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. 10-2019-0110417 dated September 6, 2019 and Korean Patent Application No. 10-2020-0106135 filed again on August 24, 2020, All contents disclosed in the literature of the Korean patent application are 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-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 a molded article 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]
However, 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 plastic feel is increasing.
[6]
As the low-gloss ASA resin, low gloss was realized by using a crystalline resin such as nylon, but there were limitations in improving weather resistance and surface texture, which are important physical properties for exterior materials as well as low gloss.
[7]
[Prior art literature]
[8]
[Patent Document] (Patent Document 1) KR 2009-0095764 A
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[9]
In order to solve the problems of the prior art as described above, the present invention has excellent weather resistance and low surface roughness while maintaining the same or higher mechanical properties and workability compared to conventional ASA-based resins, giving an emotionally soft feeling, the surface An object of the present invention is to provide a low gloss thermoplastic resin composition with even gloss and a molded article thereof.
[10]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[11]
In order to achieve the above object, the present invention provides A-1) 10 to 30 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm, A- 2) 20 to 40 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, B) 0 to 35 wt% of an aromatic vinyl polymer, and C) polymeth 100 parts by weight of a base resin consisting of 10 to 60% by weight of acrylate; and D) 0.5 to 10 parts by weight of polyamide. It provides a thermoplastic resin composition and a molded article thereof.
Effects of the Invention
[12]
According to the present invention, mechanical properties and processability are maintained at equal or higher than that of conventional ASA-based resins, excellent weather resistance, low surface roughness value, emotionally soft feeling, and a low gloss thermoplastic resin composition with an even surface gloss and There is an effect of providing a molded article thereof.
Best mode for carrying out the invention
[13]
Hereinafter, the thermoplastic resin composition of the present disclosure and a molded article thereof will be described in detail.
[14]
When the present inventors want to implement the matting effect by adding polyamide to the ASA resin, the morphology of the ASA resin is adjusted and methyl methacrylate-styrene-acrylonitrile copolymer or polymethyl methacrylate is used as an essential component. In the case of including in a composition ratio of It was confirmed that there is, and based on this, further intensive research was completed to complete the present invention.
[15]
The thermoplastic resin composition of the present invention is A-1) 10 to 30 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm, A-2) an average particle diameter 20 to 40 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber of 0.3 to 0.5 μm, B) 0 to 35 wt% of an aromatic vinyl polymer, and C) 10 to polymethacrylate 100 parts by weight of the base resin consisting of 60% by weight; and D) 0.5 to 10 parts by weight of polyamide, and 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, and even surface gloss There is an advantage to provide a thermoplastic resin composition that gives an emotionally soft feeling due to a low surface roughness value.
[16]
Hereinafter, each component constituting the thermoplastic resin composition of the present disclosure will be described in detail as follows.
[17]
A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer
[18]
A-1) The acrylate rubber of the graft copolymer may have, for example, an average particle diameter of 0.05 to 0.15 μm, preferably 0.1 to 0.15 μm, more preferably 0.12 to 0.15 μm, still more preferably 0.12 to 0.15 μm. It is 0.14 μm, or 0.13 to 0.15 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.
[19]
The acrylate rubber may preferably be a core.
[20]
In the present description, the average particle diameter may be measured using dynamic light scattering, and in detail, may be measured using Nicomp 380 equipment (product name, manufacturer: PSS).
[21]
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.
[22]
The A-1) graft copolymer is, for example, 10 to 30% by weight, preferably 15 to 25% by weight, more preferably 15 to 20% by weight, within this range weather resistance, fluidity, tensile strength and impact strength has an excellent effect.
[23]
The A-1) graft copolymer may include, for example, 40 to 60% by weight of an acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, and has weather resistance within this range. , fluidity, tensile strength and impact strength are excellent.
[24]
As a preferred example, the A-1) graft copolymer may include 45 to 55% by weight of an acrylate rubber, 30 to 50% by weight of an aromatic vinyl compound, and 5 to 20% by weight of a vinyl cyanide compound, within this range It has excellent weather resistance, fluidity, tensile strength and impact strength.
[25]
As a more preferred example, the A-1) graft copolymer may include 45 to 55% by weight of an acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, within this range It has excellent effects in weather resistance, fluidity, tensile strength and impact strength.
[26]
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.
[27]
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.
