KR20180076637A - Thermoplastic resin composition, method for preparing the resin composition and molding product comprising the resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, a method of preparing the thermoplastic resin composition, and an injection molded product including the thermoplastic resin composition. More specifically, the present invention relates to the thermoplastic resin composition and the injection molded product including the same. The thermoplastic resin composition includes: a (meth)acrylic rubber-aromatic vinyl compound-vinyl cyanide compound copolymer having a graft ratio of 32 to 42% and an average particle diameter of 500 to 1,500 Å; a (meth)acrylic rubber polymer-aromatic vinyl compound-vinyl cyanide compound copolymer having a graft ratio of 32 to 45% and an average particle diameter of 2,000 to 3,000 Å; and an (alpha-alkylstyrene)-vinyl cyanide compound copolymer in specific contents, thereby obtaining excellent impact resistance, heat resistance, durability, weatherability and other properties, and improving deposition properties, glossiness, adhesion and other properties during the non-painting process such that the thermoplastic resin composition is capable of providing an injection molded product having excellent quality.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composition, a method of producing the same, and an injection molded article containing the same. BACKGROUND OF THE INVENTION [0002]

More particularly, the present invention relates to a thermoplastic resin composition comprising two kinds of (meth) acrylic rubber-aromatic vinyl compound-vinyl cyanide copolymer having different grafting ratios, Alkylstyrene) -vinyl cyanide copolymer in a specific amount to provide an injection molded article of excellent quality with improved impact resistance, heat resistance, durability, weather resistance, and improved vapor deposition, luster, and adhesion in a non- To a thermoplastic resin composition.

Acrylonitrile-butadiene-styrene resin (ABS resin) is widely used for construction materials, interior and exterior materials for vehicles such as automobiles and motorcycles, and electric and electronic products because of excellent workability, impact resistance and chemical resistance.

When the ABS resin is used for an automobile exterior material, particularly a rear lamp housing (tail lamp or rear combination lamp) or a rear garnish, it is subjected to painting and aluminum deposition processes. However, the pre-deposition painting process causes environmental pollution and cost increase .

In order to increase the efficiency of post-processing and reduce environmental pollution, there has been an increase in the unpainted deposition process in which aluminum is directly deposited on an injection material by omitting the coating process which has been performed previously.

In the case of manufacturing the product through the non-coating deposition process as described above, the light reflectance of the deposition surface should be excellent after aluminum deposition, and the material should not be deformed due to heat generated when the product is used.

However, in the case of a rear lamp housing made of an ABS resin, the double bonds of the butadiene rubber used for impact reinforcement in the resin are decomposed by oxygen, ozone, light or the like in the air to cause problems such as discoloration and deterioration of physical properties Respectively.

Styrene-acrylonitrile-based resin (ASA-based resin) obtained by copolymerizing styrene and acrylonitrile in an acrylic rubber polymer instead of an unstable butadiene rubber polymer has been proposed instead of an ABS-based resin. However, the ASA- But it has a disadvantage in that the appearance characteristics are low.

In order to improve the disadvantage of such an ASA resin, a method of blending polymethyl methacrylate (PMMA) and polycarbonate (PC) having excellent appearance characteristics has been proposed. However, when PMMA or PC is blended, Resulting in poor processability and moldability.

Korean Patent No. 10-079519

DISCLOSURE OF THE INVENTION In order to solve the problems of the prior art as described above, it is an object of the present invention to provide an acrylic rubber-aromatic vinyl compound-vinyl cyanide copolymer (ASA resin) excellent in physical properties such as impact resistance, heat resistance, durability, Which is improved in appearance characteristics such as vapor deposition property, gloss property, adhesion property, and the like, and which can provide a high-quality molded article with high reliability, and a method for producing the same.

Another object of the present invention is to provide an injection molded article produced by thermoforming the thermoplastic resin composition.

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

(A-1) a (meth) acrylic rubber-aromatic vinyl compound-vinyl cyanide copolymer having an average particle diameter of 500 to 1,500 ANGSTROM having a graft ratio of 32 to 42%; (A-2) a (meth) acrylic rubber polymer-aromatic vinyl compound-vinyl cyanide copolymer having an average particle size of 2,000 to 3,000 ANGSTROM with a graft ratio of 32 to 45%; And B) (alpha-alkylstyrene) -vinyl cyan compound copolymer.

