Title of Invention: Thermoplastic resin composition and molded article manufactured therefrom
technology field
[One]
[Mutual Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0137207 dated 2020.10.22 and Korean Patent Application No. 10-2021-0090772 re-filed on 2021.07.12 based thereon, and the Korean patent All matter disclosed in the literature of the application is incorporated as part of this specification.
[3]
The present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom, and more particularly, to a thermoplastic resin composition having excellent alcohol resistance, transparency and processability when molded into a product, and a molded article manufactured therefrom.
background art
[4]
A vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer ('ABS-based resin'), represented by Acrylonitrile-Butadiene-Styrene (hereinafter referred to as 'ABS-based resin') resin, has processability It is used in various fields such as electronic devices, office devices, or household appliances because it has excellent impact strength, excellent appearance, and excellent transparency and color characteristics.
[5]
However, due to its poor alcohol resistance, it was difficult to use it for parts requiring alcohol disinfection.
[6]
In order to improve alcohol resistance, a method of increasing the rubber content or using expensive additives has been introduced, but increasing the rubber content has the disadvantage of lowering fluidity and using expensive additives has the disadvantage of affecting transparency. have.
[7]
Therefore, it is necessary to develop a technology for preparing a thermoplastic resin composition having excellent alcohol resistance while securing transparency and processability.
[8]
[Prior art literature]
[9]
[Patent Literature]
[10]
(Patent Document 1) Korean Patent Publication No. KR2016-0075415
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[11]
In order to solve the problems of the prior art as described above, an object of the present invention is to provide a thermoplastic resin composition that implements a physical property balance of alcohol resistance, transparency and processability characteristics.
[12]
Another object of the present invention is to provide a molded article manufactured from the above thermoplastic resin composition.
[13]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[14]
In order to achieve the above object, the present invention
[15]
a first graft copolymer comprising a conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer; a second graft copolymer comprising an alkyl (meth)acrylate-based polymer, an aromatic vinyl-based monomer, a vinyl cyan-based monomer, and an alkyl (meth)acrylate-based monomer; and a thermoplastic copolymer comprising an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer;
[16]
The first graft copolymer is included in 5 to 12% by weight of the total weight% of the thermoplastic resin composition,
[17]
The thermoplastic resin composition is characterized in that the weight of the first graft copolymer is smaller than the weight of the second graft copolymer and smaller than the weight of the thermoplastic copolymer.
[18]
The thermoplastic resin composition may include 5 to 12% by weight of the first graft copolymer; 28 to 75% by weight of the second graft copolymer; and 20 to 60% by weight of the thermoplastic copolymer.
[19]
The first graft copolymer may include 50 to 60% by weight of a conjugated diene-based polymer based on the total weight thereof; 20 to 40% by weight of the alkyl (meth)acrylate-based monomer; It may be made of 5 to 25% by weight of an aromatic vinyl monomer and 1 to 15% by weight of a vinylcyanic monomer.
[20]
The first graft copolymer may have a weight average molecular weight of 80,000 to 300,000 g/mol.
[21]
The second graft copolymer may include 30 to 70% by weight of the alkyl (meth)acrylate-based polymer based on the total weight thereof; 20 to 68% by weight of the aromatic vinyl monomer; 1 to 30% by weight of the vinyl cyan-based monomer; and 1 to 15% by weight of the alkyl (meth)acrylate-based monomer.
[22]
The alkyl (meth)acrylate-based polymer of the second graft copolymer includes an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer, and the alkyl (meth)acrylate of the alkyl (meth)acrylate-based polymer The monomer may be the same as the alkyl (meth)acrylate monomer of the second graft copolymer.
[23]
In this case, the alkyl (meth) acrylate monomer may be a butyl acrylate monomer or a 2-ethylhexyl acrylate monomer.
[24]
The second graft copolymer may have a weight average molecular weight of 50,000 to 150,000 g/mol.
[25]
A weight ratio between the first graft copolymer and the second graft copolymer may be 1:3 to 1:11.
[26]
The thermoplastic copolymer may include 40 to 75% by weight of the alkyl (meth)acrylate-based monomer based on the total weight thereof; 15 to 40% by weight of the aromatic vinyl monomer; and 3 to 20% by weight of the vinyl cyan-based monomer.
[27]
The alkyl (meth)acrylate-based monomer of the first graft copolymer and the alkyl (meth)acrylate-based monomer of the thermoplastic copolymer may be methyl methacrylate.
[28]
The thermoplastic resin composition contains a block copolymer containing an ethylene oxide unit and a propylene oxide unit in an amount of 1.5 parts by weight or less based on 100 parts by weight of the sum of the first graft copolymer, the second graft copolymer, and the thermoplastic copolymer. can be included with
[29]
The thermoplastic resin composition may be used as an alcohol-resistant reinforcing base material.
[30]
In addition, the present invention provides a molded article made of the thermoplastic resin composition described above.
Effects of the Invention
[31]
The thermoplastic resin composition according to the present invention can significantly improve alcohol resistance while realizing excellent basic physical properties, that is, excellent mechanical strength and processability.
[32]
Therefore, the molded article made of the thermoplastic resin composition according to the present invention can be widely applied to various industrial fields such as electronic devices, office devices, and household appliances that require alcohol disinfection while maintaining basic physical properties.
Brief description of the drawing
[33]
1 is a view showing the surface of a specimen treated with a chemical solvent according to Example 1.
[34]
2 is a view showing surface cracks of a specimen treated with a chemical solvent according to Comparative Example 2;
Mode for Carrying Out the Invention
[35]
Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
[36]
Terms or words used in this specification and claims should not be construed as being limited to their usual or dictionary meanings, and given that the inventors may appropriately define the concept of terms in order to best describe the invention. Therefore, it should be interpreted as a meaning and concept consistent with the technical spirit of the present invention.
