The present invention claims the benefit of priority based on Korean Patent Application No. 10-2018-0139152 filed on November 13, 2018, and includes all contents disclosed in the literature of the Korean patent application as a part of this specification.
[3]
[Technical field]
[4]
The present invention relates to a thermoplastic resin composition, and relates to a thermoplastic resin composition having improved elongation, processability, weather resistance, colorability, chemical resistance, scratch resistance, whitening phenomenon, surface gloss, and appearance quality.
[5]
background
[6]
In a conventional paint coating process including a curing process, legal regulations around the world are being strengthened due to environmental pollution in which harmful substances such as volatile organic compounds are released into the atmosphere.
[7]
For this reason, currently, PCM (polymer coated metal) is generally used for exterior panel materials of home appliances for corrosion prevention, low friction, and surface gloss. In particular, the use of VCM (vinyl coated metal) coated with vinyl resin among PCM materials is increasing in line with the demand for high-end products. VCM is a material coated with PVC and PET film on a galvanized steel sheet, and is used as a material for the exterior panel of home appliances. VCM can further be used in building materials, furniture, automobiles, electrical materials, roof tiles, and the like.
[8]
Currently, various coating materials for VCM are being developed, but the outer plate material coated with PVC and PET film has poor weather resistance, so ASA graft copolymer with excellent weather resistance can be an alternative. This ASA graft copolymer mainly uses an acrylic rubber polymer to improve impact as a core, and styrene, acrylonitrile, methyl methacrylate, etc. are used for the shell to improve colorability and dispersibility with the matrix copolymer. .
[9]
In order to apply the ASA graft copolymer to VCM, high elongation is required to prevent tearing during the press process for sheet metal, and the surface quality must be excellent even during high-temperature processing.
[10]
Accordingly, efforts are being made to develop a thermoplastic resin composition including an ASA graft copolymer that has high elongation and does not generate bubbles even during high-temperature processing.
[11]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[12]
An object of the present invention is to provide a thermoplastic resin composition with improved elongation, processability, weather resistance, colorability, chemical resistance, scratch resistance, whitening phenomenon, surface gloss, and appearance quality while maintaining basic physical properties such as impact resistance and hardness. .
[13]
means of solving the problem
[14]
In order to solve the above problems, the present invention is a graft copolymer obtained by graft polymerization of an aromatic vinyl monomer and a vinyl cyan monomer to an acrylic rubber polymer having an average particle diameter of 50.0 to 90.0 nm; C 1 To C 3 A matrix copolymer comprising an alkyl (meth)acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; And C 1 to C 3 It provides a thermoplastic resin composition comprising an additive comprising a polymer comprising an alkyl (meth) acrylate-based monomer unit.
[15]
Effects of the Invention
[16]
The thermoplastic resin composition according to the present invention is excellent in basic physical properties such as impact resistance and hardness, and the elongation, processability, weather resistance, colorability, chemical resistance, scratch resistance, whitening phenomenon, surface gloss, and appearance quality can be remarkably improved. .
[17]
Modes for carrying out the invention
[18]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[19]
The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[20]
[21]
In the present invention, the average particle diameter of the seed, core, acrylic rubber polymer and graft copolymer can be measured using a dynamic light scattering method, and specifically, Nicomp 380 HPL equipment (product name, manufacturer: Nicomp) It can be measured using
[22]
In the present specification, the average particle diameter refers to the arithmetic average particle diameter in the particle size distribution measured by the dynamic light scattering method, that is, the average particle diameter of the scattering intensity.
[23]
[24]
In the present invention, the graft rate of the graft copolymer can be calculated by the following formula.
[25]
[26]
Graft rate (%): weight of grafted monomer (g) / weight of acrylic rubbery polymer (g) × 100
[27]
[28]
Weight of grafted monomer (g): Weight of insoluble material (gel) after dissolving 1 g of graft copolymer in 30 g of acetone and centrifugation
[29]
The acrylic weight (g) of rubber polymer: graft copolymer powder of theoretical C 4 to C 10 alkyl (meth) acrylate-based monomer by weight or graft copolymer C injected in the preparation of the 4 to C 10 alkyl (meth ) Weight of acrylate-based monomer
[30]
[31]
In the present invention, the weight average molecular weight of the shell of the graft copolymer may mean the weight average molecular weight of the copolymer including the aromatic vinyl monomer unit and the vinyl cyan monomer unit grafted to the acrylic rubber polymer.
[32]
In the present invention, the weight average molecular weight of the shell of the graft copolymer is a relative value to a standard PS (standard polystyrene) sample through gel permeation chromatography after dissolving a portion (sol) dissolved in acetone in a tetrahydrofuran solution when measuring the graft rate. can be measured with
[33]
[34]
In the present invention, the weight average molecular weight of the matrix copolymer may be measured using tetrahydrofuran as an eluent and relative to poly(methyl methacrylate) manufactured by Polymer Laboratories, a standard sample, through gel permeation chromatography.
[35]
[36]
In the present invention, the polymerization conversion rate of the matrix copolymer can be calculated by the following formula.
[37]
Polymerization conversion (%) = {(weight of solid content of copolymer actually obtained)/(weight of monomers added as prescribed)} × 100
[38]
[39]
In the present invention, the weight average molecular weight of the polymer included in the additive is measured using tetrahydrofuran as an eluent and relative to poly(methyl methacrylate), a standard sample (manufacturer: Polymer Laboratories), through gel permeation chromatography. can do.
[40]
[41]
The polymerization conversion rate of the polymer included in the additive in the present invention is measured by extracting the residual monomer component from the polymer by reprecipitation using chloroform (CHCl 3 ) and methanol and quantitatively analyzing it using gas chromatography/mass spectrometry (GC/MSD). can do.
[42]
[43]
In the present invention, the polymer may be meant to include both a homopolymer formed by polymerization of one type of monomer and a copolymer formed by polymerization of two or more types of monomers.
[44]
[45]
In the present invention, the aromatic vinyl-based monomer unit may be a unit derived from an aromatic vinyl-based monomer, and the aromatic vinyl-based monomer is a group consisting of styrene, α-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene and vinyl toluene. It may be one or more selected from, among which styrene is preferable.
[46]
[47]
In the present invention, the vinyl cyan-based monomer unit may be a unit derived from a vinyl cyan-based monomer, and the vinyl cyan-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, and , of which acrylonitrile is preferable.
