CN113490719A

CN113490719A - ASA-based resin composition, molded article comprising ASA-based resin composition, and method for producing molded article

Info

Publication number: CN113490719A
Application number: CN202080016926.3A
Authority: CN
Inventors: 安勇希; 金泰勋; 朴春浩; 成多恩; 赵旺来; 金豪焄; 张正敃
Original assignee: LG Chem Ltd
Current assignee: LG Chem Ltd
Priority date: 2019-10-07
Filing date: 2020-09-28
Publication date: 2021-10-08
Also published as: TW202115180A; KR102547327B1; KR20210041493A

Abstract

The present invention relates to an ASA resin composition, a molded article comprising the ASA resin composition, and a method of manufacturing the molded article. More particularly, the present invention relates to an ASA resin composition, a molded article comprising the ASA resin composition and a method of manufacturing the molded article, the ASA resin composition comprising: 20 to 47% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an acrylate rubber having an average particle diameter of 50 to 150nm as a core; 23 to 55% by weight of an alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer; and 25 to 45 weight percent of a poly (alkyl methacrylate) resin. According to the present invention, it is possible to provide an ASA resin composition having excellent coloring properties and transparency even at a processing thickness of a predetermined value or more while having excellent mechanical properties and processability, a molded article comprising the ASA resin composition, and a method of manufacturing the molded article. In particular, the ASA resin composition can be applied to high value-added products having unpainted, transparent, high saturation or special color properties due to its excellent coloring properties and transparency.

Description

ASA-based resin composition, molded article comprising ASA-based resin composition, and method for producing molded article

Technical Field

[ Cross-reference to related applications ]

This application claims the priority of korean patent application No.10-2019-0123821, filed by the korean intellectual property office at 2019, 10.7, and korean patent application No.10-2020-0124402, filed again at 2020, 9.5, based on the priority of the above patent, the respective disclosures of which are incorporated herein by reference.

The present invention relates to an ASA-based resin composition, a molded article comprising the ASA-based resin composition, and a method of manufacturing the molded article. More particularly, the present invention relates to an ASA-based resin composition having excellent coloring properties and transparency while having excellent mechanical properties and processability even at a processing thickness of a predetermined value or more, a molded article comprising the ASA-based resin composition, and a method of manufacturing the molded article. In particular, the ASA-based resin composition can be applied to high value-added products having unpainted, transparent, high saturation or special color properties due to its excellent coloring properties and transparency.

Background

In the case of an acrylate compound-styrene-acrylonitrile copolymer (hereinafter referred to as "ASA resin"), the polymer does not contain an unstable double bond. Due to this feature, ASA resins have excellent weather resistance and thus have been used in various fields such as electric/electronic parts, building materials (e.g., vinyl sidings), extrusion profiles, and automobile parts.

Recently, there has been an increasing demand for high value-added outdoor products having unpainted, transparent, highly saturated or special color properties. ASA resins, however, have poor colorability and transparency, and thus the use of ASA resins in the manufacture of such products is limited. Therefore, there is a need to develop an ASA resin that meets such market demand.

[ related art documents ]

[ patent document ]

(patent document 1) KR 2009-0095764A

Disclosure of Invention

Technical problem

Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide an ASA-based resin composition having excellent coloring properties and transparency even at a processing thickness of a predetermined value or more while having excellent mechanical properties and processability, a molded article comprising the ASA-based resin composition, and a method of manufacturing the molded article. In particular, the ASA-based resin composition can be applied to high value-added products having unpainted, transparent, high saturation or special color properties due to its excellent coloring properties and transparency.

The above and other objects can be accomplished by the present disclosure described below.

Technical scheme

According to an aspect of the present invention, there is provided an ASA-based resin composition and a molded article comprising the ASA-based resin composition, the ASA-based resin composition comprising: 20 to 47% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an acrylate rubber having an average particle diameter of 50 to 150nm as a core; 23 to 55% by weight of an alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer; and 25 to 45 weight percent of a poly (alkyl methacrylate) resin.

According to another aspect of the present invention, there is provided a method of manufacturing a molded article, the method comprising: kneading and extruding 20 to 47 wt% of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an acrylate rubber having an average particle diameter of 50 to 150nm as a core, 23 to 55 wt% of an alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer, and 25 to 45 wt% of a poly (alkyl methacrylate) resin under conditions of 200 to 300 ℃ and 100 to 500rpm to prepare pellets; and subjecting the prepared pellets to sheet molding or injection molding at a molding temperature of 200 ℃ to 300 ℃ to manufacture a molded article.

Advantageous effects

According to the present invention, it is possible to provide an ASA-based resin composition having excellent coloring properties and transparency even at a processing thickness of a predetermined value or more while having excellent mechanical properties and processability, a molded article comprising the ASA-based resin composition, and a method of manufacturing the molded article. In particular, the ASA-based resin composition can be applied to high value-added products having unpainted, transparent, high saturation or special color properties due to its excellent coloring properties and transparency.

Detailed Description

Hereinafter, an ASA-based resin composition, a molded article comprising the ASA-based resin composition, and a method of manufacturing the molded article will be described in detail.

The present inventors confirmed that the ASA-based resin composition comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, an alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer and a poly (alkyl methacrylate) resin in a predetermined content range has excellent coloring properties and transparency at a processing thickness of 0.5T or more while maintaining mechanical properties and processability equal to or better than those of conventional ASA resin compositions. Based on these results, the present inventors have further conducted studies to complete the present invention.

The ASA resin composition of the present invention comprises: 20 to 47% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an acrylate rubber having an average particle diameter of 50 to 150nm as a core; 23 to 55% by weight of an alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer; and 25 to 45 weight percent of a poly (alkyl methacrylate) resin. Within this range, the ASA resin composition may have excellent mechanical properties and processability, and in particular, may have excellent coloring properties and transparency even at a processing thickness of a predetermined value or more. Therefore, the ASA resin composition can be applied to high value-added products having unpainted, transparent, high saturation or special color properties.

Hereinafter, each component constituting the thermoplastic resin composition of the present invention will be described in detail as follows.

A) Acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer

For example, the average particle diameter of the acrylate rubber contained in the graft copolymer (a) of the present invention may be 50nm to 150nm, preferably 60nm to 140nm, more preferably 70nm to 140nm, and still more preferably 80nm to 140 nm. Within this range, the thermoplastic resin composition prepared may have excellent weather resistance, colorability, impact strength and surface gloss.

