Title of Invention: Thermoplastic resin composition and exterior material thereof
technical field
[One]
[Cross Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0091653 dated July 23, 2020 and Korean Patent Application No. 10-2021-0028289 filed again on March 3, 2021 based thereon, and the Korean patent 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 its exterior material, and more particularly, mechanical properties and processability compared to conventional ASA-based resins are maintained at the same or higher level, excellent weather resistance, and emotionally soft feeling due to a low surface roughness value It relates to a low-gloss thermoplastic resin composition with an even surface gloss and an exterior material thereof.
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]
In the case of ASA resins in the field of exterior materials, the need for developing low-gloss ASA resins that can satisfy the demand for sensible resins away from the artificial feeling of plastic is increasing.
[6]
As the low-gloss ASA resin, a crystalline resin such as nylon was conventionally used to achieve low gloss, but there was a limit to improvement in surface texture and emotional quality.
[7]
[Prior art literature]
[8]
[Patent Literature]
[9]
KR 2009-0095764 A
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[10]
In order to solve the problems of the prior art as described above, the present invention has superior mechanical properties and processability compared to the conventional ASA resin, and has uniform and low gloss and improved surface texture, so that emotional quality such as softness, luxury and naturalness An object of the present invention is to provide an excellent low-gloss thermoplastic resin composition and an exterior material 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 is a styrene-based resin 100 parts by weight; 0.5 to 5 parts by weight of a first polyamide resin having a melting temperature (Tm) of 230° C. or less; and 0.5 to 10 parts by weight of a second polyamide resin having a melting temperature (Tm) of 250° C. or higher, wherein the first and second polyamide resins both have a relative viscosity (96% sulfuric acid solution) of 2.5 or less. A resin composition is provided.
[13]
In the present description, the relative viscosity can be measured with a Ubbelohde viscometer by the ISO 307 sulfuric acid method. Specifically, a solution prepared by dissolving 1 g of a sample to be measured in 100 ml of an aqueous solution of sulfuric acid having a concentration of 96% by weight is measured using a Brookfield rotational viscometer (Brookfield). rotational viscometer) can be used to measure at 20°C.
[14]
In addition, the present invention is a styrene-based resin 100 parts by weight; 0.5 to 5 parts by weight of a first polyamide resin having a melting temperature (Tm) of 230° C. or less; and 0.5 to 10 parts by weight of the second polyamide resin having a melting temperature (Tm) of 250° C. or higher, and the pellets extruded under 280° C. at a barrel temperature of 50° C., 190° C., 190° C., 190° C. and a die part temperature of 200° C. , 200 ℃, 200 ℃, the 60 ° gloss value of the film produced by processing the film under the conditions of 200 ℃ and the extruded pellets under 280 ℃ barrel temperature 50 ℃, 200 ℃, 210 ℃, 210 ℃, and die part temperature 220 ℃, 220 It is possible to provide a thermoplastic resin composition characterized in that the 60 ° gloss value deviation of the film produced by processing the film under the conditions of ℃, 230 ℃ is 3.0 or less.
[15]
In addition, the present invention is a styrene-based resin 100 parts by weight; 0.5 to 5 parts by weight of a first polyamide resin having a melting temperature (Tm) of 230° C. or less; and 0.5 to 10 parts by weight of a second polyamide resin having a melting temperature (Tm) of 250° C. or higher, wherein the styrenic resin includes a first styrene-based resin and a second styrene-based resin, and the first styrene-based resin is A -1) An acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing acrylate rubber having a DLS average particle diameter of 0.05 to 0.2 μm or a TEM average particle diameter of 0.03 to 0.2 μm, and A-2) DLS average particle diameter of 0.3 to 0.5 At least one selected from the group consisting of acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymers containing acrylate rubber having an average particle diameter of ㎛ or TEM of 0.25 to 0.45 μm, and the second styrene-based resin is B-1) A thermoplastic, characterized in that at least one selected from the group consisting of aromatic vinyl compound-vinyl cyan compound copolymer, B-2) heat-resistant styrene-based resin, and B-3) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer. A resin composition can be provided.
[16]
In addition, the present invention provides an exterior material comprising the thermoplastic resin composition.
[17]
The facing material may preferably be a siding material, a roofing material or a decking material.
Effects of the Invention
[18]
According to the present invention, a low-gloss thermoplastic resin composition having superior sensibility qualities such as softness, luxury and naturalness through improvement of even and low gloss and surface texture while having mechanical properties and processability equal to or greater than that of conventional ASA resins and exterior materials thereof has the effect of
Brief description of the drawing
[19]
1 is a photograph taken by the film extruder used in Examples.
Modes for carrying out the invention
[20]
Hereinafter, the thermoplastic resin composition of the present disclosure and its packaging material will be described in detail.
[21]
The present inventors have found that when two types of polyamides having different melting temperatures (Tm) of a relative viscosity of 2.5 or less are added to a predetermined styrenic resin in a predetermined amount, or when a predetermined styrenic resin has a different melting temperature (Tm) When two types of polyamides are added in a predetermined amount and the deviation of 45° film gloss according to the extrusion conditions of the thermoplastic resin composition is adjusted within a predetermined range, mechanical properties, weather resistance and processability are lowered compared to the conventional ASA resin composition It was confirmed that the gloss was low and even, and the surface texture was natural and luxurious unlike the plastic feeling, and based on this, further research was completed and the present invention was completed.
[22]
[23]
The thermoplastic resin composition of the present invention includes 100 parts by weight of a styrene-based resin; 0.5 to 5 parts by weight of a first polyamide resin having a melting temperature (Tm) of 230° C. or less; and 0.5 to 10 parts by weight of a second polyamide resin having a melting temperature (Tm) of 250° C. or higher, wherein both the first and second polyamide resins have a relative viscosity of 2.5 or less, in this case, a conventional ASA-based resin There is an advantage in providing a thermoplastic resin composition that has excellent weather resistance, low gloss, uniform surface gloss, and low surface roughness value while maintaining the same or higher mechanical properties and processability compared to resins, giving an emotionally soft feeling.
