styrenic thermoplastic resin composition capable of realizing a synergistic effect of impact resistance and heat resistance as well as low light properties by using a styrenic copolymer containing a compound having two or more unsaturated reactive groups.

The thermoplastic resin has a lower specific gravity than glass or metal and has mechanical properties such as excellent moldability and impact resistance. Plastic products using these thermoplastic resins are rapidly replacing existing areas of glass and metals, including electrical and electronic products and automobile parts.

Recently, as users' emotional quality level has increased, there has been an increasing demand for a low-gloss resin for atmospheric presentation and anti-glare. In addition, low-gloss resin is increasingly used because it does not use a matte coating or a padding process in order to protect the environment.

Conventionally, as a low-gloss resin, a method of using or modifying a large diameter rubber particle was used. However, such a method has a problem that the low light effect is insignificant, and the impact strength and heat resistance are deteriorated.

Alternatively, a method of producing a resin by graft-polymerizing a monomer such as an ethylene-unsaturated carboxylic acid has been used. This has the problem that the physical properties are good but the heat resistance is rapidly deteriorated.

U.S. Patent No. 4,460,742 (Patent Document 1) discloses a low-gloss resin composition using a crosslinked copolymer. This exhibits a quenching effect by injecting large diameter rubber particles or a quencher. However, there is a problem that an excessive amount of light extinction agent is required, thereby lowering the impact strength and heat resistance.

U. S. Patent No. 4,460, 742 (July 17, 1984)

SUMMARY OF THE INVENTION The present invention has been made to overcome the above problems, and it is an object of the present invention to provide a styrenic thermoplastic resin composition which can realize a synergistic effect of impact resistance and heat resistance while maintaining excellent low light properties.

Another object of the present invention is to provide a molded article comprising the styrene-based thermoplastic resin composition.

(A) a rubber-modified vinyl-based graft copolymer, (B) a styrenic copolymer containing a silicone compound having at least two unsaturated reactive groups, and (C) an aromatic vinyl- A styrene-based thermoplastic resin composition containing an unsaturated nitrile-based copolymer can be provided.

The styrene-based thermoplastic resin composition according to one embodiment of the present invention comprises (A) 10 to 40% by weight of a rubber-modified vinyl-based graft copolymer, (B) a styrenic copolymer containing a silicone compound having two or more unsaturated reactive groups 5 to 40% by weight of an aromatic vinyl-unsaturated nitrile-based copolymer and (C) 40 to 80% by weight of an aromatic vinyl-unsaturated nitrile-based copolymer.

In the styrenic thermoplastic resin composition according to one embodiment of the present invention, the styrenic copolymer (B) containing a silicone compound having two or more unsaturated reactive groups is obtained by copolymerizing (b1) 55 to 80% by weight of an aromatic vinyl compound b2) 15 to 40% by weight of an unsaturated nitrile compound and (b3) 0.1 to 10% by weight of a silicone compound having two or more unsaturated reactive groups.

In the styrenic thermoplastic resin composition according to one embodiment of the present invention, the silicone compound having two or more unsaturated reactive groups may include one or more compounds represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, l , m and n are each an integer of 0 to 100 (but not simultaneously 0), and R ₁ to R ₈ are each independently hydrogen, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group , A substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, a substituted or unsubstituted C ₂ to C ₃₀ alkynyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₁ to C ₃₀ heteroaryl group, a hydroxyl group, an alkoxy group, an amino group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group of the, or a mercapto group, the R At least two of R ₁ to R ₈ include a polymerizable unsaturated reactive group, and the compound may have a linear or cyclic structure. In the case of having an annular structure, any of the above-mentioned R ₁ to R _{8 is} interconnected to form an annular shape.

In the styrenic thermoplastic resin composition according to an embodiment of the present invention, the silicone compound having two or more unsaturated reactive groups may have one or more compounds represented by the following formula (2) when they have a cyclic structure can do.

(2)

In the formula (2), R ₉ to R ₁₄ independently represent a substituted or unsubstituted C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₂ to C ₂₀ An alkenyl group and a substituted or unsubstituted C ₆ to C ₂₀ And R ₁₅ to R ₁₇ are each independently hydrogen or a substituted or unsubstituted C ₁ to C ₆ alkyl group, and p is an integer of 1 to 6.