[28]
The emulsion polymerization is not particularly limited if the emulsion graft polymerization method commonly carried out in the art to which the present invention belongs.
[29]
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.
[30]
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.
[31]
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.
[32]
A-2) Acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer
[33]
A-2) The acrylate rubber of the graft copolymer may have, for example, an average particle diameter of 0.3 to 0.5 μm, preferably 0.35 to 0.5 μm, more preferably 0.4 to 0.5 μm, more preferably 0.45 to 0.45 μm. It is 0.50 ㎛, and it has good weather resistance within this range and has excellent mechanical strength such as fluidity, tensile strength and impact strength.
[34]
The acrylate rubber may preferably be a core.
[35]
The A-2) graft copolymer is, for example, 20 to 40% by weight, preferably 25 to 35% by weight, more preferably 30 to 35% by weight, within this range weather resistance, fluidity, tensile strength and impact strength has an excellent effect.
[36]
The A-2) graft copolymer may include, for example, 40 to 60% by weight of an acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, and has weather resistance within this range. , fluidity, tensile strength and impact strength are excellent.
[37]
As a preferred example, the A-2) graft copolymer may include 45 to 55% by weight of an acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, within this range It has excellent weather resistance, fluidity, tensile strength and impact strength.
[38]
The A-1) graft copolymer may be included in a smaller amount than the A-2) graft copolymer, more preferably the A-1) graft copolymer and the A-2) graft copolymer. The weight ratio of the copolymer is 1:1.1 to 1:4, more preferably 1:1.2 to 1:2, and within this range, there is an effect excellent in weather resistance, fluidity, tensile strength and impact strength.
[39]
The sum of the weights of the A-1) graft copolymer and A-2) the graft copolymer is preferably 40 to 60% by weight, more preferably 45 to 55% by weight, still more preferably 47 based on the base resin. to 53% by weight, and has excellent effects in weather resistance, fluidity, tensile strength and impact strength within this range.
[40]
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.
[41]
The emulsion polymerization is not particularly limited if the emulsion graft polymerization method commonly carried out in the art to which the present invention belongs.
[42]
B) aromatic vinyl polymer
[43]
The B) aromatic vinyl polymer may be, for example, 0 to 35% by weight, preferably 10 to 35% by weight, more preferably less than 10% by weight, still more preferably less than 5% by weight, Most preferably, it is not included, and has excellent weather resistance within this range, and in particular, the surface roughness value is significantly lowered, so that the gloss is even and the hand feels soft to the touch.
[44]
The B) aromatic vinyl polymer preferably comprises 65 to 80% by weight of an aromatic vinyl compound and 20 to 35% by weight of a vinyl cyanide compound, and has excellent chemical resistance and impact strength within this range.
[45]
The B) aromatic vinyl polymer has, for example, a weight average molecular weight of 80,000 to 180,000 g/mol, preferably 80,000 to 160,000 g/mol, and has excellent effects such as tensile strength and impact strength within this range.
[46]
The B) aromatic vinyl polymer is, for example, an aromatic vinyl compound-vinyl cyan compound copolymer, and preferably a styrene-acrylonitrile copolymer (SAN resin), alpha-methylstyrene-acrylonitrile copolymer (heat-resistant SAN resin) or It may be a mixture thereof, and in this case, there is an excellent effect of heat resistance and the like.
[47]
The styrene-acrylonitrile copolymer may be preferably 15 to 35% by weight, more preferably 15 to 25% by weight, and there is an excellent effect of heat resistance within this range.
[48]
The styrene-acrylonitrile copolymer preferably contains 65 to 80% by weight of styrene and 20 to 35% by weight of acrylonitrile, and has excellent processability and impact strength within this range.
[49]
The styrene-acrylonitrile copolymer has, for example, a weight average molecular weight of 100,000 to 180,000 g/mol, preferably 100,000 to 150,000 g/mol, and excellent heat resistance within this range.
[50]
The alpha-methylstyrene-acrylonitrile copolymer may preferably be in an amount of 10 to 20% by weight, more preferably 12 to 18% by weight, and within this range, heat resistance and the like are excellent.
[51]
The alpha-methylstyrene-acrylonitrile copolymer preferably comprises 70 to 75 wt% of alpha-methylstyrene and 25 to 30 wt% of acrylonitrile, and more preferably 60 to 75 wt% of alpha-methylstyrene. %, 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 More preferably, it comprises 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, It may include 5 to 10% by weight of styrene and 25 to 30% by weight of acrylonitrile, and within this range, there is an excellent effect of heat resistance and the like.
