WO2019182332A1 - Thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition comprising: a first copolymer containing an aromatic vinyl monomer-derived unit and a vinyl cyanide monomer-derived unit; a second copolymer containing an alkyl (meth)acrylate monomer-derived unit, an aromatic vinyl monomer-derived unit, and a vinyl cyanide monomer-derived unit; a third copolymer containing a conjugated diene polymer having an average particle diameter of 0.25-0.35 ㎛, an aromatic vinyl monomer-derived unit, and a vinyl cyanide monomer-derived unit; and a fourth copolymer containing a conjugated diene polymer having an average particle diameter of 0.05-0.15 ㎛, an aromatic vinyl monomer-derived unit, and a vinyl cyanide monomer-derived unit. The thermoplastic resin composition can be used to manufacture a molded article having excellent fundamental properties and capable of implementing selective transmittance.

Description

Thermoplastic resin composition

[Citations with Related Applications]

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, All content disclosed in the literature is included as part of this specification.

[Technical Field]

The present invention relates to a thermoplastic resin composition, while implementing a selective transmittance, and relates to a thermoplastic resin composition excellent in basic physical properties.

The transparent thermoplastic resin composition includes a matrix copolymer comprising an alkyl (meth) acrylate monomer derived unit, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit; A graft copolymer comprising a conjugated diene polymer, an alkyl (meth) acrylate monomer-derived unit, an aromatic vinyl monomer-derived unit, and a vinyl cyan monomer-derived unit, wherein the refractive index of the matrix copolymer and the graft copolymer The transparency was adjusted to 1.515 to 1.516. The molded article made of such a transparent thermoplastic resin composition was always transparent at room temperature.

Recently, the trend of home appliances demands a variety of unusual appearances, for example, it is opaque in everyday life, but it requires a physical property that the letters on the instrument panel are clearly visible when turned on, that is, visibility (selective transmittance).

However, the development of a thermoplastic resin composition excellent in basic physical properties while implementing selective permeability is currently insufficient.

An object of the present invention is to provide a thermoplastic resin composition excellent in processability, mechanical properties, color characteristics and durability, which is a basic physical property while implementing selective transmittance.

In order to solve the above problems, the present invention is a first copolymer comprising an aromatic vinyl monomer derived unit and a vinyl cyan monomer derived unit; A second copolymer comprising an alkyl (meth) acrylate monomer derived unit, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit; A third copolymer comprising a conjugated diene polymer having an average particle diameter of 0.25 to 0.35 µm, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit; And a fourth copolymer comprising a conjugated diene polymer having an average particle diameter of 0.05 to 0.15 μm, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit.

In addition, the present invention is a first copolymer comprising an aromatic vinyl monomer derived unit and a vinyl cyan monomer derived unit; A second copolymer comprising an alkyl (meth) acrylate monomer derived unit, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit; A third copolymer comprising a conjugated diene polymer having an average particle diameter of 0.25 to 0.35 µm, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit; And a fourth copolymer comprising a conjugated diene polymer having an average particle diameter of 0.05 to 0.15 μm, an aromatic vinyl monomer-derived unit, and a vinyl cyan monomer-derived unit, wherein the matrix comprises the first and second copolymers. 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 is 0.01 to 0.04.

When the molded article is manufactured from the thermoplastic resin composition according to the present invention, it is possible to implement selective permeability, and to realize excellent basic physical properties, that is, excellent processability, mechanical properties, color properties, and durability.

Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.

The terms or words used in this specification and claims are not to be construed as being limited to their ordinary or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best describe their invention. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

In the present invention, the refractive index means the absolute refractive index of the material, and the refractive index is recognized as the ratio of the speed of electromagnetic radiation in free space to the speed of radiation in the material, where the radiation is visible light having a wavelength of 450 nm to 680 nm. The refractive index can be measured using a known method, generally using an Abbe Refractometer.

In the present invention, the average particle diameter of the conjugated diene-based polymer may be measured using dynamic light scattering, and in detail, may be measured using a Nicomp 380 device (product name, manufacturer: PSS).

