Title of Invention: Thermoplastic resin composition and molded article thereof
technical field
[One]
[Cross Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0091652 dated July 23, 2020 and Korean Patent Application No. 10-2020-0178406, filed again on December 18, 2020 based thereon. All content disclosed in the literature of the application is incorporated as a part of this specification.
[3]
The present invention relates to a thermoplastic resin composition and a molded article thereof, and more particularly, mechanical properties and processability compared to conventional ASA resins are maintained at equal or higher levels, and excellent weather resistance, and in particular, artificial plastics by implementing a rough feeling on the surface of the product It relates to a thermoplastic resin composition and a molded article thereof having a luxurious appearance that is free from feeling.
background
[4]
The acrylate compound-styrene-acrylonitrile copolymer (hereinafter referred to as 'ASA resin') has weather resistance, aging resistance, chemical resistance, rigidity, impact resistance, and processability. It is widely used in the field.
[5]
Recently, the demand for a luxurious appearance for ASA resin products is increasing, and accordingly, the need for ASA resin products having a rough feeling surface has been greatly increased.
[6]
However, conventional research on ASA resins having a rough surface is insufficient, and in particular, the roughness of the surface of ASA resin is not related to the surface gloss. There was a limit to realizing a rough-feeling surface texture.
[7]
[Prior art literature]
[8]
[Patent Literature]
[9]
KR Patent Publication 2003-0003950 A (2003.01.14)
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[10]
In order to solve the problems of the prior art as described above, the present invention maintains the mechanical properties and workability equal to or higher than that of the conventional ASA resin, and has excellent weather resistance, especially by implementing a rough feeling on the surface of the product to escape from the artificial feeling of plastic. An object of the present invention is to provide a thermoplastic resin composition having a luxurious appearance and a molded article thereof.
[11]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[12]
In order to achieve the above object, the present invention provides a thermoplastic resin composition comprising 100 parts by weight of a styrenic resin and 1 to 10 parts by weight of a surface control agent, and an asymmetry Rsk of 0.65 to 1.35.
[13]
In addition, the present invention provides a thermoplastic resin composition comprising 100 parts by weight of a styrene-based resin and 1 to 10 parts by weight of a surface control agent, and having an arithmetic mean roughness Ra of 0.3 to 3 μm measured at 5 points using an optical profiler system can do.
[14]
In addition, the present invention includes 100 parts by weight of a styrenic resin and 1 to 10 parts by weight of a surface control agent, wherein the styrenic resin is a) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, b) aromatic vinyl compound- At least one selected from the group consisting of a vinyl cyan compound copolymer, c) a heat-resistant styrene-based resin, and d) a methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer, wherein the surface control agent is a polystyrene-based surface control agent, a nylon-based surface It is possible to provide a thermoplastic resin composition, characterized in that at least one selected from the group consisting of a modifier and a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound-based surface modifier.
[15]
In addition, the present invention provides a molded article comprising the thermoplastic resin composition.
Effects of the Invention
[16]
According to the present invention, the thermoplastic resin composition has excellent weather resistance and, in particular, a rough feeling on the surface of the product, while maintaining the same or higher mechanical properties and processability compared to the conventional ASA resin, to give a luxurious appearance away from the artificial plastic feeling And there is an effect of providing a molded article thereof.
Brief description of the drawing
[17]
1 schematically shows the definition, calculation method, and meaning of the degree of asymmetry Rsk according to the present invention. And, it is possible to evaluate which of the peaks and valleys on the surface form the majority of the surface. In particular, the upper figure of FIG. 1 is a graph showing the expression and meaning of the root mean square deviation (Rq), where Z means the peak height, and ℓ means the average section length (sampling length). In addition, the lower figure of FIG. 1 is a graph showing the formula for calculating the asymmetry Rsk and its meaning. As the asymmetry Rsk becomes larger than 0, the peak distribution increases with respect to the mean line. This means that the distribution of The present invention makes it a gist that when the asymmetry Rsk is adjusted within a predetermined range, a rough feeling away from the plastic feeling is realized on the surface of the product.
[18]
2 is a histogram of the asymmetry Rsk of the 0.15T film sample prepared with the thermoplastic resin composition prepared in Examples and Comparative Examples. do. Here, when there are more peak distributions, the Rsk value becomes larger than 0, and when there are many valley distributions, the Rsk value becomes smaller than 0. More specifically, in Examples 2 to 7, the Rsk value falls within the range according to the present invention, and the rough feeling away from the plastic feeling is well realized on the surface of the product. It can be seen that, in Comparative Example 2, the number of peaks and the distribution area are too large, so that the surface roughness does not appear well.
[19]
3 is a photograph of the film extruder used in Examples and Comparative Examples.
Modes for carrying out the invention
[20]
Hereinafter, the thermoplastic resin composition of the present disclosure and a molded article thereof will be described in detail.
[21]
In the process of developing an ASA resin product embodying a rough feeling to have a luxurious appearance away from the artificial plastic feeling, the present inventors mix a predetermined styrene-based resin and a predetermined surface control agent in a certain amount to determine the asymmetry Rsk value. When adjusting within the range, it is confirmed that the manufactured ASA resin product has excellent weather resistance without deterioration in mechanical properties and processability, and has a luxurious appearance that is free from artificial plastic feeling by giving a rough feeling to the product surface, Based on the research, the present invention was completed.
[22]
[23]
The thermoplastic resin composition of the present invention contains 100 parts by weight of a styrene-based resin and 1 to 10 parts by weight of a surface control agent, and is characterized in that the asymmetry Rsk is 0.65 to 1.35, and in this case, mechanical properties and processability, etc. compared to conventional ASA-based resins While maintaining this equal or higher, there is an advantage in providing a product having excellent weather resistance and, in particular, a product having a luxurious appearance that is free from artificial plastic feeling by implementing a rough feeling on the product surface. Here, the asymmetry Rsk is an independent parameter that has no correlation with the conventional gloss or roughness Ra, as can be seen from the results of Table 1 below, and is organically combined with the components according to the present invention to achieve the object of the present invention do.
[24]
The asymmetry Rsk is preferably 0.7 to 1.3, more preferably 0.8 to 1.3, still more preferably 0.9 to 1.3, and most preferably 1.0 to 1.25. Therefore, it has excellent weather resistance and, in particular, has the effect of having a luxurious appearance that is free from the artificial plastic feeling by realizing a rough feeling on the surface of the product.
