Title of the invention: Thermoplastic resin composition
Technical field
[One]
[Mutual citation with related application]
[2]
The present invention claims the benefit of priority based on Korean Patent Application No. 10-2018-0032285 filed on March 20, 2018 and Korean Patent Application No. 10-2019-0030766 filed on March 18, 2019, and All contents disclosed in the literature are included as part of this specification.
[3]
[Technical field]
[4]
The present invention relates to a thermoplastic resin composition, while implementing a selective transmittance, to a thermoplastic resin composition excellent in basic physical properties.
[5]
Background
[6]
The transparent thermoplastic resin composition comprises: a matrix copolymer comprising a unit derived from an alkyl (meth)acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; Including a graft copolymer comprising a conjugated diene polymer, a unit derived from an alkyl (meth)acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer, and the refractive index of the matrix copolymer and the graft copolymer It was adjusted to 1.515 to 1.516 to ensure transparency. Molded articles made of such a transparent thermoplastic resin composition were characterized by being always transparent at room temperature.
[7]
Recently, the trend of home appliances demands various and unique appearances. For example, although it is opaque in everyday life, when the power is turned on, the text on the instrument panel is clearly displayed, that is, visibility (selective transmittance) is required.
[8]
However, development of a thermoplastic resin composition that implements selective transmittance and has excellent basic physical properties is currently insufficient.
[9]
Detailed description of the invention
Technical challenge
[10]
An object of the present invention is to provide a thermoplastic resin composition having excellent processability, mechanical properties, color properties, and durability, which are basic physical properties, while implementing selective transmittance.
[11]
Means of solving the task
[12]
In order to solve the above problems, the present invention is a first copolymer comprising an aromatic vinyl-based monomer-derived unit and a vinyl cyano-based monomer-derived unit; A second copolymer comprising a unit derived from an alkyl (meth)acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; A third copolymer comprising a conjugated diene polymer having an average particle diameter of 0.25 to 0.35 µm, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; And a fourth copolymer comprising a conjugated diene-based polymer having an average particle diameter of 0.05 to 0.15 µm, a unit derived from an aromatic vinyl-based monomer, and a unit derived from a vinyl cyan-based monomer.
[13]
In addition, the present invention is a first copolymer comprising an aromatic vinyl-based monomer-derived unit and a vinyl cyano-based monomer-derived unit; A second copolymer comprising a unit derived from an alkyl (meth)acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyano monomer; A third copolymer comprising a conjugated diene-based polymer having an average particle diameter of 0.25 to 0.35 µm, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit; And a fourth copolymer comprising a conjugated diene-based polymer having an average particle diameter of 0.05 to 0.15 µm, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit, and comprising the first and second copolymers It provides a thermoplastic resin molded article having a difference in refractive index between the region and the impact reinforcing region including the third and fourth copolymers of 0.01 to 0.04.
[14]
Effects of the Invention
[15]
When a molded article is manufactured with the thermoplastic resin composition according to the present invention, it is possible to implement selective transmittance and to realize excellent basic physical properties, that is, excellent processability, mechanical properties, color characteristics, and durability.
[16]
Best mode for carrying out the invention
[17]
Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.
[18]
The terms or words used in the specification and claims are not to be construed as limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of ​​the present invention based on the principle that there is.
[19]
[20]
In the present invention, the refractive index refers to the absolute refractive index of a material, and the refractive index is recognized as a ratio of the speed of electromagnetic radiation in free space to the speed of radiation in the material, wherein the radiation is visible light having a wavelength of 450 nm to 680 nm. The refractive index can be measured using a known method, that is, generally an Abbe Refractometer.
[21]
[22]
In the present invention, the average particle diameter of the conjugated diene-based polymer can be measured using a dynamic light scattering method, and in detail, it can be measured using a Nicomp 380 equipment (product name, manufacturer: PSS).
[23]
In the present specification, the average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, that is, an average particle diameter of an intensity distribution.
[24]
[25]
In the present invention, the weight average molecular weight can be measured as a relative value to a standard polystyrene (PS) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent.
[26]
[27]
1. Thermoplastic resin composition
[28]
The thermoplastic resin composition according to an embodiment of the present invention comprises: 1) a first copolymer comprising a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyan-based monomer; 2) a second copolymer comprising a unit derived from an alkyl (meth)acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyano monomer; 3) a third copolymer comprising a conjugated diene polymer having an average particle diameter of 0.25 to 0.35 µm, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; And 4) a fourth copolymer comprising a conjugated diene-based polymer having an average particle diameter of 0.05 to 0.15 µm, a unit derived from an aromatic vinyl-based monomer, and a unit derived from a vinyl cyan-based monomer.
[29]
[30]
In general, a thermoplastic resin molded article made of a thermoplastic resin composition comprising a first copolymer, a third copolymer, and a fourth copolymer has opaque properties due to a difference in refractive index thereof. However, if a second copolymer having a specific composition is further included in the thermoplastic resin composition, a synergistic effect occurs with the fourth copolymer, and it has opaque characteristics in everyday life, that is, when a separate light source is not provided, but a separate light source is provided. Then, it was found that the character and light existing inside the thermoplastic resin molded article clearly appear, that is, a thermoplastic resin molded article that implements selective transmittance is manufactured, thereby completing the present invention.
