KR102718359B1 - Thermoplastic resin composition, method for preparing the same and article prepared therefrom - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article produced therefrom, and more specifically, to a thermoplastic resin composition comprising: (A) 35 to 65 wt% of an acrylate-aromatic vinyl compound-vinyl cyanate graft copolymer including an acrylate rubber having an average particle diameter of 50 to 200 nm, (B) 1 to 25 wt% of a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanate compound copolymer, (C) 10 to 35 wt% of a (meth)acrylic acid alkyl ester polymer, and (D) 1 to 30 wt% of an α-methyl styrene-based compound-vinyl cyanate copolymer; 100 parts by weight of a base resin; And (E) 0.2 to 1.0 parts by weight of a flow mark improver; and when coextruded with PVC under the condition of an output amount of 11 kg/hr at 200°C with a coextruder to produce a sheet having a thickness of 0.15 mm, the processability (P/T) measured in terms of melt pressure (P) and torque (T) is 290/30 or higher, a method for producing the same, and a molded article produced therefrom.
According to the present invention, there is provided a thermoplastic resin composition having excellent impact strength, fluidity and gloss while maintaining other mechanical properties at an equivalent level compared to a conventional ASA resin composition, and improved surface properties during coextrusion, a method for producing the same, and a molded article produced therefrom.

Description

Thermoplastic resin composition, method for preparing the same and molded article prepared therefrom {THERMOPLASTIC RESIN COMPOSITION, METHOD FOR PREPARING THE SAME AND ARTICLE PREPARED THEREFROM}

The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article produced therefrom, and more specifically, to a thermoplastic resin composition having excellent impact strength, fluidity, and gloss while maintaining other mechanical properties at an equivalent level compared to a conventional ASA resin composition, and having improved surface properties during coextrusion, a method for producing the same, and a molded article produced therefrom.

Polyvinyl chloride (hereinafter referred to as 'PVC resin') is a general-purpose resin that is inexpensive and has flame retardancy, chemical resistance, and easy controllability of product hardness, and is used as exterior building materials, especially window profiles (hereinafter referred to as 'W/P'), but has problems such as poor weather resistance and colorability, so when PVC resin is applied to exterior building materials, it is painted or laminated with a resin film that has excellent weather resistance.

Recently, as the demand for high weather resistance, high gloss and color W/P increases, the W/P coextruded with t-polymethyl methacrylate resin (hereinafter referred to as 't-PMMA resin') with PVC resin is on the rise. t-PMMA resin is a resin compounded with a polymer in which methyl methacrylate is used as a shell on an acrylic rubber core to improve the low brittleness of polymethyl methacrylate resin (hereinafter referred to as 'PMMA resin') and polymethyl methacrylate resin. Although t-PMMA resin has slightly increased impact strength compared to PMMA resin, it is still insufficient, and has problems such as low gloss, tensile strength, scratch resistance and hardness. t-PMMA resin is a material with excellent transparency, so the impact strength must be improved without damaging it, and therefore it is not easy to improve the impact strength.

Therefore, there is a demand for the development of a coextruded material for building materials that replaces t-PMMA resin and improves impact strength while securing colorability. If the impact strength is improved compared to t-PMMA resin, it can be used in cold regions, which has the advantage of expanding the range of applications.

In response to these demands, efforts are being made to coextrude with acrylate-styrene-acrylonitrile resin (hereinafter referred to as 'ASA resin'). ASA resin has excellent weather resistance, chemical resistance, and heat stability, and is used in a variety of fields, such as electrical and electronic components, construction materials, sports equipment, and automobile parts.

However, when coextruding ASA resin with PVC resin, the impact resistance is improved, but the gloss, weather resistance, and colorability are insufficient compared to t-PMMA resin, and die lines or snake skin occur on the surface, resulting in unsatisfactory surface characteristics.

Therefore, there is a need to develop an ASA resin composition that has excellent impact resistance, excellent processability and gloss when coextruded with PVC, and can improve surface properties by minimizing the occurrence of die lines, etc.

Korean Publication Patent No. 2011-0078044

In order to solve the problems of the prior art as described above, the present invention aims to provide a thermoplastic resin composition having excellent impact strength, fluidity and gloss while maintaining other mechanical properties at an equivalent level compared to a conventional ASA resin composition, and improved surface properties during coextrusion, a method for producing the same, and a molded article produced therefrom.

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

In order to achieve the above object, the present invention provides 100 parts by weight of a base resin comprising (A) 35 to 65 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 50 to 200 nm, (B) 1 to 25 wt% of a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer, (C) 10 to 35 wt% of a (meth)acrylic acid alkyl ester polymer, and (D) 1 to 30 wt% of an α-methyl styrene compound-vinyl cyan compound copolymer. And (E) 0.2 to 1.0 parts by weight of a flow mark improver; and when coextruded with PVC under conditions of a discharge amount of 11 kg/hr at 200°C with a coextruder to produce a sheet having a thickness of 0.15 mm, the thermoplastic resin composition is characterized in that the processability (P/T) measured in terms of melt pressure (P) and torque (T) is 290/30 or higher.

In addition, the present invention can provide a thermoplastic resin composition including (A) 35 to 65 wt% of an acrylate-aromatic vinyl compound-vinyl cyanate graft copolymer including an acrylate rubber having an average particle diameter of 50 to 200 nm, (B) 1 to 25 wt% of a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanate compound copolymer, (C) 10 to 35 wt% of a (meth)acrylic acid alkyl ester polymer, and (D) 1 to 30 wt% of an α-methyl styrene-based compound-vinyl cyanate copolymer; and (E) 0.2 to 1.0 wt% of a flow mark improver; and characterized in that the thermoplastic resin composition has a gloss of 55 or more as measured at 60° according to ASTM D2457.