A-1) 10 to 25% by weight of a (meth) acrylic rubber-aromatic vinyl compound-vinyl cyanide copolymer having an average particle size of 500 to 1,500 angstroms having a graft rate of 32 to 42%; A-2) 10 to 25% by weight of a (meth) acrylic rubber polymer having an average particle size of 2,000 to 3,000 ANGSTROM and an aromatic vinyl compound-vinyl cyanide copolymer having a graft ratio of 32 to 45%; And 50 to 80% by weight of (B) (alpha-alkylstyrene) -vinyl cyanide copolymer; and then extruding the kneaded mixture.

According to the present invention, two kinds of (meth) acrylic rubber-aromatic vinyl compound-vinyl cyanide copolymer having different grafting ratios and high heat resistance (alpha-alkylstyrene) -vinyl cyan compound copolymer are blended in a specific amount, It is possible to provide a highly reliable thermoplastic resin composition and injection molded article which is excellent in physical properties such as heat resistance, durability and weather resistance, and improved appearance characteristics such as vapor deposition property, gloss property and adhesion property in a non- .

Hereinafter, the thermoplastic resin composition of the present invention will be described in detail.

The present inventors have found that the use of a mixture of two kinds of (meth) acrylic rubber-aromatic vinyl compound-vinyl cyanide copolymer having different grafting ratios enables the deposition of aluminum in the underlayer process while maintaining the inherent properties of the ASA resin such as impact resistance and weather resistance And the appearance properties such as gloss, gloss and adhesion of the deposited surface are improved, and the present invention has been completed on the basis thereof.

In the present description, the graft rate can be calculated by the following equation (2).

&Quot; (2) "

Graft rate (%) = (weight of monomer component grafted to rubber polymer / weight of copolymer) * 100

(A-1) a (meth) acrylic rubber-aromatic vinyl compound-vinyl cyanide copolymer having an average particle size of 500 to 1,500 angstroms having a graft ratio of 32 to 42%; (A-2) a (meth) acrylic rubber polymer-aromatic vinyl compound-vinyl cyanide copolymer having an average particle size of 2,000 to 3,000 ANGSTROM with a graft ratio of 32 to 45%; And B) (alpha-alkylstyrene) -vinyl cyanide copolymer.

For example, the thermoplastic resin composition of the present invention may contain 10 to 25% by weight of the copolymer of the A-1), 10 to 25% by weight of the copolymer of the A-2) and the B) alkylstyrene-vinyl cyanide copolymer 50 To 80% by weight. Within this range, excellent physical properties such as mechanical strength and heat resistance of the final molded product can be obtained, and the vapor deposition property of aluminum or the like is improved during the unpainted step, thereby providing an excellent appearance quality.

In another example, the thermoplastic resin composition of the present invention comprises 10 to 20% by weight of the copolymer of the above A-1), 10 to 20% by weight of the copolymer of the above A-2), and the B) alkylstyrene-vinyl cyanide copolymer And 60 to 80% by weight, and it has an effect of improving the appearance quality after the unpainted process, while being excellent in physical properties such as impact resistance, heat resistance and weather resistance of the final product within the above-mentioned range.

As another example, the thermoplastic resin composition of the present invention may contain 15 to 20% by weight of the copolymer of the above A-1), 10 to 15% by weight of the copolymer of the above A-2) and the above B) alkylstyrene- And 65 to 75% by weight. In addition, it has an excellent balance of physical properties such as impact resistance, heat resistance and weather resistance of the final product within the above-described range, and has an advantage of excellent surface properties of the product after the unpainted process.

Hereinafter, the thermoplastic resin composition of the present invention will be described for each component in the above-described manner.

A) (meth) acrylic rubber-aromatic vinyl compound-vinyl cyan compound copolymer (hereinafter referred to as ASA-based resin)

In the present invention, the ASA resin means a copolymer obtained by grafting an aromatic vinyl compound and a vinyl cyan compound onto a (meth) acrylic rubber polymer.

In the present description, the (meth) acrylic rubber polymer means a methacrylate rubber polymer, an acrylate rubber polymer or a mixture thereof unless otherwise specified.

In the present invention, the (meth) acrylic rubber polymer means a rubber polymer polymerized with at least one selected from a methacrylate compound and an acrylate compound, unless otherwise specified.

The (meth) acrylic rubber polymer may, for example, be one comprising at least one member selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethylhexyl acrylate and derivatives thereof .

In the present description, a derivative means a compound in which a hydrogen atom or an atomic group of the original compound is substituted with another atom or atomic group, for example, a compound substituted with a halogen or an alkyl group.

As used herein, the term "aromatic vinyl compound" refers to an aromatic vinyl compound, unless otherwise specified, an aromatic vinyl compound, such as 1, 2, 3, 4, 5, Or more, and preferably includes styrene.