[52]
The alpha-methylstyrene-acrylonitrile copolymer preferably has a weight average molecular weight of 80,000 to 120,000 g/mol, and has excellent effects such as heat resistance within this range.
[53]
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 ) can be measured as a relative value for a standard PS (standard polystyrene) sample.
[54]
The B) aromatic vinyl polymer may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, and in this case, it has excellent effects such as heat resistance and fluidity.
[55]
The suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization are not particularly limited in the case of solution polymerization and bulk polymerization methods commonly performed in the art to which the present invention pertains, respectively.
[56]
C ) polymethacrylate
[57]
The C) polymethacrylate may be, for example, 10 to 60% by weight, preferably 25 to 55% by weight, more preferably 25 to 50% by weight, still more preferably 30 to 50% by weight, even more preferably 35 to 50% by weight, most preferably 45 to 50% by weight, and within this range, mechanical properties and processability are maintained at the same or higher level compared to conventional ASA-based resins, and weather resistance is greatly improved, and the surface roughness value is very low, emotionally It has a soft advantage.
[58]
C) the polymethacrylate preferably contains 55% by weight or more of methacrylate monomer, preferably 60% by weight or more, and most preferably 65% ​​by weight or more, and weather resistance is greatly improved within this range, The surface roughness value is very low, so it has an emotionally soft effect.
[59]
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, 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.
[60]
The C) polymethacrylate is preferably at least one selected from the group consisting of polymethyl methacrylate resin and methyl methacrylate-styrene-acrylonitrile copolymer, preferably polymethyl methacrylate resin or It is a methyl methacrylate-styrene-acrylonitrile copolymer, and more preferably a polymethyl methacrylate resin. Within this range, the weather resistance is more excellent, the surface roughness value is low, and there is an emotionally soft effect.
[61]
The polymethyl methacrylate resin may have, for example, a weight average molecular weight of 35,000 to 200,000 g/mol, preferably 50,000 to 200,000 g/mol, and has better weather resistance, fluidity, and tensile strength within this range. It has excellent strength and impact strength, and has an emotionally soft effect due to its low surface roughness value.
[62]
As another example, the polymethyl methacrylate resin includes a polymethyl methacrylate resin 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. mol of polymethyl methacrylate resin (hereinafter referred to as 'low molecular weight PMMA resin') may be mixed.
[63]
The high molecular weight PMMA resin and the low molecular weight PMMA resin may have, for example, a weight ratio of 1: 0.1 to 2.0, preferably 1:1.3 to 1.7, more preferably 1: 1.4 to 1.6, and fluidity, within this range, It has excellent tensile strength and impact strength, better weather resistance, and a low surface roughness value, which has an emotionally soft effect.
[64]
In the present description, the weight ratio of A and B means the weight ratio of A:B.
[65]
The methyl methacrylate-styrene-acrylonitrile copolymer comprises, for example, 65 to 85% by weight of methyl methacrylate, 5 to 30% by weight of styrene, and 5 to 10% by weight of acrylonitrile, and within this range It has better weather resistance and low surface roughness, which has an emotionally soft effect.
[66]
The methyl methacrylate-styrene-acrylonitrile copolymer may have, for example, a weight average molecular weight of 70,000 to 140,000 g/mol, and in another example 70,000 to 90,000 g/mol, or more than 90,000 g/mol to 140,000 g/mol It may be less than or equal to mol, and within this range, weather resistance is better, fluidity, tensile strength and impact strength are excellent, and the surface roughness value is low, so there is an emotionally soft effect.
[67]
As another example, the methyl methacrylate-styrene-acrylonitrile copolymer is a methyl methacrylate-styrene-acrylonitrile copolymer having a weight average molecular weight of 70,000 to 90,000 g/mol (hereinafter referred to as 'low molecular weight SAMMA resin'). ) and a methyl methacrylate-styrene-acrylonitrile copolymer having a weight average molecular weight of 120,000 to 140,000 g/mol (hereinafter referred to as 'high molecular weight SAMMA resin').