[31]
[32]
Meanwhile, the first and second copolymers may serve as a matrix resin, and the third and fourth copolymers may serve as an impact modifier.
[33]
[34]
The thermoplastic resin composition according to an embodiment of the present invention may further include at least one additive selected from the group consisting of 5) UV stabilizers and antioxidants.
[35]
[36]
Hereinafter, components of the thermoplastic resin composition according to an embodiment of the present invention will be described in detail.
[37]
[38]
1) first copolymer
[39]
The first copolymer includes a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyan-based monomer.
[40]
[41]
The first copolymer may be included to adjust the balance of physical properties of the thermoplastic resin composition, that is, mechanical properties, processability, and heat resistance.
[42]
In addition, the first copolymer provides selective transmittance to a molded article made of a thermoplastic resin composition, i.e., when a light source is not provided to the molded article, that is, in everyday life, the molded article becomes opaque, so that letters existing inside the molded article do not appear. I can.
[43]
[44]
The first copolymer may have a refractive index of 1.55 to 1.57, 1.56 to 1.57, or 1.565 to 1.57, of which 1.565 to 1.57 is preferable. If the above-described range is satisfied, the refractive indexes of the conjugated diene-based polymers of the third and fourth copolymers become similar, so that selective transmittance can be easily implemented. In addition, it is possible to more easily adjust the balance of the refractive index between the constituents of the thermoplastic resin composition of the present invention.
[45]
[46]
The unit derived from the aromatic vinyl-based monomer may be one or more derived units selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, among which styrene-derived units are preferred.
[47]
The unit derived from the vinyl cyan-based monomer may be one or more derived units selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, of which acrylonitrile is derived. Units are preferred.
[48]
[49]
The first copolymer may contain 75 to 85% by weight or 75 to 80% by weight of the aromatic vinyl-based monomer-derived unit based on the total weight of the first copolymer, of which 75 to 80% by weight It is preferable to include.
[50]
The first copolymer may contain 15 to 25% by weight or 20 to 25% by weight of the vinyl cyan-based monomer-derived unit based on the total weight of the first copolymer, of which 20 to 25% by weight It is preferable to include. If the above-described range is satisfied, the balance of physical properties of the thermoplastic resin composition, that is, the balance of mechanical properties, processability, and heat resistance can be more easily adjusted.
[51]
[52]
The first copolymer may have a weight average molecular weight of 90,000 to 180,000 g/mol or 100,000 to 150,000 g/mol, of which 100,000 to 150,000 g/mol is preferred. If the above-described range is satisfied, the balance of physical properties of the thermoplastic resin composition, that is, the balance of mechanical properties, processability, and heat resistance can be more easily adjusted.
[53]
[54]
The first copolymer may be prepared by polymerizing an aromatic vinyl-based monomer and a vinyl cyano-based monomer by one or more methods selected from the group consisting of bulk polymerization, emulsion polymerization, and suspension polymerization, of which it is preferably prepared by bulk polymerization. Do.
[55]
In the case of bulk polymerization, since additives such as an emulsifying agent or a suspending agent are not added, a high-purity copolymer in which the amount of impurities in the copolymer is minimized can be prepared. Accordingly, it may be advantageous to include a copolymer prepared by bulk polymerization in the thermoplastic resin composition implementing the selective transmittance.
[56]
[57]
As the first copolymer, a commercially available material may be used.
[58]
[59]
The first copolymer may be included in an amount of 60 to 70% by weight or 65 to 70% by weight based on the total weight of the thermoplastic resin composition, of which 65 to 70% by weight is preferable. If the above-described range is satisfied, the balance of the physical properties of the thermoplastic resin composition, that is, the balance of mechanical properties, processability, and heat resistance can be more easily adjusted, and target physical properties can be easily secured.
[60]
[61]
2) second copolymer
[62]
The second copolymer includes a unit derived from an alkyl (meth)acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer.
[63]
[64]
The second copolymer may impart excellent stiffness, scratch resistance, and colorability to the thermoplastic resin composition.
[65]
In addition, the second copolymer has a selective transmittance to a molded article made of a thermoplastic resin composition due to a synergistic effect with the fourth copolymer, that is, when a light source is provided to the molded article, light passes through the molded article, and characters present inside the molded article And it is possible to give the characteristic that the light appears clearly.
[66]
[67]
The second copolymer may have a refractive index of 1.51 to 1.53, 1.515 to 1.53, 1.515 to 1.525, or 1.515 to 1.52, of which 1.515 to 1.52 is preferred. If the above-described range is satisfied, it may be easy to selectively control the transmittance of a molded article made of a thermoplastic resin composition.
[68]
[69]
The units derived from the alkyl (meth)acrylate-based monomers are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, and It may be one or more derived units selected from the group consisting of lauryl (meth)acrylate, of which methyl methacrylate-derived units are preferred.
[70]
The unit derived from the alkyl (meth)acrylate-based monomer may be 65 to 80% by weight or 70 to 75% by weight based on the total weight of the second copolymer, of which 70 to 75% by weight is preferable. If the above-described range is satisfied, selective transmittance, rigidity, and scratch resistance of the second copolymer may be further improved.
[71]
[72]
The type of the unit derived from the aromatic vinyl-based monomer is as described in the description of the first copolymer.