[25]
[26]
In addition, the thermoplastic resin composition of the present invention contains 100 parts by weight of a styrene-based resin and 1 to 10 parts by weight of a surface control agent, and an arithmetic mean roughness Ra measured at 5 points using an optical profiler system is 0.3 to 3 μm, In this case, mechanical properties and processability are maintained at equal or higher levels compared to conventional ASA resins, and the weather resistance is excellent, and in particular, a rough feeling is implemented on the surface of the product to provide a product with a luxurious appearance that is free from artificial plastic feeling. .
[27]
The styrenic resin is preferably a) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, b) aromatic vinyl compound-vinyl cyan compound copolymer, c) heat-resistant styrene-based resin, d) methacrylate- It may be at least one selected from the group consisting of an aromatic vinyl compound-vinyl cyan compound copolymer and e) polyalkyl methacrylate.
[28]
In addition, the thermoplastic resin composition of the present invention may preferably include a lubricant, an antioxidant, and a UV stabilizer, and in this case, the ASA resin product has excellent mechanical properties while realizing a rough feeling on the surface of the product, and the desired effect of each component has the advantage of being well expressed.
[29]
In addition, the thermoplastic resin composition of the present invention includes 100 parts by weight of a styrenic resin and 1 to 10 parts by weight of a surface control agent, wherein the styrenic resin is a) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, b) At least one selected from the group consisting of aromatic vinyl compound-vinyl cyan compound copolymer, c) heat-resistant styrene-based resin, d) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer, and e) polyalkyl methacrylate, The surface control agent is characterized in that at least one selected from the group consisting of a polystyrene-based surface control agent, a nylon-based surface control agent, and a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound-based surface control agent, and in this case, mechanical compared to conventional ASA-based resins There is an advantage in providing a product having excellent weather resistance and, in particular, a luxurious appearance that is free from artificial plastic feeling by implementing a rough feeling on the surface of the product while maintaining the same or higher physical properties and processability.
[30]
said tea Preferably, the ene-based resin comprises a) 30 to 70 wt% of the acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, b) 0 to 30 wt% of the aromatic vinyl compound-vinyl cyan compound copolymer, and c) 0 to 30% by weight of a heat-resistant styrene resin, d) 30 to 70% by weight of the methacrylate-aromatic vinyl compound-vinylcyan compound copolymer, and e) 0 to 40% by weight of polyalkyl methacrylate, Within this range, it has the advantage of providing a luxurious appearance that is free from the artificial plastic feeling by giving a rough feeling to the surface of the product without deterioration of mechanical properties and weather resistance.
[31]
[32]
Hereinafter, each component constituting the thermoplastic resin composition of the present disclosure will be described in detail as follows.
[33]
[34]
a) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer
[35]
The a) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer is preferably 30 to 70% by weight, more preferably 30 to 60% by weight, still more preferably 40 to 60% by weight, even more preferably Preferably, it is 45 to 55% by weight, and most preferably 50 to 55% by weight, and within this range, there is an excellent effect of weather resistance, fluidity, tensile strength and impact strength.
[36]
The a) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer is preferably i) 40 to 60 wt % of an acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, 20 to 40 wt % of an aromatic vinyl compound, and vinyl cyanide An acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising 10 to 20 wt% of the compound, and ii) 40 to 60 wt% of an acrylate rubber having an average particle diameter of 0.05 μm or more to less than 0.3 μm, an aromatic vinyl compound It may be at least one selected from the group consisting of acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising 20 to 40 wt% and 10 to 20 wt% of a vinyl cyan compound.
[37]
The weight ratio (i:ii) of the i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and the ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer is preferably 1: 0.3 to 0.9, more preferably 1: 0.4 to 0.8, more preferably 1: 0.5 to 0.7, most preferably 0.6 to 0.7 , the tensile strength and impact strength are excellent.
[38]
[39]
i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer
[40]
The acrylate rubber of the i) graft copolymer preferably has an average particle diameter of 0.3 to 0.5 μm, more preferably 0.35 to 0.5 μm, still more preferably 0.35 to 0.45 μm, even more preferably The thickness is 0.40 to 0.45 μm, and within this range, the weather resistance is good and mechanical properties such as fluidity, tensile strength and impact strength are excellent.
[41]
In the present description, the average particle diameter can be measured using dynamic light scattering, and in detail, Nicomp 380 equipment (product name, manufacturer: PSS) is used to Gaussian mode intensity (intensity) value can be measured with
[42]
In addition, in the present description, the average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, specifically, an average particle diameter of scattering intensity. At this time, as a specific example of measurement, the sample is prepared by diluting 0.1 g of Latex (TSC 35-50 wt%) 1,000-5,000 times with distilled water, and the measurement method is auto-dilution and measured with a flow cell, and the measurement mode is dynamic light scattering ( Dynamic light scattering) method/Intensity 300KHz/Intensity-weight Gaussian Analysis can be used, and the setting value can be measured with a temperature of 23℃, a measurement wavelength of 632.8nm, and a channel width of 10μsec.
[43]
[44]
The i) graft copolymer is, for example, 20 to 40% by weight, preferably 25 to 35% by weight, more preferably 30 to 35% by weight, based on the total weight of the styrenic resin, within this range weather resistance, fluidity, It has an excellent effect on tensile strength and impact strength.
[45]
The i) graft copolymer comprises, for example, 40 to 60% by weight of an acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, 20 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, preferably 40 to 60% by weight of acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, and more preferably an average particle diameter of 0.3 to 0.5 45 to 55% by weight of acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, and excellent effect in weather resistance, fluidity, tensile strength and impact strength within this range there is
[46]
In the present description, a polymer including a certain compound means a polymer polymerized including the compound, and a unit in the polymerized polymer is derived from the compound.
[47]
[48]
The acrylate 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 an alkyl acrylate having 4 to 8 carbon atoms in the alkyl group, more preferably butyl acryl lactate or ethylhexyl acrylate.
[49]
The aromatic vinyl compound 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.
[50]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methnitrolonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, preferably acrylonitrile.
[51]
[52]
The i) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, it has excellent effects in weather resistance, fluidity, tensile strength and impact strength.