In addition, the present invention provides 100 parts by weight of a base resin comprising (A) 35 to 65 wt% of an acrylate-aromatic vinyl compound-vinyl cyanate graft copolymer comprising an acrylate rubber having an average particle diameter of 50 to 200 nm, (B) 1 to 25 wt% of a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanate compound copolymer, (C) 10 to 35 wt% of a (meth)acrylic acid alkyl ester polymer, and (D) 1 to 30 wt% of an α-methyl styrene compound-vinyl cyanate copolymer; And (E) 0.2 to 1.0 weight part of a flow mark improver; and a thermoplastic resin composition characterized in that the flow index measured at 190°C/10 kg according to ASTM D1238 is 0.65 g/10 min or more, and the flow index measured under 220°C/10 kg conditions is 5.0 g/10 min or more.

In addition, the present invention can provide a thermoplastic resin composition characterized by including: 100 parts by weight of a base resin including (A) 35 to 65 wt% of an acrylate-aromatic vinyl compound-vinyl cyanate graft copolymer including an acrylate rubber having an average particle diameter of 50 to 200 nm, (B) 1 to 25 wt% of a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanate compound copolymer, (C) 10 to 35 wt% of a (meth)acrylic acid alkyl ester polymer, and (D) 1 to 30 wt% of an α-methyl styrene-based compound-vinyl cyanate copolymer; and (E) 0.2 to 1.0 wt% of a flow mark improver.

In addition, the present invention provides a step of producing a thermoplastic resin composition pellet by mixing and extruding (A) 35 to 65 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an acrylate rubber having an average particle diameter of 50 to 200 nm, (B) 1 to 25 wt% of a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer, (C) 10 to 35 wt% of a (meth)acrylic acid alkyl ester polymer, and (D) 1 to 30 wt% of an α-methyl styrene compound-vinyl cyan compound copolymer, 100 parts by weight of a base resin; and (E) 0.2 to 1.0 parts by weight of a flow mark improver under conditions of 200 to 330° C. and 200 to 300 rpm. And the thermoplastic resin composition is coextruded with PVC under conditions of a coextruder at 200°C and an output of 11 kg/hr to produce a sheet having a thickness of 0.15 mm, and the processability (P/T) measured in terms of melt pressure (P) and torque (T) is characterized in that the composition has a processability of 290/30 or higher.

In addition, the present invention provides a molded product characterized by including the thermoplastic resin composition.

In addition, the present invention provides a step of producing thermoplastic resin composition pellets by mixing and extruding (i) 100 parts by weight of a base resin including (A) 35 to 65 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 50 to 200 nm, (B) 1 to 25 wt% of a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer, (C) 10 to 35 wt% of a (meth)acrylic acid alkyl ester polymer, and (D) 1 to 30 wt% of an α-methyl styrene-based compound-vinyl cyan compound copolymer; and (E) 0.2 to 1.0 part by weight of a flow mark improver under conditions of 200 to 330° C. and 200 to 300 rpm. And (ii) a step of co-extruding the thermoplastic resin composition pellets with a polyvinyl chloride resin; the present invention provides a method for manufacturing a molded product.

According to the present invention, compared to conventional ASA resin compositions, while maintaining other mechanical properties at an equivalent level, the impact strength, hardness, fluidity and glossiness are all excellent, and flow marks, die lines and snake skins, etc. do not occur on the surface during coextrusion, thereby improving surface properties, thereby providing a thermoplastic resin composition that can be applied with high quality in fields requiring high impact resistance, glossiness and surface quality, such as building exterior materials, a method for producing the same and a molded article produced therefrom.

Figure 1 is a photograph of the coextrusion specimens manufactured from Example 3, Comparative Example 1, and Comparative Example 4, in which the occurrence of flow marks and snake skins is observed on the surface, and the occurrence of snake skins is observed under an optical microscope at a magnification of 25 times.

Hereinafter, the thermoplastic resin composition of the present invention, its manufacturing method, and the molded product manufactured therefrom are described in detail.

The present inventors, in order to improve the impact resistance, gloss, processability and surface properties of an ASA resin coextruded with a PVC resin, have confirmed the effect of improving the surface properties by adding a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanate copolymer, a (meth)acrylic acid alkyl ester polymer, an α-methyl styrene compound-vinyl cyanate copolymer and polyvinylidene fluoride within a predetermined range to an acrylate-aromatic vinyl compound-vinyl cyanate graft copolymer having a predetermined average particle diameter and controlling the processability within a predetermined range, thereby improving the impact resistance and gloss while preventing the formation of die lines, etc., on the surface during coextrusion, and based on this, have devoted themselves to further research and completed the present invention.

The thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin comprising (A) 35 to 65 wt% of an acrylate-aromatic vinyl compound-vinyl cyanate graft copolymer including an acrylate rubber having an average particle diameter of 50 to 200 nm, (B) 1 to 25 wt% of a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanate compound copolymer, (C) 10 to 35 wt% of a (meth)acrylic acid alkyl ester polymer, and (D) 1 to 30 wt% of an α-methyl styrene-based compound-vinyl cyanate copolymer; And (E) 0.2 to 1.0 parts by weight of a flow mark improver; and when coextruded with PVC under the conditions of a discharge amount of 11 kg/hr at 200°C with a coextruder to produce a sheet having a thickness of 0.15 mm, the processability (P/T) measured in terms of melt pressure (P) and torque (T) is 290/30 or higher. In this case, compared to a conventional ASA resin composition, other mechanical properties are maintained at an equivalent level, while impact strength, hardness, fluidity, gloss, and surface characteristics are all excellent, so that the surface quality is improved.