[48]
[49]
In the present invention, the C 1 to C 3 alkyl (meth)acrylate monomer unit may be a unit derived from a C 1 to C 3 alkyl (meth)acrylate monomer, and C 1 to C 3 alkyl (meth) ) The acrylate-based monomer may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate and propyl (meth) acrylate, of which methyl methacrylate and methyl acrylate At least one selected from the group is preferred.
[50]
[51]
1. Thermoplastic resin composition
[52]
A thermoplastic resin composition according to an embodiment of the present invention comprises: 1) a graft copolymer obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to an acrylic rubber-like polymer having an average particle diameter of 50.0 to 90.0 nm; 2) C 1 to C 3 A matrix copolymer including an alkyl (meth)acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; and 3) an additive including a polymer including a C 1 to C 3 alkyl (meth)acrylate-based monomer unit.
[53]
[54]
Hereinafter, components of the thermoplastic resin composition according to an embodiment of the present invention will be described in detail.
[55]
[56]
1) graft copolymer
[57]
The graft copolymer is obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to an acrylic rubbery polymer having an average particle diameter of 50.0 to 90.0 nm.
[58]
[59]
The graft copolymer may improve weather resistance, elongation, colorability, chemical resistance, processability, surface gloss properties, and whitening properties of the thermoplastic resin composition.
[60]
[61]
The average particle diameter of the acrylic rubber polymer may be 50.0 to 90.0 nm, preferably 65.0 to 75.0 nm. When the above-described range is satisfied, the smaller the average particle diameter of the acrylic rubber polymer, the greater the specific surface area, so that the weather resistance may be increased. In addition, since visible light can pass through the acrylic rubbery polymer, the colorability can be remarkably improved. In addition, since the graft copolymer can be uniformly dispersed in a high content in the thermoplastic resin composition, elongation and whitening properties can be remarkably improved. If it is less than the above range, the impact strength may be significantly reduced, and if it exceeds the above range, the whitening property may be remarkably reduced.
[62]
[63]
The graft copolymer may be a copolymer obtained by graft copolymerizing butyl acrylate rubbery polymer with styrene and acrylonitrile.
[64]
[65]
The graft copolymer may have a graft rate of 25 to 50% or 30 to 45%, of which 30 to 45% is preferable. When the above-mentioned range is satisfied, the compatibility with the matrix copolymer is remarkably improved due to the aromatic vinyl monomer unit and the vinyl cyan monomer unit grafted to the acrylic rubber polymer, and the elongation and whitening properties of the thermoplastic resin composition and impact resistance can be remarkably improved.
[66]
[67]
The graft copolymer may have a shell weight average molecular weight of 30,000 to 200,000 g/mol, 50,000 to 180,000 g/mol, or 80,000 to 150,000 g/mol, of which 80,000 to 150,000 g/mol is preferable. When the above-described range is satisfied, compatibility with other components may be improved, and dispersibility of the acrylic rubber polymer in the thermoplastic resin composition may be improved.
[68]
[69]
On the other hand, the graft copolymer is prepared by adding at least one selected from the group consisting of C 4 to C 10 alkyl (meth)acrylate monomers, aromatic vinyl monomers and vinyl cyan monomers, and crosslinking reaction to prepare seeds. And, in the presence of the seed, a C 4 to C 10 alkyl (meth) acrylate-based monomer is added and a cross-linking reaction is performed to prepare a core, and in the presence of the core, an aromatic vinyl-based monomer and a vinyl cyan-based monomer are added, and graph It can be prepared by polymerization to prepare a shell.
[70]
Here, the core may refer to the above-described acrylic rubber polymer.
[71]
The C 4 to C 10 alkyl (meth) acrylate-based monomer is butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate , may be at least one selected from the group consisting of ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate and decyl (meth)acrylate, of which butyl acrylate is preferable. .
[72]
The C 4 to C 10 alkyl (meth)acrylate-based monomer may be added in an amount of 30 to 50% by weight or 35 to 45% by weight based on the total weight of the monomers added during the preparation of the graft copolymer, Among them, it is preferably added in an amount of 35 to 45% by weight. If the above-described range is satisfied, weather resistance, impact resistance, surface gloss properties, elongation and whitening properties of the graft copolymer may be further improved.
[73]
The aromatic vinyl-based monomer may be added in an amount of 30 to 50% by weight or 35 to 45% by weight based on the total weight of the graft copolymer, based on the total weight of the monomers added during the preparation of the graft copolymer, , of which 35 to 45% by weight is preferably added. When the above-described range is satisfied, not only the processability of the graft copolymer can be further improved, but also the graft copolymer can be more uniformly dispersed in the thermoplastic resin composition, and the colorability of the thermoplastic resin composition can be further improved. .
[74]
The vinyl cyanide-based monomer may be added in an amount of 10 to 30% by weight or 15 to 25% by weight based on the total weight of the monomers added during the preparation of the graft copolymer, of which 15 to 25% by weight. it is preferable If the above-mentioned range is satisfied, not only the chemical resistance of the graft copolymer may be further improved, but also the graft copolymer may be more uniformly dispersed in the thermoplastic resin composition, and the colorability of the thermoplastic resin composition may be further improved. have.
[75]
On the other hand, the total weight of the monomers input during the preparation of the seed may be 1 to 20 wt% or 5 to 15 wt%, of which 5 to 15 wt%, based on the total weight of the monomers input during the preparation of the graft copolymer 15% by weight is preferred.
[76]
The total weight of the monomers added during the preparation of the core may be 20 to 50% by weight or 25 to 45% by weight, of which 25 to 45% by weight, based on the total weight of the monomers added during the preparation of the graft copolymer. % is preferred.
[77]
The total weight of the monomers added during the preparation of the shell may be 40 to 70% by weight or 45 to 65% by weight, of which 45 to 65% by weight, based on the total weight of the monomers added during the preparation of the graft copolymer. % is preferred.
[78]
[79]
The graft copolymer may be included in an amount of 30 to 80 wt% or 35 to 75 wt%, based on the total weight of the thermoplastic resin composition, of which 35 to 75 wt% is preferable. If the above-mentioned range is satisfied, elongation, weather resistance, chemical resistance, colorability, processability, surface gloss properties, appearance quality and whitening properties of the thermoplastic resin composition can be remarkably improved.
[80]
[81]
2) matrix copolymer
[82]
The matrix copolymer is a random copolymer, and includes a C 1 to C 3 alkyl (meth)acrylate monomer unit, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit.