[53]
The emulsion polymerization is not particularly limited in the case of emulsion graft polymerization generally carried out in the art to which the present invention pertains.
[54]
[55]
ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer
[56]
ii) the acrylate rubber of the graft copolymer preferably has an average particle diameter of 0.05 μm or more to less than 0.3 μm, more preferably 0.05 to 0.25 μm, and still more preferably 0.05 to 0.15 μm, More preferably, it is 0.08 to 0.12 μm, and excellent weather resistance, colorability, impact strength, chemical resistance and surface gloss properties can be imparted to the finally manufactured thermoplastic resin composition within this range.
[57]
[58]
The ii) graft copolymer is, for example, 10 to 30% by weight, preferably 15 to 25% by weight, more preferably 15 to 20% by weight, and has excellent weather resistance, fluidity, tensile strength and impact strength within this range. It works.
[59]
[60]
The ii) graft copolymer may include, for example, 40 to 60% by weight of an acrylate rubber having an average particle diameter of 0.05 μm or more to less than 0.3 μm, 20 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound. and preferably 40 to 60% by weight of an acrylate rubber having an average particle diameter of 0.05 μm or more to less than 0.3 μm, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, more preferably Preferably, it comprises 45 to 55% by weight of an acrylate rubber having an average particle diameter of 0.05 μm or more to less than 0.3 μm, 30 to 50% by weight of an aromatic vinyl compound, and 5 to 20% by weight of a vinyl cyanide compound, and more preferably an average particle diameter 45 to 55% by weight of an acrylate rubber of 0.05 μm or more to less than 0.3 μm, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, and weather resistance, fluidity, and tensile strength within this range and excellent impact strength.
[61]
[62]
The ii) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, chemical resistance, weather resistance, fluidity, tensile strength and impact strength are excellent.
[63]
The emulsion polymerization is not particularly limited in the case of emulsion graft polymerization generally carried out in the art to which the present invention pertains.
[64]
[65]
b) Aromatic vinyl compound-vinyl cyan compound copolymer
[66]
The b) aromatic vinyl compound-vinyl cyan compound copolymer is preferably an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 100,000 to 150,000 g/mol; And an aromatic vinyl compound having a weight average molecular weight of more than 150,000 g/mol and 200,000 g/mol or less-vinyl cyan compound copolymer; contains at least one selected from the group consisting of, in this case, excellent heat resistance, processability and impact strength there is
[67]
In the present description, unless otherwise defined, the weight average molecular weight may be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as the eluent. ) to be measured relative to a standard PS (standard polystyrene) sample.can At this time, as a specific example of measurement, solvent: THF, column temperature: 40°C, flow rate: 0.3ml/min, sample concentration: 20mg/ml, injection amount: 5 μl, column model: 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI temperature: 35℃, data processing: Agilent ChemStation S/W, test method (Mn, Mw and PDI): It can be measured under the conditions of OECD TG 118.
[68]
[69]
The amount of the b) aromatic vinyl compound-vinyl cyan compound copolymer may be preferably 30 wt% or less, more preferably 20 wt% or less, and still more preferably 10 wt% or less, based on the total weight of the styrene-based resin. and more preferably 5% by weight or less, and most preferably not included, and has an advantage of excellent weather resistance within this range.
[70]
[71]
The b) aromatic vinyl compound-vinyl cyan compound copolymer preferably contains, for example, 65 to 80 wt% of an aromatic vinyl compound and 20 to 35 wt% of a vinyl cyanide compound, and has chemical resistance and impact strength within this range. It has an excellent effect.
[72]
The aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, m-methylstyrene, p-methylstyrene and p-tert-butylstyrene, and is preferably styrene.
[73]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methnitrolonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, preferably acrylonitrile.
[74]
[75]
The b) aromatic vinyl polymer may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, and in this case, heat resistance and fluidity are excellent.
[76]
The suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization are not particularly limited in the case of solution polymerization and block polymerization methods commonly performed in the art to which the present invention pertains, respectively.
[77]
[78]
c) Heat-resistant styrenic resin
[79]
The c) heat-resistant styrenic resin is preferably 20 wt% or less, more preferably 15 wt% or less, and may be included in an amount of 1 to 20 wt% in a preferred embodiment, 5 to 17 wt% in a more preferred embodiment, In a more preferred embodiment, it may be included in an amount of 5 to 15% by weight, and there are excellent advantages in mechanical properties and heat resistance within this range.
[80]
The c) heat-resistant styrene-based resin is a styrene-based resin containing a heat-resistant monomer, and may preferably be an α-methylstyrene-vinyl cyan compound copolymer, and in this case, mechanical properties and heat resistance are excellent.
[81]
The α-methylstyrene-vinyl cyan compound copolymer preferably contains 65 to 75% by weight of α-methylstyrene and 25 to 30% by weight of the vinyl cyan compound, and has excellent mechanical properties and heat resistance within this range. There is an advantage.
[82]
More preferably, the alpha-methylstyrene-acrylonitrile copolymer comprises 70 to 75% by weight of alpha-methylstyrene and 25 to 30% by weight of acrylonitrile, more preferably 60 to 30% by weight of alpha-methylstyrene 75% by weight, 0 to 10% by weight of styrene and 20 to 30% by weight of acrylonitrile, or 60 to 70% by weight of alpha-methylstyrene, 0 to 10% by weight of styrene and 25 to 30% by weight of acrylonitrile It may include, more preferably 60 to 75% by weight of alpha-methylstyrene, 5 to 10% by weight of styrene, and 20 to 30% by weight of acrylonitrile, or 60 to 70% by weight of alpha-methylstyrene %, 5 to 10% by weight of styrene and 25 to 30% by weight of acrylonitrile may be included, and heat resistance and the like within this range have an excellent effect.
[83]
The aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, m-methylstyrene, p-methylstyrene and p-tert-butylstyrene, and is preferably styrene.
[84]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methnitrolonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, preferably acrylonitrile.
[85]
[86]
The alpha-methylstyrene-acrylonitrile copolymer preferably has a weight average molecular weight of 80,000 to 120,000 g/mol, more preferably 80,000 to 100,000 g/mol, and has excellent heat resistance within this range. .
[87]
[88]
The c) heat-resistant styrenic resin may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, and in this case, heat resistance and fluidity are excellent.