[37]
In the present description, the meaning of "comprising" may be defined as "containing and polymerizing", "including and polymerizing" or "including as a derived unit" unless otherwise defined.
[38]
In this disclosure, unless otherwise specified, clarity refers to haze and color properties according to the standard measure ASTM D1003.
[39]
If the transparency is 15% or less, it can be determined as a transparent resin or a transparent resin composition.
[40]
In the present description, the average particle diameter can be measured using a dynamic light scattering method, and in detail, it can be measured in a Gaussian mode using a particle size distribution analyzer (Nicomp 380) in a latex state, and the dynamic light scattering method It may mean the arithmetic mean particle diameter in the particle size distribution measured by , that is, the average particle diameter of scattering intensity (Indensity Distribution).
[41]
As a specific measurement example, after preparing a sample by diluting 0.1 g of the prepared rubber latex (solid content of 35 to 50% by weight) with 100 g of deionized water or distilled water, a particle size distribution analyzer (Nicomp CW380, PPS) is used at 23 ° C. Therefore, the average value of the hydrodynamic diameter obtained from the scattering intensity distribution was obtained by measuring the particle diameter under the intensity value of 300 kHz in all of the intensity-weighted Gaussian analysis using the dynamic light scattering method.
[42]
In this description, the weight average molecular weight can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent. It is a value obtained by applying the weight average molecular weight (Mw) in terms of polystyrene by permeation chromatography (GPC: gel permeation chromatography, PL GPC220, Agilent Technologies).
[43]
Specifically, after dissolving in a THF solution, the relative value for standard PS (standard polystyrene) feed was obtained using GPC. Specific measurement conditions are as follows.
[44]
-Solvent: THF (tetrahydrofuran)
[45]
-Column temperature: 40 ℃
[46]
-Flow rate: 0.3 mL/min
[47]
- Sample concentration: 20 mg/mL
[48]
-Injection amount: 5 μl
[49]
-Column model: 1xPLgel 10 ㎛ MiniMix-B (250 Ⅹ 4.6 mm) + 1xPLgel 10 ㎛ MiniMix-B (250 Ⅹ 4.6 mm) + 1xPLgel 10 ㎛ MiniMix-B Guard (50 Ⅹ 4.6 mm)
[50]
-Equipment name: Agilent 1200 series system
[51]
-Refractive index detector: Agilent G1362 RID
[52]
-RI temperature: 35 ℃
[53]
-Data processing: Agilent ChemStation S/W
[5 4]
-Test method: Measured according to OECD TG 118
[55]
In the present description, the composition ratio of the (co)polymer may mean the amount of units constituting the (co)polymer, or the amount of units introduced during polymerization of the (co)polymer.
[56]
In this description, "content" means ideal weight unless otherwise defined.
[57]
[58]
The present inventors have confirmed that a transparent material having excellent alcohol resistance while securing processability is provided when a modified thermoplastic copolymer and two types of graft copolymers having different types of rubber are included as a thermoplastic resin composition, and completed the present invention. I did.
[59]
A thermoplastic resin composition according to an embodiment of the present invention includes a first graft copolymer comprising a conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl-based monomer; a second graft copolymer comprising an alkyl (meth)acrylate-based polymer, an aromatic vinyl-based monomer, a vinyl cyan-based monomer, and an alkyl (meth)acrylate-based monomer; and a thermoplastic copolymer comprising an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer.
[60]
The thermoplastic resin composition of the present invention includes the above components and the first graft copolymer at 5 to 12% by weight, and the weight of the first graft copolymer is greater than the weight of the second graft copolymer It is characterized in that it is smaller than the weight of the thermoplastic copolymer, and in this case, it is possible to provide a molded article having desired effects such as excellent alcohol resistance, transparency, impact strength and workability.
[61]
The thermoplastic resin composition of the present invention can be used as an alcohol-resistant reinforcing base material.
[62]
[63]
Hereinafter, the thermoplastic resin composition of the present invention will be described in detail for each component.
[64]
First Graft Copolymer
[65]
The thermoplastic resin composition of the present invention is preferably a thermoplastic transparent resin composition, and includes a first graft copolymer, wherein the first graft copolymer is a conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer, an aromatic vinyl -based monomers and vinyl cyan-based monomers are included.
[66]
The first graft copolymer can impart excellent transparency and processability as well as serve as an impact modifier in a thermoplastic resin molded product.
[67]
The conjugated diene-based polymer is a conjugated diene-based polymer modified by graft polymerization of an alkyl (meth)acrylate-based monomer, 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. can include
[68]
In the present description, (meth)acrylate-based monomers are used as a meaning including both methacrylate-based monomers and acrylate-based monomers.
[69]
The conjugated diene-based polymer may have a structure in which double bonds and single bonds are arranged over one, and the conjugated diene-based monomer may be, for example, at least one selected from 1,3-butadiene, isoprene, chloroprene, and piperylene, Of these, 1,3-butadiene is preferred.
[70]
The conjugated diene-based polymer may be included in an amount of, for example, 30 to 60% by weight, preferably 50 to 60% by weight, based on the total weight of the first graft copolymer, and within the above range, the thermoplastic resin composition of the present invention The impact strength of the molded article produced from can be further improved.
[71]
[72]
The conjugated diene-based polymer may have an average particle diameter of, for example, 0.1 to 0.5 μm, preferably 0.2 to 0.4 μm, and more preferably 0.25 to 0.35 μm, and molded articles prepared from the thermoplastic resin composition of the present invention within the above range The mechanical properties of can be further improved.
[73]
The weight average molecular weight of the shell of the copolymer may be, for example, 80,000 to 300,000 g/mol, preferably 90,000 to 150,000 g/mol, and mechanical properties are improved within the above range.