In the present specification, the mean particle size may mean an arithmetic mean particle size, that is, mean intensity of scattering intensity in the particle size distribution measured by the dynamic light scattering method.

In the present invention, the weight average molecular weight may be measured as a relative value to a standard polystyrene (PS) sample through gel permeation chromatography, water breeze (GPC) using THF (tetrahydrofuran) as an eluent.

1. Thermoplastic composition

Thermoplastic resin composition according to an embodiment of the present invention comprises: 1) a first copolymer comprising an aromatic vinyl monomer derived unit and a vinyl cyan monomer derived unit; 2) a second copolymer comprising an alkyl (meth) acrylate monomer derived unit, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit; 3) a third copolymer comprising a conjugated diene polymer having an average particle diameter of 0.25 to 0.35 µm, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit; And 4) a fourth copolymer comprising a conjugated diene polymer having an average particle diameter of 0.05 to 0.15 µm, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit.

Generally, thermoplastic resin molded articles made of a thermoplastic resin composition including a first copolymer, a third copolymer, and a fourth copolymer have opaque characteristics due to their refractive index differences. However, the inclusion of the second copolymer having a specific composition in the thermoplastic resin composition causes synergy with the fourth copolymer, and thus has an opaque characteristic in everyday life, that is, when a separate light source is not provided, but a separate light source is provided. When it was found that the thermoplastic resin molded article that implements the characteristic that the characters and light, etc., which are present in the thermoplastic resin molded article appear clearly, that is, the selective transmittance, was produced, thereby completing the present invention.

Meanwhile, the first and second copolymers may serve as matrix resins, and the third and fourth copolymers may serve as impact modifiers.

The thermoplastic resin composition according to the embodiment of the present invention may further include at least one additive selected from the group consisting of 5) a UV stabilizer and an antioxidant.

Hereinafter, the components of the thermoplastic resin composition according to an embodiment of the present invention will be described in detail.

1) first copolymer

The first copolymer includes an aromatic vinyl monomer derived unit and a vinyl cyan monomer derived unit.

The first copolymer may be included to adjust the balance of the physical properties of the thermoplastic resin composition, that is, the balance of mechanical properties, processability and heat resistance.

In addition, the first copolymer may impart a property of selectively transmitting a molded article made of a thermoplastic resin composition, that is, when a light source is not provided to the molded article, that is, the molded article is opaque in everyday life so that letters existing in the molded article do not appear. Can be.

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, and preferably 1.565 to 1.57. When the above range is satisfied, the refractive index is similar to that of the conjugated diene-based polymer of the third and fourth copolymers, thereby easily implementing selective transmittance. In addition, it is possible to more easily adjust the balance of the refractive index between the components of the thermoplastic resin composition of the present invention.

The aromatic vinyl monomer-derived unit may be one or more derived units selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, and among these, a unit derived from styrene is preferable.

The vinyl cyan monomer-derived unit may be at least one derived unit selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, among which acrylonitrile is derived. Units are preferred.

The first copolymer may include 75 to 85 wt% or 75 to 80 wt% of the aromatic vinyl monomer-derived unit with respect to the total weight of the first copolymer, of which 75 to 80 wt% It is preferable to include.

The first copolymer may include 15 to 25% by weight or 20 to 25% by weight of the vinyl cyan monomer-derived unit with respect to the total weight of the first copolymer, of which 20 to 25% by weight It is preferable to include. When the above-mentioned 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 adjusted more easily.

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 preferable. If the above-mentioned 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 adjusted more easily.

The first copolymer may be prepared by polymerizing the aromatic vinyl monomer and the vinyl cyan monomer by one or more methods selected from the group consisting of bulk polymerization, emulsion polymerization and suspension polymerization, and among them, the first copolymer may be prepared by bulk polymerization. Do.

In the case of the bulk polymerization, additives such as an emulsifier or suspending agent are not added, and thus a high purity copolymer having a minimum amount of impurities in the copolymer can be prepared. Accordingly, it may be advantageous that the thermoplastic resin composition implementing selective permeability includes a copolymer prepared by bulk polymerization.

The first copolymer may use a commercially available material.