[83]
[84]
The matrix copolymer includes a C 1 to C 3 alkyl (meth)acrylate-based monomer unit that is a component of the additive, and an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit that are a component of the shell of the graft copolymer Since it contains, it is possible to improve compatibility between the graft copolymer and the polymer as well as excellent compatibility with the graft copolymer and the additive. Accordingly, in the thermoplastic resin composition according to an embodiment of the present invention, phase separation does not occur even during high-temperature molding.
[85]
In addition, the matrix copolymer may further improve the colorability, weather resistance, and hardness of the thermoplastic resin composition.
[86]
[87]
The matrix copolymer may be a copolymer of a monomer mixture including a C 1 to C 3 alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer.
[88]
The monomer mixture may include 25 to 75% by weight or 30 to 70% by weight of the C 1 to C 3 alkyl (meth)acrylate-based monomer, and it is preferable to include it in 30 to 70% by weight. . When the above-mentioned range is satisfied, compatibility with the polymer included in the additive is remarkably improved, and the colorability, weather resistance and hardness of the thermoplastic resin composition can be remarkably improved.
[89]
The monomer mixture may include 15 to 60% by weight or 20 to 55% by weight of the aromatic vinyl-based monomer, and it is preferable to include it in an amount of 20 to 55% by weight. When the above-described range is satisfied, compatibility with the graft copolymer is remarkably improved, and colorability, weather resistance and hardness of the thermoplastic resin composition can be remarkably improved.
[90]
The monomer mixture may include 1 to 20% by weight or 5 to 15% by weight of the vinyl cyanide monomer, preferably 5 to 15% by weight of this. When the above-described range is satisfied, compatibility with the graft copolymer is remarkably improved, and colorability, weather resistance and hardness of the thermoplastic resin composition can be remarkably improved.
[91]
[92]
The matrix copolymer may be a copolymer of methyl methacrylate, styrene and acrylonitrile.
[93]
[94]
The matrix copolymer may have a weight average molecular weight of 50,000 to 200,000 g/mol, 60,000 to 170,000 g/mol, or 70,000 to 140,000 g/mol, of which 70,000 to 140,000 g/mol is preferable. If the above-mentioned range is satisfied, the balance of workability, compatibility, and hardness may be excellent.
[95]
[96]
The matrix copolymer may be included in an amount of 0.1 to 30.0 wt% or 1.0 to 25.0 wt%, based on the total weight of the thermoplastic resin composition, and preferably included in an amount of 1.0 to 25.0 wt%. If the above-described range is satisfied, compatibility between the graft copolymer and the additive may be remarkably improved, and colorability, weather resistance and hardness of the thermoplastic resin composition may be remarkably improved.
[97]
[98]
3) Additives
[99]
The additive includes a polymer including a C 1 to C 3 alkyl (meth)acrylate-based monomer unit.
[100]
[101]
The additive may improve hardness, surface gloss, scratch resistance, appearance quality and weather resistance of the thermoplastic resin composition.
[102]
[103]
The polymer may have a weight average molecular weight of 150,000 to 250,000 g/mol, 170,000 to 230,000 g/mol, or 190,000 to 210,000 g/mol, preferably 190,000 to 210,000 g/mol. If the above-described range is satisfied, gas derived from the polymer may not be generated during processing of the thermoplastic resin composition, and the polymer may not be decomposed. In addition, the hardness, weather resistance, surface gloss, scratch resistance and appearance quality of the thermoplastic resin composition can be remarkably improved.
[104]
[105]
The polymer may be poly(methyl methacrylate).
[106]
[107]
The polymer may be a copolymer including two or more C 1 to C 3 alkyl (meth)acrylate-based monomer units in order to improve transparency and processability , preferably C 1 to C 3 alkyl methacryl It may be a copolymer including a rate-based monomer unit and a C 1 to C 3 alkyl acrylate-based monomer unit. The copolymer may be a copolymer of a monomer mixture including a C 1 to C 3 alkyl methacrylate-based monomer and a C 1 to C 3 alkyl acrylate-based monomer. In this case, the monomer mixture is a C 1 to C 3 alkyl methacrylate-based monomer and C 1 to C 3may include the alkyl acrylate-based monomer of 80:20 to 99:1 or 85:15 to 95:5 by weight, of which, it is preferably included in a weight ratio of 85:15 to 95:5. If the above-mentioned range is satisfied, the balance of workability, surface gloss, hardness, and tensile strength may be excellent.
[108]
[109]
The copolymer may be a copolymer of methyl methacrylate and methyl acrylate.
[110]
[111]
The polymer may be included in an amount of 5 to 50 wt%, or 10 to 45 wt%, based on the total weight of the thermoplastic resin composition, of which 10 to 45 wt% is preferably included. When the above-described range is satisfied, hardness, weather resistance, surface gloss, scratch resistance, and appearance quality of the thermoplastic resin composition may be remarkably improved.
[112]
[113]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.
[114]
[115]
Preparation Example 1
[116]

[117]
In a nitrogen-substituted reactor, 10 parts by weight of butyl acrylate, 0.04 parts by weight of potassium persulfate as an initiator, 2 parts by weight of di-2-ethylhexyl sulfoxuccinate sodium salt as an emulsifier, 0.02 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, 0.04 parts by weight of allyl methacrylate as a grafting agent, 0.1 parts by weight of NaHCO 3 as an electrolyte, and 40 parts by weight of distilled water were put together, and the temperature was raised to 65 ° C. After polymerization for 1 hour, the butyl acrylate rubbery polymer as a seed was terminated. (average particle diameter: 52.5 nm) was obtained.
[118]
[119]

[120]
30 parts by weight of butyl acrylate in the reactor in which the seed was obtained, 0.5 parts by weight of di-2-ethylhexyl sulfoxuccinate sodium salt as an emulsifier, 0.2 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, and allyl methacrylate as a grafting agent 0.2 parts by weight, a mixture containing 0.1 parts by weight of NaHCO 3 as an electrolyte and 20 parts by weight of distilled water, and 0.06 parts by weight of potassium persulfate as an initiator, respectively, were continuously added at 70 ° C. After further polymerization for 1 hour, it was terminated to obtain a core butyl acrylate rubbery polymer (average particle diameter: 68.5 nm).
[121]
[122]

[123]
In the reactor in which the core was obtained, 40 parts by weight of styrene, 20 parts by weight of acrylonitrile, 1.4 parts by weight of potassium rosinate as an emulsifier, 0.042 parts by weight of KOH as an electrolyte, 0.05 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, and A mixture containing 63 parts by weight of distilled water and 0.1 parts by weight of potassium persulfate as an initiator were polymerized while continuously added at a constant rate for 5 hours at 70 ° C. After the continuous input was completed, further polymerization was performed at 70 ° C. for 1 hour, The polymerization was terminated by cooling to 60° C., and a graft copolymer latex (average particle diameter: 95.0 nm) was obtained. Here, the polymerization conversion rate of the graft copolymer latex was 98%, the pH was 9.5, and the graft rate was 42%.