[24]
In addition, the thermoplastic resin composition of the present invention is 100 parts by weight of a styrene-based resin; 0.5 to 5 parts by weight of a first polyamide resin having a melting temperature (Tm) of 230° C. or less; and 0.5 to 10 parts by weight of a second polyamide resin having a melting temperature (Tm) of 250 ° C. or higher, 280 ° C. extrusion and film processing 60 ° gloss value of the film produced at 190 ° C. and 280 ° C. extrusion and film processing 220 ° C. It is characterized in that the 60 ° gloss value deviation of the produced film is 3.0 or less. There is an advantage in providing a thermoplastic resin composition that is even and has a low surface roughness value, which gives an emotionally soft feeling.
[25]
In addition, the thermoplastic resin composition of the present invention is 100 parts by weight of a styrene-based resin; 0.5 to 5 parts by weight of a first polyamide resin having a melting temperature (Tm) of 230° C. or less; and 0.5 to 10 parts by weight of a second polyamide resin having a melting temperature (Tm) of 250° C. or higher, wherein the styrenic resin includes a first styrene-based resin and a second styrene-based resin, and the first styrene-based resin is A -1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having a DLS average particle diameter of 0.05 to 0.2 μm or a TEM average particle diameter of 0.03 to 0.2 μm, and A-2) DLS average particle diameter of 0.3 to At least one selected from the group consisting of acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymers containing acrylate rubber of 0.5 μm or TEM average particle diameter of 0.25 to 0.45 μm, and the second styrene-based resin is B-1 ) aromatic vinyl compound-vinyl cyan compound copolymer, B-2) heat-resistant styrene resin, and B-3) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer, characterized in that at least one selected from the group consisting of copolymers, , In this case, mechanical properties and processability are maintained at the same level or higher compared to conventional ASA-based resins, while excellent weather resistance, low gloss, uniform surface gloss, and low surface roughness provide a thermoplastic resin composition that gives an emotionally soft feeling there is an advantage to
[26]
[27]
Hereinafter, each component constituting the thermoplastic resin composition of the present disclosure will be described in detail as follows.
[28]
[29]
styrenic resin
[30]
The styrene-based resin may preferably include a first styrene-based resin and a second styrene-based resin.
[31]
In the present description, 'styrene-based resin' follows the definition of a styrene-based resin commonly recognized in the technical field to which the present invention belongs, and may mean, for example, a resin including units derived from an aromatic vinyl compound.
[32]
[33]
The styrenic resin may preferably include 10 to 70% by weight of the first styrene-based resin and 30 to 90% by weight of the second styrene-based resin, more preferably 30 to 70% by weight of the first styrene-based resin, and 30 to 70% by weight of the second styrene-based resin, more preferably 40 to 60% by weight of the first styrene-based resin, and 40 to 60% by weight of the second styrene-based resin, even more preferably the first 40 to 55% by weight of the styrenic resin and 45 to 60% by weight of the second styrenic resin, and most preferably 44 to 50% by weight of the first styrenic resin and 50 to 56% by weight of the second styrenic resin However, within this range, the mechanical properties and workability are not deteriorated, and the weather resistance is excellent, the gloss is low, the surface gloss is even, and the surface roughness value is low, so that it has the effect of giving an emotionally soft feeling.
[34]
[35]
first styrenic resin
[36]
The first styrenic resin is preferably A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having a DLS average particle diameter of 0.05 to 0.2 μm or a TEM average particle diameter of 0.03 to 0.2 μm. , and A-2) at least one selected from the group consisting of an acrylate rubber having a DLS average particle diameter of 0.3 to 0.5 μm or a TEM average particle diameter of 0.25 to 0.45 μm-aromatic vinyl compound-vinyl cyan compound graft copolymer and preferably a mixture of A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and A-2) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, in this case Compared to conventional ASA-based resins, mechanical properties and workability are equal or higher, and there is an advantage in that it has excellent emotional qualities such as softness, luxury and naturalness due to the improvement of even and low gloss and surface texture.
[37]
Weight ratio of the A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and A-2) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-1:A-2) is preferably 1: 0.5 to 2, more preferably 1: 0.6 to 1.8, in a specific example 1: 0.5 to 0.9, more preferably 1: 0.6 to 0.9, and in another specific example 1: 1.3 to 2, more A preferred example may be 1: 1.5 to 1.8, and within this range, the surface of the ASA resin product has an excellent effect in weather resistance, fluidity, tensile strength and impact strength while realizing a rough feeling.
[38]
[39]
A-1) An acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having a DLS average particle diameter of 0.05 to 0.2 μm or a TEM average particle diameter of 0.03 to 0.2 μm
[40]
A-1) The acrylate rubber of the graft copolymer preferably has a DLS or TEM average particle diameter of 0.05 to 0.18 μm, more preferably 0.05 to 0.15 μm, still more preferably 0.08 to 0.15 μm, more It is preferably 0.08 to 0.12 μm, and excellent weather resistance, colorability, impact strength, chemical resistance and surface gloss properties can be imparted to the final product within this range.
[41]
In this description, the DLS 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. 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.
[42]
In addition, in the present description, the DLS 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.