[73]
The aromatic vinyl-based monomer-derived unit may be included in an amount of 3 to 15% by weight or 5 to 10% by weight, based on the total weight of the second copolymer, and is preferably included in an amount of 5 to 10% by weight. If the above-described range is satisfied, the rigidity and processability of the second copolymer may be improved.
[74]
[75]
The kind of the unit derived from the vinyl cyano monomer is as described in the description of the first copolymer.
[76]
The vinyl cyan-based monomer-derived unit may be 10 to 25% by weight or 15 to 20% by weight based on the total weight of the second copolymer, of which 15 to 20% by weight is preferable. When the above-described range is satisfied, chemical resistance, rigidity, and mechanical properties of the second copolymer may be further improved.
[77]
[78]
The second copolymer may have a weight average molecular weight of 50,000 to 150,000 g/mol or 70,000 to 130,000 g/mol, of which 70,000 to 130,000 g/mol is preferable. If the above-described range is satisfied, the balance of physical properties of the second copolymer can be easily adjusted.
[79]
[80]
The second copolymer may be prepared by polymerizing an alkyl (meth) acrylate monomer, an aromatic vinyl monomer, and a vinyl cyan monomer by one or more methods selected from the group consisting of bulk polymerization, emulsion polymerization, and suspension polymerization, Among these, it is preferable to manufacture by bulk polymerization.
[81]
In the case of bulk polymerization, since additives such as an emulsifying agent or a suspending agent are not added, a high-purity copolymer in which the amount of impurities in the copolymer is minimized can be prepared. Accordingly, it may be advantageous to include a copolymer prepared by bulk polymerization in the thermoplastic resin composition implementing the selective transmittance.
[82]
[83]
As the second copolymer, a commercially available material may be used.
[84]
[85]
The second copolymer may be included in an amount of 10 to 20% by weight or 10 to 15% by weight based on the total weight of the thermoplastic resin composition, of which 10 to 15% by weight is preferable. If the above-described range is satisfied, the stiffness, scratch resistance, and selective transmittance of the thermoplastic resin composition can be further improved, and transparent properties can be more easily maintained when a light source is provided.
[86]
[87]
3) third copolymer
[88]
The third copolymer includes a conjugated diene polymer having an average particle diameter of 0.25 to 0.35 µm, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer.
[89]
[90]
The third copolymer may impart excellent chemical resistance, mechanical properties, processability, and surface gloss properties to the thermoplastic resin composition. In addition, the third copolymer may serve as an impact modifier in the thermoplastic resin molded article.
[91]
[92]
The third copolymer may have a refractive index of 1.51 to 1.53, 1.515 to 1.53, 1.515 to 1.525, or 1.515 to 1.52, of which 1.515 to 1.52 is preferable. If the above-described range is satisfied, the balance of the refractive index between the constituents of the thermoplastic resin composition can be more easily adjusted.
[93]
[94]
The conjugated diene-based polymer may include a conjugated diene-based polymer modified by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer to a conjugated diene-based polymer prepared by polymerization of a conjugated diene-based monomer. Here, the conjugated diene-based polymer may be a conjugated diene-based rubbery polymer.
[95]
The conjugated diene-based monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and piperylene, of which 1,3-butadiene may be preferred.
[96]
[97]
The conjugated diene-based polymer has an average particle diameter of 0.25 to 0.35 µm, and preferably 0.27 to 0.33 µm. When the average particle diameter is less than the above-described range, the mechanical properties of the thermoplastic resin composition deteriorate, and when it exceeds the above-described range, the surface gloss and strength of the thermoplastic resin composition decrease.
[98]
[99]
The conjugated diene-based polymer may be included in an amount of 55 to 70% by weight or 60 to 65% by weight, based on the total weight of the third copolymer, and it is preferably included in an amount of 60 to 65% by weight. If the above-described range is satisfied, the stiffness, mechanical properties, processability and surface gloss of the third copolymer may be further improved.
[100]
[101]
The type of the unit derived from the aromatic vinyl-based monomer is as described in the description of the first copolymer.
[102]
The aromatic vinyl-based monomer-derived unit may be included in an amount of 20 to 35% by weight or 25 to 30% by weight, based on the total weight of the third copolymer, of which 25 to 30% by weight is preferred. If the above-described range is satisfied, chemical resistance, stiffness, mechanical properties, processability, and surface gloss of the thermoplastic resin composition may be further improved.
[103]
[104]
The kind of the unit derived from the vinyl cyano monomer is as described in the description of the first copolymer.
[105]
The vinyl cyan-based monomer-derived unit may be 5 to 20% by weight or 10 to 15% by weight based on the total weight of the third copolymer, of which 10 to 15% by weight is preferable. If the above-described range is satisfied, chemical resistance, stiffness, mechanical properties, processability, and surface gloss of the thermoplastic resin composition may be further improved.
[106]
[107]
The third copolymer is prepared by polymerizing a conjugated diene-based monomer by one or more methods selected from the group consisting of bulk polymerization, emulsion polymerization, and suspension polymerization to prepare a conjugated diene-based polymer, and in the presence of the conjugated diene-based polymer, an aromatic vinyl It can be prepared by polymerizing the system monomer and the vinyl cyano-based monomer by one or more methods selected from the group consisting of bulk polymerization, emulsion polymerization, and suspension polymerization. Among these, the conjugated diene polymer and the third copolymer are preferably prepared by emulsion polymerization.