[74]
The shell of the copolymer may include an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer graft-polymerized with a conjugated diene-based polymer.
[75]
The alkyl (meth) acrylate-based monomer is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) )acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate and decyl (meth)acrylate can be selected, with double methyl (meth)acrylate being preferred.
[76]
The alkyl (meth) acrylate-based monomer may be included in an amount of, for example, 20 to 40% by weight, preferably 25 to 35% by weight, based on the total weight of the first graft copolymer, and within the above range of the present invention Transparency, rigidity and scratch resistance of a molded article manufactured from the thermoplastic resin composition can be further improved.
[77]
The aromatic vinyl-based monomer may be at least one selected from among styrene, α-methylstyrene, α-ethylstyrene, and vinyl toluene, and styrene is preferred.
[78]
The aromatic vinyl monomer may be included in an amount of, for example, 5 to 25% by weight, preferably 5 to 20% by weight, and more preferably 5 to 15% by weight, based on the total weight of the first graft copolymer. Within this range, the rigidity and processability of molded articles prepared from the thermoplastic resin composition of the present invention can be further improved.
[79]
The vinyl cyan-based monomer may be at least one selected from acrylonitrile, methacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, of which acrylonitrile is preferable.
[80]
The vinyl cyan-based monomer may be included in an amount of, for example, 1 to 15% by weight, preferably 1 to 10% by weight, and more preferably 2 to 7% by weight, based on the total weight of the first graft copolymer. Within this range, the alcohol resistance, stiffness and impact resistance of molded articles prepared from the thermoplastic resin composition of the present invention can be further improved.
[81]
The first graft copolymer is obtained by polymerizing an alkyl (meth)acrylate monomer, an aromatic vinyl monomer, and a vinyl cyan monomer in the presence of a conjugated diene polymer by at least one method selected from emulsion polymerization, suspension polymerization, and bulk polymerization. It can be produced, and among them, it is preferable to manufacture by emulsion polymerization.
[82]
The emulsion polymerization may be graft emulsion polymerization, and may be carried out, for example, at a polymerization temperature of 50 to 85 °C, preferably 60 to 80 °C.
[83]
The emulsion polymerization may be carried out in the presence of an initiator and an emulsifier.
[84]
The initiator may include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium persulfate, and hydrogen peroxide as a radical initiator; t-butyl peroxide, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide oxide, organic peroxides including 3,5,5-trimethylhexanol peroxide, t-butylperoxy isobutyrate; It may be at least one selected from among azo compounds including azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonylnitrile, and azobisisobutyrate (butyrate)methyl.
[85]
An activator may be further added to promote an initiation reaction together with the initiator.
[86]
The activator may be, for example, at least one selected from sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, sodium pyrophosphate anhydrous, and sodium sulfate.
[87]
The initiator is, for example, 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, more preferably 0.02 to 0.02 part by weight, based on 100 parts by weight of the sum of the monomers constituting the first graft copolymer and the conjugated diene-based polymer. It may be added in 0.1 parts by weight. Within this range, emulsion polymerization can be easily performed and the residual amount of the initiator in the first graft copolymer can be minimized by several tens of ppm.
[88]
The emulsifier is, for example, a potassium compound of alkylbenzenesulfonate, a sodium compound of alkylbenzenesulfonate, a potassium compound of alkylcarboxylate, a sodium compound of alkylcarboxylate, a potassium compound of oleic acid, a sodium compound of oleic acid, a potassium compound of alkylsulfate , sodium compound of alkyl sulfate, potassium compound of alkyl dicarboxylate, sodium compound of alkyl dicarboxylate, potassium compound of alkyl ether sulfonate, sodium compound of alkyl ether sulfonate, allyloxynonylphenoxypropan-2-yloxy It may be at least one selected from ammonium compounds of methyl sulfonate, alkenyl C 16-C 18 succinic acid, and dipotassium salts, of which alkenyl C 16 -C 18 succinic acid and dipotassium salts are preferable.
[89]
The emulsifier is, for example, 0.1 to 2.0 parts by weight, preferably 0.2 to 1.5 parts by weight, more preferably 0.3 to 1.5 parts by weight, based on 100 parts by weight of the sum of the monomers and the conjugated diene-based polymer constituting the first graft copolymer. It can be added in 1.0 parts by weight, and emulsion polymerization is easily performed within the above range, and the residual amount of the initiator in the copolymer can be minimized by several tens of ppm.
[90]
During the emulsion polymerization, a molecular weight modifier may be further added. The molecular weight modifier may be, for example, at least one selected from t-dodecyl mercaptan, N-dodecyl mercaptan, and alphamethylstyrene dimer, among which t-dodecyl mercaptan is preferred.
[91]
The molecular weight modifier is, for example, 0.1 to 1 part by weight, preferably 0.2 to 0.8 part by weight, more preferably 0.4 part by weight, based on 100 parts by weight of the sum of the monomers and the conjugated diene-based polymer constituting the first graft copolymer. to 0.6 parts by weight.
[92]
The emulsion polymerization is started after the monomers are collectively introduced into the reactor, or before the start of the emulsion polymerization.Emulsion polymerization may be performed by adding a portion of monomers to the reactor and then continuously adding the rest after starting, or by continuously adding monomers for a certain period of time.
[93]
The first graft copolymer obtained in this way is in the form of latex and can be recovered in the form of dry powder through a process of aggregation, dehydration and drying.
[94]
As the coagulant used for aggregation, a salt such as calcium chloride, magnesium sulfate, or aluminum sulfate, an acidic substance such as sulfuric acid, nitric acid, or hydrochloric acid, or a mixture thereof may be used.