[124]
2 parts by weight of an aqueous calcium chloride solution (concentration: 10% by weight) was added to the graft copolymer latex, coagulated under atmospheric pressure at 85°C, aged at 95°C, dehydrated and washed, dried for 30 minutes with hot air at 90°C, and then grafted t copolymer powder was prepared.
[125]
[126]
Preparation 2
[127]

[128]
In a nitrogen-substituted reactor, 7.5 parts by weight of styrene, 2.5 parts by weight of acrylonitrile, 0.2 parts by weight of di-2-ethylhexyl sulfoxuccinate sodium salt as an emulsifier, 0.04 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, allyl as a grafting agent 0.04 parts by weight of methacrylate, 0.2 parts by weight of NaHCO 3 as an electrolyte, and 40 parts by weight of distilled water were collectively added, and the temperature was raised to 70° C., and then 0.05 parts by weight of potassium persulfate was collectively added to initiate polymerization. Thereafter, after polymerization at 70° C. for 1 hour, it was terminated to obtain a seed styrene-acrylonitrile rubber polymer (average particle diameter: 160.0 nm).
[129]
[130]

[131]
In the reactor in which the seed was obtained, 40 parts by weight of butyl acrylate, 0.5 parts by weight of di-2-ethylhexyl sulfoxuccinate sodium salt as an emulsifier, 0.2 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, and allyl methacrylate as a grafting agent 0.2 parts by weight, 0.1 parts by weight of NaHCO 3 as electrolyte, 0.05 parts by weight of potassium persulfate, and 20 parts by weight of distilled water are polymerized while continuously inputting at a constant rate for 3 hours at 70° C., and for 1 hour after the continuous input is completed After further polymerization, it was completed to obtain a core butyl acrylate rubbery polymer (average particle diameter: 280.0 nm).
[132]
[133]

[134]
In the reactor in which the core was obtained, 37.5 parts by weight of styrene, 12.5 parts by weight of acrylonitrile, 0.1 parts by weight of potassium persulfate as an initiator, 1.5 parts by weight of potassium rosin acid salt as an emulsifier, and 0.05 parts by weight of t-dodecyl mercaptan as a molecular weight regulator , and a mixture containing 63 parts by weight of distilled water, and 0.1 parts by weight of potassium persulfate, each of which is an initiator, were continuously added at a constant rate for 5 hours at 70 ° C. Then, the polymerization was terminated by cooling to 60° C., and a graft copolymer latex (average particle diameter: 350.0 nm) was obtained. Here, the polymerization conversion rate of the graft copolymer latex was 98%, the pH was 9.5, and the graft rate was 38%.
[135]
2 parts by weight of an aqueous calcium chloride solution (concentration: 10% by weight) was added to the graft copolymer latex, coagulated under atmospheric pressure at 85°C, aged at 95°C, dehydrated and washed, dried for 30 minutes with hot air at 90°C, and then grafted t copolymer powder was prepared.
[136]
[137]
Preparation 3
[138]
An activator solution comprising 0.015 parts by weight of disodium ethylenediamine tetraacetate, 0.02 parts by weight of sodium formaldehyde sulfoxylate, 0.001 parts by weight of ferrous sulfate heptahydrate, and 1.165 parts by weight of distilled water was prepared.
[139]
On the other hand, 100 parts by weight of distilled water and 4 parts by weight of sodium lauryl sulfate aqueous solution (concentration: 3% by weight) as an emulsifier were added to a 3 liter four-neck reactor equipped with a thermometer, a nitrogen input device, a cooler and a stirrer, and while stirring, methyl methacrylic 9 parts by weight of the rate, 15.75 parts by weight of styrene, 5.25 parts by weight of acrylonitrile, and 0.01 parts by weight of t-dodecyl mercaptan as a molecular weight regulator were added. Then, the temperature was raised to 60° C. while continuously introducing nitrogen.
[140]
0.3 parts by weight of an aqueous solution of potassium persulfate (concentration: 3% by weight) as an initiator and 5 parts by weight of an activator solution were added as an initiator while maintaining the temperature in the reactor at 60° C., and after polymerization for 2 hours, a copolymer latex was obtained.
[141]
Meanwhile, 50 parts by weight of distilled water, 5 parts by weight of sodium lauryl sulfate aqueous solution (concentration: 3 parts by weight), 21 parts by weight of methyl methacrylate, 36.75 parts by weight of styrene, and 12.25 parts by weight of acrylonitrile were mixed and stabilized to prepare a pre-emulsion did.
[142]
After raising the temperature of the reactor to 65 ℃, 0.1 parts by weight of potassium persulfate aqueous solution (concentration: 3% by weight) as an initiator and 0.1 parts by weight of an aqueous solution of potassium persulfate as an initiator, 5 parts by weight of an activator solution, and polymerization for 2 hours to prepare a polymer latex did. In this case, the polymerization conversion of the polymer latex was 99%, the average particle diameter was 150.0 nm, and the weight average molecular weight was 80,000 g/mol.
[143]
The polymer latex was cooled slowly at room temperature, and then cooled at −15° C. for 8 hours. When the cooled copolymer latex is dissolved at room temperature, it is separated into two phases, and the part that has sunk to the bottom was collected. The collected parts were washed with distilled water and dried in a vacuum oven for 24 hours to remove moisture and unreacted monomers to obtain white and fine particles.
[144]
[145]
Preparation 4
[146]
An activator solution comprising 0.015 parts by weight of disodium ethylenediamine tetraacetate, 0.02 parts by weight of sodium formaldehyde sulfoxylate, 0.001 parts by weight of ferrous sulfate heptahydrate, and 1.165 parts by weight of distilled water was prepared.
[147]
On the other hand, 100 parts by weight of distilled water and 4 parts by weight of sodium lauryl sulfate aqueous solution (concentration: 3% by weight) as an emulsifier were added to a 3 liter four-neck reactor equipped with a thermometer, a nitrogen input device, a cooler and a stirrer, and while stirring, methyl methacrylic 21 parts by weight of the rate, 6.75 parts by weight of styrene, 2.25 parts by weight of acrylonitrile, and 0.01 parts by weight of t-dodecyl mercaptan as a molecular weight regulator were added. Then, the temperature was raised to 60° C. while continuously introducing nitrogen.