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

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

The acrylate rubber of the above graft copolymer has, for example, an average particle diameter of 50 to 200 nm, preferably 70 to 180 nm, more preferably 100 to 150 nm, and within this range, it can impart excellent weather resistance, colorability, glossiness, impact strength, and surface properties to the final thermoplastic resin composition.

In this article The average particle size can be measured using the dynamic light scattering method, and more specifically, it can be measured as an intensity value in Gaussian mode using Nicomp 380 HPL equipment.

In addition, the average particle diameter of this description may mean the arithmetic average particle diameter in the particle size distribution measured by the dynamic light scattering method, i.e., the average particle diameter of the scattering intensity (Intensity Distribution).

The above (A) graft copolymer is, for example, 35 to 65 wt%, preferably 40 to 60 wt%, more preferably 45 to 55 wt%, and within this range, other mechanical properties compared to a conventional ASA resin composition are maintained at an equivalent level, while impact strength, fluidity, and gloss are all excellent, and surface properties are improved during coextrusion.

The above (A) graft copolymer comprises, for example, 40 to 70 wt% of an acrylate rubber, 20 to 50 wt% of an aromatic vinyl compound, and 1 to 25 wt% of a vinyl cyan compound, and within this range, has excellent mechanical properties such as impact resistance, as well as excellent gloss, weather resistance, and colorability.

As a preferred example, the (A) graft copolymer can be formed by including 50 to 60 wt% of an acrylate rubber, 30 to 40 wt% of an aromatic vinyl compound, and 7 to 17 wt% of a vinyl cyan compound, and within this range, it has excellent mechanical properties such as impact resistance, while also having excellent gloss, weather resistance, and colorability.

In this description, a polymer comprising a compound means a polymer polymerized including the compound, and the units in the polymerized polymer are derived from the compound.

The above (A) graft copolymer can be produced by, for example, emulsion polymerization, in which case it has excellent impact resistance, chemical resistance, weather resistance, and colorability.

The above emulsion polymerization is not particularly limited if it is performed using an emulsion graft polymerization method commonly practiced in the technical field to which the present invention belongs.

The acrylate of the present invention may be, for example, at least one selected from the group consisting of alkyl acrylates having 2 to 8 carbon atoms in the alkyl group, preferably alkyl acrylates having 4 to 8 carbon atoms in the alkyl group, and more preferably butylacrylate or ethylhexyl acrylate.

The aromatic vinyl compound of the present invention may be, for example, at least one selected from the group consisting of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-tert-butylstyrene, and is preferably styrene.

The vinyl cyanide compound of the present invention may be, for example, at least one selected from the group consisting of acrylonitrile, metanitrile, ethylacrylonitrile, and isopropylacrylonitrile, and is preferably acrylonitrile.

(B) (Meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer

The above (B) (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer is, for example, 1 to 25 wt%, preferably 5 to 20 wt%, more preferably 7 to 17 wt%, and within this range, compared to a conventional ASA resin composition, other mechanical properties are maintained at an equivalent level, while impact strength, hardness, fluidity, and gloss are all excellent, and surface properties are improved during coextrusion.

The above (B) copolymer comprises, for example, 60 to 80 wt% of a (meth)acrylic acid alkyl ester compound, 5 to 30 wt% of an aromatic vinyl compound, and 1 to 25 wt% of a vinyl cyan compound, and within this range, the (A) graft copolymer has excellent compatibility with the (C) (meth)acrylic acid alkyl ester polymer described below, thereby improving processability and having excellent impact resistance, hardness, and gloss.

The above (B) copolymer may preferably comprise 65 to 75 wt% of a (meth)acrylic acid alkyl ester compound, 7 to 25 wt% of an aromatic vinyl compound, and 5 to 20 wt% of a vinyl cyan compound, and within this range, the (A) graft copolymer has excellent compatibility with the (C) (meth)acrylic acid alkyl ester polymer described below, thereby improving processability and having excellent impact resistance, hardness, and gloss.

The above (B) copolymer is more preferably composed of 70 to 75 wt% of a (meth)acrylic acid alkyl ester compound, 7 to 12 wt% of an aromatic vinyl compound, and 17 to 22 wt% of a vinyl cyan compound, or may be composed of 70 to 75 wt% of a (meth)acrylic acid alkyl ester compound, 20 to 25 wt% of an aromatic vinyl compound, and 5 to 10 wt% of a vinyl cyan compound, and within this range, the compatibility between the (A) graft copolymer and the (C) (meth)acrylic acid alkyl ester polymer described below is excellent, so that processability is improved and impact resistance, hardness, and gloss are all excellent.

The above (B) copolymer may specifically be a methyl methacrylate-styrene-acrylonitrile copolymer, in which case it has the advantages of improved processability and excellent impact resistance, hardness, and gloss.

The above (B) copolymer may have, for example, a weight average molecular weight of 50,000 to 150,000 g/mol, preferably 60,000 to 120,000 g/mol, more preferably 70,000 to 100,000 g/mol, and within this range, has excellent weather resistance and excellent impact resistance and hardness.

In this description, unless otherwise defined, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, it can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent.

Above The (meth)acrylic acid alkyl ester compound may be at least one selected from the group consisting of, for example, (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid decyl ester, and (meth)acrylic acid lauryl ester.

The types of the aromatic vinyl compound and vinyl cyan compound included in the above (B) copolymer may be within the same category as the types of the aromatic vinyl compound and vinyl cyan compound included in the (A) graft copolymer of the present disclosure.