[108]
If a conjugated diene-based polymer is prepared by emulsion polymerization, a conjugated diene-based polymer having the above-described average particle diameter can be easily prepared, and in the presence of such a conjugated diene-based polymer, an aromatic vinyl-based monomer and a vinyl cyan-based monomer are emulsion-polymerized. When the third copolymer is prepared, a graft copolymer having more improved mechanical properties and surface gloss properties can be prepared.
[109]
[110]
As the third copolymer, a commercially available material may be used.
[111]
[112]
The third copolymer may be included in an amount of 15 to 25% by weight or 15 to 20% by weight based on the total weight of the thermoplastic resin composition, of which 15 to 20% by weight is preferable. If the above-described range is satisfied, mechanical properties of the thermoplastic resin composition can be further improved.
[113]
[114]
4) fourth copolymer
[115]
The fourth copolymer includes a conjugated diene polymer having an average particle diameter of 0.05 to 0.15 µm, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer.
[116]
[117]
The fourth copolymer not only imparts excellent processability and surface gloss properties to the thermoplastic resin composition, but can also serve as an impact modifier in the thermoplastic resin molded article through synergy with the third copolymer.
[118]
In addition, the fourth copolymer has a selective transmittance to a molded article made of a thermoplastic resin composition due to a synergistic effect with the second copolymer, that is, when a light source is provided to the molded article, light passes through the molded article, and characters present inside the molded article And it is possible to give the characteristic that the light appears clearly.
[119]
[120]
The fourth copolymer may have a refractive index of 1.51 to 1.53, 1.515 to 1.53, 1.515 to 1.525, or 1.515 to 1.52, of which 1.515 to 1.52 is preferred. If the above-described range is satisfied, the refractive index between the first copolymer to the fourth copolymer can be more easily adjusted, and a thermoplastic resin molded article having selective transmittance can be manufactured.
[121]
[122]
The description of the conjugated diene polymer is as described in the description of the third copolymer.
[123]
[124]
The conjugated diene-based polymer has an average particle diameter of 0.05 to 0.15 µm, preferably 0.07 to 0.13 µm. If it is less than the above-described range, the mechanical properties of the thermoplastic resin composition are markedly deteriorated, and if it exceeds the above-described range, since light is refracted at the interface of the conjugated diene-based polymer, the thermoplastic resin composition cannot implement selective transmittance.
[125]
[126]
The conjugated diene-based polymer may be included in an amount of 45 to 60% by weight or 50 to 55% by weight, based on the total weight of the fourth copolymer, and it is preferably included in an amount of 50 to 55% by weight. If the above-described range is satisfied, chemical resistance, stiffness, mechanical properties, processability and surface gloss of the fourth copolymer may be further improved.
[127]
[128]
The type of the unit derived from the aromatic vinyl-based monomer is as described in the description of the first copolymer.
[129]
The aromatic vinyl-based monomer-derived unit may be included in an amount of 30 to 45% by weight or 35 to 40% by weight, based on the total weight of the fourth copolymer, and it is preferably included in an amount of 35 to 40% by weight. If the above-described range is satisfied, chemical resistance, stiffness, mechanical properties, processability, and surface gloss of the thermoplastic resin composition may be further improved.
[130]
[131]
The kind of the unit derived from the vinyl cyano monomer is as described in the description of the first copolymer.
[132]
The vinyl cyan-based monomer-derived unit may be 5 to 20% by weight or 10 to 15% by weight based on the total weight of the fourth copolymer, of which 10 to 15% by weight is preferable. If the above-described range is satisfied, chemical resistance, stiffness, mechanical properties, processability, and surface gloss of the thermoplastic resin composition may be further improved.
[133]
[134]
The fourth copolymer polymerizes a conjugated diene-based monomer by one or more methods selected from the group consisting of bulk polymerization, emulsion polymerization, and suspension polymerization to prepare a conjugated diene-based polymer, and in the presence of the conjugated diene-based polymer, an aromatic vinyl It can be prepared by polymerizing the system monomer and the vinyl cyano-based monomer by one or more methods selected from the group consisting of bulk polymerization, emulsion polymerization, and suspension polymerization. Among these, the conjugated diene polymer and the fourth copolymer are preferably prepared by emulsion polymerization. When the conjugated diene-based polymer is prepared by emulsion polymerization, a conjugated diene-based polymer having the above-described average particle diameter can be easily prepared, and in the presence of such a conjugated diene-based polymer, an aromatic vinyl-based monomer and a vinyl cyan-based monomer are emulsion-polymerized. When the fourth copolymer is prepared, a graft copolymer having more improved surface gloss properties and mechanical properties can be prepared.
[135]
[136]
As the fourth copolymer, a commercially available material may be used.
[137]
[138]
The fourth copolymer may be included in an amount of 5 to 15% by weight or 5 to 10% by weight, of which 5 to 10% by weight is preferable based on the total weight of the thermoplastic resin composition. If the above-described range is satisfied, selective transmittance may be provided to the thermoplastic resin composition.
[139]
[140]
5) additive
[141]
The additive may include at least one selected from the group consisting of UV stabilizers and antioxidants.