As used herein, the vinyl cyan compound may be at least one selected from acrylonitrile, methacrylonitrile, and ethacrylonitrile, and preferably includes acrylonitrile, unless otherwise specified.

The thermoplastic resin composition of the present invention comprises two kinds of ASA-based resins having different grafting ratios and average particle diameters. Specifically, A-1) a (meth) acrylic rubber having a graft ratio of 32 to 42% and an average particle diameter of 500 to 1,500 Å A-2) A (meth) acrylic rubber polymer having a graft ratio of 32 to 45% and an average particle size of 2,000 to 3,000 ANGSTROM (hereinafter, referred to as " small-diameter ASA resin ") and an aromatic vinyl compound- -Aromatic vinyl compound-vinyl cyanide copolymer (hereinafter referred to as " large diameter ASA-based resin "). Hereinafter, the small diameter and large diameter ASA resin will be described.

A-1) Small diameter ASA resin

In this specification, the small-diameter ASA resin is a copolymer obtained by grafting an aromatic vinyl compound and a vinyl cyan compound onto a (meth) acrylic rubber polymer having an average particle diameter of 500 to 1,500 angstroms.

The small diameter ASA resin may include 35 to 65% by weight of a (meth) acrylic rubber having an average particle diameter of 500 to 1,500 angstroms, 20 to 40% by weight of an aromatic vinyl compound and 5 to 25% by weight of a vinyl cyan compound, And excellent physical properties such as impact resistance and heat resistance of the final product.

In another example, the small diameter ASA resin may include 45 to 55% by weight of a (meth) acrylic rubber having an average particle diameter of 500 to 1,500 angstroms, 30 to 40% by weight of an aromatic vinyl compound and 10 to 15% by weight of a vinyl cyan compound Within this range, there is an effect of excellent physical properties such as impact resistance, heat resistance and weather resistance of the final product.

The (meth) acrylic rubber contained in the small-diameter ASA resin may have an average particle size of 500 to 1,500 Å and 700 to 1,500 Å, for example, and most preferably 800 to 1,200 Å. The mechanical strength such as the impact strength of the final product is excellent within the above-mentioned range.

The small diameter ASA resin may preferably have a graft rate of 32 to 42%, 34 to 40%, 32 to 37%, or 35 to 39%, and within this range, the inherent mechanical strength, heat resistance , Weather resistance and the like are not deteriorated, and appearance characteristics such as vapor deposition property and gloss property can be improved in a non-coating process.

As a specific example, the small diameter ASA resin may be a butylacrylate rubber-styrene-acrylonitrile copolymer having an average particle size of 500 to 1,500 angstroms having a graft ratio of 32 to 42%, but is not limited thereto.

A-2) Large diameter ASA resin

In the present invention, the large diameter ASA resin is a copolymer obtained by grafting an aromatic vinyl compound and a vinyl cyan compound onto a (meth) acrylic rubber polymer having an average particle diameter of 2,000 to 3,000 angstroms.

The large diameter ASA resin may include, for example, 30 to 60 wt% of a (meth) acrylic rubber polymer having an average particle diameter of 2,000 to 3,000 ANGSTROM, 30 to 50 wt% of an aromatic vinyl compound and 10 to 25 wt% of a vinyl cyan compound, In this case, there is an effect of excellent physical properties such as impact resistance, workability and gloss.

As another example, the large diameter ASA resin may include 30 to 50% by weight of a (meth) acrylic rubber polymer having an average particle diameter of 2,000 to 3,000 ANGSTROM, 40 to 50% by weight of an aromatic vinyl compound and 13 to 20% by weight of a vinyl cyan compound And has excellent properties such as impact resistance and weather resistance within the above-mentioned range.

The (meth) acrylic rubber polymer contained in the large diameter ASA resin may have an average particle size of, for example, from 2,000 to 3,000 or from 2,200 to 3,000, and most preferably from 2,300 to 2,700. Within this range, there is an excellent effect of impact resistance, weather resistance, heat resistance, coloring property and the like of the final product.

The large-diameter ASA-based resin may preferably have a graft rate of 32 to 45%, 35 to 45%, or 35 to 40%, and within this range, physical properties such as mechanical strength, heat resistance and weather resistance inherent to the ASA- And the deposition characteristics such as adhesion and luster can be improved in the unpatterned process.

As a specific example, the large diameter ASA resin may be but is not limited to a butyl acrylate rubber-styrene-acrylonitrile copolymer having an average particle size of 2,000 to 3,000 ANGSTROM having a graft ratio of 32 to 45%.