[43]
[44]
In the present description, the TEM average particle size may be measured using a transmission electron microscope (TEM) analysis, and specifically, it may be obtained as an average value by numerically measuring the particle size on a high magnification image of the TEM. In this case, specific measurement examples are as follows:
[45]
- Sample preparation: thermoplastic resin or thermoplastic resin composition prepared by extrusion kneading machine
[46]
- Sample pretreatment: Trimming (23℃) → Hydrazine treatment (72℃, 5 days) → Sectioning (-120℃) → OsO4 vapor staining 2 hours
[47]
- Analysis instrument: TEM (Jeol, JEM-1400)
[48]
- Analysis conditions: Acc. Volt 120KV, SPOT Size 1 (X 10K, X 25K, X 50K)
[49]
- Size (average particle diameter) measurement: average of diameters with the top 10% in diameter size
[50]
[51]
The A-1) graft copolymer is, for example, 10 to 35% by weight, preferably 15 to 35% by weight, more preferably 15 to 30% by weight, based on the total weight of the styrenic resin, and weather resistance, within this range, It has excellent fluidity, tensile strength and impact strength.
[52]
[53]
The A-1) graft copolymer may include, for example, 40 to 60% by weight of the acrylate rubber, 20 to 45% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyanide compound, preferably the 40 to 60% by weight of the acrylate rubber, 25 to 45% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyan compound, more preferably 45 to 55% by weight of the acrylate rubber, 30% by weight of the aromatic vinyl compound to 50% by weight and 5 to 20% by weight of a vinyl cyanide compound, more preferably 47 to 57% by weight of the acrylate rubber , 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound It has excellent effects in weather resistance, fluidity, tensile strength and impact strength within this range.
[54]
[55]
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.
[56]
In the present description, 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 acrylate or ethylhexyl acrylate.
[57]
In the present description, 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 preferably styrene.
[58]
In the present description, the vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methnitrolonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, and preferably acrylonitrile.
[59]
[60]
The A-1) 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.
[61]
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.
[62]
[63]
A-2) Acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having a DLS average particle diameter of 0.3 to 0.5 μm or a TEM average particle diameter of 0.25 to 0.45 μm
[64]
A-2) The acrylate rubber of the graft copolymer preferably has a DLS 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 0.38 to 0.42 μm, and within this range, the weather resistance is good and mechanical properties such as fluidity, tensile strength and impact strength are excellent.
[65]
The acrylate rubber of the A-2) graft copolymer preferably has a TEM average particle diameter of 0.3 to 0.45 μm, more preferably 0.35 to 0.45 μm, still more preferably 0.35 to 0.42 μm, Even more preferably, the thickness is 0.38 to 0.42 μm, and within this range, the weather resistance is good and mechanical properties such as fluidity, tensile strength and impact strength are excellent.
[66]
[67]
The A-2) graft copolymer is, for example, 15 to 40% by weight, preferably 20 to 35% by weight, more preferably 20 to 30% by weight based on the total weight of the styrenic resin, and weather resistance within this range, It has excellent fluidity, tensile strength and impact strength.
[68]
[69]
The A-2) graft copolymer comprises 40 to 60% by weight of the acrylate rubber, 20 to 45% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyanide compound, for example, and preferably, the acryl 40 to 60% by weight of the late rubber, 25 to 45% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyanide compound, more preferably 45 to 55% by weight of the acrylate rubber, 30 to 30% by weight of the aromatic vinyl compound It comprises 40 wt% and 10 to 20 wt% of the vinyl cyanide compound, and has excellent effects in weather resistance, fluidity, tensile strength and impact strength within this range.
[70]
[71]
The A-2) 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.
[72]
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.
[73]
[74]
Second Styrenic Resin
[75]
The second styrene-based resin is preferably B-1) an aromatic vinyl compound-vinyl cyan compound copolymer, B-2) a heat-resistant styrene-based resin, and B-3) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer. It may be at least one selected from the group consisting of.
[76]
[77]
B-1) Aromatic vinyl compound-vinyl cyan compound copolymer
[78]
The B-1) aromatic vinyl compound-vinyl cyan compound copolymer is preferably i) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 90,000 to 135,000 g/mol; ii) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of greater than 135,000 g/mol to 155,000 g/mol or less; and iii) an aromatic vinyl compound having a weight average molecular weight of greater than 155,000 g/mol to 200,000 g/mol or less-vinyl cyan compound copolymer; Use of vinyl cyanide compound copolymer alone; Or the above ii) aromatic vinyl compound-vinyl cyan compound copolymer and iii) aromatic vinyl compound-vinyl cyan compound copolymer are mixed use, and in this case, heat resistance, chemical resistance and impact strength, tensile strength, and processability are excellent. .
[79]
The i) aromatic vinyl compound-vinyl cyan compound copolymer is preferably included in an amount of 30 to 60% by weight, more preferably 40 to 50% by weight, based on the total weight of the styrenic resin, and in this case, heat resistance, chemical resistance and It has excellent impact strength, tensile strength, and workability.
[80]
The ii) aromatic vinyl compound-vinyl cyan compound copolymer is preferably included in an amount of 10 to 40% by weight, more preferably 20 to 30% by weight, and still more preferably 20 to 25% by weight based on the total weight of the styrenic resin. In this case, heat resistance, chemical resistance, impact strength, tensile strength, and workability are excellent.
[81]
The iii) aromatic vinyl compound-vinyl cyan compound copolymer is preferably included in an amount of 10 to 40% by weight, more preferably 20 to 30% by weight, and still more preferably 25 to 30% by weight based on the total weight of the styrenic resin. In this case, heat resistance, chemical resistance, impact strength, tensile strength, and workability are excellent.
[82]
In the present description, unless otherwise defined, the weight average molecular weight can 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 ) can be measured as a relative value with respect to a standard PS (standard polystyrene) sample. 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.
[83]
[84]
The B-1) aromatic vinyl compound-vinyl cyan compound copolymer comprises, for example, 65 to 80 wt % of an aromatic vinyl compound and 20 to 35 wt % of a vinyl cyan compound, preferably 67 to 80 wt % of an aromatic vinyl compound % and 20 to 33 wt% of a vinyl cyan compound, and more preferably 70 to 75 wt% of an aromatic vinyl compound and 25 to 30 wt% of a vinyl cyan compound, and chemical resistance and The impact strength is excellent in tensile strength and workability.