[142]
[143]
The additive may be included in an amount of 0.2 to 1.1 parts by weight or 0.3 to 0.9 parts by weight based on 100 parts by weight of the thermoplastic resin composition, that is, 100 parts by weight of the total of the first to fourth copolymers, of which 0.3 to 0.9 parts by weight It is preferable to be included as part. If the above-described range is satisfied, modification and decomposition of the thermoplastic resin composition can be prevented.
[144]
[145]
On the other hand, the UV stabilizer can prevent the modification of the thermoplastic resin composition by UV and radicals caused by environmental factors.
[146]
[147]
The antioxidant may prevent thermal discoloration that may occur during processing of the thermoplastic resin composition. In addition, it is possible to prevent decomposition of the thermoplastic resin composition by forming radicals due to environmental factors.
[148]
[149]
The UV stabilizer may be an amine compound, and the amine compound is 2-(2'-hydroxy-5'-tertiary-octylphenyl)benzotriazole (2-(2'-Hydroxy-5'-tert -octylphenyl)benzotriazole), bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate), 2-( 2H-Benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (2-(2H-Benzotriazol-2-yl)-4,6-bis(1-methyl-) 1-phenylethyl)phenol), and 2-(2H-benzotriazol-2-yl)-p-cresol (2-(2H-Benzotriazol-2-yl)-p-cresol) It can be more than that. Among these, in the group consisting of 2-(2'-hydroxy-5'-tertiary-octylphenyl)benzotriazole and bis(2,2,6,6,-tetramethyl-4-piperidyl) sebacate At least one selected is preferred.
[150]
[151]
The UV stabilizer may be included in an amount of 0.2 to 0.5 parts by weight or 0.3 to 0.4 parts by weight, based on 100 parts by weight of the total of the first to fourth copolymers, of which 0.3 to 0.4 parts by weight is preferred. If the above range is satisfied, excellent weather resistance can be secured.
[152]
[153]
The antioxidant is octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) And 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecan (3,9-Bis(octadecyloxy)-2,4, 8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane) may be one or more selected from the group consisting of.
[154]
[155]
The antioxidant may be contained in an amount of 0.2 to 0.6 parts by weight or 0.3 to 0.5 parts by weight, based on 100 parts by weight of the total of the first to fourth copolymers, of which 0.3 to 0.5 parts by weight is preferred. If the above-described range is satisfied, color characteristics and selective transmittance may be further improved.
[156]
[157]
2. Thermoplastic molded product
[158]
A thermoplastic resin molded article according to another embodiment of the present invention includes: a first copolymer comprising an aromatic vinyl-based monomer-derived unit and a vinyl cyano-based monomer-derived unit; A second copolymer comprising a unit derived from an alkyl (meth)acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; A third copolymer comprising a conjugated diene polymer having an average particle diameter of 0.25 to 0.35 µm, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; And a fourth copolymer comprising a conjugated diene-based polymer having an average particle diameter of 0.05 to 0.15 µm, an aromatic vinyl-based monomer-derived unit, and a vinyl cyano-based monomer-derived unit, and comprising the first and second copolymers The difference in refractive index between the region and the impact reinforcing region including the third and fourth copolymers is 0.01 to 0.04.
[159]
[160]
The thermoplastic resin molded article may be manufactured by extruding and injecting a thermoplastic resin composition containing the first to fourth copolymers. And, the description of the thermoplastic resin composition is as described above.
[161]
It is preferable that the difference in refractive index between the matrix region and the impact reinforcing region is 0.015 to 0.03. When the refractive indices of the matrix region and the impact reinforcing region satisfy the above-described range, selective transmittance may be implemented. In detail, when a light source is provided to a thermoplastic resin molded article, light passes through the molded article, and characters and lights that exist inside the molded article are clearly displayed. The back does not appear. However, if the difference in refractive index is less than the above-described range, the molded article is always transparent even if a light source is not provided, and if it exceeds the above-described range, the molded article is always opaque even when a light source is provided.
[162]
[163]
The matrix region is a region formed by extrusion and injection of the first and second copolymers, and may have a refractive index of 1.53 to 1.55 or 1.53 to 1.54, of which 1.53 to 1.54 is preferable. If the above-described range is satisfied, the molded article may implement selective transmittance.
[164]
[165]
The impact reinforcing region is a region formed by extrusion and injection of the third and fourth copolymers, and may have a refractive index of 1.51 to 1.52 or 1.51 to 1.515, of which 1.51 to 1.515 is preferable. If the above-described range is satisfied, the molded article may implement selective transmittance.
[166]
[167]
The thermoplastic resin molded article may have a roughness of 80 lux or more and an impact strength of 15 kg·cm/cm or more. Preferably, the thermoplastic resin molded article may have a roughness of 86 lux or more and an impact strength of 18 kg·cm/cm or more. If the above conditions are satisfied, it is possible to provide a thermoplastic resin molded article excellent in both selective transmittance and mechanical properties.
[168]
[169]
The illuminance may be the illuminance of the light source transmitted through the LED light source immediately behind the specimen after manufacturing the thermoplastic resin molded article into a 3 mm specimen, and the illuminance is an illuminance measuring device (brand name: CL-500A, manufacturer: Konica Minolta) can be used to measure. The transmittance is defined as the percentage of light passing through the sample with respect to the initially emitted beam, and can be measured using Haze-gard plus (model name, manufacturer: BYK-Gardner). The impact strength is Izod impact strength and can be measured according to ASTM D256.