The above (B) copolymer can be produced by, for example, solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, and preferably bulk polymerization, and the solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization are not particularly limited as long as they are each performed by emulsion polymerization and suspension polymerization methods commonly practiced in the technical field to which the present invention belongs.

(C) (meth)acrylic acid alkyl ester polymer

The (C) (meth)acrylic acid alkyl ester polymer may be, for example, 10 to 35 wt%, preferably 15 to 30 wt%, more preferably 18 to 28 wt%, and within this range, compared to a conventional ASA resin composition, other mechanical properties are maintained at an equivalent level, while impact strength, hardness, fluidity, and gloss are all excellent, and surface properties are improved during coextrusion.

Above (C) The (meth)acrylic acid alkyl ester polymer may be formed by including at least one selected from the group consisting of, for example, (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid decyl ester, and (meth)acrylic acid lauryl ester, and preferably, may be a polymethyl methacrylate resin, in which case, excellent gloss and weather resistance are achieved.

Unless otherwise specified herein, “(meth)acrylic acid alkyl ester” means both “acrylic acid alkyl ester” and “methacrylic acid alkyl ester”.

The above polymethyl methacrylate resin is, for example, composed of methyl methacrylate and methyl acrylate, and preferably, may be composed of 1 to 15 wt%, preferably 2 to 7 wt%, of methyl acrylate, and within this range, the resin has excellent compatibility with the (B) (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer, thereby exhibiting excellent gloss and weather resistance.

The above (C) (meth)acrylic acid alkyl ester polymer may have, for example, a weight average molecular weight of 50,000 to 200,000 g/mol, preferably 80,000 to 150,000 g/mol, more preferably 80,000 to 120,000 g/mol, and within this range, it has excellent weather resistance and excellent fluidity, hardness, and impact strength.

The above (C) (meth)acrylic acid alkyl ester polymer may have, for example, a glass transition temperature of 80 to 130°C, preferably 95 to 120°C, and has the advantage of excellent heat resistance within this range.

In this paper, the glass transition temperature (Tg) can be measured using differential scanning calorimetry (DSC), and as a specific example, it can be measured using a differential scanning calorimeter from TA Instrument.

The above (C) (meth)acrylic acid alkyl ester polymer can be produced by, for example, solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, and preferably suspension polymerization, and the solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization are not particularly limited as long as they are each performed by emulsion polymerization and suspension polymerization methods commonly practiced in the technical field to which the present invention belongs.

(D) α-Methyl styrene compound-vinyl cyanide compound copolymer

The above (D) α-methyl styrene compound-vinyl cyanide compound copolymer may be, for example, present in an amount of 1 to 30 wt%, preferably 5 to 25 wt%, and more preferably 7 to 23 wt%, and within this range, compared to a conventional ASA resin composition, other mechanical properties are maintained at an equivalent level, while impact strength, hardness, fluidity, and gloss are all excellent, and surface properties are improved during coextrusion.

The above (D) α-methyl styrene compound-vinyl cyan compound copolymer may be, for example, comprised of 60 to 80 wt% of an aromatic vinyl compound and 20 to 40 wt% of a vinyl cyan compound copolymer, preferably 65 to 75 wt% of an aromatic vinyl compound and 25 to 35 wt% of a vinyl cyan compound copolymer, and within this range, the copolymer has excellent gloss, excellent processability, and has the effect of improving surface properties by suppressing the occurrence of die lines or snake skins during coextrusion.

The above (D) α-methyl styrene compound-vinyl cyan compound copolymer preferably has a weight average molecular weight of, for example, 50,000 to 150,000 g/mol, more preferably 80,000 to 120,000 g/mol, and within this range, it has excellent gloss and processability, and has the effect of improving surface properties by suppressing the occurrence of die lines or snake skins during coextrusion.

The above α-methyl styrene compound may be, for example, at least one selected from the group consisting of α-methyl styrene and derivatives thereof, and in this case, excellent heat resistance is effective.

The above-described α-methyl styrene derivative may preferably be a compound in which at least one or two of its hydrogens are substituted with a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogen group, or the like, and more preferably may be a compound in which at least one or two of its hydrogens in its aromatic ring are substituted with a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogen group, or the like.

The above (D) copolymer may preferably be an α-methylstyrene-vinyl cyan compound copolymer, and specifically, may be an α-methylstyrene-acrylonitrile copolymer, in which case the copolymer has excellent heat resistance and has an excellent effect of improving surface properties by suppressing the occurrence of die lines or snake skins on the surface during coextrusion.

In this description, die-line refers to an unwanted surface stripe that occurs during extrusion, etc. This reduces the overall value of the product, including its aesthetic value, and damages the product characteristics.

Snake skin in this description means that when the co-extruded surface is observed with the naked eye, it looks like a snake pattern, and when this is magnified 25 times with an optical microscope, it appears as a trace similar to a micro flow mark. This reduces the overall value of the product, including its aesthetic value, and damages the product's characteristics.

The type of vinyl cyanide compound included in the above (D) α-methyl styrene compound-vinyl cyanide compound copolymer may be within the same category as the types of aromatic vinyl compounds and vinyl cyanide compounds included in the (A) graft copolymer of the present disclosure.

The above (D) α-methyl styrene compound-vinyl cyanide compound copolymer can be produced by, for example, solution polymerization or bulk polymerization, and preferably bulk polymerization, in which case it has excellent effects such as heat resistance and fluidity.

The above solution polymerization and bulk polymerization are not particularly limited when performed using solution polymerization and bulk polymerization methods commonly performed in the technical field to which the present invention belongs, respectively.