[85]
[86]
The B-1) 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.
[87]
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.
[88]
[89]
B-2) Heat-resistant styrene resin
[90]
B-2) The heat-resistant styrenic resin is preferably 1 to 25% by weight, more preferably 5 to 20% by weight, still more preferably 10 to 20% by weight, most preferably based on the total weight of the styrenic resin. It may be included in an amount of 13 to 18% by weight, and there is an advantage in that mechanical properties, heat resistance, processability, etc. are excellent within this range.
[91]
[92]
The B-2) 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.
[93]
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.
[94]
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 and 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, and there is an excellent effect of heat resistance within this range.
[95]
[96]
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 110,000 g/mol, still more preferably 8,5000 to 110,000 g/mol, and , there is an effect excellent in heat resistance and the like within this range.
[97]
[98]
The B-2) heat-resistant styrene-based 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.
[99]
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.
[100]
[101]
B-3) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer
[102]
The B-3) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer is preferably 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 It can be made including, and within this range, the weather resistance is greatly improved, and the surface roughness value is low, so there is an emotionally soft effect.
[103]
The B-3) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer is preferably 5 to 65% by weight, more preferably 5 to 45% by weight, still more preferably 5 to 20% by weight, most preferably It may be included in an amount of 5 to 15% by weight, and within this range, weather resistance is greatly improved, and the surface roughness value is low, so that there is an emotionally soft effect.
[104]
As another example, the B-3) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer is 30 to 65% by weight, preferably 35 to 60% by weight, more preferably 40 to 60% by weight, even more preferably It may be included in an amount of 40 to 58% by weight, and within this range, weather resistance is greatly improved, and the surface roughness value is low, so that there is an emotionally soft effect.
[105]
[106]
In the present description, the methacrylate monomer may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples thereof include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylbutyl methacrylate. , 2-ethylhexyl methacrylate and lauryl methacrylate may be at least one selected from the group consisting of, preferably an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, more preferably methyl methacrylate.
[107]
[108]
The B-3) 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, More preferably, it may be 120,000 to 140,000 g/mol, and within this range, the weather resistance is more excellent, the fluidity, the tensile strength and the impact strength are excellent, and the surface roughness value is low and there is an emotionally soft effect.
[109]
[110]
The B-3) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer may be prepared by, for example, solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, and is preferably prepared by bulk polymerization, and the solution Polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization are not particularly limited in the case of solution polymerization, block polymerization, emulsion polymerization, and suspension polymerization methods commonly performed in the art to which the present invention belongs, respectively.
[111]
[112]
first polyamide
[113]
The first polyamide resin of the present base is preferably 0.5 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, still more preferably 1 to 3 parts by weight, most preferably based on 100 parts by weight of the styrenic resin. 1 to 2 parts by weight, and while maintaining the same or higher mechanical properties and processability within this range, the thermoplastic resin composition has excellent weather resistance, low gloss, uniform surface gloss, and low surface roughness, giving an emotionally soft feeling has the advantage of providing
[114]
The first polyamide resin preferably has a melting temperature (Tm) of 230° C. or less, and a specific example is 210 to 230° C., preferably 220 to 230° C., and has particularly low gloss within this range, and has an even surface gloss. There is an advantage in providing a thermoplastic resin composition that has a low surface roughness value and gives an emotionally soft feeling.
[115]
[116]
secondary polyamide
[117]
The second polyamide resin of the present base is preferably 0.5 to 10 parts by weight, more preferably 1 to 6 parts by weight, still more preferably 2 to 5 parts by weight, most preferably based on 100 parts by weight of the styrenic resin. 2 to 4 parts by weight or 3 to 4 parts by weight, and while maintaining the same or higher mechanical properties and workability within this range, excellent weather resistance, low gloss, even surface gloss and low surface roughness value, emotionally soft It is advantageous to provide a thermoplastic resin composition that provides a feel.
[118]
The second polyamide resin preferably has a melting temperature (Tm) of 250° C. or higher, and a specific example is 250 to 280° C., preferably 250 to 270° C., and has particularly low gloss within this range, and has an even surface gloss It has the advantage of giving an emotionally soft feeling due to the low surface roughness value.
[119]
In the present disclosure, the melting temperature (Tm, Melting Temperature) may be measured by a measurement method commonly used in the technical field to which the present invention belongs, and specifically, it may be measured by a Dynamic Scanning Calorimeter (DSC) method. .
[120]
[121]
The first and second polyamide resins preferably both have a relative viscosity (96% sulfuric acid solution) of 2.5 or less, a specific example of 2.0 to 2.5, and a preferred example of 2.2 to 2.5, and within this range, mechanical properties and processability, etc. There is an advantage of providing a thermoplastic resin composition that has excellent weather resistance, low gloss, even surface gloss, and low surface roughness value while maintaining the same or more, giving an emotionally soft feeling.
[122]
In the present description, % means % by weight unless otherwise defined.
[123]
[124]
The sum of the weights of the first and second polyamide resins is preferably 1 to 10 parts by weight, more preferably 3 to 8 parts by weight, still more preferably 5 to 6 parts by weight based on 100 parts by weight of the total styrenic resin. Advantage of providing a thermoplastic resin composition that has excellent weather resistance, low gloss, even surface gloss, and low surface roughness value while maintaining the same or higher mechanical properties and processability within this range, giving an emotionally soft feeling There is this.
[125]
[126]
In the present base material, if the first and second polyamide resins satisfy the melting temperature and relative viscosity according to the present invention, respectively, there is no particular limitation on the type thereof, and specific examples 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, polyamide 66/12/9T, polyamide 6/12/9I and polyamide 66/12/ It may be at least one member selected from the group consisting of 6I, and preferably at least one member selected from the group consisting of polyamide 6, polyamide 12, and polyamide 66.