The first copolymer may be included in an amount of 60 to 70 wt% or 65 to 70 wt%, based on the total weight of the thermoplastic resin composition, of which 65 to 70 wt% is preferred. When the above-mentioned range is satisfied, the target physical properties can be easily secured while more easily adjusting the balance of the physical properties of the thermoplastic resin composition, that is, the balance of mechanical properties, processability and heat resistance.

2) second copolymer

The second copolymer includes an alkyl (meth) acrylate monomer derived unit, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit.

The second copolymer may impart excellent stiffness, scratch resistance and colorability to the thermoplastic resin composition.

In addition, the second copolymer synergizes with the fourth copolymer, and selectively transmits to a molded article made of a thermoplastic resin composition, that is, light is passed through the molded article when a light source is provided to the molded article, and thus exists in the molded article. And it can give the characteristic that light etc. appear clearly.

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. If the above-mentioned range is satisfied, selective transmittance control of the molded article manufactured from the thermoplastic resin composition may be easily performed.

The alkyl (meth) acrylate monomer-derived units include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, 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.

The alkyl (meth) acrylate monomer-derived unit 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 preferred. If the above range is satisfied, the selective permeability, stiffness and scratch resistance of the second copolymer can be further improved.

The kind of the aromatic vinyl monomer-derived unit is as described in the description of the first copolymer.

The aromatic vinyl monomer-derived unit may be included in 3 to 15% by weight or 5 to 10% by weight, based on the total weight of the second copolymer, of which 5 to 10% by weight is preferable. If the above range is satisfied, the rigidity and processability of the second copolymer can be improved.

The kind of the said vinyl cyanic monomer derived unit is as having described in the description about a 1st copolymer.

The vinyl cyan 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. If the above range is satisfied, the chemical resistance, rigidity and mechanical properties of the second copolymer may be further improved.

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 range is satisfied, the balance of physical properties of the second copolymer can be easily adjusted.

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, It is preferable to manufacture by block polymerization among these.

In the case of the bulk polymerization, additives such as an emulsifier or suspending agent are not added, and thus a high purity copolymer having a minimum amount of impurities in the copolymer can be prepared. Accordingly, it may be advantageous that the thermoplastic resin composition implementing selective permeability includes a copolymer prepared by bulk polymerization.

The second copolymer may use a commercially available material.

The second copolymer may be included in 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 preferred. When the above-mentioned 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.

3) third copolymer

The third copolymer includes a conjugated diene polymer having an average particle diameter of 0.25 to 0.35 µm, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit.

The third copolymer may impart excellent chemical resistance, mechanical properties, processability and surface gloss to the thermoplastic resin composition. In addition, the third copolymer may serve as an impact modifier in the thermoplastic resin molded article.

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 range is satisfied, the balance of the refractive index between the components of the thermoplastic resin composition can be adjusted more easily.

The conjugated diene polymer may include a conjugated diene polymer modified by graft polymerization of an aromatic vinyl monomer and a vinyl cyan monomer to a conjugated diene polymer prepared by polymerization of a conjugated diene monomer. Here, the conjugated diene polymer may be a conjugated diene rubber polymer.

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 preferable.

The conjugated diene polymer has an average particle diameter of 0.25 to 0.35 탆, preferably 0.27 to 0.33 탆. If the average particle diameter is less than the above-mentioned range, the mechanical properties of the thermoplastic resin composition will be lowered, and if it exceeds the above-mentioned range, the surface gloss and strength of the thermoplastic resin composition will be lowered.

The conjugated diene polymer may be included in an amount of 55 to 70 wt% or 60 to 65 wt% based on the total weight of the third copolymer, and preferably 60 to 65 wt%. If the above range is satisfied, the stiffness, mechanical properties, processability and surface gloss of the third copolymer can be further improved.

The kind of the aromatic vinyl monomer-derived unit is as described in the description of the first copolymer.

The aromatic vinyl monomer-derived unit may be included in 20 to 35% by weight or 25 to 30% by weight, based on the total weight of the third copolymer, it is preferably included in 25 to 30% by weight. When the above range is satisfied, chemical resistance, rigidity, mechanical properties, processability, and surface glossiness of the thermoplastic resin composition may be further improved.