In the present specification, the average particle diameter may be measured by dynamic light scattering, specifically, as an intensity value in a Gaussian mode using a Nicomp 380 particle size analyzer (manufacturer: PSS).

For example, the content of the graft copolymer (a) may be 20 to 47% by weight, preferably 20 to 40% by weight, more preferably 20 to 35% by weight, and still more preferably 20 to 30% by weight. Within this range, the balance between mechanical strength and fluidity may be excellent, and in particular, transparency, coloring property and weather resistance may be excellent.

For example, the graft copolymer (a) may include 40 to 60% by weight of the acrylate rubber, 25 to 45% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyanide compound. Within this range, weather resistance, flowability, tensile strength, and impact strength may be excellent.

As a preferred example, the graft copolymer (a) may include 45 to 55% by weight of the acrylate rubber, 30 to 50% by weight of the aromatic vinyl compound, and 5 to 20% by weight of the vinyl cyanide compound. Within this range, weather resistance, flowability, tensile strength, and impact strength may be excellent.

As a more preferred example, the graft copolymer (a) may include 45 to 55% by weight of the acrylate rubber, 30 to 40% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyanide compound. Within this range, weather resistance, flowability, tensile strength, and impact strength may be excellent.

In the present specification, a polymer containing a compound refers to a polymer prepared by polymerizing the compound, and a unit in the polymerized polymer is derived from the compound.

For example, the acrylate may include one or more selected from alkyl acrylates including an alkyl group having 2 to 8 carbon atoms, and preferably may include one or more selected from alkyl acrylates including an alkyl group having 4 to 8 carbon atoms. More preferably, the acrylate is butyl acrylate or ethylhexyl acrylate.

For example, the aromatic vinyl compound may include one or more selected from styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene and p-tert-butylstyrene, preferably styrene.

For example, the vinyl cyanide compound may include one or more selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, and isopropylacrylonitrile, preferably acrylonitrile.

For example, the gel content of the graft copolymer (a) may be less than 90% by weight, 30% to 90% by weight, preferably 50% to 90% by weight. Within this range, mechanical properties such as impact strength and flexural strength may be excellent, and weather resistance may be improved.

For example, the swelling index of the graft copolymer (a) may be 6 to 14, 6 to 12, preferably 6 to 10. Within this range, mechanical properties such as impact strength and flexural strength may be excellent, and weather resistance may be improved.

For example, the graft degree of the graft copolymer (a) may be 20% to 80%, preferably 25% to 60%, more preferably 25% to 40%. Within this range, mechanical properties such as impact strength and flexural strength may be excellent, and weather resistance may be improved.

In the present specification, in order to measure the gel content and the swelling index, acetone was added to 1g of the graft copolymer powder, stirred at room temperature for 24 hours, centrifuged to obtain an acetone-insoluble fraction, and the fraction was dried. Then, the weights of the part before and after drying were measured, and the gel content and the swelling index were calculated by substituting these weight values into the following equations.

Gel content (%) × 100 [ weight after drying after centrifugation/sample weight ] × 100

Swelling index ═ weight after centrifugation before drying/weight after centrifugation after drying

In the present specification, in order to measure the degree of grafting, the resin latex of the graft polymer was coagulated, washed and dried to obtain a powdery resin latex, and then 2g of the obtained powder was added to 300ml of acetone, followed by stirring for 24 hours. Then, the stirred solution was separated using an ultracentrifuge, and then methanol was added dropwise to the separated acetone solution to obtain an ungrafted portion, followed by drying. Thereafter, the weight of the ungrafted portion after drying was measured, and the degree of grafting was calculated by substituting the measured weight value into the following equation.

Degree of grafting (%) - (weight (g) of grafted monomer/weight (g) of rubber)) × 100

For example, the graft copolymer (A) may be prepared by emulsion polymerization. Emulsion polymerization generally carried out in the art to which the present invention pertains may be employed in the present invention without particular limitation. As a specific example, the graft copolymer (a) may be prepared by graft-emulsion polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer onto an alkyl acrylate rubber.

For example, the alkyl acrylate rubber contained in the graft copolymer (a) may be prepared by emulsion polymerization of alkyl acrylate. As a specific example, the alkyl acrylate rubber may be prepared by mixing an alkyl acrylate, an emulsifier, an initiator, a grafting agent, a crosslinking agent, an electrolyte, and water and by subjecting the mixture to emulsion polymerization.

For example, the emulsifier is preferably an aqueous solution having a pH of 3 to 9 and containing a metal salt derivative of sulfosuccinic acid alkyl ester having 12 to 18 carbon atoms, or an alkyl sulfate having 12 to 20 carbon atoms or a metal sulfonate derivative thereof.

As a specific example, in an aqueous solution having a pH of 3 to 9 and containing a sulfosuccinic acid alkyl ester metal salt derivative having 12 to 18 carbon atoms, the sulfosuccinic acid alkyl ester metal salt derivative is preferably a sulfosuccinic acid dicyclohexyl ester sodium salt, a sulfosuccinic acid dihexyl ester sodium salt, a sulfosuccinic acid di-2-ethylhexyl potassium salt, or a sulfosuccinic acid di-2-ethylhexyl lithium salt, and the alkyl sulfate having 12 to 20 carbon atoms or the sulfonic acid metal salt derivative thereof is preferably a sodium lauryl sulfate, a sodium dodecylbenzene sulfate, a sodium stearyl sulfate, a sodium oleate sulfate (sodium oleic sulfate), a potassium lauryl sulfate, or a potassium stearyl sulfate.

The emulsifier is preferably used in an amount of 0.1 to 1 part by weight, based on 100 parts by weight of the alkyl acrylate rubber.

For example, the initiator is preferably an inorganic or organic peroxide. Specifically, the initiator is preferably a water-soluble initiator such as potassium persulfate, sodium persulfate, or ammonium persulfate, or a fat-soluble initiator such as cumene hydroperoxide or benzoyl peroxide.

The initiator is preferably used in an amount of 0.05 to 0.2 parts by weight, based on 100 parts by weight of the alkyl acrylate rubber.