In the styrenic thermoplastic resin composition according to an embodiment of the present invention, the silicone compound having two or more unsaturated reactive groups may be 1,3,5-trimethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3 , 5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinyl-cyclo Pentasiloxane, 1,3,5-triethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetraethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane , 1,3,5,7,9-pentaethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, and mixtures thereof.

In the styrene-based thermoplastic resin composition according to an embodiment of the present invention, the silicone compound having two or more unsaturated reactive groups may have a weight average molecular weight of 150 to 6,000 g / mol.

In the styrenic thermoplastic resin composition according to an embodiment of the present invention, the styrenic copolymer may be at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, And at least one aromatic vinyl compound selected from the group consisting of chlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and mixtures thereof.

In the styrenic thermoplastic resin composition according to an embodiment of the present invention, the styrenic copolymer is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, And a mixture thereof. [0043] The term " unsaturated nitrile compound "

In the styrenic thermoplastic resin composition according to an embodiment of the present invention, the styrenic copolymer may contain 5 to 100% by weight of the insoluble content measured by the Soxhlet extraction method.

The extract obtained by the solvent in the Soxhlet extraction may contain 5 to 100% by weight of the insoluble content.

In the styrene-based thermoplastic resin composition according to an embodiment of the present invention, the styrene-based copolymer may have a silicone content of 0.1 to 2.0% by weight as measured by an X-ray fluorescence analysis (XRF).

In the styrenic thermoplastic resin composition according to an embodiment of the present invention, the styrenic copolymer may have a glass transition temperature (Tg) of 95 to 115 캜.

The present invention can provide a molded article comprising the styrene-based thermoplastic resin composition.

The molded article according to an embodiment of the present invention has a surface hardness (Rs) of 100 to 115 as measured by the evaluation method defined in ASTM D785, and a gloss measured at an angle of 60 from the evaluation method defined in ASTM D523 32% or less.

The molded article according to an embodiment of the present invention has an Izod impact strength of 8 to 20 kgf · cm / cm measured at Notched condition of a 1/8 "thick specimen by the evaluation method defined in ASTM D256, And a surface hardness (Rs) of 100 to 115 as measured by the evaluation method.

The molded article according to an embodiment of the present invention is characterized by having a non-cut softening point (VST) of 101 to 110 DEG C measured at 5 kgf and 50 DEG C / hour under the evaluation method defined in ISO 306B50 for 1/4 " .

The styrenic thermoplastic resin composition according to the present invention has an advantage that a synergistic effect of impact resistance and heat resistance can be realized while maintaining excellent low light characteristics.

The present invention also has an advantage of being able to provide a molded article having excellent impact resistance and heat resistance, which is produced by using the styrene-based thermoplastic resin composition, and has low light properties.

FIG. 1 shows a slime-ladle extraction reactor in accordance with an embodiment of the present invention.

Hereinafter, a styrenic thermoplastic resin composition capable of remarkably improving impact resistance and heat resistance while maintaining the low light properties of the present invention will be described in detail. The following embodiments are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. It will be apparent to those skilled in the art that, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, And a description of the known function and configuration will be omitted.

In the present invention, the weight average molecular weight (unit: g / mol) is obtained by dissolving a powder sample in tetrahydrofuran (THF) and then measuring the gel using a Gel Permeation Chromatography (GPC; At this time, Shodex LF-804 (8.0.1.D. × 300 mm) was used as a column and polystyrene (Shodex) was used as a standard sample.

The inventors of the present invention have studied a thermoplastic resin composition having low light properties and as a result discovered that a styrenic copolymer containing two kinds of compounds having two or more unsaturated reactive groups is contained to provide a synergistic effect of impact resistance and heat resistance The present inventors have found a styrenic thermoplastic resin composition capable of realizing the present invention.

The styrenic copolymer of the present invention is a styrene-based copolymer containing (A) a rubber-modified vinyl-based graft copolymer, (B) a styrenic copolymer containing a silicone compound having two or more unsaturated reactive groups, and (C) an aromatic vinyl- Based on the total weight of the styrene-based thermoplastic resin composition.

Hereinafter, each component will be described in more detail.

(A) a rubber-modified vinyl-based graft copolymer

The rubber-modified vinyl-based graft copolymer contained in the thermoplastic resin composition of the present invention is capable of improving impact strength, mechanical rigidity and appearance characteristics in combination with other components in the composition, and it is preferable that 10 to 40% by weight . Preferably 15 to 30% by weight. If it is less than the above range, the impact strength may be lowered, and if it is more than the above range, the fluidity may be lowered.