[127]
[128]
The method for preparing the first and second polyamide resins is not particularly limited as long as it is a polymerization method commonly carried out in the art to which the present invention belongs, and is commercially purchased and used if it meets the definition of polyamide according to the present invention. is also free
[129]
[130]
Thermoplastic resin composition
[131]
The thermoplastic resin composition of the present disclosure is preferably produced by processing the extruded pellets under 280 ℃ into a film under the conditions of barrel temperature 50 ℃, 190 ℃, 190 ℃, 190 ℃ and die part temperature 200 ℃, 200 ℃, 200 ℃ A film produced by processing the 45 ° gloss value of one film and pellets extruded under 280 ° C under the conditions of barrel temperature 50 ° C, 200 ° C, 210 ° C, 210 ° C and die temperature 220 ° C, 220 ° C, 230 ° C. The deviation of the 45° gloss value is 1 or less, preferably 0.7 or less, and within this range, it provides an exterior material with excellent emotional quality such as softness, luxury and naturalness, and processing stability through the improvement of even and low gloss and surface texture within this range. there is an advantage to
[132]
[133]
The thermoplastic resin composition is preferably a film produced by processing the extruded pellets under 280 ℃ into a film under the conditions of barrel temperature 50 ℃, 190 ℃, 190 ℃, 190 ℃ and die part temperature 200 ℃, 200 ℃, 200 ℃ 60 ° Gloss value of 60 ° of the film produced by processing the extruded pellets at 280 ° C under the conditions of barrel temperature 50 ° C, 200 ° C, 210 ° C, 210 ° C and die temperature 220 ° C, 220 ° C, 230 ° C. ° Deviation of gloss value is 3.0 or less, 2.8 or less, 2.0 or less, 1.5 or less, preferably 1 or less, and within this range, the emotional quality such as softness, luxury and naturalness is improved through the improvement of even and low gloss and surface texture. It has the advantage of providing an excellent exterior material.
[134]
The thermoplastic resin composition is preferably a film produced by processing the extruded pellets under 280 ℃ into a film under the conditions of barrel temperature 50 ℃, 190 ℃, 190 ℃, 190 ℃ and die part temperature 200 ℃, 200 ℃, 200 ℃ The 75 ° gloss value of the film produced by processing the pellets extruded under 280 ° C under the conditions of the barrel temperature of 50 ° C, 200 ° C, 210 ° C, 210 ° C, and the die temperature of 220 ° C, 220 ° C, 230 ° C. ° Deviation of gloss value is 8.2 or less, 8.1 or less, 8.0 or less, preferably 6.5 or less. There are advantages to providing.
[135]
[136]
The thermoplastic resin composition is, for example, 0.1 to 5 parts by weight of the inorganic pigment in 100 parts by weight of the total thermoplastic resin composition, preferably 0.1 to 2 parts by weight, more preferably 0.1 to 1 parts by weight, more preferably 0.3 to 0.6 It may be included in parts by weight, and there is an excellent effect of weather resistance and hiding power within this range.
[137]
The inorganic pigment may be, for example, at least one selected from the group consisting of a metal compound such as Ti, Pb, Fe, Cr, and carbon black, and the metal compound is preferably a metal oxide or a metal hydroxide. For example, TiO 2 , zinc oxide (Zinc Oxide) as a white inorganic pigment ; Carbon black, graphite as black inorganic pigments; IOR, Cadmium Red, Red Lead (Pb3O4) as red inorganic pigments; Chrome Yellow, Zinc Chromate, Cadmium Y.; and at least one selected from the group consisting of Chrome Green and Zinc Green as the green inorganic pigment, and the most preferred inorganic pigment may be TiO 2 which is a white inorganic pigment .
[138]
[139]
The thermoplastic resin composition preferably has an average surface roughness (Ra) of 2.3 or less , more preferably 2.1 or less, measured at 5 points with an optical profiler system, preferably 1.9 to 2.3, more preferably 1.9 to 2.1 In this range, softness, luxury, and naturalness have excellent effects.
[140]
The thermoplastic resin composition may be a matte thermoplastic resin composition having a film gloss of 15 or less, preferably 10 or less, and still more preferably 7 or less, as measured at 60° with a gloss meter VG7000. It may be a resin composition, and within this range, there is an effect of excellent matt properties and excellent balance of physical properties. Accordingly, the thermoplastic resin composition of the present disclosure may also be referred to as a matte thermoplastic resin composition.
[141]
[142]
For example, the thermoplastic resin composition may have a weather resistance (ΔE) of 7.0 or less, preferably 6.5 or less, and more preferably 6.0 or less, measured for 2000 hours by the SAE J1960 method.
[143]
The thermoplastic resin composition has, for example, a flow index (MI) (220°C, load 10 kg) according to ASTM D1238 of 4 g/10 min or more, preferably 4 to 10 g/10 min, and preferably 4 to 8 g/ 10 min, and more preferably 4 to 6.5 g/10 min, within this range, the workability is excellent within this range, and the surface roughness value is low, and there are excellent effects such as softness, luxury and naturalness.
[144]
The thermoplastic resin composition has, for example, a tensile strength (1/8 inch) of 350 kg/cm 2 or more according to ASTM 638, preferably 370 kg/cm 2 or more, more preferably 400 kg/cm 2 or more, and still more preferably 420 kg/cm 2 or more, and may be 380 to 490 kg/cm 2 as a specific example.
[145]
The thermoplastic resin composition has an Izod impact strength (1/4 inch) of 8 kg·cm/cm or more, preferably 10 kg·cm/cm or more, more preferably 11 kg·cm/cm according to ASTM 256, for example. Above, it may be 10 to 12 kg · cm / cm as a specific example, there is an advantage suitable for siding, roof and decking materials within this range.