In the present specification, 100 parts by weight of the alkyl acrylate rubber means the weight of the prepared alkyl acrylate rubber, or the total weight of monomers added for preparing the alkyl acrylate rubber.

For example, the grafting agent preferably includes one or more selected from the group consisting of allyl methacrylate, triallylisocyanurate, triallylamine and diallylamine, and the amount of the grafting agent is preferably 0.01 to 0.07 parts by weight based on 100 parts by weight of the alkyl acrylate rubber. Within this range, the object of the present invention can be more easily achieved.

For example, the crosslinking agent preferably includes one or more selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1, 3-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate and trimethylolmethane triacrylate, and the crosslinking agent is preferably used in an amount of 0.02 to 0.3 parts by weight, based on 100 parts by weight of the alkyl acrylate rubber.

When the grafting agent and the crosslinking agent are used, the elasticity of the alkyl acrylate rubber according to the present invention can be further enhanced, thereby further improving physical properties such as impact strength.

The electrolyte preferably comprises a compound selected from NaHCO₃、Na₂S₂O₇And K₂CO₃And the amount of the electrolyte is preferably 0.05 to 0.4 parts by weight based on 100 parts by weight of the alkyl acrylate rubber.

In this specification, water serves as the medium for carrying out the emulsion polymerization and is preferably deionized water. The amount of water to be used may be appropriately selected as required.

For example, for the preparation of the alkyl acrylate rubber, the components for preparing the alkyl acrylate rubber may be continuously fed into the reactor, or may be fed into the reactor in a combination of continuous feeding and batch feeding, and then emulsion polymerization may be performed under polymerization conditions well known in the art to which the present invention pertains. In this case, the alkyl acrylate rubber may be obtained in the form of a latex.

For example, immediately after the polymerization is completed, the pH of the alkyl acrylate rubber in the form of latex is preferably 5 to 9, more preferably 6 to 8. Within this range, the stability of the latex may be excellent.

In the present specification, pH can be measured using a pH meter.

The graft copolymer (a) is a graft copolymer prepared by grafting an aromatic vinyl compound-vinyl cyan compound copolymer to the main chain of an alkyl acrylate rubber polymer. As a specific example, the graft copolymer (a) may be prepared by mixing an alkyl acrylate rubber with an aromatic vinyl compound, a vinyl cyanide compound and, if necessary, a polymerization additive and performing emulsion polymerization.

For example, the polymeric additive may comprise a grafting agent and/or a crosslinking agent. In this case, the grafting agent and the crosslinking agent are the same as those used for preparing the alkyl acrylate rubber, and the content of each of the grafting agent and the crosslinking agent may be determined in the same range as that used for preparing the alkyl acrylate rubber, based on 100 parts by weight of all monomers except the rubber.

In the present specification, the monomer may include alkyl acrylate, alkyl methacrylate, aromatic vinyl compound, and vinyl cyanide compound.

When the emulsion polymerization of the graft copolymer (a) is carried out, an emulsifier, a polymerization initiator, a molecular weight regulator and water, which are generally used in the art to which the present invention pertains, may be used in addition to the alkyl acrylate rubber, the aromatic vinyl compound and the vinyl cyanide compound. Further, immediately after the emulsion polymerization is completed, the prepared graft copolymer may be obtained in the form of a latex.

For example, the pH of the aqueous solution containing the emulsifier may be 9 to 13, and the emulsifier is preferably a carboxylic acid metal salt derivative such as a fatty acid metal salt having 12 to 20 carbon atoms and a rosin acid metal salt having 12 to 20 carbon atoms.

For example, the fatty acid metal salt having 12 to 20 carbon atoms preferably includes one or more selected from sodium fatty acid, sodium laurate, sodium oleate and potassium oleate, and the rosin acid metal salt having 12 to 20 carbon atoms preferably is sodium rosin acid, potassium rosin acid or a mixture thereof.

For example, the emulsifier is preferably used in an amount of 1 to 2 parts by weight based on 100 parts by weight of the reaction mixture comprising the alkyl acrylate rubber, the aromatic vinyl compound and the vinyl cyanide compound.

For example, the initiator may be the same as that used for preparing the alkyl acrylate rubber, and the amount of the initiator is preferably 0.05 to 0.3 parts by weight based on 100 parts by weight of the above reaction mixture.

For example, the molecular weight regulator may be t-dodecyl mercaptan, n-octyl mercaptan, or a mixture thereof, and may be used in an amount of 0.02 to 0.2 parts by weight, based on 100 parts by weight of the above reaction mixture.

The water used in the present invention is preferably deionized water, and may be used in an amount generally used in the art to which the present invention pertains.

When graft emulsion polymerization is carried out, when the reaction mixture and a polymerization additive such as an emulsifier are fed in portions, the pH of the polymerization system temporarily rises, which makes grafting difficult. In addition, the stability of the copolymer particles is lowered, whereby the internal structure of the particles becomes nonuniform. Thus, when the graft copolymer (A) is prepared by graft emulsion polymerization, the reaction mixture and the polymerization additive are preferably fed continuously, and as a specific example, the reaction mixture and the polymerization additive are fed continuously for 1 hour to 10 hours or 1 hour to 5 hours within the total reaction time.

It should be noted that polymerization conditions not described herein are obvious to those skilled in the art, and polymerization conditions well known in the art may be appropriately selected.

In the present specification, continuous feeding is a feeding method as opposed to batch feeding, and means continuous feeding for a certain period of time or stepwise feeding over a certain period of time.

For example, immediately after the polymerization is completed, the pH of the graft copolymer (a) in the form of a latex is preferably 8 to 11, more preferably 9 to 10.5. Within this range, the stability of the latex may be excellent.

As a specific example, the graft copolymer latex (a) may be coagulated at a temperature of 80 ℃ to 90 ℃ or 82 ℃ to 88 ℃ under atmospheric pressure using an aqueous calcium chloride solution, aged at a temperature of greater than 90 ℃ and less than or equal to 100 ℃ or at a temperature of 92 ℃ to 98 ℃, dehydrated and washed, and then dried with hot air of 85 ℃ to 95 ℃ or 88 ℃ to 92 ℃ for 20 minutes to 1 hour or 30 minutes to 40 minutes to obtain a powder.