[68]
The low molecular weight SAMMA resin and the high molecular weight SAMMA resin may have, for example, a weight ratio of 1: 0.1 to 0.45, preferably 1: 0.2 to 0.45, more preferably 1: 0.3 to 0.45, and more preferably 1: It may be 0.35 to 0.45, and there is an advantage of excellent weather resistance within this range.
[69]
The C) polymethacrylate 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 commonly used in the art to which the present invention pertains. In the case of emulsion polymerization and suspension polymerization to be carried out, it is not particularly limited.
[70]
D) polyamide
[71]
D) polyamide is, for example, 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, more preferably 4 to 8 parts by weight, even more preferably 4 to 6 parts by weight based on 100 parts by weight of the base resin There is an advantage in that the gloss is lowered within this range and the matte effect is large and the physical property balance is excellent.
[72]
D) polyamide means a thermoplastic polymer including an amide bond, 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, poly Amide 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 66/12/6I may be at least one selected from the group consisting of, preferably polyamide 66 (PA 6.6).
[73]
The D) polyamide, for example, has a melting point of 230 °C or higher, preferably 240 °C or higher, more preferably 250 °C or higher, and even more preferably 260 to 270 °C.
[74]
D) The polyamide, 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.
[75]
In the present description, the relative viscosity can be measured with an Ubbelohde viscometer by the ISO 307 sulfuric acid method.
[76]
D) The method for preparing polyamide 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 may be commercially purchased and used if it meets the definition of polyamide according to the present invention.
[77]
Thermoplastic resin composition
[78]
For example, the thermoplastic resin composition of the present disclosure may have a surface roughness value of 4 or less, preferably 3.5 or less, more preferably 3 or less, and still more preferably 2.5 or less, measured at 5 points using an optical profiler system and averaged.
[79]
For example, the thermoplastic resin composition may have a weather resistance (ΔE) measured for 2000 hours by the SAE J1960 method of 4.0 or less, preferably 3.5 or less, more preferably 3.2 or less, and still more preferably 3.0 or less.
[80]
The thermoplastic resin composition has, for example, a flow index (MI) (220° C., load 10 kg) according to ASTM D1238 of 3 g/10 min or more, preferably 7 g/10 min or more, and more preferably 10 g/10 min or more. and more preferably 12 g/10 min or more, and may be 12 to 15 g/10 min as a specific example.
[81]
The thermoplastic resin composition, for example, has a tensile strength (1/8 inch) according to ASTM 638 of 290 kg/cm 2 or more, preferably 380 kg/cm 2 or more, more preferably 400 kg/cm 2 or more, and still more preferably 470 kg/cm 2 or more, and may be 380 to 490 kg/cm 2 as a specific example.
[82]
The thermoplastic resin composition has an Izod impact strength (1/4 inch) of 7 kg·cm/cm or more, preferably 9 kg·cm/cm or more, according to ASTM 256, as an example, and specifically, 7 to 11 kg·cm /cm or 8 to 11 kg·cm/cm.
[83]
The thermoplastic resin composition has, for example, a film gloss measured at 60° with a gloss meter VG7000 of 14 or less, 11 or less, or 10.5 or less, preferably 9.5 or less, more preferably 9.3 or less, and in one embodiment 4.8 to 14.0 or 4.8 to 11.0, there is an effect of excellent balance of properties while excellent matte properties within this range. Accordingly, the thermoplastic resin composition of the present disclosure may also be referred to as a matte thermoplastic resin composition.
[84]
The thermoplastic resin composition is optionally a heat stabilizer, a light 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 abrasion resistance. 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 There is an effect that the necessary physical properties are well realized without lowering the
[85]
The method for producing the thermoplastic resin composition of the present invention is, for example, A-1) 10 to 30% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm, A -2) 20 to 40 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, B) 0 to 35 wt% of an aromatic vinyl polymer, and C) poly 100 parts by weight of a base resin consisting of 10 to 60% by weight of methacrylate; And D) 0.5 to 10 parts by weight of polyamide; characterized in that it comprises a step of preparing pellets using an extrusion kneader under 220 to 280 ℃ conditions after mixing, in this case, mechanical compared to the conventional ASA-based resin There is an advantage in 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 physical properties and processability, giving an emotionally soft feeling.
[86]
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.
[87]
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.
[88]
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.