The rubber-modified vinyl-based graft copolymer can be produced by graft-polymerizing a mixture containing a rubbery polymer, an aromatic vinyl compound and an unsaturated nitrile compound.

For example, 30 to 70% by weight of a mixture of an aromatic vinyl compound and an unsaturated nitrile compound in the presence of 30 to 70% by weight of a rubbery polymer can be graft polymerized by the emulsion polymerization method to prepare the rubber-modified vinyl-based graft copolymer have.

At this time, the rubbery polymer may have an average particle diameter of 0.1 to 10 탆, preferably 0.2 to 1.0 탆, which is excellent in impact strength, mechanical rigidity and miscibility.

The rubbery polymer may be at least one selected from the group consisting of a polybutadiene rubber, an acrylic rubber, an ethylene / propylene rubber, a styrene / butadiene rubber, an acrylonitrile / butadiene rubber, an isoprene rubber, an ethylene / propylene / diene terpolymer (EPDM) and a polyorganosiloxane / (Meth) acrylate rubber composite, and a polybutadiene rubber can be preferably used.

The aromatic vinyl compound in the mixture to be graft polymerized to the rubbery polymer may be at least one selected from the group consisting of styrene, C ₁ to C ₁₀ alkyl-substituted styrene, halogen-substituted styrene, vinyl toluene, vinyl naphthalene and combinations thereof . Specific examples of the alkyl-substituted styrene include? -Methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, pt-butylstyrene and 2,4-dimethylstyrene. Styrene may be preferably used as the aromatic vinyl compound.

The unsaturated nitrile compound in the mixture to be graft polymerized to the rubbery polymer may be at least one selected from acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof. Preferably, acrylonitrile may be used as the unsaturated nitrile compound.

The grafted rubbery polymer may be graft-polymerized by further adding monomers such as C ₁ to C ₈ methacrylic acid alkyl esters, C ₁ to C ₈ acrylic acid alkyl esters, or maleic anhydride. The C ₁ to C ₈ methacrylic acid alkyl esters or C ₁ to C ₈ acrylic acid alkyl esters are alkyl esters of methacrylic acid or acrylic acid, respectively, and esters obtained from monohydric alcohols containing 1 to 8 carbon atoms to be. Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester, acrylic acid ethyl ester and acrylic acid methyl ester.

As a preferred example, the rubber-modified vinyl-based graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer (g-ABS).

(B) a styrenic copolymer containing a silicone compound having two or more unsaturated reactive groups

In the present invention, the styrenic copolymer containing a silicone compound having two or more unsaturated reactive groups is obtained by copolymerizing (b1) 55 to 80% by weight of an aromatic vinyl compound, (b2) 15 to 40% by weight of an unsaturated nitrile compound, and And 0.1 to 10% by weight of a silicone compound having at least one unsaturated reactive group.

When the above range is satisfied, not only excellent extinction characteristics but also impact resistance and heat resistance can be improved.

(b1) an aromatic vinyl compound

In the present invention, the aromatic vinyl compound is at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, And mixtures thereof. However, the present invention is not limited thereto.

The aromatic vinyl compound is preferably at least one selected from the group consisting of styrene,? -Methylstyrene, and mixtures thereof.

In the present invention, the aromatic vinyl compound may include 55 to 80% by weight based on the total weight of the monomer mixture for producing the styrenic copolymer. In the above range, the impact resistance and heat resistance of the thermoplastic resin composition can be improved.

(b2) unsaturated nitrile compound

In the present invention, the unsaturated nitrile compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, fumaronitrile, But are not necessarily limited thereto.

The unsaturated nitrile compound may preferably be acrylonitrile.

In the present invention, the unsaturated nitrile compound may include 15 to 40% by weight based on the total weight of the monomer mixture for producing the styrenic copolymer.

The unsaturated nitrile compound may preferably have a weight mixing ratio (aromatic vinyl: unsaturated nitrile) with an aromatic vinyl compound of 7: 3 to 9: 1. When the above range is satisfied, the extinction characteristics can be improved without deteriorating the mechanical properties and moldability of the thermoplastic resin composition in combination with other components.