The kind of the said vinyl cyanic monomer derived unit is as having described in the description about a 1st copolymer.

The vinyl cyan 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. When the above range is satisfied, chemical resistance, rigidity, mechanical properties, processability, and surface glossiness of the thermoplastic resin composition may be further improved.

The third copolymer polymerizes the conjugated diene-based monomer by at least one method selected from the group consisting of bulk polymerization, emulsion polymerization and suspension polymerization to prepare a conjugated diene polymer, and in the presence of the conjugated diene polymer, aromatic vinyl The monomer and the vinyl cyan monomer can be prepared by polymerization by one or more methods selected from the group consisting of bulk polymerization, emulsion polymerization and suspension polymerization. Among them, the conjugated diene polymer and the third copolymer are preferably prepared by emulsion polymerization.

When the conjugated diene polymer is prepared by emulsion polymerization, the conjugated diene polymer having the above-described average particle diameter can be easily produced. In the presence of such conjugated diene polymer, the aromatic vinyl monomer and the vinyl cyan monomer can be emulsion polymerized. By preparing the third copolymer, it is possible to prepare a graft copolymer having improved mechanical properties and surface gloss properties.

The third copolymer may use a commercially available material.

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. When the above range is satisfied, the mechanical properties of the thermoplastic resin composition can be further improved.

4) fourth copolymer

The fourth copolymer includes a conjugated diene polymer having an average particle diameter of 0.05 to 0.15 µm, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit.

The fourth copolymer may not only impart excellent processability and surface gloss characteristics to the thermoplastic resin composition, but may also act as an impact modifier in the thermoplastic resin molded product by synergistic action with the third copolymer.

In addition, the fourth copolymer has a selective transmittance to a molded article made of a thermoplastic resin composition by synergizing with the second copolymer, that is, light is passed through the molded article when a light source is provided to the molded article, and thus exists in the molded article. And it can give the characteristic that light etc. appear clearly.

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 preferable. When the above-described range is satisfied, the refractive index between the first copolymer and the fourth copolymer can be more easily adjusted, and a thermoplastic resin molded article having selective transmittance can be manufactured.

Description of the conjugated diene-based polymer is as described in the description for the third copolymer.

The conjugated diene polymer has an average particle diameter of 0.05 to 0.15 탆, preferably 0.07 to 0.13 탆. If it is less than the above-mentioned range, the mechanical properties of the thermoplastic resin composition are significantly lowered, and if it exceeds the above-mentioned range, the light may be refracted at the interface of the conjugated diene-based polymer, so that the thermoplastic resin composition may not realize selective transmittance.

The conjugated diene-based polymer may be included in 45 to 60% by weight or 50 to 55% by weight, based on the total weight of the fourth copolymer, it is preferably included in 50 to 55% by weight. If the above range is satisfied, the chemical resistance, rigidity, mechanical properties, processability and surface gloss of the fourth copolymer may be further improved.

The kind of the aromatic vinyl monomer-derived unit is as described in the description of the first copolymer.

The aromatic vinyl 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 preferably 35 to 40% by weight. When the above range is satisfied, chemical resistance, rigidity, mechanical properties, processability, and surface glossiness of the thermoplastic resin composition may be further improved.

The kind of the said vinyl cyanic monomer derived unit is as having described in the description about a 1st copolymer.

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. When the above range is satisfied, chemical resistance, rigidity, mechanical properties, processability, and surface glossiness of the thermoplastic resin composition may be further improved.

The fourth copolymer polymerizes the conjugated diene monomer by one or more methods selected from the group consisting of bulk polymerization, emulsion polymerization and suspension polymerization, to prepare a conjugated diene polymer, and in the presence of the conjugated diene polymer, aromatic vinyl The monomer and the vinyl cyan monomer can be prepared by polymerization by one or more methods selected from the group consisting of bulk polymerization, emulsion polymerization and suspension polymerization. Among them, the conjugated diene polymer and the fourth copolymer are preferably prepared by emulsion polymerization. When the conjugated diene polymer is prepared by emulsion polymerization, the conjugated diene polymer having the above-described average particle diameter can be easily produced. In the presence of such conjugated diene polymer, the aromatic vinyl monomer and the vinyl cyan monomer can be emulsion polymerized. By preparing the fourth copolymer, a graft copolymer having improved surface gloss and mechanical properties can be produced.