[95]
The first graft copolymer may be included in an amount of 5 to 12% by weight, preferably 5 to 10% by weight, based on the total weight of the thermoplastic resin composition. When the above-described range is satisfied, mechanical properties and transparency of a molded article produced by injection from the thermoplastic resin composition of the present invention may be excellent.
[96]
[97]
Second Graft Copolymer
[98]
The thermoplastic resin composition of the present invention is preferably a thermoplastic transparent resin composition, and includes the second graft copolymer, wherein the second graft copolymer is, for example, an alkyl (meth)acrylate-based polymer, an aromatic vinyl-based monomer , It consists of a vinyl cyan-based monomer and an alkyl (meth) acrylate-based monomer.
[99]
The second graft copolymer can impart excellent impact resistance and alcohol resistance to the thermoplastic resin composition, and can impart compatibility between the first graft copolymer described above and the thermoplastic copolymer described later.
[100]
The second graft copolymer may have a structure of a core and a shell.
[101]
The core may include a polymer prepared by polymerizing an alkyl (meth)acrylate-based monomer alone or by polymerizing an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer together.
[102]
The shell surrounds the core and may be polymerized by including at least one selected from aromatic vinyl-based monomers, vinylcyanic monomers, and the alkyl (meth)acrylate-based monomers.
[103]
The weight average molecular weight of the shell of the copolymer may be, for example, 50,000 to 150,000 g / mol, preferably 60,000 to 130,000 g / mol, and there are advantages in that impact resistance, processability and transparency are improved within the above range.
[104]
Polymerization used in the preparation of the second graft copolymer may be performed using a method selected from emulsion polymerization, suspension polymerization, and bulk polymerization, and polymerization is preferably performed by emulsion polymerization.
[105]
The core of the second graft copolymer is prepared by emulsion polymerization after adding the alkyl (meth)acrylate-based monomers in batches or continuously, or collectively or continuously adding the alkyl (meth)acrylate-based monomers and aromatic vinyl-based monomers. After adding, it can be manufactured by emulsion polymerization.
[106]
In the shell of the second graft copolymer, at least one selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer, and the alkyl (meth)acrylate monomer is added in batch or continuously in the presence of the core, and then emulsified. It can be produced by polymerization.
[107]
Alkyl (meth)acrylate-based monomers included in the core and shell are independently methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethyl It may be at least one selected from hexyl (meth) acrylate, decyl (meth) acrylate, and lauryl (meth) acrylate, and a double butyl acrylate monomer or a 2-ethylhexyl acrylate monomer may be used.
[108]
The alkyl (meth)acrylate-based polymer is, for example, 30 to 70% by weight, preferably 40 to 60% by weight, more preferably 40 to 50% by weight, based on the total weight of the second graft copolymer. can be included If the above range is satisfied, the impact strength, processability and transparency of a molded article prepared from the thermoplastic resin composition of the present invention can be further improved.
[109]
When the alkyl (meth) acrylate polymer is prepared from an aromatic vinyl monomer and an alkyl (meth) acrylate monomer, the aromatic vinyl monomer is, for example, 1 to 10% based on the total weight of the alkyl (meth) acrylate polymer. It may be included in 25% by weight, preferably 1 to 15% by weight, and within this range, the stiffness, processability and transparency of the copolymer may be further improved.
[110]
The alkyl (meth)acrylate-based monomers included in the alkyl (meth)acrylate polymer are, for example, 70% by weight or more, preferably 70 to 99% by weight, based on the total weight of the alkyl (meth)acrylate polymer. Preferably, it may be included in 80 to 99% by weight, more preferably 90 to 99% by weight, and within this range, the copolymer's transparency, weatherability, colorability and alcohol resistance may be further improved.
[111]
The aromatic vinyl-based monomer is as described in the description of the first graft copolymer.
[112]
The aromatic vinyl monomer may be included in an amount of, for example, 50% by weight or less, preferably 10 to 40% by weight, more preferably 20 to 40% by weight, and even more preferably, based on the total weight of the second graft copolymer. Preferably, it may be included in an amount of 3 to 40% by weight, and within this range, the stiffness, processability and transparency of the copolymer may be further improved.
[113]
The average particle diameter of the alkyl (meth)acrylate-based polymer may be, for example, 0.03 to 0.2 μm, preferably 0.05 to 0.17 μm, and more preferably 0.05 to 0.12 μm. When the above-mentioned range is satisfied, the mechanical properties and processability of a molded article manufactured from the thermoplastic resin composition of the present invention can be further improved.
[114]
The alkyl (meth)acrylate-based monomer included in the shell may be included in an amount of, for example, 1 to 15% by weight, preferably 1 to 10% by weight, based on the total weight of the second graft copolymer, and within the above range The transparency, weatherability and colorability of the copolymer can be further improved.
[115]
The aromatic vinyl monomer included in the shell is, for example, 20 to 68% by weight, preferably 25 to 60% by weight, more preferably 30 to 55% by weight, based on the total weight of the second graft copolymer. Preferably, it may be included in 30 to 50% by weight, and within this range, the stiffness, processability and transparency of the copolymer may be further improved.
[116]
The vinyl cyan-based monomer is as described in the description of the first graft copolymer.
[117]
The vinyl cyan-based monomer may be included in an amount of, for example, 1 to 30% by weight, preferably 5 to 25% by weight, and more preferably 10 to 20% by weight, based on the total weight of the second graft copolymer. Within this range, the stiffness, impact resistance and alcohol resistance of the copolymer may be further improved.
[118]
The second graft copolymer may be included in the thermoplastic resin composition in an amount of, for example, 28 to 75% by weight, preferably 30 to 60% by weight, and more preferably 35 to 55% by weight. If the above range is satisfied, the transparency, alcohol resistance, mechanical properties and processability of the molded article manufactured from the thermoplastic resin composition of the present invention can be further improved.