[89]
molded product
[90]
The molded article 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 maintained at the same level or higher compared to the conventional molded article, but the weather resistance is excellent, the gloss is low, and the surface gloss is uniform. It has the advantage of giving an emotionally soft feeling due to the low surface roughness value.
[91]
The molded article may be, for example, an extrusion-molded article or an injection-molded article, preferably a building exterior material, and more preferably a siding, sliding door or window.
[92]
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 that excellent matting effect is expressed within this range.
[93]
In describing the thermoplastic resin composition of the present invention, its manufacturing method and molded article, 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.
[94]
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.
[95]
[Example]
[96]
Materials used in Examples 1 to 10 and Comparative Examples 1 to 3 below are as follows.
[97]
A-1) First graft copolymer of emulsion polymerization (50 wt% of butyl acrylate polymer having an average particle diameter of 100 nm, shell: 36 wt% of styrene, 14 wt% of acrylnitrile)
[98]
A-2) Second graft copolymer of emulsion polymerization (50 wt% of butyl acrylate polymer having an average particle diameter of 400 nm, shell: 38 wt% of styrene, 12 wt% of acrylnitrile)
[99]
B-1) Bulk polymerization type SAN resin (92RF),
[100]
B-2) Bulk polymerization type heat-resistant SAN resin (200UH),
[101]
C-1) Bulk polymerization method SAMMA resin (XT500),
[102]
C-2) Bulk polymerization method SAMMA resin (XT510),
[103]
C-3) PMMA resin (IH830);
[104]
C-4) PMMA resin (BA611)
[105]
D) PA 6.6
[106]
Examples 1 to 10 and Comparative Examples 1 to 3
[107]
Each of the components and contents listed in Table 1 below were kneaded and extruded in a twin-screw extruder at 280° C. to prepare pellets. Melt index was measured with the prepared pellets. In addition, a sheet of 0.15T was prepared at a molding temperature of 220 °C with the prepared pellets, and film gloss and surface roughness values ​​were measured. 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.
[108]
[Test Example]
[109]
The properties of the pellets, sheets and specimens prepared in Examples 1 to 10 and Comparative Examples 1 to 3 were measured by the following method, and the results are shown in Table 1 below.
[110]
* Melt index (MI): The prepared pellets were measured by the ASTM D1238 method under the conditions of 220 °C / 10 kg.
[111]
* Tensile strength (kg/cm 2 ): Measured by ASTM 638 method.
[112]
* Izod impact strength (kg.cm/cm): Measured by ASTM 256 method.
[113]
* Film gloss (gloss): was measured at 60 ° with a gloss meter (gloss meter) VG7000.
[114]
* Surface roughness value: Optical profiler system (NV-2700, Nanosystem Co., Ltd.) Objective lens: 10x X eyepiece 1x (FOV: 628㎛ X 471㎛), Mode: WSI Envelope and Scan range: ±30㎛ condition 5 points were measured and averaged. When the surface roughness value is low, the hand feels soft to the touch and the gloss is even.
[115]
* 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.
[116]
[Equation 1]
[117]

[118]
[Table 1]
(parts by weight) Example comparative example
One 2 3 4 5 6 7 8 9 10 One 2 3
A-1 20 20 20 20 20 20 10 25 30 20 20 20 20
A-2 30 30 30 30 30 30 40 25 20 30 30 30 30
B-1 - - - 25 - 15 50 - -
B-2 - - - - 15 - - 50 -
C-1 - 35 35 - 35 35 35 - -
C-2 - 15 - - - - 15 - -
C-3 20 15 25 - - 20 20 20 - - 20
C-4 30 - - - - - 30 30 30 - - 30
D 5 5 5 5 5 5 5 5 5 3 5 5 -
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
flow index 16.2 12.7 10.3 3.1 7.3 14.3 14.6 17 17.8 14.7 6.3 2.9 20.1
tensile strength 388 470 474 405 490 298 370 397 406 478 384 420 389
impact strength 8.7 8.01 8.4 10.88 11.0 7.4 9.2 8.5 8.1 11.6 12.9 12.4 16
Gloss 10.3 7.0 6.0 4.8 7.4 7.1 9.3 10.5 11.0 13.5 4.9 5.6 67
surface roughness 2.1 2.34 3.0 3.5 3.4 3.1 2.2 2.0 2.0 1.93 4.54 5.3 0.04
△E 1.6 2 1.6 2.6 2.9 3.1 1.8 1.5 1.3 1.9 4.3 4.1 0.6
[119]
As shown in Table 1, the thermoplastic resin compositions (see Examples 1 to 10) according to the present invention have mechanical properties such as flow index, tensile strength and impact strength compared to Comparative Examples 1 and 2 that do not contain polymethacrylate resin. It was confirmed that the physical properties were equal to or higher, but the weather resistance was excellent, the surface roughness value was low, giving an emotionally soft feeling, and the surface gloss was even and low. In particular, referring to Table 1, the polymethacrylate resin In the case of Examples 1 to 3 and Examples 7 to 9 including 40 to 60% by weight, more specifically 45 to 55% by weight, the surface roughness value is 3.0 or less, specifically 2.0 to 3.0, and the weather resistance (ΔE ) is 3.1 or less, specifically 1.3 to 3.3, which is very excellent compared to Comparative Examples 1 and 2, confirming that a high quality sensitivity resin was manufactured.