The weight ratio of the A-1) small-diameter ASA resin to the A-2) large diameter ASA resin in the present invention may be preferably from 1: 0.5 to 1: 1, more preferably from 1: 0.5 to 1: 0.8 will be. When a small-diameter ASA-based resin and a large-diameter ASA-based resin are mixed in the above-mentioned range, the properties such as impact resistance, heat resistance and weather resistance inherent to the ASA-based resin are not deteriorated, Adhesion, and glossiness of the vapor deposition surface are improved.

B) (alpha-alkyl styrene) -vinyl cyanide copolymer

The (alpha-alkylstyrene) -vinyl cyanide copolymer may include, for example, 50 to 80% by weight of an alpha-alkylstyrene and 20 to 50% by weight of a vinyl cyanide compound. Within this range, , Weather resistance and the like are not deteriorated, and heat resistance and workability are excellent.

In another example, the (alpha-alkylstyrene) -vinyl cyanide copolymer may comprise from 65 to 75% by weight of an alpha-alkylstyrene and from 25 to 35% by weight of a vinyl cyanide compound, wherein the impact resistance, weather resistance, , Processability, and the like.

In the present description, the alpha-alkylstyrene may be at least one selected from alpha-methylstyrene and alpha-ethylstyrene, preferably alpha-methylstyrene.

The vinyl cyan compound of the (alpha-alkylstyrene) -vinyl cyan compound copolymer may be the same as the vinyl cyan compound contained in the ASA-based resin.

As a specific example, the (alpha-alkylstyrene) -vinyl cyanide copolymer may be (alpha-methylstyrene) -acrylonitrile copolymer but is not limited thereto.

The (alpha-alkylstyrene) -vinyl cyanide copolymer may have a glass transition temperature of 115 ° C or higher, 115-140 ° C or 120-125 ° C, for example. Within this range, thermal strain There is an advantage that the heat resistance of the final molded product is excellent because of high temperature.

In the present specification, the glass transition temperature can be measured by differential scanning calorimetry (DSC).

The (alpha-alkylstyrene) -vinyl cyanide copolymer may preferably have a weight average molecular weight of 90,000 to 150,000 g / mol or 90,000 to 120,000 g / mol, for example. In this category, the heat resistance , And workability.

In the present invention, the weight average molecular weight can be measured by gel permeation chromatography after the sample is dissolved in a solvent (for example, THF) and pretreated.

C) Additive

The thermoplastic resin composition of the present invention may optionally further include additives known in the art.

The additive may be at least one selected from, for example, an antioxidant, an antistatic agent, a release agent, and a colorant, but is not limited thereto.

The lubricant may be at least one selected from ethylene bis stearamide, oxidized polyethylene wax, and magnesium stearate, but is not limited thereto.

Examples of the antioxidant include, but are not limited to, a phenol-based antioxidant, a phosphorus-based antioxidant, and the like.

As the antistatic agent, for example, one or more of an anionic surfactant and a nonionic surfactant may be used, but the present invention is not limited thereto.

The releasing agent may be at least one selected from, for example, glycerin stearate, polyethylene tetrastaurate, and the like.

The colorant may be, for example, an organic pigment, an inorganic pigment, or a mixture thereof.

The additive may be used in an amount of 0.1 to 5 parts by weight or 0.5 to 2 parts by weight per 100 parts by weight of the total of the A-1) copolymer, the A-2) copolymer and the B) The physical properties such as mechanical strength, heat resistance and weather resistance are not lowered, and the effect of additives can be exhibited.

Furthermore, the thermoplastic resin composition of the present invention can be characterized by not containing a maleimide compound capable of improving heat resistance. Even when the maleimide compound is not included, the thermal resistance of the final resin composition and the injection molded article Has excellent heat resistance characteristics at a temperature of 100 ° C or higher and is excellent in appearance quality such as vapor deposition property, adhesion property and gloss property in a non-coating deposition process.

When the maleimide compound is included in the thermoplastic resin composition, the heat resistance of the finished product can be improved, but the surface light reflectance of the molded article on which aluminum is deposited may be undesirable.

In the present description, the maleimide-based compound is at least one compound selected from the group consisting of N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide. Or more of the polymer.

Examples of the polymer containing the maleimide compound include a maleimide compound-aromatic vinyl compound copolymer, a maleimide compound-aromatic vinyl compound-vinyl cyan compound copolymer, a maleimide compound-aromatic vinyl compound-maleic anhydride copolymer But are not limited thereto.