(b3) a silicone compound having two or more unsaturated reactive groups

In the present invention, a silicone compound having two or more unsaturated reactive groups can be used to realize excellent extinction characteristics while maintaining various physical properties such as impact resistance and heat resistance.

The silicone compound having two or more unsaturated reactive groups may include one or more compounds represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, l , m and n are each an integer of 0 to 100 (but not simultaneously 0), and R ₁ to R ₈ are each independently hydrogen, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group , A substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, a substituted or unsubstituted C ₂ to C ₃₀ alkynyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₁ to C ₃₀ heteroaryl group, a hydroxyl group, an alkoxy group, an amino group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group of the, or a mercapto group, the R At least two of R ₁ to R ₈ include a polymerizable unsaturated reactive group, and the compound may have a linear or cyclic structure. In the case of having an annular structure, any of R1 to R8 is linked to form an annular shape.

The styrenic copolymer may include a compound represented by the following formula (2) having a cyclic structure, and the silicone compound having two or more unsaturated reactive groups may include a compound represented by the following formula (2).

(2)

In the formula (2), R ₉ to R ₁₄ independently represent a substituted or unsubstituted C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₂ to C ₂₀ An alkenyl group and a substituted or unsubstituted C ₆ to C ₂₀ And R ₁₅ to R ₁₇ are each independently hydrogen or a substituted or unsubstituted C ₁ to C ₆ alkyl group, and p is an integer of 1 to 6.

The silicone compound having two or more unsaturated reactive groups may be, for example, 1,3,5-triisopropyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetraisopropyl- 1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentaisopropyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, 1,3, 1, 3, 5-tributyl-cyclotrisiloxane, 1,3,5,7-tetra-sec-butyl- Butyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, 1,3,5-triisopropyl-1,3,5-trimethyl-cyclotri Siloxane, 1,3,5,7-tetraisopropyl-1,3,5,7-tetramethyl-cyclotetrasiloxane, 1,3,5,7,9-pentaisopropyl-1,3,5,7 , 9-pentamethyl-cyclopentasiloxane, 1,3,5-triisopropyl-1,3,5-triethyl-cyclotrisiloxane, 1,3,5,7-tetraisopropyl-1,3,5 , 7-tetraethyl-cyclotetra 1,3,5,7,9-pentaisopropyl-1,3,5,7,9-pentaethyl-cyclopentasiloxane, 1,1,3,3,5,5-hexaisopropyl-cyclo Trisiloxane, 1,1,3,3,5,5,7,7-octaisopropyl-cyclotetrasiloxane, 1,1,3,3,5,5,7,7,9,9-decaisopropyl -Cyclopentasiloxane, 1,3,5-tri-sec-butyl-1,3,5-trimethyl-cyclotrisiloxane, 1,3,5,7-tetra- Methyl-cyclotetrasiloxane, 1,3,5,7,9-pentac-butyl-1,3,5,7,9-pentamethyl-cyclopentasiloxane, 1,3,5-tri-sec- , 3,5-triethyl-cyclotrisiloxane, 1,3,5,7-tetra-sec-butyl-1,3,5,7-tetraethyl-cyclotetrasiloxane, 1,3,5,7,9- Penta- sec-butyl-1,3,5,7,9-pentaethyl-cyclopentasiloxane, 1,3,5-triisopropyl-cyclotrisiloxane, 1,3,5,7-tetraisopropyl-cyclotetra Siloxane, 1,3,5,7,9-pentaisopropyl-cyclopentasiloxane, 1,3,5-tri-sec-butyl-cyclotri Butyl-cyclotetrasiloxane, 1,3,5,7,9-pentac-butyl-cyclopentasiloxane, 1,3,5-trimethyl-1,3, 5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentamethyl- 1,3,5-triethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetraethyl-1, 3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentaethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, and mixtures thereof , But are not necessarily limited thereto. Preferred are 1,3,5-trimethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, 1,3,5-triethyl-1,3,5-trivinyl- Siloxane, 1,3,5,7-tetraethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentaethyl-1,3,5,7,9 - pentabinyl-cyclopentasiloxane, and mixtures thereof. More preferably, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane can be used.

In the present invention, the silicone compound having two or more unsaturated reactive groups alone or in combination with other components can realize various physical properties such as excellent impact resistance and heat resistance as well as extinction characteristics which are difficult to achieve with conventional crosslinking agents.