[170]
[171]
In addition, the thermoplastic resin molded article may have a yellow index, that is, a b value measured using a CIE calorimeter of 1 or less, preferably 0.8 or less. If the above-described conditions are satisfied, a thermoplastic resin molded article having excellent color characteristics can be manufactured.
[172]
[173]
In addition, the thermoplastic resin molded article may have a color change (ΔE) of 0.1, preferably 0.09 or less. If the above-described conditions are satisfied, a thermoplastic resin molded article having excellent weather resistance can be manufactured.
[174]
The change over time (△E) was measured after exposing the specimen for 100 hours using a UV2000 (brand name, manufacturer: ATLAS (USA)), a fluorescent UV lamp (340 nm), and then substituting it into the following equation. Can be calculated.
[175]

[176]
In the above formula, L', a'and b'are measured with a CIE LAB color coordinate system after exposing the specimen for 100 hours using UV2000 (brand name, manufacturer: ATLAS (USA)) and a fluorescent UV lamp (340 nm). L, a and b values, and L 0 , a 0 and b 0 are UV2000 (brand name, manufacturer: ATLAS (USA)), a specimen before exposure to a fluorescent UV lamp (340 nm) was measured with a CIE LAB color coordinate system. L, a and b values.
[177]
Mode for carrying out the invention
[178]
Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in various different forms, and is not limited to the embodiments described herein.
[179]
[180]
Examples and Comparative Examples
[181]
[182]
The specifications of the components used in the following Examples and Comparative Examples are as follows.
[183]
[184]
(A) SAN copolymer: 81HF (refractive index: 1.57, constituent: styrene unit 77% by weight, acrylonitrile unit 23% by weight) manufactured by LG Chem was used.
[185]
[186]
(B) MSAN copolymer
[187]
(B-1): LG Chem's XT500 (refractive index: 1.52, composition: methyl methacrylate unit 72% by weight, styrene unit 9% by weight, acrylonitrile unit 19% by weight, weight average molecular weight: 80,000 g/mol ) Was used.
[188]
(B-2) Crompton's Bledex866 (refractive index: 1.59, methyl methacrylate unit 5% by weight, styrene unit 70% by weight, acrylonitrile unit 25% by weight, weight average molecular weight: 3,000,000 g / mol) was used.
[189]
[190]
(C) Graft Copolymer
[191]
(C-1): DP270M of LG Chem (refractive index: 1.52, a graft copolymer obtained by graft copolymerization of 30% by weight of styrene and 10% by weight of acrylonitrile to 60% by weight of a butadiene rubber polymer having an average particle diameter of 0.3 μm) Was used.
[192]
(C-2): DP229M of LG Chem (refractive index: 1.52, a graft copolymer obtained by graft copolymerization of 36% by weight of styrene and 14% by weight of acrylonitrile to 50% by weight of a butadiene rubber polymer having an average particle diameter of 0.1 μm) Was used.
[193]
(C-3): SA180 (refractive index: 1.52, average particle diameter of 0.1 µm) of LG Chem Co., graft copolymer obtained by graft copolymerization of styrene and acrylonitrile to butadiene rubbery polymer having an average particle diameter of 0.3 µm , A butadiene rubbery polymer having an average particle diameter of 0.1 μm: a weight ratio of a butadiene rubbery polymer having an average particle diameter of 0.3 μm: 3:7) was used.
[194]
[195]
(D) UV stabilizer
[196]
(D-1): BASF AG's Tinuvin® 329 was used.
[197]
(D-2): Tinuvin® 770 manufactured by BASF AG was used.
[198]
[199]
(E) antioxidant
[200]
(E-1): CIBA's IR1076 was used.
[201]
(E-2): ADEKA's PEP-8 was used.
[202]
[203]
Components (A) to (E) were mixed according to the contents shown in the following [Table 1] to [Table 3] and stirred to prepare a thermoplastic resin composition.
[204]
[205]
Experimental Example 1
[206]
The thermoplastic resin compositions of Examples and Comparative Examples were put into a twin screw extruder set at 230° C. and extruded to prepare pellets. The physical properties of the pellets were measured by the method described below, and the results are shown in the following [Table 1] to [Table 3].
[207]
[208]
① Flow index (g/10 min): In accordance with ASTM D1238, F-B01 (brand name, manufacturer: TOYOSEIKI) was measured at 220° C. under 10 kg.
[209]
[210]
Experimental Example 2
[211]
The pellet prepared in Experimental Example 1 was injected at 220° C. to prepare a specimen. The prepared specimens were measured for physical properties by the method described below, and the results are shown in the following [Tables 1] to [Table 3].
[212]
[213]
① Refractive index: The refractive index of the matrix region and the impact reinforcement region of the specimen were measured with an Abbe refractor.
[214]
② Izod impact strength (kg·cm/cm, 1/4 In): It was measured using an impact strength tester (brand name, manufacturer: Tinius Olsen) in accordance with ASTM D256.
[215]
③ Change over time (△E): After exposing the specimen for 100 hours using UV2000 (brand name, manufacturer: ATLAS (USA)) and a fluorescent UV lamp (340 nm), measure the color change and substitute it in the following equation to △ E value was calculated.