[119]
[120]
thermoplastic copolymer
[121]
The thermoplastic resin composition of the present invention is preferably a thermoplastic transparent resin composition, and includes a thermoplastic copolymer, wherein the thermoplastic copolymer includes an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer. .
[122]
The thermoplastic copolymer may be prepared by copolymerizing an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer.
[123]
Specifically, the thermoplastic copolymer is obtained by adding an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinylcyan-based monomer in batch or continuously, and at least one selected from the group consisting of emulsion polymerization, suspension polymerization, and bulk polymerization. It can be produced by polymerization.
[124]
The alkyl (meth) acrylate-based monomer is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) )acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate and decyl (meth)acrylate can be selected, with double methyl (meth)acrylate being preferred.
[125]
The alkyl (meth)acrylate-based monomer may be included in an amount of, for example, 40 to 80% by weight, preferably 55 to 75% by weight, based on the total weight of the thermoplastic copolymer. If the above range is satisfied, the transparency, scratch resistance, rigidity, processability and impact resistance of the molded article manufactured from the thermoplastic resin composition of the present invention can be further improved.
[126]
The aromatic vinyl monomer and the vinyl cyan monomer are as described in the description of the first graft copolymer.
[127]
The aromatic vinyl-based monomer may be included in an amount of, for example, 15 to 45% by weight, preferably 15 to 35% by weight, based on the total weight of the thermoplastic copolymer. If the above range is satisfied, the rigidity and processability of a molded article manufactured from the thermoplastic resin composition of the present invention can be further improved.
[128]
The vinyl cyan-based monomer may be included in an amount of, for example, 3 to 20% by weight, preferably 5 to 15% by weight, based on the total weight of the thermoplastic copolymer. If the above range is satisfied, the impact resistance, rigidity and alcohol resistance of the molded article manufactured from the thermoplastic resin composition of the present invention can be further improved.
[129]
The thermoplastic copolymer may be included in the thermoplastic resin composition in an amount of, for example, 20 to 60% by weight, preferably 20 to 55% by weight. If the above-mentioned range is satisfied, mechanical properties of a molded article produced by injection from the thermoplastic resin composition of the present invention can be further improved.
[130]
above column The plastic copolymer may be prepared by polymerizing an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer by at least one method selected from emulsion polymerization, suspension polymerization, and bulk polymerization, and is, for example, produced by bulk polymerization. In this case, not only the manufacturing cost is reduced, but also the mechanical properties are excellent.
[131]
In the case of the bulk polymerization, additives such as an emulsifier or a suspending agent are not added, so that a high-purity copolymer with a minimized content of impurities in the copolymer can be prepared. Accordingly, it may be advantageous to include a copolymer prepared by bulk polymerization in the thermoplastic resin composition for maintaining transparency.
[132]
The bulk polymerization may be, for example, a polymerization method in which an organic solvent as a reaction medium and, if necessary, additives including a molecular weight regulator and a polymerization initiator are added to the monomer mixture.
[133]
As a specific example, in the method for preparing the thermoplastic copolymer, 20 to 40 parts by weight of a reaction medium and 0.05 to 0.5 parts by weight of a molecular weight modifier are added to 100 parts by weight of a monomer mixture including an alkyl (meth)acrylate-based compound, an aromatic vinyl compound, and a vinyl cyan compound. It may include mixing parts by weight and polymerizing for 2 to 4 hours while maintaining a reaction temperature of 130 to 170 °C.
[134]
The reaction medium is not particularly limited if it is a solvent commonly used in the art, and may be, for example, an aromatic hydrocarbon-based compound such as ethylbenzene, benzene, toluene, or xylene.
[135]
The method for producing the thermoplastic copolymer is, for example, a raw material input pump, a continuous stirring tank into which reaction raw materials are continuously introduced, a preliminary heating tank for preliminarily heating the polymerization solution discharged from the continuous stirring tank, unreacted monomers and / or reactions It can be performed in a continuous process machine consisting of a volatilization tank for volatilizing the medium, a polymer transfer pump, and an extrusion machine for producing the polymer in the form of pellets.
[136]
At this time, the extrusion processing conditions may be 210 to 240 ℃ as an example, but is not limited thereto.
[137]
[138]
thermoplastic resin composition
[139]
According to one embodiment of the present invention, when the weight of the first graft copolymer described above is smaller than the weight of the second graft copolymer, the thermoplastic resin composition has a physical property balance of transparency, impact strength and processability, Alcohol resistance can be further improved.
[140]
The thermoplastic resin composition is preferably a thermoplastic transparent resin composition, and when the weight of the first graft copolymer described above is smaller than the weight of the thermoplastic copolymer, the alcohol resistance, transparency, impact strength and processability of the thermoplastic resin composition The physical property balance can be improved.
[141]
In addition, in the thermoplastic resin composition, the weight ratio of the first graft copolymer and the second graft copolymer is, for example, 1:3 to 1:11 (first graft copolymer: second graft copolymer), preferably Preferably, it may be 1:4 to 1:10 (first graft copolymer:second graft copolymer). If the above range is satisfied, the mechanical properties, processability and alcohol resistance of the molded article prepared from the thermoplastic resin composition of the present invention can be further improved.
[142]
The thermoplastic resin composition according to an embodiment of the present invention may include a block copolymer including an ethylene oxide unit and a propylene oxide unit, and in this case, the block copolymer may act as a processing aid capable of maintaining transparency. have.
[143]
The block copolymer including an ethylene oxide unit and a propylene oxide unit may be, for example, a copolymer represented by Formula 1 below.