(E) Flow mark improvement agent

The (E) flow mark improvement agent may be, for example, present in an amount of 0.2 to 1.0 parts by weight, preferably 0.25 to 0.8 parts by weight, and more preferably 0.3 to 0.6 parts by weight, relative to 100 parts by weight of the base resin. Within this range, the impact strength and gloss are excellent, while the occurrence of die lines or snake skins on the surface during coextrusion is suppressed, thereby improving surface properties.

The above (E) flow mark improving agent may have, for example, a weight average molecular weight of 160,000 to 200,000 g/mol, preferably 170,000 to 190,000 g/mol, and within this range has the effect of improving surface properties by suppressing the occurrence of die lines and snake skins, etc.

The above (E) flow mark improver may have, for example, a fluidity index (230°C/3.8 kg) of 15 to 40 g/10 min, more preferably 20 to 35 g/10 min, and within this range, has the effect of improving surface properties by suppressing the occurrence of die lines and snake skins.

The above (E) flow mark improving agent may be, for example, at least one selected from the group consisting of a fluoropolymer, a perfluoroalkoxy polymer resin, polyethylenetetrafluoroethylene, polyvinyl fluoride, polyethylenechlorotrifluoroethylene, polyvinylidene fluoride, polychlorotrifluoroethylene, perfluoroelastomer (FFKM), and fluoroelastomer (FPM/FKM), preferably polyvinylidene fluoride, and in this case, there is an effect of improving surface properties by minimizing the occurrence of die lines or snake skins.

Additives

The thermoplastic resin composition may further contain, if necessary, at least one selected from the group consisting of an activator, an antioxidant, an ultraviolet stabilizer, a dye, a pigment, a flame retardant, and an inorganic filler, in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, and even more preferably 0.5 to 1 part by weight, per 100 parts by weight of the base resin, and within this range, the thermoplastic resin composition of the present disclosure has an effect of well implementing the required properties without lowering the inherent properties thereof.

Thermoplastic resin composition

The thermoplastic resin composition of the present invention is preferably co-extruded with PVC under conditions of a discharge amount of 11 kg/hr at 200°C with a co-extruder, so that when a sheet having a thickness of 0.15 mm is produced, the processability (P/T) measured in terms of melt pressure (P) and torque (T) may be 290/30 or higher, more preferably 300/32 or higher, and even more preferably 302/32 to 330/45, and within this range, not only is there an excellent effect of property balance, but there is an advantage in that the thermoplastic resin composition can be extruded instead of a t-PMMA resin using a conventional extruder. That is, the t-PMMA resin has high torque despite its low melt pressure, and the thermoplastic resin composition of the present invention makes such rheological properties similar to those of the t-PMMA resin, so that excellent processability can be realized with a conventional extruder for t-PMMA resin without replacing the extruder or changing the extrusion conditions, thereby having an economical advantage.

In addition, the thermoplastic resin composition may have a flow index of, for example, 0.65 g/10 min or more, preferably 0.7 g/10 min or more, and more preferably 0.7 to 1.7 g/10 min, as measured under conditions of 190°C/10 kg according to ASTM D1238, and within this range, the surface properties are further improved while the fluidity is excellent, so that it is advantageous in that it can be easily molded into various shapes.

In addition, the thermoplastic resin composition may have a flow index of, for example, 5.0 g/10 min or more, preferably 5.3 g/10 min or more, and more preferably 5.3 to 8.3 g/10 min, as measured under conditions of 220°C/10 kg according to ASTM D1238, and within this range, the surface properties are further improved while the fluidity is excellent, so that it is advantageous in that it can be easily molded into various shapes.

The thermoplastic resin composition may have, for example, a gloss of 55 or more, preferably 55 to 70, and more preferably 55 to 65 as measured at 60° according to ASTM D2457, and within this range, it has an excellent balance of all physical properties and excellent surface characteristics.

The thermoplastic resin composition may have a hardness of 90 or higher, preferably 90 to 110, and more preferably 95 to 105 as measured by the R-scale according to ASTM D785, for example, and has an excellent balance of all physical properties within this range while exhibiting excellent scratch resistance.

The thermoplastic resin composition may have, for example, an Izod impact strength of 8 kgf·cm/cm or more, preferably 8.5 to 17 kgf·cm/cm, and more preferably 8.5 to 15 kgf·cm/cm, as measured with a specimen thickness of 1/4" according to ASTM D256, and within this range, the composition has excellent balance of all properties and has an effect exceeding the impact strength standards required by the market. In order to be applied to exterior materials for buildings, the Izod impact strength must be 8 kgf·cm/cm or more, and if the impact strength is high, it can be used in cold regions, which has the advantage of expanding the range of applications.

Hereinafter, a method for producing a thermoplastic resin composition of the present invention and a molded article comprising the composition will be described. When describing a method for producing a thermoplastic resin composition of the present invention and a molded article comprising the composition, all of the contents of the thermoplastic resin composition described above are included.

Method for producing a thermoplastic resin composition

The method for producing a thermoplastic resin composition of the present invention comprises the steps of: (A) mixing and extruding 100 parts by weight of a base resin including 35 to 65 wt% of an acrylate-aromatic vinyl compound-vinyl cyanate graft copolymer comprising an acrylate rubber having an average particle diameter of 50 to 200 nm, (B) 1 to 25 wt% of a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanate compound copolymer, (C) 10 to 35 wt% of a (meth)acrylic acid alkyl ester polymer, and (D) 1 to 30 wt% of an α-methyl styrene-based compound-vinyl cyanate copolymer; and (E) 0.2 to 1.0 part by weight of a flow mark improver under conditions of 200 to 330°C and 200 to 300 rpm to produce thermoplastic resin composition pellets; And the thermoplastic resin composition is characterized in that, when coextruded with PVC under the condition of an output of 11 kg/hr at 200°C with a coextruder, a sheet having a thickness of 0.15 mm is produced, the processability (P/T) measured in terms of melt pressure (P) and torque (T) is 290/30 or higher. In this case, compared to the conventional ASA resin composition, other mechanical properties are maintained at an equivalent level, while impact strength, hardness, fluidity, and glossiness are all excellent, and the surface characteristics are improved during coextrusion.