[148]
0.3 parts by weight of an aqueous solution of potassium persulfate (concentration: 3% by weight) as an initiator and 5 parts by weight of an activator solution were added as an initiator while maintaining the temperature in the reactor at 60° C., and after polymerization for 2 hours, a copolymer latex was obtained.
[149]
Meanwhile, 50 parts by weight of distilled water, 5 parts by weight of sodium lauryl sulfate aqueous solution (concentration: 3 parts by weight), 49 parts by weight of methyl methacrylate, 15.75 parts by weight of styrene, and 5.25 parts by weight of acrylonitrile were mixed and stabilized to prepare a pre-emulsion did.
[150]
After raising the temperature of the reactor to 65 ℃, 0.1 parts by weight of potassium persulfate aqueous solution (concentration: 3% by weight) as an initiator and 0.1 parts by weight of an aqueous solution of potassium persulfate as an initiator, 5 parts by weight of an activator solution, and polymerization for 2 hours to prepare a polymer latex did. In this case, the polymerization conversion of the polymer latex was 99%, the average particle diameter was 150.0 nm, and the weight average molecular weight was 80,000 g/mol.
[151]
The polymer latex was cooled slowly at room temperature, and then cooled at −15° C. for 8 hours. When the cooled copolymer latex is dissolved at room temperature, it is separated into two phases, and the part that has sunk to the bottom was collected. The collected parts were washed with distilled water and dried in a vacuum oven for 24 hours to remove moisture and unreacted monomers to obtain white and fine particles.
[152]
[153]
Preparation 5
[154]
An activator solution comprising 0.015 parts by weight of disodium ethylenediamine tetraacetate, 0.02 parts by weight of sodium formaldehyde sulfoxylate, 0.001 parts by weight of ferrous sulfate heptahydrate, and 1.165 parts by weight of distilled water was prepared.
[155]
On the other hand, 100 parts by weight of distilled water and 4 parts by weight of sodium lauryl sulfate aqueous solution (concentration: 3% by weight) as an emulsifier were added to a 3 liter four-neck reactor equipped with a thermometer, a nitrogen input device, a cooler and a stirrer, and while stirring, methyl methacrylic The rate was 4.5 parts by weight, 19.12 parts by weight of styrene, 6.38 parts by weight of acrylonitrile, and 0.01 parts by weight of t-dodecyl mercaptan as a molecular weight regulator. Then, the temperature was raised to 60° C. while continuously introducing nitrogen.
[156]
0.3 parts by weight of an aqueous solution of potassium persulfate (concentration: 3% by weight) as an initiator and 5 parts by weight of an activator solution were added as an initiator while maintaining the temperature in the reactor at 60° C., and after polymerization for 2 hours, a copolymer latex was obtained.
[157]
Meanwhile, 50 parts by weight of distilled water, 5 parts by weight of sodium lauryl sulfate aqueous solution (concentration: 3 parts by weight), 10.5 parts by weight of methyl methacrylate, 44.63 parts by weight of styrene, and 14.87 parts by weight of acrylonitrile were mixed and stabilized to prepare a pre-emulsion did.
[158]
After raising the temperature of the reactor to 65 ℃, 0.1 parts by weight of potassium persulfate aqueous solution (concentration: 3% by weight) as an initiator and 0.1 parts by weight of an aqueous solution of potassium persulfate as an initiator, 5 parts by weight of an activator solution, and polymerization for 2 hours to prepare a polymer latex did. In this case, the polymerization conversion of the polymer latex was 99%, the average particle diameter was 150.0 nm, and the weight average molecular weight was 80,000 g/mol.
[159]
The polymer latex was cooled slowly at room temperature, and then cooled at −15° C. for 8 hours. When the cooled copolymer latex is dissolved at room temperature, it is separated into two phases, and the part that has sunk to the bottom was collected. The collected parts were washed with distilled water and dried in a vacuum oven for 24 hours to remove moisture and unreacted monomers to obtain white and fine particles.
[160]
[161]
Preparation 6
[162]
An activator solution comprising 0.015 parts by weight of disodium ethylenediamine tetraacetate, 0.02 parts by weight of sodium formaldehyde sulfoxylate, 0.001 parts by weight of ferrous sulfate heptahydrate, and 1.165 parts by weight of distilled water was prepared.
[163]
On the other hand, 100 parts by weight of distilled water and 4 parts by weight of sodium lauryl sulfate aqueous solution (concentration: 3% by weight) as an emulsifier were added to a 3 liter four-neck reactor equipped with a thermometer, a nitrogen input device, a cooler and a stirrer, and while stirring, methyl methacrylic 25.5 parts by weight of the rate, 3.38 parts by weight of styrene, 1.12 parts by weight of acrylonitrile, and 0.01 parts by weight of t-dodecyl mercaptan as a molecular weight regulator were added. Then, the temperature was raised to 60° C. while continuously introducing nitrogen.
[164]
0.3 parts by weight of an aqueous solution of potassium persulfate (concentration: 3% by weight) as an initiator and 5 parts by weight of an activator solution were added as an initiator while maintaining the temperature in the reactor at 60° C., and after polymerization for 2 hours, a copolymer latex was obtained.
[165]
Meanwhile, 50 parts by weight of distilled water, 5 parts by weight of sodium lauryl sulfate aqueous solution (concentration: 3 parts by weight), 59.5 parts by weight of methyl methacrylate, 7.88 parts by weight of styrene, and 2.62 parts by weight of acrylonitrile were mixed and stabilized to prepare a pre-emulsion did.
[166]
After raising the temperature of the reactor to 65 ℃, 0.1 parts by weight of potassium persulfate aqueous solution (concentration: 3% by weight) as an initiator and 0.1 parts by weight of an aqueous solution of potassium persulfate as an initiator, 5 parts by weight of an activator solution, and polymerization for 2 hours to prepare a polymer latex did. In this case, the polymerization conversion of the polymer latex was 99%, the average particle diameter was 150.0 nm, and the weight average molecular weight was 80,000 g/mol.
[167]
The polymer latex was cooled slowly at room temperature, and then cooled at −15° C. for 8 hours. When the cooled copolymer latex is dissolved at room temperature, it is separated into two phases, and the part that has sunk to the bottom was collected. The collected parts were washed with distilled water and dried in a vacuum oven for 24 hours to remove moisture and unreacted monomers to obtain white and fine particles.