[144]
[Formula 1]
[145]

[146]
In Chemical Formula 1, a1 may be an integer of 10 to 80, b1 may be an integer of 10 to 50, and c1 may be an integer of 10 to 80.
[147]
In the copolymer represented by Formula 1, the content of ethylene oxide units derived from ethylene glycol (corresponding to a1 + c1 in Formula 1) may be, for example, 70 to 90 mol%, preferably 75 to 85 mol%. .
[148]
The block copolymer comprising an ethylene oxide unit and a propylene oxide unit may have a melting point of, for example, 30 to 90 °C, preferably 30 to 80 °C, and more preferably 40 to 70 °C. If the above range is satisfied, impact resistance, workability, and flame retardancy may be further improved.
[149]
Melting point in this description can be measured by a known method using a Brookfield viscometer.
[150]
The block copolymer comprising an ethylene oxide unit and a propylene oxide unit has a surface tension of, for example, 80 mN/m or less, preferably 1 to 80 mN/m, based on DIN 53814 (1 g/l in distilled water at 23 °C). m, more preferably 20 to 70 mN/m, more preferably 30 to 60 mN/m.
[151]
In addition, the block copolymer comprising an ethylene oxide unit and a propylene oxide unit has a weight average molecular weight of, for example, 5,000 to 30,000 g/mol, preferably 5,000 to 25,000 g/mol, and more preferably 8,000 to 20,000 g/mol It may be a phosphorus copolymer. If the above range is satisfied, the polymer represented by Formula 1 may not be eluted during processing and use due to excellent compatibility with the base resin.
[152]
The block copolymer including the ethylene oxide unit and the propylene oxide unit is, for example, 1.5 parts by weight or less, preferably 1.5 parts by weight or less, based on the total of 100 parts by weight of the total of the first graft copolymer, the second graft copolymer and the thermoplastic copolymer Preferably 0.5 to 1.5 parts by weight, more preferably 1 to 1.5 parts by weight.
[153]
When the above range is satisfied, excellent transparency, impact resistance and fluidity can be imparted to the thermoplastic resin composition.
[154]
The thermoplastic resin composition may further include, for example, at least one selected from among heat stabilizers, UV stabilizers, lubricants, antioxidants, processing aids, pigments, and colorants.
[155]
For example, the additive may be 0.01 to 5 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the total of the first graft copolymer, the second graft copolymer and the thermoplastic copolymer. More preferably, it may be included in 1 to 2 parts by weight, and within this range, there is an effect of expressing the inherent properties of the additive without affecting the physical properties of the thermoplastic resin composition.
[156]
As another example, the additive may include 0.1 to 2 parts by weight of the lubricant, preferably 0.5 to 1.5 parts by weight, and 0.1 to 1 part by weight, preferably 0.1 to 0.5 parts by weight of the antioxidant, within this range of the thermoplastic resin. There is an effect of expressing the natural properties of the lubricant and antioxidant without affecting the physical properties of the composition.
[157]
[158]
Manufacturing method of thermoplastic resin composition
[159]
Hereinafter, a method for preparing the thermoplastic resin composition of the present invention will be described. In describing the manufacturing method of the thermoplastic resin composition of the present invention, all contents of the above-described thermoplastic resin composition are included.
[160]
A method for producing the thermoplastic resin composition of the present disclosure includes, for example, a first graft copolymer comprising a conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer; a second graft copolymer comprising an alkyl (meth)acrylate-based polymer, an aromatic vinyl-based monomer, a vinyl cyan-based monomer, and an alkyl (meth)acrylate-based monomer; and a thermoplastic copolymer comprising an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinylcyan-based monomer, including 5 to 12% by weight of the first graft copolymer, wherein the first The step of melt-kneading and extruding a thermoplastic resin composition having a weight of the graft copolymer that is smaller than that of the second graft copolymer and at the same time smaller than that of the thermoplastic copolymer is introduced into an extruder.
[161]
The melt-kneading step may include, for example, other additives described above.
[162]
The melt-kneading and extruding may be performed using, for example, at least one selected from the group consisting of a single-screw extruder, a twin-screw extruder, and a Banbury mixer, preferably a twin-screw extruder, using which the composition is uniformly mixed. After extrusion, for example, a thermoplastic resin composition in the form of pellets can be obtained. In this case, mechanical properties, thermal properties, coating adhesion and appearance quality are excellent.
[163]
The kneading and extrusion may be carried out, for example, at a barrel temperature of 180 to 280 ° C, preferably 210 to 250 ° C, and in this case, melt-kneading may be sufficiently performed with an appropriate amount per unit time, and the resin component There is an effect of not causing problems such as thermal decomposition.
[164]
The kneading and extruding may be performed under the condition that the number of rotations of the screw is, for example, 200 to 300 rpm, preferably 250 to 300 rpm.
[165]
After extruding the thermoplastic resin composition, the prepared pellets may be dried in a convection oven at, for example, 60 to 90 ° C. for 4 hours or more, and then injection molded.
[166]
The injection molding is performed using an injection molding machine (ENGEL, 100 ton) at an injection temperature of 190 to 260 ° C, specific examples of 210 to 230 ° C, mold temperature of 40 to 80 ° C, specific examples of 50 to 70 ° C, and an injection speed of 10 to 80 mm. /sec, specific examples may include the step of injecting under 20 to 40 mm/sec.
[167]
[168]
Furthermore, a molded article containing the thermoplastic resin composition of the present invention will be described. In describing the molded article containing the thermoplastic resin composition of the present invention, all contents of the above-described thermoplastic resin composition are included.
[169]
[170]

[171]
According to another embodiment of the present invention, it is made of the thermoplastic transparent resin composition described above.A rough molded article can be provided. Within the above range, the physical property balance of mechanical properties, transparency, alcohol resistance and processability may be improved.