The above mixing and extrusion can be performed, for example, using a single-screw extruder, a twin-screw extruder, or a Banbury mixer, in which case the composition is uniformly dispersed, resulting in excellent compatibility.

The above mixing and extrusion can be performed, for example, at a barrel temperature of, for example, 200 to 330°C, preferably 210 to 300°C, more preferably 210 to 280°C, and even more preferably 220 to 250°C, in which case, sufficient melt mixing can be achieved while the processing amount per unit time is appropriate, and there is an effect of not causing problems such as thermal decomposition of the resin component.

The above mixing and extrusion can be performed under conditions where the screw rotation speed is, for example, 100 to 500 rpm, 150 to 400 rpm, 100 to 350 rpm, 200 to 310 rpm, and preferably 250 to 350 rpm, in which case the processing amount per unit time is appropriate, so the process efficiency is excellent, and there is an effect of suppressing excessive cutting.

Molded product

The molded article of the present invention may, for example, include the thermoplastic resin composition of the present invention, and in this case, compared to a conventional ASA resin composition, other mechanical properties are maintained at an equivalent level, while impact strength, hardness, fluidity, and glossiness are all excellent, thereby having the effect of improving surface characteristics.

The above-mentioned molded product may be, for example, an exterior material for building, specifically a window profile, and in this case, there is an advantage in that it can be provided with a high quality higher than that required by the market by the thermoplastic resin composition of the present invention.

Method for manufacturing molded products

The method for manufacturing a molded article of the present invention comprises the steps of: (i) mixing and extruding 100 parts by weight of a base resin including (A) 35 to 65 wt% of an acrylate-aromatic vinyl compound-vinyl cyanate graft copolymer comprising an acrylate rubber having an average particle diameter of 50 to 200 nm, (B) 1 to 25 wt% of a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanate compound copolymer, (C) 10 to 35 wt% of a (meth)acrylic acid alkyl ester polymer, and (D) 1 to 30 wt% of an α-methyl styrene-based compound-vinyl cyanate copolymer; and (E) 0.2 to 1.0 part by weight of a flow mark improver under conditions of 200 to 330° C. and 200 to 300 rpm to manufacture thermoplastic resin composition pellets; And (ii) a step of co-extruding the thermoplastic resin composition pellets with a polyvinyl chloride resin; In this case, there is provided a method for manufacturing a molded product having excellent impact strength, hardness, fluidity, and gloss while maintaining other mechanical properties at an equivalent level compared to a molded product manufactured from a conventional ASA resin composition, and improved surface properties during co-extrusion.

Hereinafter, preferred examples are presented to help understand the present invention, but the following examples are only illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and technical idea of the present invention, and it is natural that such changes and modifications fall within the scope of the appended patent claims.

[Example]

(A-1) Graft copolymer by emulsion polymerization method (Core: 50 wt% of butylacrylate polymer having an average particle size of 120 nm, Shell: 33 wt% of styrene and 12 wt% of acrylonitrile)

(A-2) Graft copolymer by emulsion polymerization method (core: 50 wt% of butylacrylate polymer with an average particle size of 450 nm, shell: 35 wt% of styrene and 15 wt% of acrylonitrile)

(B) MSAN resin using a strange polymerization method (XT500) from LG Chemical

(C) Suspension polymerization PMMA resin (IH830 from LG MMA)

(D) Heat-resistant SAN resin by strange polymerization method (LG Chemical's 200UH)

(E) Flow mark improvement agent (PVDF; 6000HD from ARKEMA)

Examples 1 to 5, Comparative Examples 1 to 6 and Additional Comparative Examples 1 to 3

Each of the components and contents described in Tables 1 to 3 below was mixed and extruded at 230°C to produce pellets. The melting index of the produced pellets was measured. In addition, the produced pellets were injected at a molding temperature of 220°C to produce specimens for measuring physical properties, and a coextruder was used to coextrude them with PVC at 200°C and an output of 11 kg/hr to produce sheets having a thickness of 0.15 mm.

[Example]

The properties of the pellets, injection molded specimens and coextruded sheets manufactured in Examples 1 to 5, Comparative Examples 1 to 6 and Additional Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Tables 1 and 2 below. The impact strength and hardness were measured for the injection molded specimens, and the gloss, processability and surface properties were measured for the coextruded sheets.

* Melt index (g/10min): The manufactured pellets were measured using the ASTM D1238 method under the conditions of 190℃/10㎏ and 220℃/10㎏.

* Izod impact strength (IMP; kgf cm/cm): Measured according to ASTM D256 with a specimen thickness of 1/4".

* Gloss: Measured at 60° on coextruded sheet according to ASTM D2457.

* Hardness: Hardness was measured using the R-scale according to ASTM D785.

* Processability (P/T): Using a coextruder (Manufacturer: KraussMaffei Berstorff GmbH (Germany), Main extruder: Counter Rotating Twin Screw Extruder Berstorff ZE 25x33D, Side feeding extruder: HAAKE PolyLab OS RheoBrive 7 single extruder) at 200℃ and an output of 11 kg/hr, a sheet with a thickness of 0.15 mm was produced by coextrusion with PVC. The melt pressure (P) and torque (T) were measured to evaluate the processability (P/T).