Hereinafter, the method for producing the thermoplastic resin composition of the present invention will be described.

(A-1) 10 to 25% by weight of a (meth) acrylic rubber-aromatic vinyl compound-vinyl cyanide copolymer having an average particle diameter of 500 to 1,500 angstroms having a graft ratio of 32 to 42%; A-2) 10 to 25% by weight of a (meth) acrylic rubber-aromatic vinyl compound-vinyl cyanide copolymer having an average particle size of 2,000 to 3,000 ANGSTROM with a graft rate of 32 to 45%; And 50 to 80% by weight of B) (alpha-alkylstyrene) -vinyl cyan compound copolymer; and extruding the kneaded product.

Examples of the A-1) copolymer and the A-2) copolymer include a monomer mixture containing a (meth) acrylic rubber polymer, an aromatic vinyl compound and a vinyl cyan compound in the presence of an emulsifier, an initiator, a graft, Can be prepared by emulsion polymerization.

Examples of the emulsifying agent include carboxylic acid metal salts such as fatty acid metal salts and rosin acid metal salts having 12 to 20 carbon atoms and may be used in an amount of 1 to 3 parts by weight based on 100 parts by weight of the monomer mixture.

The initiator may be selected from the group consisting of cumene hydroperoxide, diisopropylbenzene hydroperoxide, azobisisobutyronitrile, tertiary butyl hydroperoxide, para-methane hydroperoxide, benzoyl peroxide, potassium persulfate, Sodium sulfate, ammonium persulfate, and 0.05 to 0.3 parts by weight based on 100 parts by weight of the monomer mixture.

The grafting agent may be aryl methacrylate, triaryl isocyanurate, triarylamine or diarylamine unless otherwise specified, and may be used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the monomer mixture.

Unless otherwise specified, the molecular weight modifier may be selected from t-dodecylmercaptan, n-tetradecylmercaptan, n-octylmercaptan, sec-octylmercaptan, n-nonylmercaptan, n-decylmercaptan, And mercaptans such as n-octadecylmercaptan can be used, and 0.02 to 0.2 parts by weight based on 100 parts by weight of the monomer mixture can be used.

The (meth) acrylic rubber polymer contained in the A-1) copolymer and the A-2) copolymer is prepared by mixing and emulsifying a (meth) acrylate compound, an emulsifier, an initiator, a crosslinking agent and an electrolyte And the average particle diameter of the (meth) acrylic rubber polymer finally produced can be controlled by varying the amount of reactants used. (In this connection, it will be described in detail in the following production example).

Examples of the emulsifier used in the production of the (meth) acrylic rubber polymer include a rosin acid salt, a fatty acid salt, sodium lauryl sulfonate, sodium alkylbenzene sulfonate, sodium dodecyl allyl sulfosuccinate, Alkenyl succinic acid salts and the like can be used.

The electrolyte may be, for example, KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , Na ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ and Na ₂ HPO ₄ .

Examples of the crosslinking agent include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neo At least one selected from the group consisting of trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate and trimethylolmethane triacrylate.

Also, the B) (alpha-alkylstyrene) -vinyl cyanide copolymer may be prepared by emulsion polymerization including an alpha-alkylstyrene, a vinyl cyanide compound, an emulsifier, an electrolyte, a molecular weight modifier, and an initiator.

Further, at least one additive selected from the group consisting of a lubricant, an antioxidant, an antistatic agent, a releasing agent, and a coloring agent may be further added as an additive known in the art at the time of kneading.

The kneading and extruding can be carried out under the conditions of 100 to 800 rpm or 120 to 750 rpm and 200 to 300 ° C or 220 to 270 ° C, and the processability and moldability are excellent within the range.

In describing the thermoplastic resin composition of the present invention, other reactants such as polymerized water, oxidation-reduction catalyst, and other reaction conditions not specifically specified are not particularly limited when they are within the range usually practiced in the art, .

Further, the thermoplastic resin composition of the present invention may be manufactured as an injection molded product through an injection process, and the injection may be performed at a temperature of 200 to 300 ° C or 220 to 270 ° C, for example.

The injection-molded article according to the present invention has excellent properties such as heat resistance, impact resistance and weather resistance, and is excellent in vapor deposition property, adhesion property, surface gloss property, and the like when it is vapor-deposited during aluminum-free process.

For example, the injection-molded article of the present invention can be used for a car-mounted lamp housing, a rear garnish, and other parts requiring high aluminum vapor deposition.