B) Alkyl methacrylate-aromatic vinyl Compound-vinyl cyanide Compound copolymer

The content of the alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer of the present invention is preferably 23 to 55% by weight, more preferably 25 to 50% by weight, still more preferably 25 to 45% by weight, and most preferably 30 to 40% by weight, based on the total weight of the ASA resin composition (a + B + C). Within this range, transparency and coloring properties may be excellent.

The alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer preferably includes 40 to 90% by weight of an alkyl methacrylate, 9 to 40% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyanide compound, more preferably includes 50 to 85% by weight of an alkyl methacrylate, 12 to 35% by weight of an aromatic vinyl compound, and 3 to 15% by weight of a vinyl cyanide compound, and still more preferably includes 55 to 65% by weight of an alkyl methacrylate, 25 to 35% by weight of an aromatic vinyl compound, and 5 to 10% by weight of a vinyl cyanide compound. Within this range, transparency and coloring properties may be excellent.

For example, the alkyl methacrylate may be an alkyl methacrylate containing an alkyl group having 1 to 15 carbon atoms. As a specific example, the alkyl methacrylate may include one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate, preferably an alkyl methacrylate including an alkyl group having 1 to 4 carbon atoms, and more preferably methyl methacrylate.

For example, the aromatic vinyl compound may include one or more selected from the group consisting of styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene and p-tert-butylstyrene, preferably styrene.

The weight average molecular weight of the alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer is preferably 10,000g/mol to 150,000g/mol, more preferably 40,000g/mol to 120,000 g/mol. Within this range, the rubber dispersibility can be improved, thereby improving impact strength, processability, transparency and coloring property.

In the present specification, unless otherwise defined, when measuring the weight average molecular weight, the powder is dissolved in acetone, the sol portion dissolved in acetone is extracted, and the extracted sol portion is dissolved in Tetrahydrofuran (THF). Then, the weight average molecular weight was measured by Gel Permeation Chromatography (GPC). In this case, the weight average molecular weight is obtained as a relative value to a standard Polystyrene (PS) sample.

For example, the alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer may be prepared by solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization. Solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization, which are carried out in the field to which the present invention pertains, may be used in the present invention without particular limitation.

As a preferred example, in order to prepare the alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer, 0.01 to 0.5 parts by weight, preferably 0.02 to 0.15 parts by weight, more preferably 0.02 to 0.1 parts by weight of each of one or more initiators and molecular weight regulators may be added to a total of 100 parts by weight of alkyl methacrylate, aromatic vinyl compound and vinyl cyanide compound in the absence of a solvent or in a reaction solvent, and then bulk polymerization or solution polymerization may be performed in a continuous reactor. In this case, the economy can be improved, and the residual impurities can be reduced.

The reaction solvent for bulk polymerization or solution polymerization, which is generally used in the art to which the present invention pertains, may be used as the reaction solvent of the present invention without particular limitation. For example, the reaction solvent may be an aromatic hydrocarbon. The reaction solvent preferably includes one or more selected from the group consisting of toluene, xylene, ethylbenzene, cumene and tetralin, more preferably toluene.

Preferably, the weight of the graft copolymer (a) is not more than that of the alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer (B). More preferably, the weight ratio (a: B) of the graft copolymer (a) to the alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer (B) is 1:1 to 1:2.5, more preferably 1:1 to 1:2. Within this range, the balance between mechanical strength and fluidity may be excellent, and in particular, transparency, coloring property and weather resistance may be excellent.

C) Poly (alkyl methacrylate) resin

The content of the poly (alkyl methacrylate) resin (C) of the present invention is preferably 25 to 45% by weight, more preferably 30 to 45% by weight, and still more preferably 30 to 40% by weight. Within this range, the transparency and coloring properties can be greatly improved while maintaining mechanical properties and processability equal to or superior to those of conventional ASA resin compositions.

For example, the poly (alkyl methacrylate) resin may be a polymer including an alkyl methacrylate including an alkyl group having 1 to 15 carbon atoms.

The alkyl methacrylate preferably includes one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate, more preferably an alkyl methacrylate containing an alkyl group having 1 to 4 carbon atoms, and still more preferably methyl methacrylate.

The weight average molecular weight of the poly (alkyl methacrylate) resin is preferably 50,000 to 200,000g/mol, more preferably 50,000 to 150,000g/mol, and still more preferably 50,000 to 100,000 g/mol. Within this range, weather resistance, flowability, tensile strength, impact strength, transparency, and coloring properties may be excellent.

For example, the poly (alkyl methacrylate) resin may be prepared by adding a crosslinking agent and an initiator to a monomer including alkyl methacrylate and performing bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, preferably suspension polymerization or emulsion polymerization.

As the initiator of the present invention, an initiator generally used for preparing a poly (alkyl methacrylate) resin may be used. For example, azo initiators such as 2,2' -azobis 2, 4-dimethyl-valeronitrile may be used.

From among materials or conditions commonly used when preparing the poly (alkyl methacrylate) resin, materials such as a solvent and an emulsifier, which must be added according to each polymerization method, may be appropriately selected according to need, or conditions such as a polymerization temperature and a polymerization time, which must be changed according to each polymerization method, may be appropriately selected without particular limitation.

ASA resin composition

The total rubber content of the ASA resin composition of the present invention is preferably 8 to 23 wt%, more preferably 10 to 20 wt%, still more preferably 10 to 17 wt%, and most preferably 10 to 15 wt%. Within this range, mechanical properties may be excellent, and particularly, weather resistance, transparency, and coloring properties may be excellent.

In the present specification, the ASA-based resin refers to an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound copolymer.

The ASA-based resin composition preferably includes one or more of a lubricant, a heat stabilizer and an ultraviolet stabilizer in an amount of 0.05 to 5 parts by weight, based on 100 parts by weight of the total of the acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer, the alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer and the poly (alkyl methacrylate) resin. Within this range, the inherent properties of the ASA-based resin composition can be effectively exhibited without deterioration of the physical properties of the ASA-based resin composition.

The content of the lubricant is preferably more than 0.3 parts by weight and less than 2 parts by weight, more preferably 0.5 parts by weight to 1.9 parts by weight, and still more preferably 0.9 parts by weight to 1.5 parts by weight. Within this range, impact strength and flowability may be excellent.