[89]
The suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization are not particularly limited in the case of solution polymerization and block polymerization methods commonly performed in the art to which the present invention pertains, respectively.
[90]
[91]
d) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer
[92]
The d) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer preferably comprises 65 to 85 wt% of a methacrylate-based monomer, 10 to 30 wt% of an aromatic vinyl compound, and 5 to 10 wt% of a vinyl cyanide compound This can be achieved, and within this range, weather resistance is greatly improved, and there is an advantage of excellent mechanical properties.
[93]
[94]
The d) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer is preferably 30 to 70% by weight, more preferably 35 to 60% by weight, still more preferably 40 to 55% by weight, most preferably It may be included in an amount of 40 to 50% by weight, and the weather resistance is improved within this range, and there are excellent advantages such as scratch resistance and colorability.
[95]
[96]
The methacrylate monomer may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2 - May be at least one selected from the group consisting of ethylhexyl methacrylate and lauryl methacrylate, preferably an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, more preferably methyl methacrylate It may be a acrylate.
[97]
The aromatic vinyl compound 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.
[98]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methnitrolonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, preferably acrylonitrile.
[99]
[100]
The d) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer may preferably have a weight average molecular weight of 70,000 to 200,000 g/mol, more preferably 100,000 to 150,000 g/mol, still more preferably It may be 120,000 to 140,000 g/mol, and within this range, the weather resistance is better, the fluidity, tensile strength and impact strength are excellent, and the surface roughness value is low, so there is an emotionally soft effect.
[101]
[102]
The d) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer may be prepared by, for example, solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, and the solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization are each In the case of emulsion polymerization and suspension polymerization methods commonly carried out in the art to which the present invention belongs, it is not particularly limited.
[103]
[104]
e) polyalkyl methacrylate
[105]
e) the polyalkyl methacrylate may be, for example, 0 to 40% by weight, preferably 1 to 40% by weight, more preferably 10 to 40% by weight, even more preferably 20 to 40% by weight, most Preferably, it is 30 to 40 wt%, and within this range, mechanical properties and processability are maintained at the same or higher level compared to conventional ASA resins, and weather resistance is greatly improved.
[106]
The e) polyalkyl methacrylate preferably comprises 70 to 100% by weight of an alkyl methacrylate and 0 to 30% by weight of an alkyl acrylate, more preferably 75 to 99% by weight of an alkyl methacrylate, and 1 to 25% by weight of an alkyl acrylate, more preferably 80 to 98% by weight of an alkyl methacrylate and 2 to 20% by weight of an alkyl acrylate, most preferably an alkyl methacrylate It consists of 84 to 98% by weight and 2 to 16% by weight of an alkyl acrylate, and within this range, there is an advantage in that the weather resistance is significantly improved while maintaining the same or more mechanical properties and processability compared to the conventional ASA resin.
[107]
The alkyl methacrylate may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2 - May be at least one selected from the group consisting of ethylhexyl methacrylate and lauryl methacrylate, preferably alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, more preferably methyl methacrylate It may be a acrylate.
[108]
The alkyl acrylate may be, for example, at least one selected from the group consisting of alkyl acrylates having 1 to 8 carbon atoms in the alkyl group, and preferably An alkyl acrylate having 1 to 3 carbon atoms, more preferably methyl acrylate or ethyl acrylate.
[109]
[110]
The e) polyalkyl methacrylate may have, for example, a weight average molecular weight of 35,000 to 200,000 g/mol, and preferably 50,000 to 200,000 g/mol, and has better weather resistance within this range, and fluidity, There is an effect excellent in tensile strength and impact strength.
[111]
As another example, e) the polyalkyl methacrylate includes a polyalkyl methacrylate having a weight average molecular weight of 50,000 to 200,000 g/mol (hereinafter referred to as 'high molecular weight PMMA resin') and a weight average molecular weight of 35,000 to 45,000 g /mol of polyalkyl methacrylate (hereinafter referred to as 'low molecular weight PMMA resin') may be mixed.
[112]
The high molecular weight PMMA resin and the low molecular weight PMMA resin may have, for example, a weight ratio (high molecular weight PMMA resin: low molecular weight PMMA resin) of 1: 0.1 to 2.0, preferably 1: 1.3 to 1.7, more preferably 1: 1.4 to It may be 1.6, and within this range, fluidity, tensile strength and impact strength are excellent, weather resistance is more excellent, and the surface roughness value is low, so there is an emotionally soft effect.
[113]
[114]
surface conditioner
[115]
The surface control agent of the present substrate is preferably at least one selected from the group consisting of a nylon-based surface control agent, a polystyrene-based surface control agent, and a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound-based surface control agent, and in this case, compared to conventional ASA resins While mechanical properties and workability are maintained at the same or higher level, weather resistance is excellent, and in particular, a rough feeling is realized on the surface of the product to have a luxurious appearance that is free from the artificial feeling of plastic.
[116]
Specific examples of the nylon-based surface control agent include polyamide 6, polyamide 66 (PA 6.6), polyamide 46, polyamide ll, polyamide 12, polyamide 610, polyamide 612, polyamide 6/66, polyamide 6/ 612, polyamide MXD6, polyamide 6/MXD6, polyamide 66/MXD6, polyamide 6T, polyamide 6I, polyamide 6/6T, polyamide 6/6I, polyamide 66/6T, polyamide 66/6I, Polyamide 6/6T/6I, Polyamide 66/6T/6I, Polyamide 9T, Polyamide 9I, Polyamide 6/9T, Polyamide 6/9I, Polyamide 66/9T, Polyamide 6/12/9T, It may be at least one selected from the group consisting of polyamide 66/12/9T, polyamide 6/12/9I and polyamide 66/12/6I, preferably polyamide 66 (PA 6.6), polyamide 6 (PA) 6) or a mixture thereof, and in this case, mechanical properties and processability are maintained at the same level or higher compared to conventional ASA-based resins, and the weather resistance is excellent, and in particular, a luxurious appearance that is free from artificial plastic feeling by realizing a rough feeling on the surface of the product has the effect of having
[117]
The nylon-based surface control agent, for example, a melting point of 210 ℃ or more, preferably 215 ℃ or more, more preferably 220 ℃ or more, as a specific example, it is good to use a thing of 210 to 270 ℃.