The injection-molded product has an excellent reflectance and excellent appearance characteristics on the evaporated surface after the aluminum deposition because the diffuse reflectance is 4 or less, 3.1 or less, 2.8 or less or 2.5 or less.

In the present description, the diffuse reflectance can be measured, for example, according to ASTM D2805.

In addition, the injection-molded product has an advantage that the difference in the diffuse reflectance calculated by the following formula (1) after aluminum deposition is 1 or less, 0.5 or less or 0.3 or less, and the stability of the deposition surface is excellent.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

The materials used in the following examples and comparative examples are as follows.

A-1) Small diameter ASA resin

1) Manufacture of small diameter acrylic rubber polymer

10 wt% of butyl acrylate, 1.5 wt% of di-2-ethylhexyl sulfosuccinate sodium salt, 0.02 wt% of ethylene glycol dimethacrylate, 0.1 wt% of sodium hydrogencarbonate (NaHCO ₃ ) 0.04% by weight of sulfuric acid, and water, and the reaction temperature was raised to 70 캜, followed by reaction for 1 hour to prepare a polymer seed (sead). To the mixture, a mixture of 30 wt% of butyl acrylate, 0.5 wt% of di-2-ethylhexylsulfosuccinate sodium salt, 0.1 wt% of sodium hydrogencarbonate, and water and 0.06 wt% of potassium persulfate Followed by polymerization for 3 hours at 70 캜 for 3 hours to prepare a small-diameter acrylic rubber polymer having an average particle diameter of 800 to 1,000 Å.

2) Manufacture of small diameter ASA resin

To 100 parts by weight of a reaction mixture prepared by mixing 40% by weight of a small-diameter acrylic rubber polymer having an average particle size of 800 to 1,000 Å, 40% by weight of styrene and 20% by weight of acrylonitrile, 63 parts by weight of distilled water, , 0.042 part by weight of potassium hydroxide, and 0.05 part by weight of tertiary dodecyl mercaptan (TDDM) and 0.1 part by weight of potassium persulfate as a polymerization initiator were continuously added to the mixture at 70 DEG C for 5 hours, After further reaction at 80 DEG C for 1 hour in order to increase polymerization conversion rate, it was cooled to 60 DEG C to prepare an ASA resin containing a small-diameter acrylic rubber polymer. The ASA resin thus prepared had an average particle diameter of 1,200 Å, a polymerization conversion of 98%, a pH of 9.5, and a grafting rate of 40%.

The ASA resin latex prepared as described above was agglomerated at 85 ° C under atmospheric pressure using an aqueous calcium chloride solution, aged at 95 ° C for dehydration and washing, and then dried with hot air at 90 ° C for 30 minutes to finally contain 1,500 ppm of CaCl 2 A small diameter ASA resin powder was obtained.

A'-1) Small diameter ASA resin

1) Manufacture of small diameter acrylic rubber polymer

10 wt% of butyl acrylate, 1.5 wt% of di-2-ethylhexyl sulfosuccinate sodium salt, 0.02 wt% of ethylene glycol dimethacrylate, 0.1 wt% of sodium hydrogencarbonate (NaHCO ₃ ) 0.04% by weight of sulfuric acid, and water, and the reaction temperature was raised to 65 캜, followed by reaction for 1 hour to prepare a polymer seed (sead). To the mixture, a mixture of 30 wt% of butyl acrylate, 0.5 wt% of di-2-ethylhexylsulfosuccinate sodium salt, 0.1 wt% of sodium hydrogencarbonate, and water and 0.06 wt% of potassium persulfate Followed by polymerization for 3 hours at 70 캜 for 3 hours to polymerize the acrylic rubber of small diameter having an average particle diameter of 700 to 800 Å

2) Manufacture of small diameter ASA resin

To 100 parts by weight of the reaction mixture prepared by mixing 40% by weight of small-diameter acrylic rubber polymer having an average particle diameter of 700 to 800 Å, 40% by weight of styrene and 20% by weight of acrylonitrile, 63 parts by weight of distilled water, , 0.042 part by weight of potassium hydroxide, and 0.05 part by weight of tertiary dodecyl mercaptan (TDDM) and 0.1 part by weight of potassium persulfate as a polymerization initiator were continuously added to the mixture at 70 DEG C for 5 hours, After further reaction at 70 DEG C for 1 hour in order to increase polymerization conversion, the resin was cooled to 60 DEG C to prepare an ASA resin containing a small-diameter acrylic rubber polymer. The ASA resin thus prepared had an average particle diameter of 1,000 Å, a polymerization conversion of 96%, a pH of 9.5, and a grafting rate of 30%.