[168]
[169]
Preparation 7
[170]
25 parts by weight of toluene, 75 parts by weight of styrene, 25 parts by weight of acrylonitrile, and 1,1-bis(t-butylperoxy)-3,3,5-trimethyl cyclo as an initiator in a nitrogen-substituted 26 liter first reactor While continuously introducing a polymerization solution containing 0.02 parts by weight of hexane and 0.08 parts by weight of n-dodecyl mercaptan as a molecular weight modifier for 1 hour at a rate of 14 L/hour, polymerization was performed at 140° C. to obtain a first copolymer, The first copolymer was polymerized at 150° C. while continuously inputting the first copolymer into a nitrogen-substituted 26 liter second reactor at a rate of 14 ℓ/hr for 1 hour to obtain a second copolymer. At this time, the polymerization conversion rate was 60%. The obtained second copolymer was transferred to a volatilization tank to remove unreacted monomers and a reaction medium at 215° C., and a copolymer in pellet form (weight average molecular weight: 120,000 g/mol) was prepared.
[171]
[172]
Examples and Comparative Examples
[173]
[174]
The specifications of the components used in the following Examples and Comparative Examples are as follows.
[175]
[176]
(A) graft copolymer
[177]
(A-1) Graft copolymer of small particle size: The graft copolymer of Preparation Example 1 was used.
[178]
(A-2) Large particle size graft copolymer: The graft copolymer of Preparation Example 2 was used.
[179]
[180]
(B) matrix copolymer
[181]
(B-1) First matrix copolymer: The copolymer of Preparation Example 3 was used.
[182]
(B-2) Second matrix copolymer: The copolymer of Preparation Example 4 was used.
[183]
(B-3) Third matrix copolymer: The copolymer of Preparation Example 5 was used.
[184]
(B-4) Fourth matrix copolymer: The copolymer of Preparation Example 6 was used.
[185]
(B-5) Fifth matrix copolymer: The copolymer of Preparation Example 7 was used.
[186]
[187]
(C) Additive: IH830 (a copolymer of methyl methacrylate and methyl acrylate) manufactured by LG MMA was used as it was after drying.
[188]
[189]
A thermoplastic resin composition was prepared by mixing and stirring the above-mentioned components according to the contents shown in [Table 1] to [Table 3].
[190]
[191]
Experimental Example 1
[192]
Specimens were prepared by extrusion and injection of the thermoplastic resin compositions of Examples and Comparative Examples. The physical properties of the specimen were evaluated by the method described below, and the results are described in [Table 1] to [Table 3] below.
[193]
[194]
① Impact strength (kg·cm/cm): Measured according to ASTM 256.
[195]
② Hardness: Measured according to ASTM 785.
[196]
③ Elongation (%): Measured according to ASTM D638.
[197]
④ Weather resistance (ΔE): accelerated weather resistance test device (weather-o-meter, ATLAS Ci4000, xenon arc lamp, Quartz(inner)/S.Boro(outer) filter, irradiance 0.55 W/㎡ at 340 nm) applied SAE The test was conducted under J1960 condition for 2,000 hours, and the following ΔE is the arithmetic mean value before and after the accelerated weather resistance test, and the closer the value is to 0, the better the weather resistance is.
[198]

[199]
In the above formula, L', a', and b' are L, a, and b values ​​measured with the CIE LAB color coordinate system after irradiating the specimen with light under SAE J1960 conditions for 2,000 hours, and L O , a 0 and b 0 are light L, a and b values ​​measured in the CIE LAB color coordinate system prior to irradiation.
[200]
[201]
Experimental Example 2
[202]
The thermoplastic resin composition of Examples and Comparative Examples was compounded with CB5093 of Muil-Hwaseong, a black pigment, and a sheet having a width of 10 cm and a thickness of 0.15 mm was prepared using a sheet extruder, and the physical properties of the sheet were evaluated by the method described below. and the results are described in [Table 1] to [Table 3] below.
[203]
[204]
⑤ Trimming properties: After cutting at 300rpm with SJ600 of Sujeong Hi-Tech, the cut surface was visually checked.
[205]
○: good, ×: bad
[206]
[207]
Experimental Example 3
[208]
A specimen was prepared by bonding the sheet prepared in Experimental Example 2 and a galvanized steel sheet at 200° C. using an adhesive. The physical properties of the specimen were evaluated by the method described below, and the results are described in [Table 1] to [Table 3] below.
[209]
[210]
⑥ Whitening: After dropping a 1 kg metal ball on the specimen from a height of 1 m using FDI (Ball Drop Tester) of Labthink Co., it was measured.
[211]
○: No whitening phenomenon
[212]
×: Whitening occurs or the sheet is torn or cracked
[213]
[214]
⑦ Surface gloss: According to ASTM D523, the gloss was measured at 60° using NIPPON DENSHOKU's VG7000 (gloss meter).
[215]
[216]
⑧ Appearance quality: The appearance of the specimen was visually observed.
[217]
○: There is no difference in gloss and no surface curvature as a whole
[218]
x: There is a glossiness difference locally, and there exists a surface undulation.