[146]
[147]
The thermoplastic resin composition optionally includes a lubricant, a pigment, a heat stabilizer, a light stabilizer, a dye, 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 It may further include 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 of at least one selected from the group consisting of anti-wear agents, and within this range, the thermoplastic resin composition of the present invention is naturally There is an advantage in that the necessary physical properties are well realized without degrading the physical properties of the product.
[148]
[149]
The method for producing the thermoplastic resin composition of the present invention preferably comprises: 100 parts by weight of a styrene-based resin; 0.5 to 5 parts by weight of a first polyamide resin having a relative viscosity of 2.5 or less and a melting temperature (Tm) of 230° C. or less; And after mixing 0.5 to 10 parts by weight of a second polyamide resin having a relative viscosity of 2.5 or less and a melting temperature (Tm) of 250 ° C. or higher, preparing pellets using an extrusion kneader under conditions of 220 to 280 ° C. It is characterized in that, in this case, mechanical properties and processability are maintained at the same level or higher compared to conventional ASA-based resins, but the weather resistance is excellent, the gloss is low, the surface gloss is uniform, and the surface roughness value is low, so a thermoplastic that gives an emotionally soft feeling There is an advantage of providing a resin composition.
[150]
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.
[151]
[152]
The step of preparing the pellets using the extrusion kneader may be carried out preferably under 220 to 290 ℃, more preferably under 250 to 290 ℃, more preferably under 270 to 290 ℃, wherein the temperature is It means the temperature set in the reader.
[153]
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.
[154]
[155]
< Exterior material >
[156]
The exterior material of the present substrate is characterized in that it contains the thermoplastic resin composition of the present substrate, and in this case, mechanical properties and processability are equal to or higher than that of the conventional ASA resin, and smoothness, luxury and nature due to the improvement of even and low gloss and surface texture There is an advantage in that the emotional quality such as sensibility is excellent.
[157]
The exterior material may be, for example, a co-extrusion extrusion molding product or an injection molding product, preferably a siding material, a decking material, a roofing material, and more preferably a sliding door or a window. .
[158]
[159]
The exterior material is preferably extruded or injected at a molding temperature of 190 to 250 ° C., preferably at 190 to 230 ° C., more preferably at 190 to 220 ° C. It can be manufactured including the step of extruding or injecting the thermoplastic resin composition of the present invention. , there is an advantage that the matting effect is well expressed on the product within this range.
[160]
In describing the thermoplastic resin composition of the present invention, its manufacturing method and the exterior material, other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art, and it is specified that there is no particular limitation do.
[161]
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.
[162]
[163]
[Example]
[164]
Materials used in Examples 1 to 7 and Comparative Examples 1 to 7 below are as follows.
[165]
A-1) First graft copolymer of emulsion polymerization (Core: 50 wt% of butyl acrylate polymer having an average particle diameter of 100 nm, Shell: 36 wt% of styrene, 14 wt% of acrylnitrile)
[166]
A-2) Second graft copolymer of emulsion polymerization (Core: 50 wt% of butyl acrylate polymer having an average particle diameter of 400 nm, Shell: 37 wt% of styrene, 13 wt% of acrylnitrile)
[167]
B-1) Bulk polymerization method SAN resin with weight average molecular weight of 120,000 g/mol (92RF)
[168]
B-2) Bulk polymerization method SAN resin with weight average molecular weight of 150,000 g/mol (90HR)
[169]
B-3) Bulk polymerization type SAN resin with a weight average molecular weight of 173,000 g/mol (97HC)
[170]
B-4) Bulk polymerization method SAN resin with a weight average molecular weight of 90,000 g/mol (200UH)
[171]
B-5) Bulk polymerization method SAMMA resin (XT510) with a weight average molecular weight of 130,000 g/mol
[172]
C-1) PA 6 with a melting temperature (Tm) of 221 °C and a relative viscosity of 2.5
[173]
C-2) Melting temperature (Tm) of 180 ℃ PA 12 (Rilsamid Aesno TL)
[174]
C-3) PA 6.6 with a melting temperature (Tm) of 259 °C and a relative viscosity of 2.4
[175]
C-4) PA 6.6 with a melting temperature (Tm) of 261 °C and a relative viscosity of 2.7
[176]
[177]
Examples 1 to 7 and Comparative Examples 1 to 7
[178]
Each of the components and contents listed in Table 1 below were prepared into pellets using an extrusion kneader (twin screw extruder) of 28 pie, L/D 36 standard under 280 °C.
[179]
Melt index was measured with the prepared pellets.
[180]
In addition, the prepared pellets were uniformly prepared into a film with a thickness of 0.15T through a film extruder, and film gloss and surface roughness values ​​(Ra) were measured by the following 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 conditions are 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. 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 sheet was 0.15T. Here, film gloss and surface roughness (Ra), etc. were measured for the surface in contact with the first roll among the extruded sheet surfaces. For reference, when measuring with a surface that is not in contact with the first roll, a difference in surface roughness may occur.
[181]
Furthermore, the prepared pellets were injected at a molding temperature of 220° C. to prepare a specimen for measuring physical properties, and tensile strength and impact strength were measured using this.
[182]
[183]
[Test Example 1]
[184]
The properties of the pellets, sheets and specimens prepared in Examples 1 to 7 and Comparative Examples 1 to 7 were measured by the following method, and the results are shown in Table 1 below.
[185]
* Melt index (MI): The prepared pellets were measured by the ASTM D1238 method under the conditions of 220 ℃ / 10 kg.
[186]
* Tensile strength (kg/cm 2 ): Measured by ASTM 638 method.
[187]
* Izod impact strength (kg.cm/cm): Measured by ASTM 256 method.
[188]
* Film Gloss: Measured at 60° with a gloss meter VG7000.
[189]
* Surface roughness value (Ra): Optical profiler system (NV-2700, Nanosystem Co., Ltd.) Objective lens: 10x X eyepiece 1x (FOV: 628㎛ x 471㎛), Mode: WSI Envelope and Scan range: ± 5 points were measured under the condition of 30 μm and averaged. When the surface roughness value is low, the hand feels soft to the touch and the gloss is even.