The ASA resin latex prepared as described above was agglomerated at 85 ° C under atmospheric pressure using an aqueous calcium chloride solution and aged at 95 ° C for dehydration and washing and then dried with hot air at 90 ° C for 30 minutes to finally obtain 1,500 ppm of CaCl ₂ A small diameter ASA resin powder was obtained.

A-2) Large diameter ASA resin

25 parts by weight of a styrene-styrene polymer, 40 parts by weight of a core-butyl acrylate rubber, and 35 parts by weight of a styrene-acrylonitrile polymer as a shell, the butyl acrylate rubber having an average particle diameter of 2,500 angstroms, And a graft rate of 35% was used.

A'-2) large diameter ASA resin

10 parts by weight of a styrene-styrene polymer, 55 parts by weight of a core-butyl acrylate rubber, and 35 parts by weight of a styrene-acrylonitrile polymer as a shell. The rubber had an average particle diameter of 2500 Å and a graft rate of 28%.

B) alpha methyl styrene-acrylonitrile copolymer

98 UHM of LG Chem, having a weight average molecular weight of 100,000 g / mol, as a copolymer consisting of 73% by weight of alpha methylstyrene and 27% by weight of acrylonitrile was used without purification.

D) N-phenylmaleimide-based SAN resin

DENKA IP MS-NB from Denki Kagaku was used.

E) styrene-acrylonitrile copolymer

A 92HR copolymer of LG Chem, having a weight average molecular weight of 130,000 g / mol, as a copolymer consisting of 73% by weight of styrene and 27% by weight of acrylonitrile was used without purification.

[Example]

Examples 1 to 4 and Comparative Examples 1 to 4

The components and contents in the following Table 1 were mixed and extruded at 250 DEG C and 200 rpm using a twin-screw extruder to prepare a resin composition in the form of a pellet.

The resin composition in the form of pellets was injected (250 DEG C) to prepare specimens for measurement of physical properties.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 A-1 15 20 20 15 A'-1 - - - - 15 15 20 20 A-2 15 10 15 10 - - - - A'-2 - - - - 15 15 10 15 B 70 70 65 75 70 20 20 20 D - - - - - 20 20 20 E - - - - - 30 30 25

(Parts by weight based on 100 parts by weight of (A-1 or A'-1) + (A-2 or A'-2) + (B)

[Test Example]

The properties of the specimens prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 2 below.

1) Izod Impact Strength (IMP, kgfcm / cm): A notch was measured on a specimen of 3.2 mm thickness according to ASTM D256.

2) Heat deformation temperature (HDT, 占 폚): Measured by applying a surface pressure of 1.8 MPa according to ASTM D648.

3) Diffuse Reflectance: The aluminum was deposited on the surface of the specimen in a lab vacuum evaporator, and the diffuse reflectance was measured using a reflectometer according to ASTM D2805. The lower the value, the better the appearance quality.

In order to evaluate the thermal stability of the deposition surface, the specimen was held at 250 ° C for 10 minutes in an extruder and the diffuse reflectance was measured. In addition, the aluminum-deposited specimen was aged in an oven at 100 ° C for 24 hours, and the diffuse reflectance was measured and the difference in diffuse reflectance before and after aging was calculated.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 IMP (kgfcm / cm) 8 7 9 6 8 5 4 6 HDT (° C) 103 103 101 105 100 103 103 102 Diffuse reflectance After deposition 3.1 2.8 3.0 2.5 4.5 6.5 6.2 6.4 Deposition - after injection residence 3.5 3.0 3.3 2.9 6.2 8.5 8.5 8.7 Difference before and after aging 0.2 0.3 0.5 0.2 1.2 1.5 1.2 1.1

As shown in Table 2, Examples 1 to 4 made of the thermoplastic resin composition according to the present invention had impact strength and heat distortion temperature that were equivalent or superior to Comparative Examples not according to the present invention, I could confirm.

In particular, it was confirmed that the thermoplastic resin composition according to the present invention had thermal deformation temperatures similar to those of Comparative Examples 2 to 4 including no maleimide compound.

In addition, it was confirmed that the specimens of Examples 1 to 4 according to the present invention had excellent diffuse reflectance after deposition, but did not significantly deteriorate the deposition characteristics after being left at high temperature.

On the other hand, the specimens of Comparative Examples 1 to 4, which were not in accordance with the present invention, had poor reflectivity of the specimen after the aluminum deposition, and the deposition characteristics were significantly lowered after the deposition specimen was left under the same conditions as in Example.