[219]
[220]
[Table 1]
division Example
One 2 3 4 5 6 7 8
(A) Graft copolymer (parts by weight) (A-1) 60 40 80 70 60 40 60 60
(A-2) - - - - - - - -
(B) matrix copolymer (parts by weight) (B-1) 15.0 - - - - - - -
(B-2) - 20.0 5.0 10.0 - - - -
(B-3) - - - - 20.0 - 15.0 -
(B-4) - - - - - 30 - 15.0
(C) Additives (parts by weight) 25 40 15 20 20 30 25 25
impact strength 10.80 7.50 18.30 13.90 7.50 3.50 4.20 4.50
Hardness 86 101 65 76 85 98 78 85
elongation 88 58 156 132 25 17 29 25
weather resistance 0.60 0.58 0.74 0.61 2.27 0.61 2.96 1.21
trimming ○ ○ ○ ○ ○ × × ×
all sorts of flowers ○ ○ ○ ○ × × × ×
surface gloss 113 119 91 99 55 105 48 55
appearance quality ○ ○ ○ ○ × × × ×
(A-1) small particle size of the graft copolymer : a mean particle diameter of 68.5 ㎚ of butyl acrylate graft copolymers of the manufacturing cost is grafted acrylonitrile in the rubber-like polymer in styrene and acrylic Example 1 (A-2) is substituted diameter graft Copolymer : Graft copolymer (B-1) of Preparation Example 2 in which styrene and acrylonitrile were grafted onto butyl acrylate rubbery polymer having an average particle diameter of 280.0 nm (B-1) First matrix copolymer : methyl methacrylate 30 parts by weight , 52.5 parts by weight of styrene and 17.5 parts by weight of acrylonitrile copolymer of Preparation Example 3 (weight average molecular weight: 80,000 g/mol) (B-2) Second matrix copolymer : 70 parts by weight of methyl methacrylate, styrene 22.5 parts by weight and 7.5 parts by weight of acrylonitrile copolymer of Preparation Example 4 (weight average molecular weight: 80,000 g/mol) (B-3) Third matrix copolymer : 15 parts by weight of methyl methacrylate, 63.75 parts by weight of styrene Copolymer of Preparation Example 5 (weight average molecular weight: 80,000 g/mol), which is a copolymer of 21.25 parts by weight and 21.25 parts by weight of acrylonitrile (B-4) 4th matrix copolymer : Copolymer of Preparation Example 6, which is a copolymer of 85 parts by weight of methyl methacrylate, 11.26 parts by weight of styrene, and 3.74 parts by weight of acrylonitrile (weight average molecular weight: 80,000 g/mol) (C) Additive : IH830 (methyl copolymer of methacrylate and methyl acrylate)
[221]
[Table 2]
division comparative example
One 2 3 4 5
(A) Graft copolymer (parts by weight) (A-1) - - 30 60 60
(A-2) 60 40 30 - -
(B) matrix copolymer (parts by weight) (B-1) - - - - -
(B-2) - 60.0 - - -
(B-5) 40.0 - 40.0 - 15.0
(C) Additives (parts by weight) - - - 40 25
impact strength 40.30 13.60 30.80 4.40 5.20
Hardness 90 104 84 85 77
elongation 40 25 89 25 26
weather resistance 12.50 1.27 5.18 0.93 3.26
trimming ○ × ○ × ×
all sorts of flowers × × ○ × ×
surface gloss 42 67 45 50 44
appearance quality × × × × ×
(A-1) small particle size of the graft copolymer : a mean particle diameter of 68.5 ㎚ of butyl acrylate graft copolymers of the manufacturing cost is grafted acrylonitrile in the rubber-like polymer in styrene and acrylic Example 1 (A-2) is substituted diameter graft Copolymer : Graft copolymer (B-1) of Preparation Example 2 in which styrene and acrylonitrile were grafted onto butyl acrylate rubbery polymer having an average particle diameter of 280.0 nm (B-1) First matrix copolymer : methyl methacrylate 30 parts by weight , 52.5 parts by weight of styrene and 17.5 parts by weight of acrylonitrile copolymer of Preparation Example 3 (weight average molecular weight: 80,000 g/mol) (B-2) Second matrix copolymer : 70 parts by weight of methyl methacrylate, styrene Copolymer of Preparation Example 4 (weight average molecular weight: 80,000 g/mol), which is a copolymer of 22.5 parts by weight and 7.5 parts by weight of acrylonitrile (B-5) 5th matrix copolymer : 75 parts by weight of styrene and 25 parts by weight of acrylonitrile Copolymer of Preparation Example 7 as a copolymer (weight average molecular weight: 120,000 g/mol) (C) Additive : LG MMA IH830 (copolymer of methyl methacrylate and methyl acrylate)
[222]
[Table 3]
division comparative example
6 7 8 9 10
(A) Graft copolymer (parts by weight) (A-1) 40 80 67 - -
(A-2) - - - 60 40
(B) matrix copolymer (parts by weight) (B-1) - - 33.0 15.0 -
(B-2) - 20.0 - - 20.0
(B-5) 20.0 - - - -
(C) Additives (parts by weight) 40 - - 25 40
impact strength 3.10 21.50 7.20 49.60 35.00
Hardness 84 54 65 87 103
elongation 19 142 101 121 81
weather resistance 2.73 1.82 2.51 1.84 1.25
trimming × × × ○ ○
all sorts of flowers × ○ × × ×
surface gloss 54 72 70 92 96
appearance quality × ○ ○ ○ ○
(A-1) small particle size of the graft copolymer : a mean particle diameter of 68.5 ㎚ of butyl acrylate graft copolymers of the manufacturing cost is grafted acrylonitrile in the rubber-like polymer in styrene and acrylic Example 1 (A-2) is substituted diameter graft Copolymer : Graft copolymer (B-1) of Preparation Example 2 in which styrene and acrylonitrile were grafted onto butyl acrylate rubbery polymer having an average particle diameter of 280.0 nm (B-1) First matrix copolymer : methyl methacrylate 30 parts by weight , 52.5 parts by weight of styrene and 17.5 parts by weight of acrylonitrile copolymer of Preparation Example 3 (weight average molecular weight: 80,000 g/mol) (B-2) Second matrix copolymer : 70 parts by weight of methyl methacrylate, styrene Copolymer of Preparation Example 4 (weight average molecular weight: 80,000 g/mol), which is a copolymer of 22.5 parts by weight and 7.5 parts by weight of acrylonitrile (B-5) 5th matrix copolymer : 75 parts by weight of styrene and 25 parts by weight of acrylonitrile Copolymer of Preparation Example 7 as a copolymer (weight average molecular weight: 120,000 g/mol) (C) Additive : LG MMA IH830 (copolymer of methyl methacrylate and methyl acrylate)
[223]
Referring to Tables 1 to 3, it was confirmed that the thermoplastic resin compositions of Examples 1 to 4 were excellent in impact strength and elongation as the content of the graft copolymer having a small particle size increased. In addition, it was confirmed that the thermoplastic resin compositions of Examples 2 to 4 were excellent in hardness, weather resistance, and surface gloss as the content of the matrix copolymer and additives increased.
[224]
Comparing Examples 1, 7, and 8, the thermoplastic resin composition of Example 1 comprising the matrix copolymer prepared with 30 parts by weight of methyl methacrylate, the matrix copolymer prepared with 15 parts by weight of methyl methacrylate It was confirmed that the impact strength, hardness, elongation, weather resistance, trimming property, whitening, surface gloss and appearance quality were all excellent compared to the thermoplastic resin composition of Example 7 including the coalescence. Comparing Example 1 and Example 8, the thermoplastic resin composition of Example 1 including the matrix copolymer prepared by 30 parts by weight of methyl methacrylate contains a matrix copolymer prepared by 85 parts by weight of methyl methacrylate. Compared to the thermoplastic resin composition of Example 7, it was confirmed that the impact strength, elongation, weather resistance, trimming property, whitening, surface gloss and appearance quality were all excellent. From these results, when a matrix copolymer containing an appropriate amount of methyl methacrylate is used, compatibility with the graft copolymer and additives is remarkably improved, and impact strength, elongation, weather resistance, trimming properties, whitening, surface gloss and appearance are significantly improved. It was confirmed that the quality was improved.