For example, the lubricant may include one or more selected from the group consisting of ester-based lubricants, metal salt-based lubricants, carboxylic-based lubricants, hydrocarbon-based lubricants, and amide-based lubricants, preferably amide-based lubricants, more preferably stearamide-based lubricants, and still more preferably alkylenebis (stearamide) containing an alkylene group having 1 to 10 carbon atoms. In this case, the inherent properties of the lubricant can be well expressed without deterioration of the mechanical properties and thermal stability of the resin.

In the present specification, the stearamide-based lubricant may include stearamide and a stearamide substituent(s) obtained by substituting at least one hydrogen of the stearamide with another substituent (e.g., C1 to C10 alkyl, halogen, etc.).

Ester lubricants, metal salt lubricants, carboxylic acid lubricants, hydrocarbon lubricants and amide lubricants, which are generally used in the art to which the present invention pertains, may be used in the present invention without particular limitation.

For example, the heat stabilizer may include one or more selected from the group consisting of an amine-based heat stabilizer and a phosphorus-based heat stabilizer in an amount of 0.01 to 3 parts by weight each. Within this range, thermal stability, transparency, and coloring properties may be excellent.

For example, the amine-based heat stabilizer may include one or more selected from the group consisting of N, N-di-tert-butylhydroxylamine, N-Distearylhydroxylamine (DSHA), N-Diphenylhydroxylamine (DPHA), N-dibenzylhydroxylamine, N-benzylphenylhydroxylamine, N-bis (2, 4-dimethylphenyl) hydroxylamine and N, N-naphthylhydroxylamine. For example, the amine-based heat stabilizer may be contained in an amount of 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, and more preferably 0.1 to 1 part by weight. Within this range, thermal stability, transparency, and coloring properties may be excellent.

For example, the phosphorus-based heat stabilizer may include one or more selected from the group consisting of tris (nonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite (TBPP), 2,4, 6-tri-t-butylphenyl-2-butyl-2-ethyl-1, 3-propanediol phosphite, diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite (PEP24), bis (2, 4-diisopropylphenylphenyl) pentaerythritol diphosphite, and tetrakis (2, 4-di-t-butylphenyl) [1, 1-biphenyl ] -4,4' -diyl diphosphite. For example, the phosphorus-based heat stabilizer may be contained in an amount of 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, and more preferably 0.1 to 1 part by weight. Within this range, thermal stability, transparency, and coloring properties may be excellent.

For example, the ultraviolet stabilizer may include 0.1 to 2.5 parts by weight of one or more selected from the group consisting of a benzotriazole-based ultraviolet absorber and a HALS-based ultraviolet stabilizer, preferably 0.1 to 2.0 parts by weight of the benzotriazole-based ultraviolet absorber and 0.1 to 2.0 parts by weight of the HALS-based ultraviolet stabilizer, more preferably 0.1 to 1.0 parts by weight of the benzotriazole-based ultraviolet absorber and 0.1 to 1.0 parts by weight of the HALS-based ultraviolet stabilizer, still more preferably 0.2 to 0.7 parts by weight of the benzotriazole-based ultraviolet absorber and 0.2 to 0.7 parts by weight of the HALS-based ultraviolet stabilizer, most preferably 0.3 to 0.6 parts by weight of the benzotriazole-based ultraviolet absorber and 0.3 to 0.6 parts by weight of the HALS-based ultraviolet stabilizer. Within this range, the weather resistance can be greatly improved without deterioration in impact strength and flowability.

For example, the benzotriazole-based ultraviolet absorber may be hydroxybenzotriazole, preferably 2- (2' -hydroxyphenyl) benzotriazole. More preferably, the benzotriazole-based ultraviolet absorber includes a compound selected from the group consisting of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2- (3',5' -di-tert-butyl-2 '-hydroxyphenyl) benzotriazole, 2- (5' -tert-butyl-2 '-hydroxyphenyl) benzotriazole, 2- (2' -hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3',5 '-di-tert-butyl-2' -hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 '-tert-butyl-2' -hydroxy-5 '-methylphenyl-5-chlorobenzotriazole, 2- (3' -sec-butyl-5 '-tert-butyl-2' -hydroxyphenyl) Benzotriazole, 2- (2' -hydroxy-4 ' -octyloxyphenyl) benzotriazole, 2- (3',5' -di-tert-amyl-2 ' -hydroxyphenyl) benzotriazole, 2- (3',5' -bis (. alpha.,. alpha. -dimethylbenzyl) -2' -hydroxyphenyl) benzotriazole, 2- (3' -tert-butyl-2 ' -hydroxy-5 ' - (2-octyloxy-carbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3' -tert-butyl-5 ' - [2- (2-ethylhexyloxy) carbonylethyl ] -2' -hydroxyphenyl) -5-chlorobenzotriazole, 2- (3' -tert-butyl-2 ' -hydroxy-5 ' - (2-methoxycarbonylethyl) benzotriazole Yl) phenyl) -5-chlorobenzotriazole, 2- (3' -tert-butyl-2 ' -hydroxy-5 ' - (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3' -tert-butyl-2 ' -hydroxy-5 ' - (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3' -tert-butyl-5 ' - [2- (2-ethylhexyloxy) carbonylethyl ] -2' -hydroxyphenyl) benzotriazole, 2- (3' -dodecyl-2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- (3' -tert-butyl-2 ' -hydroxy-5 ' - (2-isooctyloxycarbonylethyl) phenylbenzotriazole, a salt thereof, a pharmaceutically acceptable carrier thereof, and a pharmaceutically acceptable carrier, 2,2 '-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol ], and one or more of the transesterification product of 2- [3' -tert-butyl-5 '- (2-methoxycarbonylethyl) -2' -hydroxyphenyl ] -2H-benzotriazole with polyethylene glycol. In this case, the weather resistance can be greatly improved without deterioration in impact strength and fluidity.