Particularly, in the case of Comparative Examples 2 to 4 including the N-phenylmaleimide-based copolymer improving the heat resistance property, it was confirmed that the deposition characteristics were even worse.

Claims (16)

(A-1) a (meth) acrylic rubber-aromatic vinyl compound-vinyl cyanide copolymer having an average particle size of 500 to 1,500 ANGSTROM with a graft ratio of 32 to 42%;
(A-2) a (meth) acrylic rubber-aromatic vinyl compound-vinyl cyanide copolymer having an average particle size of 2,000 to 3,000 ANGSTROM with a graft ratio of 32 to 45%; And
B) (alpha-alkylstyrene) -vinyl cyanide copolymer;
Thermoplastic resin composition. The method according to claim 1,
10 to 25% by weight of a copolymer of the A-1), 10 to 25% by weight of a copolymer of the A-2) and 50 to 80% by weight of the B) (alpha-alkylstyrene) Characterized in that
Thermoplastic resin composition. The method according to claim 1,
The copolymer of the above A-1) comprises 35 to 65% by weight of a (meth) acrylic rubber polymer having an average particle diameter of 500 to 1,500 angstroms, 20 to 40% by weight of an aromatic vinyl compound and 5 to 25% by weight of a vinyl cyan compound To
Thermoplastic resin composition. The method according to claim 1,
(A-2) comprises 30 to 60% by weight of a (meth) acrylic rubber polymer having an average particle size of 2,000 to 3,000 ANGSTROM, 30 to 50% by weight of an aromatic vinyl compound and 10 to 25% by weight of a vinyl cyan compound To
Thermoplastic resin composition. The method according to claim 1,
Wherein the weight ratio of the copolymer of A-1) to the copolymer of A-2) is from 1: 0.5 to 1: 1
Thermoplastic resin composition. The method according to claim 1,
The (B) (alpha-alkylstyrene) -vinyl cyanide copolymer has a glass transition temperature of 115 ° C or higher
Thermoplastic resin composition. The method according to claim 1,
The (B) (alpha-alkylstyrene) -vinyl cyan compound copolymer has a weight average molecular weight of 90,000 to 150,000 g / mol
Thermoplastic resin composition. The method according to claim 1,
Wherein said B) (alpha-alkylstyrene) -vinyl cyanide copolymer comprises 50 to 80% by weight of alpha-alkylstyrene and 20 to 50% by weight of vinyl cyanide
Thermoplastic resin composition. 9. The method of claim 8,
Wherein the alpha-alkylstyrene is at least one selected from alpha-methylstyrene and alpha-ethylstyrene.
Thermoplastic resin composition. The method according to claim 1,
Wherein the thermoplastic resin composition further comprises at least one additive selected from the group consisting of a lubricant, an antioxidant, an antistatic agent, a releasing agent and a coloring agent
Thermoplastic resin composition. The method according to claim 1,
Wherein the thermoplastic resin composition does not contain a maleimide compound
Thermoplastic resin composition. A-1) 10 to 25% by weight of a (meth) acrylic rubber-aromatic vinyl compound-vinyl cyanide copolymer having an average particle size of 500 to 1,500 angstroms having a graft rate of 32 to 42%; A-2) 10 to 25% by weight of a (meth) acrylic rubber-aromatic vinyl compound-vinyl cyanide copolymer having an average particle size of 2,000 to 3,000 ANGSTROM with a graft rate of 32 to 45%; And (B) 50 to 80% by weight of an (alpha-alkylstyrene) -vinyl cyan compound copolymer; and then extruding the kneaded mixture
A method for producing a thermoplastic resin composition. A thermoplastic resin composition which is produced by injecting the thermoplastic resin composition according to any one of claims 1 to 11
Injection molded article. 14. The method of claim 13,
Wherein the injection molded article has a diffuse reflectance measured according to ASTM D2805 after aluminum deposition of 4 or less
Injection molded article. 14. The method of claim 13,
The injection-molded article is characterized in that, after aluminum deposition, the diffuse reflectance difference calculated by the following formula (1) is 1 or less
Injection molded article.
[Equation 1]
Diffuse reflectance difference = R ₁ - R ₀
(Where R ₀ is the initial diffuse reflectance of the aluminum-deposited molded article, and R ₁ is the diffuse reflectance measured after the aluminum-deposited molded article is left at 100 ° C. for 24 hours). 14. The method of claim 13,
Characterized in that the molded article is an automotive lamp housing or a rear garnish
Injection molded article.