[190]
* Weather resistance: After 2000 hours of measurement by the SAE J1960 method, it was evaluated as ΔE calculated by Equation 1 below. When the ΔE value is low, the weather resistance is excellent.
[191]
[Equation 1]
[192]
ΔE = √{(ΔL) 2 + (Δa) 2 + (Δb) 2 }
[193]
(In Equation 1, √ is the radical.)
[194]
[195]
[Table 1]
(parts by weight) Example comparative example
One 2 3 4 5 6 7 One 2 3 4 5 6 7
A-1 30 30 26 20 16 16 29 20 30 26 12 16 16 30
A-2 20 20 22 30 28 28 22 30 20 22 26 28 28 20
B-1 45 45
B-2 22 22 20 22 20 40 22
B-3 28 28 32 39 28 32 22 28
B-4 15 15
B-5 41 56 10 41 56
C-1 One One 2 One One One One
C-2 One
C-3 4 4 4 4 4 4 4 4 5 5 5 5 5
C-4 4
TiO 2 pigment 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
flow index 4.8 5.1 4.5 6.3 4.8 5.0 4.3 7.0 4.6 4.0 7.8 4.6 4.8 4.7
The tensile strength 420 424 427 385 431 422 412 388 423 430 483 434 416 419
impact strength 11.31 11.27 11.9 10.39 11.19 10.2 10.1 13.19 10.0 10.7 7.6 9.8 10.0 10.27
Gloss 6.8 8.6 7.7 6.8 7.0 7.8 8.8 7.2 6.5 6.4 6.7 5.9 6.7 5.2
surface roughness 2.27 1.56 2.3 2.3 2.3 1.9 2.16 2.69 2.9 2.92 4.54 3.1 2.5 2.83
△E 1.8 - 1.4 5.9 5.9 2.6 - - - - 6.1 5.9 -
[196]
As shown in Table 1, the thermoplastic resin composition (see Examples 1 to 7) according to the present invention has mechanical properties and surface gloss, such as flow index, tensile strength, and impact strength, compared to Comparative Examples 1 to 7, which have different configurations. It was confirmed that the surface roughness value was absolutely low while maintaining the same or higher value, giving an emotionally soft feeling and a sense of luxury. In particular, Example 2 containing both PA 12 and PA 6.6 according to the present invention and the polyamide poly In Example 6 containing the methacrylate resin in the range of 50 to 60 wt %, it was confirmed that the surface roughness was less than 2.0, and particularly high quality sensitivity resin was prepared.
[197]
On the other hand, in the case of Comparative Example 7 including PA 6.6 of a viscosity that does not conform to the present invention even if it contains heterogeneous polyamides, it was confirmed that the surface roughness and the like were poor.
[198]
[199]
[Test Example 2]
[200]
The pellets prepared in Examples 1 to 7 and Comparative Examples 1 to 6 were uniformly produced as a film with a thickness of 0.15T through a film extruder, and using this as a sample, a film gloss according to the present substrate, etc. was measured, and the results are shown in Table 2 below. 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 190 ° C. In the case of processing, the barrel temperature is 50, 190 in order from the extruder inlet. , 190, 190 ℃ and die temperature 200, 200, 200 ℃, in the case of 220 ℃ processing, in order from the extruder inlet, barrel temperature 50, 200, 210, 210 ℃, and die part temperature 220, 220, 230 ℃ was set to 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. 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 sheet was 0.15T.
[201]
[202]
[Table 2]
　division Film gloss (75°) Film gloss (60°)
220℃ processing 190℃ processing Gloss
Range (190℃-220℃) 220℃ processing 190℃ processing Gloss
Range (190℃-220℃)
Example 1 19.2 27.3 8.1 6.8 9.6 2.8
Example 2 23.5 31.1 7.6 9.6 10.6 1.0
Example 3 20.1 26.4 6.3 7.7 8.7 1.0
Example 4 19.7 16.3 -3.4 6.8 5.0 -1.8
Example 5 20.0 25.0 5.0 7.0 7.6 0.6
Example 6 20.8 26.0 5.2 7.8 8.6 0.8
Example 7 21.2 27.7 6.5 8.8 10.3 1.5
Comparative Example 1 16.9 27.9 11.0 7.2 10.9 3.7
Comparative Example 2 16.5 27.9 11.4 6.5 9.9 3.4
Comparative Example 3 16.4 25.3 8.9 6.4 10.9 4.5
Comparative Example 4 16.7 25.2 8.5 6.7 11.1 4.4
Comparative Example 5 15.1 23.5 8.4 5.9 10.2 4.3
Comparative Example 6 16.7 25.0 8.3 6.7 11.2 4.5
[203]
Here, film gloss was measured on the surface of the extruded sheet surface in contact with the first roll. As shown in Table 2, Examples 1 to 7 according to the present invention did not, Comparative Examples 1 to 6 Unlike , it was confirmed that the gloss deviation due to the difference in sheet extrusion conditions was small, so that even if the processing conditions were shaken, uniform physical properties, in particular, a uniform gloss value could be realized.
[204]
[205]
[Test Example 3]
[206]
In Example 3 and Comparative Example 3, a sheet having a thickness of 0.15T was prepared in the same manner and under the same conditions, except that the extrusion temperature during pellet production and the processing temperature during sheet production were as shown in Table 3 below to produce a film gloss ( Film Gloss) was measured, and the results are shown in Table 3 below.