The silicone compound having two or more unsaturated reactive groups may have a molecular weight or a weight average molecular weight of 150 to 6,000 g / mol. When the above range is satisfied, the degree of crosslinking is easily controlled and the crosslinking reaction progresses smoothly, thereby achieving excellent light extinction characteristics.

In the present invention, the silicone compound having two or more unsaturated reactive groups may be contained in an amount of 0.1 to 10% by weight, preferably 1.5 to 7% by weight, more preferably 2 to 5% by weight of the styrenic copolymer. When the above range is satisfied, the extinction characteristics can be improved without deteriorating impact resistance and heat resistance, and a uniform extinction characteristic can be realized as a whole.

The styrenic copolymer according to the present invention may be linear or cross-linked. It may preferably be crosslinked. At this time, crosslinking of the styrenic copolymer can be confirmed by measuring the amount of the insoluble content of the extract extracted by the solvent using the Soxhlet extraction method. The soxhlet extraction may be performed using an organic solvent selected from the group consisting of toluene, tetrahydrofuran, ethyl acetate, chloroform, and mixtures thereof, but is not limited thereto. Preferably, tetrahydrofuran (THF) can be used.

The Soxhlet extraction can be carried out using a Soxhlet extraction reactor in which a mixture of the styrene copolymer according to the present invention and a solvent is mixed. In one embodiment of the Soxhlet extraction, the tetrahydrofuran contained in the vessel during the extraction is heated using a heater to vaporize the vaporized tetrahydrofuran, and the vaporized tetrahydrofuran is passed through a vaporization line to form a condenser (consisting of a cooling water inlet and a cooling water outlet ). The tetrahydrofuran cooled in the cooler is liquefied and stored in the storage member contained in the cylindrical filter. Thereafter, when the amount of tetrahydrofuran is exceeded so that the tetrahydrafuran is released from the storage member and flows into the vessel through the purification line in the circulation line, the resin is extracted into tetrahydrofuran circulating in the cylindrical filter.

The styrenic copolymer may be subjected to Soxhlet extraction using tetrahydrofuran (THF) for 48 hours, and then the remaining insoluble content may be 5 to 100% by weight.

The styrene-based copolymer may have a silicon content of 0.1 to 2.0% by weight as measured by an X-ray fluorescence analysis (XRF).

At this time, XRF analysis is a fluorescent X-ray spectrometry method in which a wavelength distribution of an X-ray emitted from a site collided with an X-ray is analyzed to estimate the kind or composition ratio of the element in the material. This can be done using conventional equipment. In the present invention, an X-ray Fluorescence Spectrometer (Model: Axios advanced.Maker.Panalyticl (Nvderland)) was used.

In the present invention, as a method of analyzing silicon by XRF, a specimen using the styrenic copolymer according to the present invention is prepared. Also prepare standard specimens for analysis. The silicon (Si) element contained in the standard specimen is measured by X-ray fluorescence analysis (XRF) and its calibration curve is prepared. Next, the silicon (Si) element in the specimen can be quantitatively analyzed by X-ray fluorescence analysis (XRF) and substituting it into the calibration curve prepared above.

The styrene-based copolymer may have a glass transition temperature (Tg) of 95 to 115 캜. Within the above range, the thermoplastic resin composition comprising the styrenic copolymer can exhibit excellent extinction characteristics without deteriorating impact resistance and heat resistance.

The styrenic copolymer can be produced by a conventional polymerization method such as suspension polymerization, emulsion polymerization, solution polymerization, and the like, but is not limited thereto. In one embodiment of the copolymer production method, suspension polymerization may be used. When the styrenic copolymer is prepared by the suspension polymerization method, the dispersibility and the suspension stability can be improved by using an inorganic dispersant or an organic dispersant.

Examples of the inorganic dispersant include aluminum hydroxide, ferric hydroxides, titanium hydroxides, phosphate compounds, carbonate compounds, sulfate compounds and the like, preferably phosphate compounds. More preferably, a metal phosphate-based inorganic compound selected from the group consisting of tricalcium phosphate and tridosodium phosphate can be used.

As the organic dispersing agent, a homopolymer or copolymer of acrylic acid or methacrylic acid can be used. When a copolymer is used as the organic dispersant, the content of acrylic acid or methacrylic acid used may be 50 parts by weight or more based on 100 parts by weight of the copolymer. In addition, the acrylic acid or methacrylic acid may preferably be in the form of a salt of sodium, potassium or ammonium to maintain adequate solubility.