[172]
The molded article can be used, for example, for electronic equipment, office equipment, and household appliances that require alcohol disinfection.
[173]
In describing the thermoplastic resin composition of the present description, its manufacturing method and molded article, it is stated that other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art and are not particularly limited. do.
[174]
[175]
Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.
[176]
[Example]
[177]
Materials used in the following Examples and Comparative Examples are as follows.
[178]
A) First graft copolymer (ABS-based resin: (rubber) 50% by weight of butadiene polymer having an average particle diameter of 300 nm, 35% by weight of methyl methacrylate, 12% by weight of styrene, 3% by weight of acrylonitrile)
[179]
B-1) second graft copolymer (ASA resin: (rubber) 42% by weight of butyl acrylate, 3% by weight of styrene, 37% by weight of styrene, 14% by weight of acrylonitrile, butyl acrylate with an average particle diameter of 90 nm, 4% by weight of butyl acrylate % by weight, weight average molecular weight 85,000 g/mol)
[180]
B-2) Second graft copolymer (ASA-based resin: (rubber) 42% by weight of butyl acrylate and 3% by weight of styrene, 40% by weight of styrene and 15% by weight of acrylonitrile, weight average molecular weight of 90 nm, weight average molecular weight 83,000 g/mol)
[181]
C) thermoplastic copolymer (MSAN resin of bulk polymerization method: methyl methacrylate 70% by weight, styrene 25% by weight, acrylonitrile 5% by weight, weight average molecular weight 150,000 g / mol)
[182]
D) Block copolymer having ethylene oxide units and propylene oxide units (Pluronic F108, a product of BASF, weight average molecular weight 14,600 g/mol)
[183]
E) methyl methacrylate polymer (IH830 from LG MMA, weight average molecular weight 101,000 g/mol)
[184]
[185]
Examples 1 to 5, Comparative Examples 1 to 4, Reference Examples 1 to 2
[186]
The components and contents shown in Tables 1 and 2 below were kneaded and extruded in a twin screw extruder at 230 ° C to prepare pellets, and the pellets were injected at a molding temperature of 230 ° C to prepare specimens for measuring physical properties.
[187]
The properties of the pellets and specimens prepared in Examples 1 to 5, Comparative Examples 1 to 4, and Reference Examples 1 to 2 were measured by the following method, and the results are shown in Tables 1 and 2 below.
[188]
* Melt index (MI): The prepared pellets were measured by the ASTM D1238 method under the condition of 220 kg.
[189]
* Transparency (%): Haze and color characteristics of a specimen having a thickness of 3 mm were measured according to ASTM D1003.
[190]
* Notched Izod Impact Strength (kg.cm/cm): The notched Izod impact strength of a specimen having a thickness of 1/4 inch was measured according to ASTM D-256.
[191]
* Alcohol resistance: After fixing a tensile specimen with a thickness of 1/8 inch (3.2 mm) to a jig (Zig, radius of curvature: 226.97 mm) with both ends bent, 70% isopropyl alcohol is applied to the gaze, and the specimen is It was placed in the middle, allowed to permeate the specimen, and left for 12 hours. Then, changes in the surface appearance of the specimen and the presence or absence of cracks were confirmed with the naked eye. If there was no change as a result of visual inspection, it was described as No Crack, if there were fine cracks and slight color changes, it was described as Micro Crack, and if cracks occurred and the color change was severe, it was described as Crack.
[192]
Unless otherwise defined in this description, % means weight %.
[193]
[Table 1]
Classification Example 1 Example 2 Example 3 Example 4 Example 5
A 5 10 7 10 5
B-1 50 35 43 50 50
B-2 - - - - -
C 45 55 50 40 45
D-1 1 1 1.5
E - - - -
Melt index 2.7 5.8 5.1 3.5 4.5
Transparency 12.5 11.6 11.2 14.6 12.5
Impact strength 13.5 10.9 11.7 16.9 13.3
Alcohol Resistance No Crack No Crack No Crack No Crack No Crack
[194]
(* The content of D is a part by weight based on 100 parts by weight of the total of A, B-1, B-2, C, and E.)
[195]
[Table 2]
Division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Reference Example 1 Reference Example 2
A 43 10 15 3 5 5
B-1 7 0 35 45 45 45
B-2 - 50 - - - -
C 50 40 50 52 50 40
D - - - - 2 -
E - - - - - 10
Melt index 3.5 2.2 4.4 4.1 6.1 4.2
Transparency 4.6 75 16.3 9.3 9.5 8.9
Impact strength 27 17.8 13.8 8.5 10.5 11.5
Alcohol resistance Crack No Crack No Crack No Crack Micro Crack No Crack
[196]
(* The content of D is a part by weight based on 100 parts by weight of the total of A, B-1, B-2, C, and E.)
[197]
As shown in Tables 1 and 2, the first graft copolymer, the second graft copolymer and the thermoplastic copolymer are included in appropriate amounts, but the alkyl (meth) acrylic contained in the shell of the second graft copolymer Examples 1 to 5, which include the same type of alkyl (meth)acrylate-based monomers as the alkyl (meth)acrylate-based monomers included in preparing the alkyl (meth)acrylate polymer included in the second graft copolymer, form the composition of the present invention Compared to Comparative Examples 1 to 4 in which the shell of the second graft copolymer does not contain the alkyl (meth) acrylate-based monomer or the alkyl (meth) acrylate-based monomer, while maintaining the same or higher melt index, transparency and impact strength, the alcohol resistance It was confirmed that the representative chemical resistance was remarkably excellent.
[198]
In particular, it was confirmed that Comparative Example 1, in which the weight of the first graft copolymer was greater than that of the second graft copolymer, had poor alcohol resistance.