* Die-line and snake skin: A sheet with a thickness of 0.15 mm was produced by co-extrusion with PVC resin at 200℃ and an output of 11 kg/hr using a co-extruder. The occurrence of die-line and snake skin on the surface was visually determined and evaluated as follows.

Die line evaluation

◎: Excellent surface quality as no die lines occur on the surface

○: The die line is faint on the surface, so the surface quality is average.

X: Die lines are clearly visible on the surface, resulting in poor surface quality.

snake skin review

○: Excellent surface properties as snake skin does not form on the surface

X: Snake skin occurs on the surface, resulting in poor surface properties

* Flow mark: The occurrence of flow marks in the sheets of Example 1 and Comparative Examples 1 and 4, which evaluated die-lines and snake skins, was visually determined, and the results were photographed and shown in Fig. 1.

division Example 1 Example 2 Example 3 Example 4 Example 5 (A-1) ASA 55 50 45 55 55 (B) MSAN 10 15 10 10 - (C) PMMA 20 25 25 20 30 (D) Heat-resistant SAN 15 10 20 15 15 (E) PVDF 0.5 0.5 0.3 0.8 0.3 Fluid index (190℃) 0.8 1.3 1.5 0.9 0.7 Fluid index (220℃) 5.3 7.7 8.1 5.5 5.3 Impact strength 13.7 8.9 9.0 13.5 12.8 Glossiness 63.1 59.9 56.4 63.5 60.4 hardness 91.4 97.5 102.5 90.9 92.5 Processability (P/T) 311/36 303/32 304/34 324/38 334/40 Die line ○ ○ ◎ ○ ◎ snake skin ○ ○ ○ ○ ○

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 (A-1) ASA 55 30 50 55 25 45 (A-2) Large diameter ASA 10 (B) MSAN 0 10 20 30 40 30 (C) PMMA 25 40 30 15 25 15 (D) Heat-resistant SAN 20 20 0 0 0 10 (E) PVDF 0 0.1 1.2 0 0.5 0.5 Fluid index (190℃) 0.9 2.8 0.7 2.9 2.9 2.2 Fluid index (220℃) 5.2 18.8 5.9 15.4 23.8 13.2 Impact strength 13.9 5.3 12.4 7.1 10.3 6.2 Glossiness 55.0 69.4 58.4 66.7 45.3 63.1 hardness 92.9 101.1 92.8 88.5 106.4 100.1 Processability (P/T) 249/31 216/26 240/29 220/25 225/27 265/28 Die line X X X X ○ ○ snake skin X X X X ○ ○

(In the above Tables 1 and 2, each content of (A-1), (A-2), (B), (C), and (D) is weight% based on the total weight thereof, and the content of (E) is weight parts based on 100 weight parts of the total weight of (A-1), (A-2), (B), (C), and (D).)

As shown in Tables 1 to 2 above, the thermoplastic resin compositions (Examples 1 to 5) according to the present invention, compared to Comparative Examples 1 to 6, had processability (P/T) of 290/30 or higher, excellent impact strength, fluidity, and gloss, and no die lines or snake skins were generated during coextrusion, confirming improved surface properties.

Specifically, Comparative Example 1, which did not include either (B) MSAN resin or (E) PVDF, had poor processability, resulting in die lines and snake skins on the sheet surface, and thus poor surface properties, while Comparative Example 2, which included a small amount of both (A-1) ASA resin and (E) PVDF, had poor impact strength, a rapidly increased flow index, and poor processability, resulting in die lines and snake skins on the surface, and thus poor surface properties.

In addition, Comparative Example 3, which did not include (D) heat-resistant SAN resin and (E) contained an excessive amount of PVDF, had low processability, resulting in die lines and snake skins on the sheet surface, which deteriorated surface properties, and Comparative Example 5, which included (A-2) large-diameter ASA resin and did not include (D) heat-resistant SAN resin, had low processability, and no die lines or snake skins on the sheet surface, but the glossiness was greatly reduced and the flow index increased rapidly, resulting in poor coextrudability.

In addition, Comparative Example 6 containing an excessive amount of (B) MSAN resin not only had a reduced processability but also a rapid increase in the fluidity index, which resulted in a reduced extrudability and a significantly reduced impact strength. This was a value that fell short of the impact strength required by the market, and there was a problem that it could not be applied to exterior materials for buildings, etc. The Izod impact strength required for exterior materials for buildings is 8 kgf·cm/cm or higher, but it was confirmed that Examples 1 to 5 according to the present invention were very excellent at 9.5 kgf·cm/cm or higher.

In addition, although (A-1) ASA resin, (B) MSAN resin, (C) PMMA resin and (D) heat-resistant SAN resin are within the scope of the present invention, the properties of additional comparative examples 1 to 2 containing a small amount or an excessive amount of (E) PVDF and additional comparative example 3 containing an excessive amount of (D) heat-resistant SAN resin were measured and are shown in Table 3 below.

division Additional Comparison Example 1 Additional comparison example 2 Additional comparison example 3 (A-1) ASA 55 55 45 (B) MSAN 10 10 10 (C) PMMA 20 20 10 (D) Heat-resistant SAN 15 15 35 (E) PVDF 0.1 1.5 0.5 Fluid index (190℃) 0.7 0.8 1.4 Fluid index (2200℃) 4.9 5.5 7.9 Impact strength 13.9 11.2 10.6 Glossiness 63.2 59.0 44.6 hardness 91.5 91.2 97.4 Die line X X ○ snake skin X ○ ○

As shown in Table 3 above, Additional Comparative Examples 1 and 2 had poor surface properties due to the occurrence of die lines or stake skins, and Additional Comparative Example 3 did not have die lines or stake skins on the sheet surface, but flow marks occurred and the glossiness was greatly reduced, making it difficult to apply to exterior building materials. In order to be applied to exterior building materials, the glossiness must be at least 55 or higher.