As the polymerization initiator in the copolymerization of the styrenic copolymer, azobisisobutyronitrile may preferably be used, but not always limited thereto.

The thermoplastic resin composition containing the styrenic copolymer can exhibit excellent extinction properties without deteriorating physical properties such as impact resistance and heat resistance.

(C) an aromatic vinyl-unsaturated nitrile-based copolymer

In the present invention, the aromatic vinyl-unsaturated nitrile-based copolymer may be a copolymer of an aromatic vinyl compound and an unsaturated nitrile compound.

As the aromatic vinyl compound, at least one selected from the group consisting of styrene, C ₁ to C ₁₀ alkyl-substituted styrene, halogen-substituted styrene, vinyl toluene, vinyl naphthalene, and combinations thereof may be used. Specific examples of the alkyl-substituted styrene include? -Methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, pt-butylstyrene and 2,4-dimethylstyrene.

As the unsaturated nitrile compound, at least one selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations thereof may be used.

Specific examples of the aromatic vinyl-unsaturated nitrile-based copolymer include copolymers of styrene and acrylonitrile; copolymers of? -methylstyrene and acrylonitrile; Or copolymers of styrene,? -Methylstyrene and acrylonitrile, and preferably styrene-acrylonitrile copolymers.

In the present invention, the aromatic vinyl-unsaturated nitrile-based copolymer may be contained in an amount of 40 to 80% by weight based on the total weight of the composition. If the content of the aromatic vinyl-unsaturated nitrile-based copolymer is out of the above range, it may be difficult to ensure impact resistance.

The styrenic thermoplastic resin composition of the present invention may further include an additive optionally in accordance with the use. Examples of the additive include surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, heat stabilizers, antioxidants, light stabilizers, compatibilizers, inorganic additives, colorants, stabilizers, lubricants, , Dyes and flame retardants, and the like. These may be used alone or in combination.

The styrenic thermoplastic resin composition of the present invention can be produced in the form of a molded resin product according to a known resin production method. In one embodiment, the components of the present invention and other additives may be simultaneously mixed and then melt-extruded in an extruder to form a pellet. Such pellets can be used to produce plastic injection or compression molded articles. The molding method is not particularly limited. For example, extrusion molding, injection molding, calender molding, vacuum molding, and the like can all be applied.

The present invention provides a molded article produced from the above-mentioned thermoplastic resin composition. The molded article according to one embodiment of the present invention has a surface hardness (Rs) of 100 to 115 as measured by the evaluation method defined in ASTM D785, and a glossiness measured at an angle of 60 from the evaluation method defined in ASTM D523 Is 32% or less. The molded article according to an embodiment of the present invention has an Izod impact strength of 8 to 20 kgf · cm / cm measured at Notched condition of a 1/8 "thick specimen by the evaluation method defined in ASTM D256, The surface hardness (Rs) measured by the evaluation method defined in D785 is 100 to 115. Further, the molded article according to one embodiment of the present invention is characterized by having a surface hardness And a non-cut softening point (VST) measured at 5 kgf and 50 占 폚 / hour according to the evaluation method is 101 to 110 占 폚.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples.

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

(A) a rubber-modified vinyl-based graft copolymer (g-ABS)

G-ABS resin having a core-shell type in which styrene and acrylonitrile were graft-polymerized with butadiene rubber having a rubber content of 58% by weight and an average particle diameter of 2,580 Å was used.

(B) a styrenic copolymer (crosslinked SAN) containing a silicone compound having at least two unsaturated reactive groups,

Tetramethyl-1, 3, 5, 7-tetravinyl-cyclotetrasiloxane (SKC, density: 50% by weight) was added to 100 parts by weight of a monomer composed of 76% by weight of styrene and 24% by weight of acrylonitrile. A styrene-based copolymer having a weight average molecular weight of 170,000 g / mol, which was prepared using 2% by weight of polyvinyl alcohol (trade name: Vinyl D-4, molecular weight: 344.7 g / mol).

(C) an aromatic vinyl-unsaturated nitrile copolymer (SAN)

A styrene-acrylonitrile copolymer (SAN) resin having a weight average molecular weight of 150,000 g / mol copolymerized with 76% by weight of acrylonitrile and 24% by weight of styrene was used.