[120]
On the other hand, in the case of Comparative Example 3 that does not contain polyamide, the gloss was 67, and compared to the gloss of Examples 1 to 9, at least 6 to 14 times higher, high quality by realizing matte properties It was confirmed that it did not match the purpose of the present invention to make a sensitivity resin of
Claims
[Claim 1]
A-1) 10 to 30 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing acrylate rubber having an average particle diameter of 0.05 to 0.15 μm, A-2) An acrylate having an average particle diameter of 0.3 to 0.5 μm A base resin comprising 20 to 40 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing rubber, B) 0 to 35 wt% of an aromatic vinyl polymer, and C) 10 to 60 wt% of polymethacrylate 100 parts by weight; and D) 0.5 to 10 parts by weight of polyamide.
[Claim 2]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a matte property of which film gloss measured at 60° with a gloss meter VG7000 is 14 or less.
[Claim 3]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an average surface roughness of 4 or less measured at 5 points using an optical profiler system.
[Claim 4]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a weather resistance (ΔE) of 4.0 or less as measured by the SAE J1960 method.
[Claim 5]
The method according to claim 1, wherein the A-1) graft copolymer comprises 40 to 60 wt% of an acrylate rubber, 25 to 45 wt% of an aromatic vinyl compound, and 10 to 20 wt% of a vinyl cyanide compound. Thermoplastic resin composition.
[Claim 6]
The method according to claim 1, wherein the A-2) graft copolymer comprises 40 to 60 wt% of an acrylate rubber, 25 to 45 wt% of an aromatic vinyl compound, and 10 to 20 wt% of a vinyl cyanide compound. Thermoplastic resin composition.
[Claim 7]
The thermoplastic resin composition according to claim 1, wherein the A-1) graft copolymer is included in a smaller amount than the A-2) graft copolymer.
[Claim 8]
The thermoplastic resin composition according to claim 1, wherein the sum of the weights of the graft copolymer A-1) and the graft copolymer A-2) is 40 to 60% by weight based on the base resin.
[Claim 9]
The thermoplastic resin composition according to claim 1, wherein the B) aromatic vinyl polymer is 10 to 35 wt%.
[Claim 10]
The thermoplastic resin composition according to claim 1, wherein the B) aromatic vinyl polymer is contained in less than 10% by weight or not.
[Claim 11]
The thermoplastic resin composition according to claim 1, wherein B) the aromatic vinyl polymer is an aromatic vinyl compound-vinyl cyan compound copolymer.
[Claim 12]
The thermoplastic resin composition according to claim 1, wherein C) the polymethacrylate resin comprises 55 wt% or more of a methacrylate monomer.
[Claim 13]
13. The thermoplastic resin composition of claim 12, wherein C) the polymethacrylate resin is at least one selected from the group consisting of polymethyl methacrylate resin and methyl methacrylate-styrene-acrylonitrile copolymer.
[Claim 14]
14. The method of claim 13, wherein the methyl methacrylate-styrene-acrylonitrile copolymer comprises 65 to 85% by weight of methyl methacrylate, 5 to 30% by weight of styrene, and 5 to 10% by weight of acrylonitrile. Thermoplastic resin composition characterized in that.
[Claim 15]
The thermoplastic resin composition according to claim 1, wherein the polyamide D) is polyamide 6.6.
[Claim 16]
A molded article comprising the thermoplastic resin composition of any one of claims 1 to 15.