The HALS type UV-stabiliser preferably comprises a compound selected from the group consisting of 1, 1-bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) -N-butyl-3, 5-di-tert-butyl-4-hydroxybenzylmalonate, condensation product of 1- (2-hydroxyethyl) -2,2,6, 6-tetramethyl-4-hydroxypiperidine with succinic acid, Linear or cyclic condensation products of N, N '-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3, 4-butanetetracarboxylate, 1' - (1, 2-ethanediyl) -bis (3,3,5, 5-tetramethylpiperazinone), 4-benzoyl-2, 2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine (4-stearyloxy-2,2,6,6-tetramethylpiperidine), a linear or cyclic condensation product of N, N' -bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 4-morpholinyl-2, 6-dichloro-1, 3, 5-triazine, and one or more of the reaction products of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro- [4,5] decane (7,7,9, 9-tetramethyll-2-cyclocyclic-1-oxa-3, 8-diaza-4-oxospiro- [4,5] decane) with epichlorohydrin, more preferably bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (bis (2,2,6, 6-tetramethylyl-4-piperidyl) rebanate), 2- (2H-benzotriazol-2-yl) -4- (- (1,1,3,3-tetramethylbutyl) phenol (2- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethyllbutyl) phenol), or a mixture thereof. In this case, the weather resistance can be greatly improved without deterioration in impact strength and fluidity.

The ASA-based resin composition may further include one or more additives selected from the group consisting of dyes, pigments, colorants, release agents, antistatic agents, antibacterial agents, processing aids, metal deactivators, flame retardants, smoke suppressants, anti-drip agents, friction reducing agents and anti-wear agents in an amount of 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight or 0.5 to 1 part by weight, based on 100 parts by weight of the above-mentioned substances, as needed. Within this range, the effects of the additives can be well exhibited without deterioration of the inherent physical properties of the ASA resin composition.

The ASA-based resin composition preferably has a melt index (220 ℃, 10kg) measured according to ASTM D1238 of 8g/10min or more, more preferably from 8g/10min to 11g/10min, and still more preferably from 9g/10min to 11g/10 min. Within this range, the balance between impact strength, weather resistance, and flowability may be excellent.

The ASA-based resin composition preferably has an Izod impact strength (1/4 inches, 23 ℃) measured according to ASTM D256 of 3kgf cm/cm²More preferably 3kgf cm/cm²To 8kgf cm/cm²Still more preferably 3kgf cm/cm²To 4kgf cm/cm². Within this range, the balance between impact strength, weather resistance and fluidity may be excellent.

For example, the ASA-based resin composition is measured according to ASTM 638The tensile strength of the amount (1/8 inches) may be 570kg/cm²Above, preferably 570kg/cm²To 700kg/cm²More preferably 580kg/cm²To 650kg/cm²Still more preferably 580kg/cm²To 610kg/cm². Within this range, the balance among impact strength, tensile strength, weather resistance and fluidity may be excellent.

For example, the ASA-based resin composition may have a flexural strength of 850kg/cm as measured according to ASTM 790²Above, preferably 850kg/cm²To 1,000kg/cm²More preferably 860kg/cm²To 950kg/cm²Still more preferably 870kg/cm²To 920kg/cm². Within this range, the balance among impact strength, tensile strength, flexural strength, weather resistance, and fluidity may be excellent.

The ASA resin composition preferably has a surface gloss (45 °) of 80 or more, more preferably 85 or more or 95 or more, measured according to ASTM D528. Within this range, transparency and coloring properties may be excellent, and the balance between physical properties may be good.

The transparency (haze) of the ASA resin composition measured according to ASTM D1003 is preferably 7 or less, more preferably 6 or less, and still more preferably 5 or less. Within this range, mechanical properties, processability, transparency and colorability may be excellent.

The ASA-based resin composition has a Weather resistance (. DELTA.E) as measured by a Weather-Ometer of preferably 1.3 or less, more preferably 1.2 or less, when 6,000 hours have elapsed according to ASTM J1960. Within this range, mechanical properties, processability, colorability and weatherability may be excellent.

The method of preparing the ASA-based resin composition preferably comprises: a step of kneading and extruding 20 to 47 wt% of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an acrylate rubber having an average particle diameter of 50 to 150nm as a core, 23 to 55 wt% of an alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer, and 25 to 45 wt% of a poly (alkyl methacrylate) resin under conditions of 200 to 300 ℃ and 100 to 500rpm to prepare pellets.

In the kneading and extruding step, an extrusion kneader generally used in the field to which the present invention pertains may be used without particular limitation. For example, a single screw extruder, a twin screw extruder or a banbury mixer may be used, with a twin screw extruder being preferred. In this case, since the composition is uniformly dispersed, the compatibility may be excellent.

The kneading and extrusion are preferably carried out at a barrel temperature (temperature condition) of from 210 ℃ to 300 ℃, more preferably from 210 ℃ to 280 ℃, still more preferably from 220 ℃ to 250 ℃. In this case, the amount of production per unit time may be sufficient, melt kneading may be sufficiently performed, and thermal decomposition of the resin component may be prevented.

Kneading and extrusion are preferably performed at a screw rotation speed (rpm) of 150rpm to 400rpm, more preferably 100rpm to 350rpm, still more preferably 200rpm to 310rpm, most preferably 250rpm to 350 rpm. In this case, the throughput per unit time may be sufficient, whereby the process efficiency may be improved and the excessive cutting may be prevented.

The method for preparing the ASA resin composition has all the technical characteristics of the ASA resin composition described above. Therefore, a repetitive description thereof will be omitted.

Molded article

The molded article of the present invention can be produced using the thermoplastic resin composition of the present invention. In this case, since the compatibility is improved, mechanical properties such as impact strength, transparency and coloring properties may be excellent.

For example, the molded article may be an extrusion molded article or an injection molded article. Preferably, the molded article comprises: housings of household appliances such as air conditioners, vacuum cleaners, washing machines, refrigerators, and rear covers of televisions; housings for OA equipment such as computers, notebook computers, monitors, facsimile machines, telephones, copiers, and scanners; automobile parts such as automobile interior and exterior materials; interior and exterior materials of buildings; a toy material; leisure articles; and interior decoration products, more preferably exterior materials, decorative materials, unpainted products, or extruded profiles. In this case, by using the thermoplastic resin composition of the present invention, a product having a quality superior to that required in the market can be provided.

The processed thickness, for example, the surface thickness of the molded article is preferably 0.5t (mm) or more.