[118]
The nylon-based surface control agent, for example, has a relative viscosity (96% sulfuric acid solution) of 2.0 to 4.0, preferably 2.0 to 3.5, more preferably 2.0 to 3.0, more preferably 2.4 to 2.7.
[119]
In the present description, the relative viscosity can be measured with an Ubbelohde viscometer by the ISO 307 sulfuric acid method.
[120]
[121]
The polystyrene-based surface control agent is preferably at least one selected from the group consisting of glass fiber reinforced SPS, flame retardant SPS, nylon-containing SPS, blended SPS, copolymerized SPS and homopolymer SPS, more preferably homopolymer SPS, In the case of a conventional ASA resin, mechanical properties and processability are maintained at the same level or higher, and the weather resistance is excellent, and in particular, a rough feeling is implemented on the surface of the product to have a luxurious appearance that is free from the artificial plastic feeling.
[122]
Homopolymer SPS in the present description means syndiotatic polystyrene that does not contain a copolymer, and is not particularly limited in the case of homopolymer SPS commonly used in the art to which the present invention belongs.
[123]
[124]
The shape of the particles of the vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound-based surface control agent may not be constant, and the distribution of the particles is preferably 5 μm or more, more preferably 5 to 20 μm, even more preferably It may have a particle size distribution of 10 to 20 μm, and may have excellent impact properties along with a rough surface within this range.
[125]
The particle size distribution is a particle size distribution for secondary particles in which primary particles having an average particle diameter of 300 to 800 nm are aggregated, and is affected by the film extrusion temperature.
[126]
In the present description, the particle size distribution may be measured by a TEM method.
[127]
The surface control agent is, for example, 1 to 10 parts by weight, preferably 1 to 8 parts by weight, more preferably 1 to 6 parts by weight, even more preferably 1 to 5 parts by weight, based on 100 parts by weight of the styrenic resin; Most preferably, it may be 3 to 5, and within this range, the effect of implementing a rough feeling on the surface of the ASA product is very large, and there is an advantage of excellent balance of physical properties.
[128]
[129]
The method for preparing the surface control agent is not particularly limited as long as it is a method conventionally prepared in the technical field to which the present invention pertains, and may be commercially purchased and used if it meets the definition of the surface control agent according to the present invention.
[130]
[131]
additional additives
[132]
The thermoplastic resin composition of the present invention may preferably include a lubricant, an antioxidant and a UV stabilizer.
[133]
The lubricant may preferably be included in an amount of 0.3 to 2 parts by weight based on 100 parts by weight of the styrenic resin, more preferably in an amount of 1 to 2 parts by weight, and more preferably in an amount of 1.2 to 1.7 parts by weight, and , while realizing a rough feeling on the surface within this range, it has the advantage of excellent impact strength and fluidity.
[134]
The lubricant is preferably at least one selected from the group consisting of an ester lubricant, a metal salt lubricant, a carboxylic acid lubricant, a hydrocarbon lubricant, and an amide lubricant, more preferably an amide lubricant, and more preferably It is a steramide-based lubricant, and most preferably is alkylene bis (steramide) having 1 to 10 carbon atoms in the alkylene, and in this case, there is an advantage in that both the impact strength and the fluidity are excellent while realizing a rough feeling on the surface.
[135]
In the present description, the steramide-based lubricant may include steramide and a steramide substituent in which at least one of hydrogen is substituted with another substituent.
[136]
The ester-based lubricant, metal salt-based lubricant, carboxylic acid-based lubricant, hydrocarbon-based lubricant, and amide-based lubricant are not particularly limited if each of the materials is commonly used as a corresponding type of lubricant in the technical field to which the present invention belongs.
[137]
The antioxidant is preferably at least one selected from the group consisting of phenolic antioxidants and phosphorus antioxidants, and more preferably a mixture of phenolic antioxidants and phosphorus antioxidants.
[138]
The phenolic antioxidant and the phosphorus antioxidant may each preferably contain 0.05 to 1.5 parts by weight based on 100 parts by weight of the styrenic resin, more preferably 0.1 to 1.0 parts by weight, respectively, and more preferably Each may be included in an amount of 0.2 to 0.5 parts by weight, and while implementing a rough feeling on the surface within this range, there is an excellent antioxidative effect.
[139]
The phenolic antioxidant is preferably tetrakis[ethylene-3-(3,5-di-t-butyl-hydroxyphenyl)propionate](IR-1010), octadecyl 3-(3,5- di-t-butyl-4-hydroxyphenyl)propionate (IR-1076), pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], and 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, more preferably octadecyl 3-(3 ,5-di-t-butyl-4-hydroxyphenyl)propionate (IR-1076) has an excellent antioxidant effect while realizing a rough feeling on the surface within this range.
[140]
The phosphorus-based antioxidant is preferably tris (2,4-di-tertbutylphenyl) phosphite (tris (2,4-di-tertbutylphenyl) phosphite), tris (nonylphenyl) phosphite (Tris (nonylphenyl) It can be at least one selected from the group consisting of phosphite; TNPP) and di-(2,4-di-tert-butylphenyl) pentaerythritol diphosphide (Di-(2,4-di-t-butylphenyl) pentaerythritol diphosphite) and more preferably tris (2,4-di-tertiary-butylphenyl) phosphite, and within this range, a rough feeling is realized on the surface and an excellent antioxidant effect is obtained.
[141]
[142]
The UV stabilizer is preferably at least one selected from the group consisting of a benzotriazole-based UV stabilizer and a HALS-based UV stabilizer, and more preferably a mixture of a benzotriazole-based UV stabilizer and a HALS-based UV stabilizer.
[143]
The ultraviolet stabilizer may preferably include 0.1 to 1.0 parts by weight of a benzotriazole-based ultraviolet stabilizer and 0.1 to 1.0 parts by weight of a HALS-based ultraviolet stabilizer based on 100 parts by weight of a styrene-based resin, and more preferably 0 to a benzotriazole-based ultraviolet stabilizer It may contain .2 to 0.7 parts by weight and 0.2 to 0.7 parts by weight of a HALS-based UV stabilizer, more preferably 0.3 to 0.6 parts by weight of a benzotriazole-based UV stabilizer and 0.3 to 0.6 parts by weight of a HALS-based UV stabilizer, Within this range, there is an effect of providing a rough feeling to the surface and excellent light resistance.