[225]
Comparing Example 1 and Comparative Example 4, the thermoplastic resin composition of Example 1 including the matrix copolymer, compared to the thermoplastic resin composition of Comparative Example 4 not including the matrix copolymer, impact strength, elongation, weather resistance, trimming It was confirmed that the properties, whitening, surface gloss and appearance quality were excellent.
[226]
Comparing Example 1 and Comparative Example 5, the thermoplastic resin composition of Example 1 has impact strength, hardness, elongation, weather resistance, It was confirmed that the trimming property, whitening, surface gloss and appearance quality were remarkably excellent. From these results, when the matrix copolymer containing methyl methacrylate is used, compatibility with the graft copolymer and additives is remarkably improved, and impact strength, elongation, weather resistance, trimming properties, whitening, surface gloss and appearance quality are remarkably improved. It was confirmed that this was remarkably improved.
[227]
Comparing Example 1 and Comparative Example 8, the thermoplastic resin composition of Example 1 contains 67 parts by weight of the small particle size graft copolymer, but has impact strength, hardness, weather resistance, trimming properties, compared to Comparative Example 8, which does not contain an additive , whitening, surface gloss and appearance quality were remarkably excellent. From these results, when the matrix copolymer containing methyl methacrylate is used, compatibility with the graft copolymer and additives is remarkably improved. It was confirmed that whitening and surface gloss were improved.
[228]
Comparing Example 1 and Comparative Example 9, the thermoplastic resin composition of Example 1 including the graft copolymer having a small particle diameter, compared to the thermoplastic resin composition of Comparative Example 9 including the graft copolymer having a large particle diameter, the impact strength is lowered However, it was confirmed that the weather resistance, whitening and surface gloss were remarkably excellent.
[229]
Comparing Example 2 and Example 6, the thermoplastic resin composition of Example 2 including the matrix copolymer prepared by 70 parts by weight of methyl methacrylate contains a matrix copolymer prepared by 85 parts by weight of methyl methacrylate. Compared to the thermoplastic resin composition of Example 6, it was confirmed that the impact strength, elongation, trimming property, whitening, surface gloss and appearance quality were excellent.
[230]
Comparing Example 2 and Comparative Example 6, the thermoplastic resin composition of Example 2 has impact strength, hardness, elongation, weather resistance, compared to the thermoplastic resin composition of Comparative Example 6 comprising a styrene/acrylonitrile polymer as a matrix copolymer It was confirmed that the trimming property, whitening, surface gloss and appearance quality were excellent.
[231]
Comparing Example 2 and Comparative Example 10, the thermoplastic resin composition of Example 2 including a graft copolymer having a small particle size has impact strength and elongation compared to the thermoplastic resin composition of Comparative Example 10 including a graft copolymer having a large particle size Although the silver was lowered, it was confirmed that the weather resistance, whitening, and surface gloss were remarkably excellent.
[232]
Comparing Example 3 and Comparative Example 7, the thermoplastic resin composition of Example 2 had impact strength, elongation, weather resistance, trimming properties, whitening, surface gloss and It was confirmed that all appearance quality was excellent.
[233]
Comparing Example 5 and Example 7, the thermoplastic resin composition of Example 5 containing 20 parts by weight of the matrix copolymer has impact strength and weather resistance compared to the thermoplastic resin composition of Example 7 containing 15 parts by weight of the matrix copolymer. , it was confirmed that trimming properties and surface gloss were slightly improved.
[234]
In addition, when comparing Example 5 and Comparative Example 4, it was confirmed that the thermoplastic resin composition of Example 5 was superior in impact strength and trimming properties compared to the thermoplastic resin composition of Comparative Example 4 not including the matrix copolymer.
[235]
Comparing Comparative Example 1 and Comparative Example 2, the thermoplastic resin composition of Comparative Example 1 containing an excess of the large particle diameter graft copolymer had excellent impact strength, elongation, and trimming properties compared to the thermoplastic resin composition of Comparative Example 2, but weather resistance And it was confirmed that the surface gloss is lowered.
[236]
In addition, comparing Comparative Example 1 and Comparative Example 3, the thermoplastic resin composition of Comparative Example 3 further comprising a small particle size graft copolymer, compared to the thermoplastic resin composition of Comparative Example 3, elongation, weather resistance, whitening, and surface gloss were Although excellent, both were not excellent in overall physical properties.
Claims
[Claim 1]
a graft copolymer obtained by graft polymerization of an aromatic vinyl monomer and a vinyl cyanide monomer to an acrylic rubber polymer having an average particle diameter of 50.0 to 90.0 nm; C 1 To C 3 A matrix copolymer comprising an alkyl (meth)acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; And C 1 To C 3 A thermoplastic resin composition comprising an additive comprising a polymer comprising an alkyl (meth) acrylate-based monomer unit.
[Claim 2]
The thermoplastic resin composition of claim 1, wherein the acrylic rubber polymer has an average particle diameter of 65.0 to 75.0 nm.
[Claim 3]
The thermoplastic resin composition of claim 1, wherein the matrix copolymer is a copolymer of a monomer mixture including a C 1 to C 3 alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer.
[Claim 4]
The method according to claim 3, wherein the monomer mixture is 25 to 75% by weight of the C 1 to C 3 alkyl (meth)acrylate-based monomer; 15 to 60% by weight of the aromatic vinyl-based monomer; and 1 to 20% by weight of the vinyl cyanide monomer.
[Claim 5]
The thermoplastic resin composition of claim 3, wherein the matrix copolymer is a copolymer of methyl methacrylate, styrene, and acrylonitrile.
[Claim 6]
The thermoplastic resin composition of claim 1, wherein the matrix copolymer has a weight average molecular weight of 50,000 to 200,000 g/mol.
[Claim 7]
The thermoplastic resin composition of claim 1, wherein the polymer is a copolymer including two or more C 1 to C 3 alkyl (meth)acrylate-based monomer units.
[Claim 8]
The method according to claim 1, wherein the thermoplastic resin composition, based on the total weight of the thermoplastic resin composition, 30 to 80% by weight of the graft copolymer; 0.1 to 30.0 wt% of the matrix copolymer; and 5 to 50% by weight of the additive.