Method for producing molded articles

Preferably, the method of manufacturing a molded article of the present invention comprises: a step of kneading and extruding 20 to 47 wt% of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an acrylate rubber having an average particle diameter of 50 to 150nm as a core, 23 to 55 wt% of an alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer, and 25 to 45 wt% of a poly (alkyl methacrylate) resin under conditions of 200 to 300 ℃ and 100 to 500rpm to prepare pellets; and a step of subjecting the prepared pellets to sheet molding or injection molding at a molding temperature of 200 ℃ to 300 ℃ to produce a molded article. In this case, the molded article can have excellent coloring properties and transparency even at a processing thickness of a predetermined value or more, and thus, the molded article can be applied to high value-added ASA-based resin products having unpainted, transparent, high-saturation, or special color properties.

As a preferred example, the step of preparing a molded article may include a step of sheet-molding the prepared pellets at a molding temperature of 180 ℃ to 300 ℃. As a more preferred example, the step of preparing the molded article may include molding at a molding temperature of 180 ℃ to 300 ℃ at 50kgf/cm²To 300kgf/cm²The step of sheet molding is performed under the molding pressure of (1). In this case, a large-sized molded sheet having excellent transparency and coloring properties can be easily produced.

The molding temperature is preferably 200 ℃ to 230 ℃, more preferably 210 ℃ to 220 ℃. Within this range, a large-sized molded sheet having excellent transparency and coloring properties can be easily produced.

The molding pressure is preferably 190kgf/cm²To 270kgf/cm²More preferably 200kgf/cm²To 250kgf/cm². Within this range, a large injection molded article having high impact strength can be easily produced.

As another preferred example, the step of manufacturing the molded article may include the step of injection molding the prepared pellets at an injection temperature of 200 ℃ to 260 ℃, an injection pressure of 60 bar to 100 bar, and a holding pressure of 25 bar to 55 bar. In this case, a large injection molded article having excellent transparency and coloring properties can be easily produced.

The injection temperature is preferably 200 ℃ to 230 ℃, more preferably 210 ℃ to 220 ℃. Within this range, large injection molded articles having excellent transparency and coloring properties can be easily produced.

The injection pressure is preferably 70 to 90 bar, more preferably 75 to 85 bar. Within this range, a large injection molded article having high impact strength can be easily produced.

The holding pressure is preferably 30 to 50 bar, more preferably 35 to 45 bar. Within this range, a large-area injection molded article having high impact strength can be easily produced.

In describing the thermoplastic resin composition, the method of preparing the thermoplastic resin composition, and the molded article according to the present invention, it should be noted that other conditions or apparatuses not explicitly described in the present specification may be appropriately selected within the scope of general practice in the art without particular limitation.

Hereinafter, the present invention will be described in more detail with reference to the following preferred examples. However, these examples are provided for illustrative purposes only, and should not be construed as limiting the scope and spirit of the present invention. Further, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are also within the scope of the appended claims.

[ examples ]

The materials used in the following examples are as follows.

A) Graft copolymer prepared by emulsion polymerization (core: 50% by weight of units from a butyl acrylate polymer having an average particle diameter of 150nm, shell: 35% by weight of units derived from styrene and 15% by weight of units derived from acrylonitrile)

B) SAMMA resin prepared by bulk polymerization: SAMMA resin was prepared by the following method.

A polymerization solution was prepared by adding 0.02 parts by weight of 1, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 0.08 parts by weight of n-dodecylmercaptan and 0.1 parts by weight of Irgacure (1,3, 5-tris (4-t-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione) as a hindered phenol antioxidant to a mixed solution containing 20 parts by weight of toluene, 24 parts by weight of styrene, 50 parts by weight of methyl methacrylate and 6 parts by weight of acrylonitrile, and fed into a 26L reactor at a rate of 14L/hr while carrying out polymerization at a temperature of 140 ℃ in a first reactor, and the polymerization was carried out in the second reactor at a temperature of 150 ℃. When the polymerization rate reached more than about 60%, unreacted monomers and the reaction medium were removed in a volatilization tank at 215 ℃ to prepare a styrene-acrylonitrile-methyl methacrylate (SAMMA) resin in the form of pellets. The weight average molecular weight of the prepared SAMMA resin was 70,000 g/mol.

C) PMMA resin prepared by bulk polymerization: a PMMA resin was prepared by the following method.

100 parts by weight of methyl methacrylate, 200 parts by weight of distilled water, 0.3 part by weight of polyvinyl alcohol as a suspending agent, and 2.0 parts by weight of n-octyl mercaptan were fed in portions to a reactor purged with nitrogen. Then, the temperature inside the reactor was increased to 80 ℃, 0.05 parts by weight of AIBN as an initiator was added thereto to initiate the reaction, and the temperature inside the reactor was maintained at 80 ℃ to perform polymerization for 90 minutes. Thereafter, the temperature of the reactor was increased to 110 ℃ for 30 minutes to perform additional polymerization. The resulting beads were washed using a dehydrator and dried in a fluid bed dryer at 80 ℃ for 2 hours. The weight average molecular weight of the PMMA resin prepared was 100,000 g/mol.

Examples 1 to 5 and comparative examples 1 to 6

1 part by weight of each of EBS resin (Sunkoo Co.) as a lubricant, 0.5 part by weight of each of SONGNOX 1076 and SONGNOX 1680(Songwan Co.) as an antioxidant, and 0.5 part by weight of each of Tinuvin 770(BASF Co.) and Sunsorb 329(Sunfine global Co.) as an ultraviolet stabilizer were added to the compositions and contents shown in table 1 below, and the mixture was kneaded and extruded at 230 ℃ and 150rpm in a twin-screw extruder to prepare pellets. The melt index of the prepared pellets was measured. Further, the pellets thus prepared were used at a molding temperature of 220 ℃ and a molding temperature of 200kgf/cm²A 0.5T sheet was prepared under the molding pressure of (a). The prepared sheet was used to measure surface gloss, Tt and haze. Further, the prepared pellets were injected at a molding temperature of 220 ℃, an injection pressure of 50 bar and a holding pressure of 35 bar to prepare a sample for measuring physical properties. The prepared test specimens were used to measure impact strength, tensile strength, flexural strength, coloring property and weather resistance.

[ test examples ]

The properties of the pellets, sheets and test specimens prepared in examples 1 to 5 and comparative examples 1 to 6 were measured according to the following methods, and the results are shown in table 1 below.