[144]
[145]
The benzotriazole-based UV stabilizer may be, for example, a hydroxybenzotriazole-based compound, preferably a 2-(2'-hydroxyphenyl)benzotriazole-based compound, and more preferably a 2-(2'- Hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2' -Hydroxyphenyl)benzotriazole, 2-(2'-hydroxyl-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di -tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3 ',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole Sol, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxy-carbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl -5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxyl -5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl) )phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl -5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl ) benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis[4-( 1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol], and 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2 '-Hydroxyphenyl]-2H-benzotriazole and It may be at least one selected from the group consisting of transesterification products of polyethylene glycol, and within this range, there is an effect of excellent light resistance while implementing a rough feeling on the surface.
[146]
[147]
The HALS-based UV stabilizer is preferably 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethyl-4-pi). Peridyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4- piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-N-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate , 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid condensation product, N,N'-bis(2,2,6,6- Linear or cyclic condensation product of tetramethyl-4-piperidyl)hexamethylene diamine and 4-tert-octylamino-2,6-di-chloro-1,3,5-triazine, tris(2,2, 6,6-Tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate , 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-Stearyloxy-2,2,6,6-tetramethylpiperidine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine and 4- linear or cyclic condensation products of morpholino-2,6-dichloro-1,3,5-triazine, and 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3; 8-diaza-4-oxospiro-[4,5] at least one selected from the group consisting of a reaction product of decane and epichlorohydrin, more preferably bis(2,2,6,6-tetramethyl -4-piperidyl) sebacate (Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate), 2-(2H-benzotriazole-2-yl)-4-(-(1, 1,3,3-tetramethylbutyl)phenol (2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) or a mixture thereof, within this range It has excellent light resistance while realizing a rough feeling on the surface.
[148]
[149]
The thermoplastic resin composition of the present disclosure is optionally made of a heat stabilizer, a dye, a pigment, a colorant, a mold release agent, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a flame retardant, a flame retardant, an anti-drip agent, an anti-friction agent and a wear-resisting agent. 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.5 to 1 parts by weight, based on 100 parts by weight of the styrene-based resin, of at least one selected from the group may further include, within this range, the ASA-based resin There is an effect that necessary physical properties are well realized without reducing the original physical properties of the resin composition.
[150]
[151]
Thermoplastic resin composition
[152]
The thermoplastic resin composition of the present disclosure has a surface roughness Ra of 0.3 to 3 μm, preferably 0.35 to 2.8 μm, more preferably 0.35 to 2.5 μm, even more preferably 0.38 to 2.4 μm, more preferably 1 to 2.4 μm, and most preferably 1.5 to 2.4 μm. Within this range, mechanical properties and processability of the product are not deteriorated, weather resistance is excellent, and artificial plastic feel It provides a luxurious appearance that is out of the way.
[153]
The thermoplastic resin composition may have, for example, a melt flow index (MI) of 4 to 15 g/10min, preferably 10 to 15 g/10min, measured at 220°C under 10 kg according to ASTM D-1238. There is an advantage in that the workability is excellent within this range and the physical property balance is excellent.
[154]
The thermoplastic resin composition is, for example, ASTM 256 cm / cm, preferably 7 to 25 kg cm / cm with a thickness of 1/4 inch of the specimen, and has an advantage of excellent impact strength and excellent balance of properties within this range.
[155]
The method for producing the thermoplastic resin composition of the present invention preferably comprises the step of mixing 100 parts by weight of a styrene-based resin and 1 to 10 parts by weight of a surface control agent, and then preparing pellets using an extrusion kneader under 220 to 280 ° C. conditions, It is characterized in that the asymmetry Rsk of the thermoplastic resin composition is 0.65 to 1.35, and in this case, it has excellent weather resistance, low gloss, and even surface gloss while maintaining the same or higher mechanical properties and processability compared to conventional ASA resins. There is an advantage of providing an ASA resin product that has a low roughness value and gives an emotionally soft feeling.
[156]
In addition, the method for producing the thermoplastic resin composition of the present invention preferably includes the step of mixing 100 parts by weight of a styrene-based resin and 1 to 10 parts by weight of a surface control agent, and then preparing pellets using an extrusion kneader under 220 to 280 °C conditions. However, it is characterized in that the arithmetic mean roughness Ra measured at 5 points with the optical profiler system of the thermoplastic resin composition is 0.3 to 3 μm. Excellent, low gloss, even surface gloss and low surface roughness value, there are advantages of giving an emotionally soft feeling.
[157]
In addition, the method for producing the thermoplastic resin composition of the present invention preferably includes the step of mixing 100 parts by weight of a styrene-based resin and 1 to 10 parts by weight of a surface control agent, and then preparing pellets using an extrusion kneader under 220 to 280 °C conditions. However, the styrenic resin is a) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, b) aromatic vinyl compound-vinyl cyan compound copolymer, c) heat-resistant styrene-based resin, and d) methacrylate-aromatic At least one selected from the group consisting of a vinyl compound-vinyl cyan compound copolymer, wherein the surface control agent is a polystyrene-based surface control agent, a nylon-based surface control agent, and a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound-based surface control agent from the group consisting of It is characterized in that it is one or more selected, and in this case, mechanical properties and workability are maintained at the same or higher level compared to conventional ASA resins, but the weather resistance is excellent, the gloss is low, the surface gloss is uniform, and the surface roughness value is low, so emotionally soft feeling has the advantage of giving
[158]
[159]
The method for producing the thermoplastic resin composition shares all the technical characteristics of the aforementioned thermoplastic resin composition. Therefore, a description of the overlapping portion will be omitted.
[160]
[161]
The step of preparing the pellets using the extrusion kneader may be preferably carried out under 220 to 280 ℃, more preferably 240 to 280 ℃, wherein the temperature means the temperature set in the cylinder.
[162]
The extrusion kneader is not particularly limited if it is an extrusion kneader commonly used in the art to which the present invention belongs, and may preferably be a twin-screw extrusion kneader.