The fourth copolymer may use a commercially available material.

The fourth copolymer may be included in 5 to 15% by weight or 5 to 10% by weight based on the total weight of the thermoplastic resin composition, of which 5 to 10% by weight is preferable. If the above-mentioned range is satisfied, it is possible to impart selective transmittance to the thermoplastic resin composition.

5) additive

The additive may comprise one or more selected from the group consisting of UV stabilizers and antioxidants.

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 sum of the first to fourth copolymers. It is preferable to be contained by the part. When the above-mentioned range is satisfied, modification and decomposition of the thermoplastic resin composition can be prevented.

On the other hand, the UV stabilizer can prevent the modification of the thermoplastic resin composition due to UV and radicals due to environmental factors.

The antioxidant may prevent heat discoloration and the like that may occur during processing of the thermoplastic resin composition. In addition, decomposition of the thermoplastic resin composition may be prevented by radical formation due to environmental factors.

The UV stabilizer may be an amine compound, 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 may be abnormal. Among them, 2- (2'-hydroxy-5'-tertiary-octylphenyl) benzotriazole and bis (2,2,6,6, -tetramethyl-4-piperidyl) sebacate At least one selected is preferable.

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 first to fourth copolymers, and preferably 0.3 to 0.4 parts by weight. If the above range is satisfied, excellent weather resistance can be ensured.

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] undecane (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.

The antioxidant may be included 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 first to fourth copolymers, and preferably 0.3 to 0.5 parts by weight. If the above range is satisfied, color characteristics and selective transmittance may be further improved.

2. Thermoplastic molded article

The thermoplastic resin molded article according to another embodiment of the present invention may include a first copolymer including an aromatic vinyl monomer-derived unit and a vinyl cyan monomer-derived unit; A second copolymer comprising an alkyl (meth) acrylate monomer derived unit, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit; A third copolymer comprising a conjugated diene polymer having an average particle diameter of 0.25 to 0.35 µm, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit; And a fourth copolymer comprising a conjugated diene polymer having an average particle diameter of 0.05 to 0.15 μm, an aromatic vinyl monomer-derived unit, and a vinyl cyan monomer-derived unit, wherein the matrix comprises the first and second copolymers. The refractive index difference between the region and the impact reinforcing region including the third and fourth copolymers is 0.01 to 0.04.

The thermoplastic resin molded article may be manufactured by extruding and injecting a thermoplastic resin composition including the first to fourth copolymers. The description of the thermoplastic resin composition is as described above.

The difference in refractive index between the matrix region and the impact reinforcement region is preferably 0.015 to 0.03. When the refractive indexes of the matrix region and the impact reinforcement region satisfy the above range, selective transmittance may be realized. In detail, when the light source is provided to the thermoplastic molded article, light passes through the molded article, and letters and light, etc., present in the molded article appear vividly, and when the light source is not provided, the molded article is opaque and letters present inside the molded article. The back does not appear. However, if the difference in refractive index is less than the above-mentioned range, the molded article is always transparent even if no light source is provided, and if it exceeds the above-mentioned range, the molded article is always opaque even if a light source is provided.

The matrix region is formed by extruding and injecting the first and second copolymers, and may have a refractive index of 1.53 to 1.55 or 1.53 to 1.54, and preferably 1.53 to 1.54. If the above range is satisfied, the molded article may implement selective transmittance.

The impact reinforcing region is a region formed by extruding and injecting 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. If the above range is satisfied, the molded article may implement selective transmittance.

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, a thermoplastic resin molded article excellent in both selective transmittance and mechanical properties can be provided.