Rubber content (wt%): the rubber content was measured according to FT-IR.

Surface gloss (%): surface gloss was measured at 45 ° according to ASTM D528.

Izod impact strength (kgf · cm/cm): izod impact strength was measured according to ASTM 256.

Flexural Strength (kgf/cm)²): flexural strength was measured according to ASTM 790.

Tensile strength (kgf/cm)²): tensile strength was measured according to ASTM 638.

Melt Index (MI): the melt index was measured according to ASTM D1238 using the prepared pellets at 220 ℃ and 10 kg.

Transparency (light diffusivity and light transmittance): the haze value and total light transmittance (Tt) of a 0.5mm thick sheet were measured according to ASTM D-1003. As the haze value decreases, the transparency becomes better, and as the light transmittance increases, the transparency becomes better.

Surface hardness: surface hardness was measured according to ASTM D785.

Coloring performance: the L value of the sample was measured in CIELAB mode using a Color difference meter (Color-Eye 7000A, X-Rite Co.). As the L value increases, the degree to which the color of the white board located behind the test piece is projected onto the test piece increases, that is, the coloring performance improves.

Weather resistance (Δ E): under the conditions of ASTM J1960, when 6,000 hours have elapsed, the color was measured using a Weather resistance analyzer (Weather-Ometer), and the measured color was compared with the initial color. Small Δ E values indicate that the degree of color change is not significant. Therefore, weather resistance becomes better as Δ E value decreases.

[ Table 1]

(parts by weight)	Example 1	Example 2	Example 3	Example 4	Example 5
						A	30	30	20	40	46
B	40	30	40	30	24
						C	30	40	40	30	30
Rubber content	15	15	10	20	23
						Melt Index (MI)	10.7	9.7	15	9	8
Impact strength	3.5	3.2	2.3	4.3	4.5
						Tensile strength	600	590	650	500	450
Flexural Strength	900	880	960	800	700
						Tt	86	88	88	83	83
Haze degree	5	4	4	6	7
						Surface gloss	100	106	105	95	93
Surface hardness	110	110	109	95	90
						Coloring Properties	80	81	80	76	76
Weatherability (Delta E)	1.1	1.2	1.1	1.6	1.7

[ Table 2]

(parts by weight)	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6
							A	30	30	65	10	30	56
B	70	40	15	40	65	20
							C	-	30	20	50	5	24
Rubber content	15	15	32.5	5	15	28
							Melt Index (MI)	12	12	14	18	16	6
Impact strength	3.4	3.4	9	2.1	3.5	8.5
							Tensile strength	540	560	380	700	590	420
Flexural Strength	840	860	590	1060	885	660
							Tt	80	85	82	88	83	84
Haze degree	17	9.1	10	8	15	9.5
							Surface gloss	98	96	75	97	97	90
Surface hardness	109	105	65	109	105	86
							Coloring Properties	75	76	75	78	76	75
Weatherability (Delta E)	1.4	1.6	2.3	1.5	1.4	1.9

As shown in tables 1 and 2, it can be confirmed that the ASA resin compositions according to the present invention (examples 1 to 5) have excellent transparency (haze), coloring property and weather resistance while having mechanical strength such as impact strength and tensile strength, and processability as indicated by MI equal to or better than those of comparative examples 1 to 6, as compared to comparative examples 1 to 6 not according to the present invention. Specifically, it was confirmed that examples 1 to 3 having preferred composition ratios and rubber contents have excellent transparency (haze), coloring properties, and weather resistance. Therefore, it was confirmed that the ASA resin composition according to the present invention has excellent coloring properties and transparency even at a processing thickness of a predetermined value or more while maintaining mechanical properties and processing properties equal to or better than those of conventional ASA compositions, and thus, the ASA resin composition is suitable for use in high value-added products having unpainted, transparent, high saturation or special color properties.

Claims

1. An ASA-based resin composition comprising:

20 to 47% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an acrylate rubber having an average particle diameter of 50 to 150nm as a core;

23 to 55% by weight of an alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer; and

25 to 45 weight percent of a poly (alkyl methacrylate) resin.

2. The ASA-based resin composition according to claim 1, wherein the ASA-based resin composition has a transparency (haze) of 7 or less measured according to ASTM D1003.

3. The ASA-based resin composition as claimed in claim 1, wherein the ASA-based resin composition has a total rubber content of 10 to 23 wt%.

4. The ASA-based resin composition as claimed in claim 1, wherein the acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprises 40 to 60% by weight of an acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound.

5. The ASA-based resin composition as claimed in claim 1, wherein the alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer comprises 45 to 65% by weight of alkyl methacrylate, 25 to 35% by weight of aromatic vinyl compound, and 10 to 20% by weight of vinyl cyanide compound.

6. The ASA-based resin composition as claimed in claim 1, wherein the alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer has a weight average molecular weight of 10,000 to 150,000 g/mol.

7. The ASA-based resin composition as claimed in claim 1, wherein the poly (alkyl methacrylate) resin is a polymer comprising an alkyl methacrylate comprising an alkyl group having 1 to 15 carbon atoms.

8. The ASA-based resin composition as claimed in claim 1, wherein the poly (alkyl methacrylate) resin has a weight average molecular weight of 50,000 to 200,000 g/mol.

9. The ASA-based resin composition as claimed in claim 1, wherein the ASA-based resin composition comprises one or more of a lubricant, a heat stabilizer and an ultraviolet stabilizer in an amount of 0.05 to 5 parts by weight.

10. A molded article manufactured using the ASA-based resin composition according to any one of claims 1 to 9.

11. The molded article of claim 10, wherein the molded article is an exterior material, a trim material, an unpainted product, or an extruded profile.

12. A method of making a molded article, the method comprising:

kneading and extruding 20 to 47 wt% of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing an acrylate rubber having an average particle diameter of 50 to 150nm as a core, 23 to 55 wt% of an alkyl methacrylate-aromatic vinyl compound-vinyl cyanide compound copolymer, and 25 to 45 wt% of a poly (alkyl methacrylate) resin under conditions of 200 to 300 ℃ and 100 to 500rpm to prepare pellets; and

the molded article is manufactured by subjecting the prepared pellet to sheet molding or injection molding at a molding temperature of 200 to 300 ℃.