(Example 1)

10% by weight of a styrenic copolymer (crosslinked SAN) containing (A) 25% by weight of a rubber-modified vinyl-based graft copolymer (g-ABS), (B) a silicone compound having two or more unsaturated reactive groups, 0.1 part by weight of di-stearyl-pentaerythritol-diphosphite and 0.1 part by weight of octadecyl 3- (3, 4-di-tert-butylphenol) were added to 100 parts by weight of a base resin mixed with 65% by weight of an aromatic vinyl-unsaturated nitrile copolymer (SAN) 0.03 part by weight of octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) in a usual mixer was added to L / D = 35 and? = 45 mm to prepare pellets. The prepared pellets were dried for more than 5 hours in an air flow dryer at 80 ° C before injection molding, and then specimens for measuring properties were prepared using a 10 oz injection machine at an injection temperature of 230 ° C.

(Example 2)

20% by weight of a styrene-based copolymer (crosslinked SAN) containing (A) 25% by weight of a rubber-modified vinyl-based graft copolymer (g-ABS) as a base resin, (B) a silicone compound having two or more unsaturated reactive groups, And (C) 55% by weight of an aromatic vinyl-unsaturated nitrile copolymer (SAN) were used in place of the aromatic vinyl-unsaturated nitrile copolymer (SAN).

(Example 3)

(B) 25% by weight of a rubber-modified vinyl-based graft copolymer (g-ABS), (B) 30% by weight of a styrenic copolymer (crosslinked SAN) containing a silicone compound having two or more unsaturated reactive groups, And (C) 45% by weight of an aromatic vinyl-unsaturated nitrile copolymer (SAN) were used.

(Example 4)

(B) 20 wt% of a rubber-modified vinyl-based graft copolymer (g-ABS), (B) 30 wt% of a styrenic copolymer (crosslinked SAN) containing a silicone compound having two or more unsaturated reactive groups, And (C) 50% by weight of an aromatic vinyl-unsaturated nitrile copolymer (SAN) were used.

(Example 5)

(B) 15% by weight of a styrene-based copolymer (crosslinked SAN) containing a silicone compound having two or more unsaturated reactive groups, (B) 15% by weight of a rubber-modified vinyl-based graft copolymer (g- And (C) 55% by weight of an aromatic vinyl-unsaturated nitrile copolymer (SAN) were used in place of the aromatic vinyl-unsaturated nitrile copolymer (SAN).

(Comparative Example 1)

ABS resin (D) obtained by copolymerizing styrene and acrylonitrile in a butadiene rubber having a rubber content of 14.5% by weight as a base resin and having an average particle diameter of 13 탆 was used in the same manner as in Example 1 .

(Comparative Example 2)

Except that 25% by weight of (A) a rubber-modified vinyl-based graft copolymer (g-ABS) and 75% by weight of an aromatic vinyl-unsaturated nitrile copolymer (SAN) The same procedure was followed.

(evaluation)

(1) Izod impact strength (unit: kgf · cm / cm)

Was measured in a notched condition of 1/8 "thickness by the evaluation method specified in ASTM D256.

(2) Melt-flow index (MI) (unit: g / 10 min)

Measured at 220 캜 / 10 kg in accordance with the evaluation method defined in ASTM D1238.

(3) Surface gloss (unit:%)

The degree of gloss was measured at an angle of 60 ° using the BYK-Gardner Gloss Meter of BYK Co., Ltd. according to the evaluation method defined in ASTM D523.

(4) Vicat Softening Temperature (VST) (unit: ° C)

1/4 "thick specimens were measured under the conditions of 5 kgf and 50 ° C / hour by the evaluation method specified in ISO 306B50.

(5) Surface hardness (R scale, Rs)

Was measured under notched conditions for 1/8 "thick specimens by the evaluation method specified in ASTM D785.

[Table 1]

It was confirmed that Examples 1 to 5 of the present invention exhibited excellent heat resistance and impact resistance while maintaining low light properties. On the other hand, in Example 5, although the rubber content in the resin was low, the impact resistance was not deteriorated and a high heat resistance degree could be realized.