[163]
[164]
molded product
[165]
The molded article of the present base material is characterized in that it contains the thermoplastic resin composition of the present base material, and in this case, mechanical properties and processability are maintained at the same level or higher compared to conventional ASA resin products, and the weather resistance is excellent, and in particular, a rough feeling on the surface of the product It has the advantage of having a luxurious appearance that is free from the artificial feeling of plastic by implementing it.
[166]
The molded article may be, for example, an extrusion-molded article or an injection-molded article, preferably a building exterior material, and more preferably for decking It can be a building material for flooring or roofing.
[167]
The molded article may preferably be manufactured including the step of extruding or injecting the thermoplastic resin composition of the present invention at a molding temperature of 190 to 250 °C, and has the advantage of exhibiting an excellent matting effect within this range.
[168]
The extruding step may be performed using, for example, a film extruder.
[169]
[170]
In describing the thermoplastic resin composition of the present invention, its manufacturing method and molded article, other conditions or equipment not explicitly described can be appropriately selected within the range commonly practiced in the art, and it is specified that there is no particular limitation do.
[171]
[172]
Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely 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 spirit of the present invention, It goes without saying that such variations and modifications fall within the scope of the appended claims.
[173]
[174]
[Example]
[175]
Materials used in Examples 1 to 7 and Comparative Examples 1 to 2 below are as follows.
[176]
A-1) Small-diameter ASA resin with an average particle diameter of 100 nm of butyl acrylate rubber
[177]
A-2) Large-diameter ASA resin with an average particle diameter of 400 nm of butyl acrylate rubber
[178]
B-1) SAMMA resin (LG Chemical's XT500, weight average molecular weight: 80,000 g/mol)
[179]
B-2) SAMMA resin (LG Chem's XT510, weight average molecular weight: 130,000 g/mol)
[180]
C-1) SPS surface control agent (manufacturer: Idemitsu, trade name: 300ZC)
[181]
C-2) Nylon 66 (Manufacturer: Invista, Product Name: Poly amide N66 U4800)
[182]
C-3) Nylon 6 (Manufacturer: KP Chemtech, product name: Poly amide N6 EN300)
[183]
C-4) MA210 (Manufacturer: LG Chem, trade name: MA210)
[184]
C-4) SL0100 (Manufacturer: Lotte Advanced Materials, Product Name: SL0100)
[185]
C -4) AM808 (Manufacturer: Zeon Kasei, product name: AM808)
[186]
[187]
Example 1
[188]
21 parts by weight of small diameter ASA resin, 32 parts by weight of large diameter ASA resin, 47 parts by weight of SAMMA resin, 5 parts by weight of SPS surface control agent, 1.5 parts by weight of EBS (manufactured by pioneer) as lubricant, octadecyl 3-(3,5) as antioxidant - 0.5 parts by weight of di-t-butyl-4-hydroxyphenyl)propionate (octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate) and tris(2,4-di-tertiary- 0.5 parts by weight of butylphenyl)phosphite (Tris(2,4-di-tert.-butylphenyl)phosphite), 0.5 parts by weight of Tinuvin P (manufactured by BASF), a benzotriazole-based UV stabilizer as a UV stabilizer, and a HALS UV stabilizer After uniformly mixing 0.5 parts by weight of Tinuvin770 (manufactured by BASF), it was 28 pie under 220° C., L/D: 36 using an extrusion kneader to prepare ASA resin composition pellets.
[189]
The prepared ASA resin composition pellets are uniformly made into a film with a thickness of 0.15T through a film extruder, and then measured by the following measurement method using this as a sample. At this time, the film extruder uses a single screw extruder for sheet molding (manufactured by Collin, E20T product, 20 pie, L/D: 25), and the temperature condition is 50, 200, 210, 210 ° C. And the die part temperature was set to 220, 220, 230 ℃. The pellets were sufficiently dried in an oven at 80° C. for 3 hours or longer before input into the film extruder to remove the moisture influence, and then put into the inlet of the film extruder to uniformly produce a film with a thickness of 0.15T. The temperature of the used rear roller was set to 85° C. using water as a medium, and as shown in FIG. 3 below, a type in which only one side of the resin extruded through the T-die was in contact with the roller was used. Here, the RPM of the film extruder screw was fixed at 100 and the linear speed of the roll was adjusted so that the thickness of the film was 0.15T. Here, the asymmetry Rsk, the surface roughness value Ra, and the film gloss were measured for the surface in contact with the first roll among the extruded film surfaces, and surface roughness sensory evaluation was also performed. For reference, when measuring with a surface that is not in contact with the first roll, a difference in surface roughness may occur.
[190]
On the other hand, the prepared ASA resin composition pellets were injected under the conditions of injection temperature (inlet standard) 200, 210, 210, 220 ℃, mold temperature 60 ℃, holding pressure 3 bar, and injection speed 80 bar to obtain a specimen, the measurement method described below Melt index and Izod impact strength were measured.
[191]
[192]
Examples 2 to 7 and Comparative Examples 1 to 2
[193]
The SPS surface control agent in Example 1 was carried out in the same manner as in Example 1, except that the materials and contents of Table 1 were used.
[194]
[195]
[Test Example]
[196]
The properties of the 0.15T films prepared in Examples 1 to 7 and Comparative Examples 1 to 2 were measured by the following method, and the results are shown in Table 1 below.
[197]
* Asymmetry Rsk: Referring to FIG. 1 below, the optical profiler system (Nano View NV-2700, manufacturer: Nano System) was used as the equipment, and the analysis conditions were 20 times the objective lens × eyepiece in WSI Envelope mode. Scanning was performed over a range of ±40 μm using a 1x lens. Measurements were carried out for 5 points after the sample was flatly fixed on the stage. For the measured values, the average value for 5 points was calculated using the formula to find the root mean square deviation (Rq) shown in the upper figure and the asymmetry Rsk shown in the lower figure.
[198]
* Surface roughness value (Ra): 5 points were measured with an optical profiler system (NV-2700, Nanosystem Co., Ltd.) and averaged. When the surface roughness value is low, the hand feels soft to the touch and the gloss is even.
[199]
* Film gloss (gloss): was measured at 60 ° with a gloss meter (gloss meter) VG7000.
[200]
* Surface roughness sensory evaluation: When the surface was rubbed by hand, it was evaluated as ◎ if it was very rough, ○ if it was rough, △ if it was slightly rough, and X if it was smooth.