The illuminance may be the illuminance of the light source transmitted through the LED light source immediately after the specimen after manufacturing the thermoplastic resin molded article with a 3 mm specimen, and the illuminance may be illuminance measuring equipment (trade name: CL-500A, manufacturer: Konica Minolta) can be used. The transmittance is defined as the percentage of the light passing through the sample with respect to the beam (beam) to be initially fired, it can be measured using Haze-gard plus (model name, manufacturer: BYK-Gardner). The impact strength is an Izod impact strength, it can be measured according to ASTM D256.

In addition, the thermoplastic resin molded article may have a yellow value, that is, a b value measured using a CIE colorimeter of 1 or less, preferably 0.8 or less. If the conditions mentioned above are satisfied, the thermoplastic resin molded article excellent in the color characteristic can be manufactured.

In addition, the thermoplastic resin molded article may have a change in color over time (ΔE) of 0.1, preferably 0.09 or less. If the conditions mentioned above are satisfied, the thermoplastic resin molded article excellent in weatherability can be manufactured.

The change over time (ΔE) is UV2000 (trade name, manufacturer: ATLAS (USA) Co., Ltd.), using a fluorescent UV lamp (340 nm) after exposure of the specimen for 100 hours to measure the color change, and substituted by the following equation Can be calculated.

In the above formula, L ', a' and b 'is measured by CIE LAB color coordinate system after exposing the specimen for 100 hours using UV2000 (trade name, manufacturer: ATLAS (USA)), fluorescent UV lamp (340 nm) L, a and b values, and L ₀ , a ₀ and b ₀ are measured using a CIE LAB color coordinate system for specimens exposed to UV2000 (trade name, ATLAS, USA), fluorescent UV lamps (340 nm). L, a and b values.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

Example  And Comparative example

Specifications of the components used in the following Examples and Comparative Examples are as follows.

(A) SAN copolymer: 81HF (refractive index: 1.57, component: 77 weight% of styrene unit, 23 weight% of acrylonitrile unit) of LG Chemical Co., Ltd. was used.

(B) MSAN copolymer

(B-1): LG Chem XT500 (refractive index: 1.52, components: 72% by weight of methyl methacrylate units, 9% by weight of styrene units, 19% by weight of acrylonitrile units, weight average molecular weight: 80,000 g / mol ) Was used.

(B-2) Bledex866 (refractive index: 1.59, methyl methacrylate unit 5 wt%, styrene unit 70 wt%, acrylonitrile unit 25 wt%, weight average molecular weight: 3,000,000 g / mol) of Crompton's was used.

(C) graft copolymer

(C-1): DP270M of LG Chemical Co., Ltd. (graft copolymer obtained by graft copolymerization of 30% by weight of styrene and 10% by weight of acrylonitrile to 60% by weight of butadiene rubbery polymer having a refractive index of 1.52 and an average particle diameter of 0.3 µm) Was used.

(C-2): DP229M (refractive index: 1.52 from LG Chemical Co., Ltd. (graft copolymer obtained by graft copolymerization of 36% by weight of styrene and 14% by weight of acrylonitrile to 50% by weight of butadiene rubbery polymer having an average particle diameter of 0.1 µm)) Was used.

(C-3): Graft copolymer obtained by graft copolymerization of styrene and acrylonitrile to SA180 (refractive index: 1.52, butadiene rubbery polymer having an average particle diameter of 0.1 µm and butadiene rubbery polymer having an average particle diameter of 0.3 µm) manufactured by LG Chemical. , Butadiene rubber polymer having an average particle diameter of 0.1 mu m: a weight ratio of butadiene rubber polymer having an average particle diameter of 0.3 mu m: 3: 7).

(D) UV stabilizer

(D-1): Tinuvin® 329 from BASF AG was used.

(D-2): Tinuvin® 770 from BASF AG was used.

(E) antioxidant

(E-1): IR1076 from CIBA was used.

(E-2): ADEKA Corporation PEP-8 was used.

The components (A) to (E) were mixed and stirred in the contents described in the following [Table 1] to [Table 3] to prepare a thermoplastic resin composition.

Experimental Example  One

The thermoplastic resin compositions of Examples and Comparative Examples were introduced into a twin screw extruder set at 230 ° C. and extruded to prepare pellets. Physical properties of the pellets were measured by the methods described below, and the results are shown in the following [Table 1] to [Table 3].