[216]

[217]
In the above formula, L', a'and b'are measured with a CIE LAB color coordinate system after exposing the specimen for 100 hours using UV2000 (brand name, manufacturer: ATLAS (USA)) and a fluorescent UV lamp (340 nm). L, a and b values, and L 0 , a 0 and b 0 are UV2000 (brand name, manufacturer: ATLAS (USA)), a specimen before exposure to a fluorescent UV lamp (340 nm) was measured with a CIE LAB color coordinate system. L, a and b values.
[218]
④ Color: The b value was measured using a CIE color meter.
[219]
⑤ Illuminance (Lux): The illuminance of the transmitted light source by illuminating an LED light source immediately behind the specimen having a thickness of 3 mm was measured using an illuminance measuring device (brand name: CL-500A, manufacturer: Konica Minolta).
[220]
⑥ Clarity: The color and shape of the transmitted letters were visually checked by illuminating the LED light source immediately behind the 3 mm thick specimen.
[221]
○: sharp, △: normal, ×: cloudy
[222]
[223]
[Table 1]
division Example
One 2 3 4 5
(A) SAN copolymer (parts by weight) 70 65 60 60 70
(B) MSAN copolymer (parts by weight) (B-1) 10 10 10 10 10
(B-2) - - - - -
(C) Graft copolymer (parts by weight) (C-1) 15 15 15 20 15
(C-2) 5 10 15 10 5
(C-3) - - - - -
(D) UV stabilizer (parts by weight) (D-1) 0.15 0.15 0.15 0.1 0.1
(D-2) 0.15 0.15 0.15 0.1 0.1
(E) Antioxidant (parts by weight) (E-1) 0.2 0.2 0.2 0.2 0.2
(E-2) 0.2 0.2 0.2 0.2 0.2
Flow index 53 49 45 42 52
Refractive index of the matrix region 1.534 1.534 1.534 1.534 1.534
Refractive index of impact reinforcement area 1.513 1.513 1.513 1.513 1.513
Impact strength 18 20 22 25 18
Change over time (△E) 0.06 0.07 0.09 0.09 0.08
Color (b value) 0.4 0.5 0.9 0.9 0.5
Illuminance (lux) 100 92 86 82 101
Clarity ○ ○ ○ ○ ○
[224]
[Table 2]
division Example
6 7 8 9
(A) SAN copolymer (parts by weight) 60 60 75 60
(B) MSAN copolymer (parts by weight) (B-1) 15 10 5 10
(B-2) - - - -
(C) Graft copolymer (parts by weight) (C-1) 20 15 15 10
(C-2) 5 15 5 20
(C-3) - - - -
(D) UV stabilizer (parts by weight) (D-1) 0.1 0.1 0.15 0.15
(D-2) 0.1 0.1 0.15 0.15
(E) Antioxidant (parts by weight) (E-1) 0.2 0.25 0.2 0.2
(E-2) 0.2 0.25 0.2 0.2
Flow index 51 47 55 43
Refractive index of the matrix region 1.534 1.534 1.534 1.534
Refractive index of impact reinforcement area 1.513 1.513 1.513 1.513
Impact strength 20 23 16 15
Change over time (△E) 0.07 0.09 0.06 0.1
Color (b value) 0.5 0.8 0.5 0.6
Illuminance (lux) 96 90 80 88
Clarity ○ ○ △ ○
[225]
[Table 3]
division Comparative example
One 2 3 4 5 6
(A) SAN copolymer (parts by weight) 80 70 70 70 70 70
(B) MSAN copolymer (parts by weight) (B-1) - 10 10 10 - -
(B-2) - - - - 10 10
(C) Graft copolymer (parts by weight) (C-1) 15 20 - - - 20
(C-2) 5 - 20 - 20 -
(C-3) - - - 20 - -
(D) UV stabilizer (parts by weight) (D-1) 0.15 0.1 0.1 0.15 0.15 0.15
(D-2) 0.15 0.1 0.1 0.15 0.15 0.15
(E) Antioxidant (parts by weight) (E-1) 0.2 0.2 0.2 0.2 0.2 0.2
(E-2) 0.2 0.2 0.2 0.2 0.2 0.2
Flow index 52 55 40 45 8 10
Refractive index of the matrix region 1.568 1.535 1.535 1.535 1.574 1.574
Refractive index of impact reinforcement area 1.513 1.513 1.513 1.513 1.513 1.513
Impact strength 17 18 6 12 5 21
Change over time (△E) 0.08 0.07 0.1 0.08 0.1 0.1
Color (b value) 0.4 0.4 0.8 1.1 0.8 0.8
Illuminance (lux) 78 78 101 76 28 26
Clarity × × ○ × × ×
[226]
Referring to Tables 1 to 3, in the case of Examples 1 to 7, since it was prepared with a thermoplastic resin composition containing the first to fourth copolymers in an optimal ratio, the flow index was 42 g/10 min or more, It was confirmed that the impact strength was 18 kg·cm/cm or more, the change over time was 0.09 or less, the b value was 0.9 or less, the illuminance was 82 lux or more, and the sharpness was also excellent. From these results, it could be predicted that, by using the thermoplastic resin composition of the present invention, a molded article having excellent processability, mechanical properties, color properties, and durability can be produced, and can implement selective transmittance. In the case of Example 8, roughness and Since the clarity was above average, the selective transmittance could be implemented, but it was confirmed that the impact strength was lowered compared to Examples 1 to 7 because the components were not included in the optimal ratio.