[199]
In addition, Comparative Example 2, in which the shell of the second graft copolymer did not include an alkyl (meth)acrylate-based monomer, was confirmed to have poor transparency.
[200]
In addition, it was confirmed that the transparency of Comparative Example 3 in which the weight of the first graft copolymer was excessive was reduced, and the impact strength of Comparative Example 4 in which the weight of the first graft copolymer was small was reduced.
[201]
Furthermore, referring to the optical micrographs of FIGS. 1 and 2, the molded article according to Example 1 of the present invention did not crack by alcohol, but the molded article according to Comparative Example 1 outside the scope of the present invention Cracks occurred due to insufficient weight of the graft copolymer and poor alcohol resistance could be confirmed with the naked eye.
[202]
On the other hand, when the processing aid is included in an excessive amount, as shown in Reference Example 1, alcohol resistance and transparency, which are the main characteristics to be achieved in the present invention, are poor, and even if the methyl methacrylate polymer known to have excellent transparency is included, the transparency depends on the amount used. was confirmed to decrease.
[203]
[204]
In conclusion, in the case of providing a thermoplastic resin composition containing two different types of rubber in an appropriate composition as a graft copolymer while modifying and applying a thermoplastic copolymer, a material with excellent alcohol resistance while securing transparency and processability, which are basic physical properties It was confirmed that it was suitable for the molded article by providing.
claims
[Claim 1]
a first graft copolymer comprising a conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer; a second graft copolymer comprising an alkyl (meth)acrylate-based polymer, an aromatic vinyl-based monomer, a vinyl cyan-based monomer, and an alkyl (meth)acrylate-based monomer; and a thermoplastic copolymer comprising an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinylcyan-based monomer, including 5 to 12% by weight of the first graft copolymer, wherein the first The thermoplastic resin composition, characterized in that the weight of the graft copolymer is smaller than the weight of the second graft copolymer and smaller than the weight of the thermoplastic copolymer.
[Claim 2]
The method of claim 1, wherein the thermoplastic resin composition comprises 5 to 12% by weight of the first graft copolymer; 28 to 75% by weight of the second graft copolymer; and 20 to 60% by weight of the thermoplastic copolymer.
[Claim 3]
The method of claim 1, wherein the first graft copolymer is 30 to 60% by weight of a conjugated diene-based polymer based on the total weight; 20 to 40% by weight of the alkyl (meth)acrylate-based monomer; A thermoplastic resin composition comprising 5 to 25% by weight of an aromatic vinyl monomer and 1 to 15% by weight of a vinylcyanic monomer.
[Claim 4]
The thermoplastic resin composition according to claim 1, wherein the first graft copolymer has a weight average molecular weight of 80,000 to 300,000 g/mol.
[Claim 5]
The method of claim 1, wherein the second graft copolymer comprises 30 to 70% by weight of the alkyl (meth)acrylate-based polymer; 20 to 68% by weight of the aromatic vinyl monomer; 1 to 30% by weight of the vinyl cyan-based monomer; and 1 to 15% by weight of the alkyl (meth)acrylate-based monomer.
[Claim 6]
The method of claim 1, wherein the alkyl (meth) acrylate-based polymer of the first graft copolymer includes an alkyl (meth) acrylate-based monomer and an aromatic vinyl-based monomer, and the alkyl (meth) acrylate-based polymer Alkyl (meth)acrylate-based monomers of polymers The thermoplastic resin composition, characterized in that the body is the same as the alkyl (meth) acrylate-based monomer of the second graft copolymer.
[Claim 7]
The thermoplastic resin composition according to claim 6, wherein the alkyl (meth)acrylate-based monomer is a butyl acrylate monomer or a 2-ethylhexyl acrylate monomer.
[Claim 8]
The thermoplastic resin composition according to claim 1, wherein the second graft copolymer has a weight average molecular weight of 50,000 to 150,000 g/mol.
[Claim 9]
The thermoplastic resin composition according to claim 1, wherein a weight ratio of the first graft copolymer to the second graft copolymer is 1:3 to 1:11.
[Claim 10]
According to claim 1, wherein the thermoplastic copolymer is based on the total weight, 40 to 80% by weight of the alkyl (meth) acrylate-based monomer; 15 to 40% by weight of the aromatic vinyl monomer; and 3 to 20% by weight of the vinyl cyan-based monomer.
[Claim 11]
The thermoplastic resin composition according to claim 1, wherein the alkyl (meth)acrylate-based monomer of the first graft copolymer and the alkyl (meth)acrylate-based monomer of the thermoplastic copolymer are methyl methacrylate.
[Claim 12]
The method of claim 1, wherein the thermoplastic resin composition comprises a block copolymer comprising an ethylene oxide unit and a propylene oxide unit in a total amount of 100 parts by weight of the first graft copolymer, the second graft copolymer, and the thermoplastic copolymer. A thermoplastic resin composition characterized in that it comprises 1.5 parts by weight or less relative to.
[Claim 13]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is an alcohol-resistant reinforced base material.
[Claim 14]
a first graft copolymer comprising a conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer; a second graft copolymer comprising an alkyl (meth)acrylate-based polymer, an aromatic vinyl-based monomer, a vinyl cyan-based monomer, and an alkyl (meth)acrylate-based monomer; and a thermoplastic copolymer comprising an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinylcyan-based monomer, including 5 to 12% by weight of the first graft copolymer, wherein the first A method for producing a thermoplastic resin composition comprising the steps of melt-kneading and extruding a thermoplastic resin composition in which the weight of the graft copolymer is smaller than that of the second graft copolymer and at the same time smaller than the weight of the thermoplastic copolymer.
[Claim 15]
A molded article made of the thermoplastic resin composition according to any one of claims 1 to 13.