① Flow index (g / 10 min): It measured under 220 degreeC and 10 kg using F-B01 (brand name, manufacturer: TOYOSEIKI) based on ASTMD1238.

Experimental Example  2

The pellet prepared in Experimental Example 1 was injected at 220 ° C to prepare a specimen. The physical properties of the prepared specimens were measured by the methods described below, and the results are shown in the following [Table 1] to [Table 3].

① Refractive index: The refractive index of the matrix region and the impact reinforcement region of the specimen was measured with an Abbe refractor.

② Izod impact strength (kg · cm / cm, 1/4 In): Measured using an impact strength tester (trade name: Tinius Olsen) in accordance with ASTM D256.

③ Change over time (△ E): After exposure of the specimen for 100 hours using UV2000 (trade name, manufacturer: ATLAS (USA)), fluorescent UV lamp (340 nm), measure the color change and substitute in the following equation △ E values were calculated.

In the above formula, L ', a' and b 'is measured by CIE LAB color coordinate system after exposing the specimen for 100 hours using UV2000 (trade name, manufacturer: ATLAS (USA)), fluorescent UV lamp (340 nm) L, a and b values, and L ₀ , a ₀ and b ₀ are measured using a CIE LAB color coordinate system for specimens exposed to UV2000 (trade name, ATLAS, USA), fluorescent UV lamps (340 nm). L, a and b values.

④ Color: b value was measured using a CIE colorimeter.

⑤ Illuminance (Lux): The illuminance of the transmitted light source was measured using an illuminance measuring instrument (trade name: CL-500A, manufacturer: Konica Minolta) immediately after the 3 mm thick specimen.

⑥ Clarity: The color and shape of the transmitted characters were visually confirmed by illuminating the LED light source directly behind the specimen having a thickness of 3 mm.

○: clear, △: normal, ×: cloudy

division		Example
		One	2	3	4	5
(A) SAN copolymer (part by weight)		70	65	60	60	70
(B) MSAN copolymer (part 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 Zone		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
Lux		100	92	86	82	101
Sharpness		○	○	○	○	○

division		Example
		6	7	8	9
(A) SAN copolymer (part by weight)		60	60	75	60
(B) MSAN copolymer (part 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 Zone		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
Lux		96	90	80	88
Sharpness		○	○	△	○

division		Comparative example
		One	2	3	4	5	6
(A) SAN copolymer (part by weight)		80	70	70	70	70	70
(B) MSAN copolymer (part 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 Zone		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
Lux		78	78	101	76	28	26
Sharpness		×	×	○	×	×	×

Referring to Tables 1 to 3, in Examples 1 to 7, it was made of a thermoplastic resin composition containing the first to fourth copolymers in an optimum ratio, the flow index is 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 can be predicted that by using the thermoplastic resin composition of the present invention, a molded article excellent in workability, mechanical properties, color characteristics, and durability can be manufactured. Since the clarity was more than normal, selective transmittance could be implemented, but since the components were not included in an optimal ratio, it was confirmed that the impact strength was lowered as compared with Examples 1 to 7.

In the case of Example 9, since the roughness and clarity is excellent, selective permeability can be realized, but since the components are not included in an optimal ratio, the impact strength is lowered and the change over time is severe compared to Examples 1 to 7, so that the mechanical properties and It was confirmed that weather resistance is reduced.

In Comparative Example 1 without the second copolymer, the refractive index of the matrix region was increased, and as a result, the difference in refractive index between the matrix region and the impact reinforcing region was increased, and the roughness was lowered and the sharpness was lowered. From these results, the comparative example 1 could always predict that it is opaque.

In Comparative Example 2 not containing the fourth copolymer, since light was scattered in the impact reinforcing region, it was confirmed that the illuminance was low and the sharpness was lowered. From these results, the comparative example 2 was always able to predict that it is opaque.

In Comparative Example 3 not containing the third copolymer, it was confirmed that the impact strength was significantly reduced.

In addition, Comparative Example 4 including the bimodal ABS graft copolymer instead of the third and fourth copolymers showed that the impact strength, the color characteristics, and the vividness were all reduced, and the illuminance was low. From these results, the comparative example 4 could always predict that it was opaque.