Referring to FIG. 1 below, which is a photograph observing the surface of a sheet coextruded with PVC, it was confirmed that Example 3 according to the present invention had excellent surface properties because no flow marks or snake skins occurred. On the other hand, Comparative Example 1 had deteriorated surface properties because flow marks and snake skins occurred, and Comparative Example 4, which did not contain (D) heat-resistant SAN and (E) PVDF, had no flow marks but had snake skins occurred, which deteriorated surface properties.

Claims (15)

(A) 35 to 65 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle size of 50 to 200 nm,
(B) 1 to 25 wt% of (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer,
(C) 10 to 35 wt% of (meth)acrylic acid alkyl ester polymer, and
(D) 100 parts by weight of a base resin comprising 1 to 30 wt% of an α-methyl styrene compound-vinyl cyanide compound copolymer; and
(E) Containing 0.2 to 1.0 parts by weight of a flow mark improver;
It is characterized by having a processability (P/T) of 290/30 or more, measured by melt pressure (P) and torque (T), when co-extruded with PVC under conditions of an output of 11 kg/hr at 200°C using a co-extruder to produce a sheet with a thickness of 0.15 mm.
Thermoplastic resin composition.
In the first paragraph,
The above (A) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer is characterized in that it comprises 40 to 70 wt% of acrylate rubber, 20 to 50 wt% of aromatic vinyl compound, and 1 to 25 wt% of vinyl cyan compound.
Thermoplastic resin composition.
In the first paragraph,
The above (B) (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer is characterized in that it comprises 60 to 80 wt% of (meth)acrylic acid alkyl ester compound, 5 to 30 wt% of aromatic vinyl compound, and 1 to 25 wt% of vinyl cyan compound.
Thermoplastic resin composition.
In the first paragraph,
The above (B) (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer is characterized by having a weight average molecular weight of 50,000 to 150,000 g/mol.
Thermoplastic resin composition.
In the first paragraph,
Above (C) The (meth)acrylic acid alkyl ester polymer is characterized in that it comprises at least one selected from the group consisting of (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid decyl ester, and (meth)acrylic acid lauryl ester.
Thermoplastic resin composition.
In the first paragraph,
Above (C) (Meth)acrylic acid alkyl ester polymer is characterized by having a weight average molecular weight of 50,000 to 200,000 g/mol.
Thermoplastic resin composition.
In the first paragraph,
The above (D) α-methyl styrene compound-vinyl cyan compound copolymer is characterized in that it comprises 60 to 80 wt% of α-methyl styrene compound, 20 to 40 wt% of vinyl cyan compound copolymer, and 0 to 10 wt% of styrene compound.
Thermoplastic resin composition.
In the first paragraph,
The above (D) α-methyl styrene compound-vinyl cyanide compound copolymer is characterized by having a weight average molecular weight of 50,000 to 150,000 g/mol.
Thermoplastic resin composition.
In the first paragraph,
The thermoplastic resin composition is characterized in that it has a flow index of 0.65 g/10 min or more measured at 190°C/10 kg according to ASTM D1238 and a flow index of 5.0 g/10 min or more measured under 220°C/10 kg conditions.
Thermoplastic resin composition.
In the first paragraph,
The thermoplastic resin composition is characterized in that it has a gloss of 55 or more as measured at 60° according to ASTM D2457.
Thermoplastic resin composition.
In the first paragraph,
The thermoplastic resin composition is characterized in that it has a hardness of 90 or more as measured by the R-scale according to ASTM D785.
Thermoplastic resin composition.
(A) 100 parts by weight of a base resin comprising 35 to 65 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an acrylate rubber having an average particle size of 50 to 200 nm, (B) 1 to 25 wt% of a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer, (C) 10 to 35 wt% of a (meth)acrylic acid alkyl ester polymer, and (D) 1 to 30 wt% of an α-methyl styrene-based compound-vinyl cyan compound copolymer; and (E) 0.2 to 1.0 part by weight of a flow mark improver; mixing and extruding under conditions of 200 to 330° C. and 200 to 300 rpm to produce thermoplastic resin composition pellets; and
The thermoplastic resin composition is characterized in that the processability (P/T) measured by melt pressure (P) and torque (T) is 290/30 or more when co-extruded with PVC under conditions of an output of 11 kg/hr at 200°C using a co-extruder to produce a sheet having a thickness of 0.15 mm.
A method for producing a thermoplastic resin composition.
A thermoplastic resin composition comprising any one of claims 1 to 11.
Molded product.
In Article 13,
The above molded product is characterized as being an exterior material for construction.
Molded product.
(i) a step of preparing thermoplastic resin composition pellets by mixing and extruding (A) 35 to 65 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 50 to 200 nm, (B) 1 to 25 wt% of a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer, (C) 10 to 35 wt% of a (meth)acrylic acid alkyl ester polymer, and (D) 1 to 30 wt% of an α-methyl styrene-based compound-vinyl cyan compound copolymer, and (E) 0.2 to 1.0 wt% of a flow mark improver under conditions of 200 to 330° C. and 200 to 300 rpm; and
(ii) a step of co-extruding the thermoplastic resin composition pellets with a polyvinyl chloride resin; characterized in that it comprises;
Method for manufacturing a molded product.