[227]
In the case of Example 9, since the illuminance and clarity are excellent, the selective transmittance can be implemented, but since the components were not included in the optimal ratio, the impact strength was lowered and the change over time was severe compared to Examples 1 to 7 and thus mechanical properties and It was confirmed that the weather resistance was decreased.
[228]
In Comparative Example 1 not including the second copolymer, the refractive index of the matrix region was increased, thereby increasing the difference in refractive index between the matrix region and the impact reinforcing region, and it was confirmed that the roughness was low and the clarity decreased. From these results, it was possible to predict that Comparative Example 1 was always opaque.
[229]
In Comparative Example 2 not including the fourth copolymer, since light was scattered in the impact reinforcing region, it was confirmed that the illuminance was low and the clarity was deteriorated. From these results, it was possible to predict that Comparative Example 2 was always opaque.
[230]
In Comparative Example 3 not including the third copolymer, it was confirmed that the impact strength was significantly reduced.
[231]
In addition, in Comparative Example 4 including the bimodal ABS graft copolymer instead of the third and fourth copolymers, it was confirmed that the impact strength, color characteristics, and clarity were all deteriorated, and the illuminance was low. From these results, it was possible to predict that Comparative Example 4 was always opaque.
[232]
In Comparative Examples 5 and 6 containing the MSAN copolymer having a high refractive index and not containing the third or fourth copolymer, it was confirmed that the flow index and roughness were very low, and the clarity was deteriorated. From these results, it was predicted that the processability of Comparative Examples 6 and 7 was markedly deteriorated and that they were always opaque.
Claims
[Claim 1]
A first copolymer comprising a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyan-based monomer; A second copolymer comprising a unit derived from an alkyl (meth)acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; A third copolymer comprising a conjugated diene polymer having an average particle diameter of 0.25 to 0.35 µm, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; And a fourth copolymer comprising a conjugated diene-based polymer having an average particle diameter of 0.05 to 0.15 µm, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit.
[Claim 2]
The method according to claim 1, wherein the thermoplastic resin composition comprises 60 to 70% by weight of the first copolymer; 10 to 20% by weight of the second copolymer; 15 to 25% by weight of the third copolymer; And 5 to 15% by weight of the fourth copolymer.
[Claim 3]
The thermoplastic resin composition of claim 1, wherein the first copolymer has a refractive index of 1.55 to 1.57.
[Claim 4]
The thermoplastic resin composition according to claim 1, wherein the second to fourth copolymers each independently have a refractive index of 1.51 to 1.53.
[Claim 5]
The method according to claim 1, wherein the second copolymer is 65 to 80% by weight of units derived from the alkyl (meth)acrylate-based monomer; 3 to 15% by weight of units derived from the aromatic vinyl-based monomer; And 10 to 25% by weight of the unit derived from the vinyl cyano-based monomer.
[Claim 6]
The thermoplastic resin composition of claim 1, wherein the second copolymer has a weight average molecular weight of 50,000 to 150,000 g/mol.
[Claim 7]
The method according to claim 1, wherein the third copolymer is 55 to 70% by weight of the conjugated diene-based polymer; 20 to 35% by weight of units derived from the aromatic vinyl-based monomer; And 5 to 20% by weight of the unit derived from the vinyl cyan-based monomer.
[Claim 8]
The method according to claim 1, wherein the fourth copolymer is 45 to 60% by weight of the conjugated diene-based polymer; 30 to 45% by weight of units derived from the aromatic vinyl-based monomer; And 5 to 20% by weight of the unit derived from the vinyl cyano-based monomer.
[Claim 9]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition further comprises at least one additive selected from the group consisting of a UV stabilizer and an antioxidant.
[Claim 10]
The thermoplastic resin composition of claim 9, wherein the additive is contained in an amount of 0.2 to 1.1 parts by weight based on 100 parts by weight of the total of the first to fourth copolymers.
[Claim 11]
A first copolymer comprising a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyan-based monomer; A second copolymer comprising a unit derived from an alkyl (meth)acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; A third copolymer comprising a conjugated diene polymer having an average particle diameter of 0.25 to 0.35 µm, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; And a fourth copolymer comprising a conjugated diene-based polymer having an average particle diameter of 0.05 to 0.15 µm, a unit derived from an aromatic vinyl-based monomer, and a unit derived from a vinyl cyan-based monomer, and comprising the first and second copolymers A thermoplastic resin molded article having a refractive index difference of 0.01 to 0.04 between the region and the impact reinforcing region including the third and fourth copolymers.
[Claim 12]
The thermoplastic resin molded article of claim 11, wherein the matrix region has a refractive index of 1.53 to 1.55.
[Claim 13]
The thermoplastic resin molded article of claim 11, wherein the impact reinforcing region has a refractive index of 1.51 to 1.52.
[Claim 14]
The method according to claim 11, wherein the thermoplastic resin molded article has a roughness of 80 lux or more, an impact strength of 15 kg·cm/cm or more, and the roughness is immediately after the thermoplastic resin molded article is prepared as a 3 mm specimen. A thermoplastic resin molded article that is the illuminance of the light source transmitted through the LED light source from behind.