Comparative Examples 5 and 6, which contained an MSAN copolymer having a high refractive index and did not include a third or fourth copolymer, were found to have very low flow index and roughness, and deteriorated sharpness. From these results, the comparative examples 6 and 7 could remarkably fall workability, and were always opaque.

Claims (14)

1. A first copolymer comprising an aromatic vinyl monomer derived unit and a vinyl cyan monomer derived unit;

   A second copolymer comprising an alkyl (meth) acrylate monomer derived unit, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit;

   A third copolymer comprising a conjugated diene polymer having an average particle diameter of 0.25 to 0.35 µm, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit; And

   A thermoplastic resin composition comprising a fourth copolymer comprising a conjugated diene polymer having an average particle diameter of 0.05 to 0.15 μm, an aromatic vinyl monomer-derived unit, and a vinyl cyan monomer-derived unit.
2. The method according to claim 1,

   The thermoplastic resin composition

   60 to 70 wt% 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.
3. The method according to claim 1,

   The first copolymer has a refractive index of 1.55 to 1.57 thermoplastic resin composition.
4. The method according to claim 1,

   The second copolymer to the fourth copolymer is a thermoplastic resin composition of which the refractive index is independently 1.51 to 1.53.
5. The method according to claim 1,

   The second copolymer

   65 to 80 wt% of the alkyl (meth) acrylate monomer-derived unit;

   3 to 15 wt% of the aromatic vinyl monomer-derived unit; And

   10 to 25% by weight of the vinyl cyanic monomer-derived unit.
6. The method according to claim 1,

   The second copolymer has a weight average molecular weight of 50,000 to 150,000 g / mol thermoplastic resin composition.
7. The method according to claim 1,

   The third copolymer

   55 to 70 wt% of the conjugated diene polymer;

   20 to 35% by weight of the aromatic vinyl monomer-derived unit; And

   The thermoplastic resin composition comprising 5 to 20% by weight of the vinyl cyan-based monomer-derived unit.
8. The method according to claim 1,

   The fourth copolymer is

   45 to 60 wt% of the conjugated diene polymer;

   30 to 45 wt% of the aromatic vinyl monomer-derived unit; And

   The thermoplastic resin composition comprising 5 to 20% by weight of the vinyl cyan-based monomer-derived unit.
9. The method according to claim 1,

   The thermoplastic resin composition further comprises at least one additive selected from the group consisting of UV stabilizers and antioxidants.
10. The method according to claim 9,

    The additive is a thermoplastic resin composition containing 0.2 to 1.1 parts by weight based on 100 parts by weight of the sum of the first to fourth copolymers.
11. A first copolymer comprising an aromatic vinyl monomer derived unit and a vinyl cyan monomer derived unit;

    A second copolymer comprising an alkyl (meth) acrylate monomer derived unit, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit;

    A third copolymer comprising a conjugated diene polymer having an average particle diameter of 0.25 to 0.35 µm, an aromatic vinyl monomer derived unit, and a vinyl cyan monomer derived unit; And

    A fourth copolymer comprising a conjugated diene polymer having an average particle diameter of 0.05 to 0.15 µm, an aromatic vinyl monomer-derived unit, and a vinyl cyan monomer-derived unit,

    The thermoplastic resin molded article having a refractive index difference of 0.01 to 0.04 between the matrix region including the first and second copolymers and the impact reinforcement region including the third and fourth copolymers.
12. The method according to claim 11,

    The matrix region is a thermoplastic resin molded article having a refractive index of 1.53 to 1.55.
13. The method according to claim 11,

    The impact reinforcing region is a thermoplastic resin molded article having a refractive index of 1.51 to 1.52.
14. The method according to claim 11,

    The thermoplastic resin molded article

    Illuminance is above 80 lux,

    The impact strength is 15 kg · cm / cm or more,

    The illuminance is a thermoplastic resin molded article prepared by manufacturing the thermoplastic resin molded article into a 3 mm specimen, and then illuminance of the light source transmitted through the LED light source immediately after the specimen.