[207]
[208]
[Table 3]
division Pellet extrusion temperature (℃) Sheet processing temperature (℃) Film Gloss Gloss Deviation (75)°
45° 60° 75°
Example 3 270 190 8.1 8.6 22.7 -3
280 190 8.1 8.7 26.4 -6
270 220 7.2 7.5 17.6 3
280 220 7.4 7.7 20.1 -
Comparative Example 3 270 190 8.6 10.2 22.8 -6.4
280 190 9 10.9 25.3 -8.9
270 220 6.7 7.7 18.4 -2
280 220 5.9 6.4 16.4 -
[209]
As shown in Table 3, in Example 3 according to the present invention, compared to Comparative Example 3, which is not, the gloss deviation due to the difference in sheet extrusion conditions is small, so that even if the processing conditions are shaken, uniform physical properties, especially uniform gloss values, are realized. was able to confirm that
Claims
[Claim 1]
100 parts by weight of a styrene-based resin; 0.5 to 5 parts by weight of a first polyamide resin having a melting temperature (Tm) of 230° C. or less; and 0.5 to 10 parts by weight of a second polyamide resin having a melting temperature (Tm) of 250° C. or higher, wherein both the first and second polyamide resins have a relative viscosity of 2.5 or less.
[Claim 2]
According to claim 1, wherein the thermoplastic resin composition has a 60 ° gloss value of the film produced at 280 ° C. extrusion and film processing at 190 ° C. and the 60 ° gloss value of the film produced at 280 ° C. extrusion and film processing at 220 ° C. A deviation of 3.0 A thermoplastic resin composition characterized by the following.
[Claim 3]
According to claim 1, wherein the styrenic resin comprises a first styrene-based resin and a second styrene-based resin, wherein the first styrene-based resin is A-1) DLS average particle diameter of 0.05 to 0.2 μm or TEM average particle diameter of 0.03 to 0.2 Acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing acrylate rubber of μm and A-2) Acrylic containing acrylate rubber having a DLS average particle diameter of 0.3 to 0.5 μm or a TEM average particle diameter of 0.25 to 0.45 μm It is at least one selected from the group consisting of a rate-aromatic vinyl compound-vinyl cyan compound graft copolymer, and the second styrene-based resin is B-1) an aromatic vinyl compound-vinyl cyan compound copolymer, B-2) a heat-resistant styrene-based resin Resin, and B-3) A thermoplastic resin composition, characterized in that at least one selected from the group consisting of methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer.
[Claim 4]
The thermoplastic resin composition according to claim 3, wherein the styrene-based resin comprises 10 to 70% by weight of the first styrene-based resin and 30 to 90% by weight of the second styrene-based resin.
[Claim 5]
The method according to claim 3, wherein the A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprises 40 to 60 wt% of an acrylate rubber having a DLS average particle diameter of 0.05 to 0.2 μm or a TEM average particle diameter of 0.03 to 0.2 μm. , 20 to 40 wt% of an aromatic vinyl compound and 10 to 20 wt% of a vinyl cyan compound, wherein the A-2) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer has a DLS average particle diameter of 0.3 to 0.5 It consists of 40 to 60 wt% of an acrylate rubber having an average particle diameter of 0.25 to 0.45 μm or TEM, 25 to 45 wt% of an aromatic vinyl compound, and 10 to 20 wt% of a vinyl cyanide compound, wherein B-1) an aromatic vinyl compound -The vinyl cyan compound copolymer comprises 65 to 80 wt% of an aromatic vinyl compound and 20 to 35 wt% of a vinyl cyan compound, and B-2) the heat-resistant styrene-based resin comprises 65 to 75 wt% of α-methylstyrene and It comprises 25 to 30 wt% of a vinyl cyan compound, and B-3) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer is 65 to 85 wt% of a methacrylate-based monomer, and 10 to 30 wt% of an aromatic vinyl compound A thermoplastic resin composition comprising 5 to 10% by weight of a vinyl cyanide compound and 5 to 10% by weight.
[Claim 6]
4. The method according to claim 3, wherein the first styrenic resin comprises 10 to 35% by weight of A-1) acrylate-aromatic vinyl compound-vinylcyanide graft copolymer, and A-2) acrylate based on the total weight of the styrene-based resin. -Aromatic vinyl compound- The thermoplastic resin composition comprising 15 to 40% by weight of the vinyl cyan compound graft copolymer.
[Claim 7]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition contains 0.1 to 5 parts by weight of an inorganic pigment.
[Claim 8]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an average surface roughness (Ra) of 2.3 or less measured at 5 points using an optical profiler system.
[Claim 9]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a matte thermoplastic resin composition having a film gloss of 15 or less measured at 60°.
[Claim 10]
4. The method of claim 3, wherein the B-1) aromatic vinyl compound-vinyl cyan compound copolymer comprises: i) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 90,000 to 135,000 g/mol; ii) an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of greater than 135,000 g/mol to 155,000 g/mol or less; and iii) an aromatic vinyl compound having a weight average molecular weight of greater than 155,000 g/mol to 200,000 g/mol or less-vinyl cyan compound copolymer; Thermoplastic resin composition comprising at least one selected from the group consisting of.
[Claim 11]
11. The method of claim 10, wherein i) the aromatic vinyl compound-vinyl cyan compound copolymer is included in an amount of 30 to 60 wt% based on the total weight of the styrenic resin, and ii) the aromatic vinyl compound-vinyl cyan compound copolymer is a styrene-based resin. It is included in an amount of 10 to 40 wt% based on the total weight of the resin, and iii) the aromatic vinyl compound-vinyl cyan compound copolymer is included in an amount of 10 to 40 wt% based on the total weight of the styrenic resin.
[Claim 12]
The method according to claim 3, wherein the B-2) heat-resistant styrene-based resin is included in an amount of 1 to 25% by weight based on the total weight of the styrene-based resin, or B-3) methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer A thermoplastic resin composition, characterized in that it is included in an amount of 5 to 65% by weight based on the total weight of the styrenic resin.
[Claim 13]
The exterior material comprising the thermoplastic resin composition of any one of claims 1 to 12.
[Claim 14]
14. The facing material according to claim 13, wherein the facing material is a siding material, a roofing material or a decking material.