[201]
[202]
* Melt flow index (MI): Measured at 220°C under 10 kg according to ASTM D-1238.
[203]
* Izod impact strength (kg/cm2): The thickness of the specimen was 1/4 inch, and it was measured according to ASTM 256.
[204]
[205]
[Table 1]
Category Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2
Surface conditioner SPS Nylon 66 Nylon 66 Nylon 66 MA210 AM808 Nylon 66 + Nylon 6 Nylon 6 SL0100
Content (parts by weight) 5 1 3 5 5 5 6 (Nylon 66: 4 parts by weight, Nylon 6: 2 parts by weight) 5 5
Rsk 0.8 1.01 1.25 1.02 1.05 0.86 1.07 0.49 1.67
Ra 1.51 0.53 1.93 2.35 0.38 0.59 2.12 0.14 0.66
Film gloss 6.1 42.9 13.5 7.7 51.1 18 7 62.5 42.9
Roughness sensory evaluation ○ ○ ◎ ◎ ○ ○ ○ X △
Flow Index 10.4 15.0 14.3 13.1 10.8 11.5 13.5 14.2 11.8
Impact strength 7.07 17.6 12.7 8.6 24.2 22.9 8.8 9.5 23.8
[206]
As shown in Table 1, the thermoplastic resin composition (see Examples 1 to 7) having an Rsk value according to the present invention realized a very rough feeling on the sample surface as a result of the sensory evaluation, showing a luxurious appearance away from the artificial plastic feeling was able to confirm that
[207]
However, the thermoplastic resin composition (refer to Comparative Examples 1 and 2) that is less than or exceeding the Rsk value according to the present invention does not implement a rough feeling on the sample surface as a result of sensory evaluation, and is smooth like a general plastic surface. was able to confirm that the
Claims
[Claim 1]
A thermoplastic resin composition comprising 100 parts by weight of a styrenic resin and 1 to 10 parts by weight of a surface control agent, and having an asymmetry Rsk of 0.65 to 1.35.
[Claim 2]
According to claim 1, wherein the styrenic resin is a) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, b) aromatic vinyl compound-vinyl cyan compound copolymer, c) heat-resistant styrene-based resin, d) meta A thermoplastic resin composition, characterized in that at least one selected from the group consisting of acrylate-aromatic vinyl compound-vinyl cyan compound copolymer and e) polyalkyl methacrylate.
[Claim 3]
The method according to claim 2, wherein the styrenic resin comprises: a) 30 to 70 wt % of the acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, and b) 0 to 30 wt % of the aromatic vinyl compound-vinyl cyan compound copolymer. %, the c) 0 to 30% by weight of the heat-resistant styrene-based resin, d) 30 to 70% by weight of the methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer, and e) 0 to 40% by weight of polyalkyl methacrylate A thermoplastic resin composition comprising a.
[Claim 4]
The method according to claim 2, wherein the a) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprises i) 40 to 60 wt% of an acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, and 20 to 45 wt% of an aromatic vinyl compound And an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising 10 to 20 wt% of a vinyl cyan compound, and ii) an average particle diameter of 0.05 An acrylate-aromatic vinyl compound-vinyl cyan compound graft aerial comprising 40 to 60 wt% of an acrylate rubber having a size of ㎛ or more and less than 0.3 μm, 20 to 40 wt% of an aromatic vinyl compound, and 10 to 20 wt% of a vinyl cyan compound A thermoplastic resin composition, characterized in that at least one selected from the group consisting of coalescing.
[Claim 5]
The method according to claim 4, wherein the weight ratio (i:ii) of the i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and the ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer is 1 : A thermoplastic resin composition, characterized in that 0.3 to 0.9.
[Claim 6]
3. The method according to claim 2, wherein b) the aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight of 100,000 to 150,000 g/mol, and the weight average molecular weight is greater than 150,000 g/mol. , 200,000 g/mol or less of an aromatic vinyl compound-vinyl cyan compound copolymer A thermoplastic resin composition comprising at least one selected from the group consisting of copolymers.
[Claim 7]
The thermoplastic resin composition according to claim 2, wherein c) the heat-resistant styrene-based resin is an α-methylstyrene-vinyl cyan compound copolymer.
[Claim 8]
The method according to claim 2, wherein the d) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer comprises 65 to 85% by weight of methacrylate, 10 to 30% by weight of an aromatic vinyl compound, and 5 to 10% by weight of a vinylcyan compound. A thermoplastic resin composition comprising:
[Claim 9]
The thermoplastic resin composition according to claim 1, wherein the surface control agent is at least one selected from the group consisting of a polystyrene-based surface control agent, a nylon-based surface control agent, and a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound-based surface control agent.
[Claim 10]
According to claim 1, wherein the polystyrene-based surface control agent is at least one selected from the group consisting of glass fiber reinforced SPS, flame-retardant SPS, nylon-containing SPS, blended SPS, copolymerized SPS and homopolymer SPS, and the nylon-based Surface modifiers are polyamide 6, polyamide 66 (PA 6.6), polyamide 46, polyamide ll, polyamide 12, polyamide 610, polyamide 612, polyamide 6/66, polyamide 6/612, polyamide MXD6 , Polyamide 6/MXD6, Polyamide 66/MXD6, Polyamide 6T, Polyamide 6I, Polyamide 6/6T, Polyamide 6/6I, Polyamide 66/6T, Polyamide 66/6I, Polyamide 6/6T /6I, Polyamide 66/6T/6I, Polyamide 9T, Polyamide 9I, Polyamide 6/9T, Polyamide 6/9I, Polyamide 66/9T, Polyamide 6/12/9T, Polyamide 66/12 /9T, at least one selected from the group consisting of polyamide 6/12/9I and polyamide 66/12/6I, wherein the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound-based surface control agent has a particle diameter of 5 to 25 μm A thermoplastic resin composition, characterized in that it has a distribution.
[Claim 11]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an arithmetic mean roughness Ra of 0.3 to 3 μm measured at 5 points using an optical profiler system.
[Claim 12]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises a lubricant, an antioxidant and a UV stabilizer.
[Claim 13]
A molded article comprising the thermoplastic resin composition of any one of claims 1 to 12.
[Claim 14]
The molded article according to claim 13, wherein the molded article is a flooring material for decking, a roofing material, or a building exterior material.