On the other hand, Comparative Example 1 was able to realize low light properties, but the impact resistance and heat resistance were degraded. In Comparative Example 2, a styrenic copolymer (crosslinked SAN) containing a silicone compound having two or more unsaturated reactive groups according to the present invention was used It is not possible to realize low light characteristics and heat resistance is also deteriorated.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Various modifications and variations are possible in light of the above teachings.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

11: container, 12: tetrahydrofuran, 13: heater,
14: vaporization line, 15: cooler, 16: cooling water inlet,
17: cooling water outlet part, 18: cylindrical filter, 19: circulation line

Claims (17)

(A) a rubber-modified vinyl-based graft copolymer;
(B) a styrenic copolymer containing a silicone compound having at least two unsaturated reactive groups; And
(C) an aromatic vinyl-unsaturated nitrile-based copolymer,
Wherein the styrenic copolymer (B) has an insoluble content measured by Soxhlet extraction method of 5 to 100% by weight, a silicon content measured by an X-ray fluorescence analyzer of 0.1 to 2.0% by weight, a glass transition temperature Tg) of 95 to 115 占 폚.
The method according to claim 1,
(A) 10 to 40% by weight of a rubber-modified vinyl-based graft copolymer, (B) 5 to 40% by weight of a styrenic copolymer containing a silicone compound having two or more unsaturated reactive groups, and (C) -Unsaturated nitrile-based copolymer in an amount of 40 to 80% by weight based on the total weight of the styrene-based thermoplastic resin composition.
The method according to claim 1,
The styrenic copolymer (B) containing a silicone compound having two or more unsaturated reactive groups (B) is obtained by copolymerizing (b1) 55 to 80% by weight of an aromatic vinyl compound, (b2) 15 to 40% by weight of an unsaturated nitrile compound, And 0.1 to 10% by weight of a silicone compound having two or more unsaturated reactive groups.
The method according to claim 1,
Wherein the silicone compound having two or more unsaturated reactive groups is represented by the following formula (1).
[Chemical Formula 1]

(1), l , m and n are each an integer of 0 to 100 (provided that they are not simultaneously 0), and R ₁ to R ₈ are each independently hydrogen, a substituted or unsubstituted C ₁ to C ₃₀ Alkyl group, a substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, a substituted or unsubstituted C ₂ to C ₃₀ alkynyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₁ to C ₃₀ heteroaryl group, a hydroxyl group, an alkoxy group, an amino group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group of the, or a mercapto group, the At least two of R &_lt; ₁ > to R &_lt; ₈ &_gt; include a polymerizable unsaturated reactive group, and the compound may have a linear or cyclic structure.
The method according to claim 1,
Wherein the silicone compound having two or more unsaturated reactive groups is represented by the following formula (2).
(2)

(Wherein R ₉ to R ₁₄ independently represent a substituted or unsubstituted C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₂ to C ₂₀ An alkenyl group and a substituted or unsubstituted C ₆ to C ₂₀ And R ₁₅ to R ₁₇ are independently hydrogen or a substituted or unsubstituted C ₁ to C ₆ alkyl group, and p is an integer of 1 to 6.)
6. The method of claim 5,
The silicone compound having two or more unsaturated reactive groups may be 1,3,5-trimethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7 - tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, 1,3,5-triethyl-1,3 , 5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetraethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9- , 3,5,7,9-pentavinyl-cyclopentasiloxane, and mixtures thereof.
The method according to claim 1,
Wherein the silicone compound having two or more unsaturated reactive groups has a weight average molecular weight of 150 to 6,000 g / mol.
delete The method of claim 3,
The aromatic vinyl compound may be at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, Based on the total weight of the styrene-based thermoplastic resin composition.
The method of claim 3,
Wherein the unsaturated nitrile compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, fumaronitrile, Thermoplastic resin composition.
delete delete delete A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 7, 9 and 10.
15. The method of claim 14,
Wherein the molded article has a surface hardness (Rs) of 100 to 115 as measured by an evaluation method defined in ASTM D785, and a gloss measured at an angle of 60 degrees by the evaluation method defined in ASTM D523 of not more than 32%.
15. The method of claim 14,
The molded product was measured for Izod impact strength of 8 to 20 kgf · cm / cm measured in Notched condition on a specimen of 1/8 "thickness by the evaluation method specified in ASTM D256, and measured according to the evaluation method specified in ASTM D785 And a surface hardness (Rs) of 100 to 115.
15. The method of claim 14,
Wherein the molded article has a non-cut softening point (VST) of 101 to 110 DEG C measured under a load of 5 kg and 50 DEG C / hr according to the evaluation method defined in ISO 306B50 for a 1/4 "thick specimen.

Images