The present invention claims the benefit of priority based on Korean Patent Application No. 10-2018-0139153 filed on November 13, 2018 and Korean Patent Application No. 10-2019-0142395 filed on November 8, 2019, and the corresponding Korean patent All content disclosed in the literature of the application is incorporated 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, weather resistance, surface gloss, appearance quality, scratch resistance and whitening.
[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 plate materials of home appliances for corrosion prevention, low friction, and appearance 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]
It is an object of the present invention to provide a thermoplastic resin composition with improved elongation, weather resistance, surface gloss, appearance quality, scratch resistance and whitening 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 cyanide monomer to an acrylic rubber polymer; C 1 To C 3 A first matrix copolymer comprising an alkyl (meth) acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; C 1 To C 3 A second matrix copolymer comprising an alkyl (meth) acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; and an additive comprising a polymer comprising a C 1 to C 3 alkyl (meth)acrylate-based monomer unit, wherein the first matrix copolymer and the second matrix copolymer have different weight average molecular weights A thermoplastic resin composition is provided.
[15]
Effects of the Invention
[16]
The thermoplastic resin composition according to the present invention has excellent basic physical properties such as impact resistance and hardness, and can significantly improve elongation, weather resistance, surface gloss, appearance quality, scratch resistance and whitening.
[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 in detail, using Nicomp 380 HPL equipment from Particle Sizing Systems. can be measured
[22]
In the present specification, the average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, specifically, a scattering intensity average particle diameter.
[23]
[24]
In the present invention, the graft rate of the graft copolymer can be calculated by the following formula.
[25]
[26]
Graft ratio (%): Weight of grafted monomer (g) / Weight of 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]
Rubber-like polymer weight (g): a graft copolymer powder of theoretical C 4 to C 10 alkyl (meth) acrylate-based monomers having a weight or graft manufacture of inputted C of the copolymer 4 to C 10 alkyl (meth) acrylate Weight of the rate-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 determined by dissolving a portion (sol) dissolved in acetone in a THF (tetrahydrofuran) solution when measuring the graft rate, and then passing the standard PS (standard polystyrene) sample through a gel permeation chromatograph. can be measured relative to
[33]
[34]
In the present invention, the weight average molecular weight of the first matrix copolymer and the second matrix copolymer is determined using THF as an eluent, and poly(methyl methacrylate) as a standard sample (manufacturer: Polymer Laboratories) through gel permeation chromatography. It can be measured as a relative value.
[35]
[36]
In the present invention, the polymerization conversion of the first matrix copolymer and the second matrix copolymer may 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 selected from the group consisting of styrene, α-methyl styrene, p-methyl styrene, and 2,4-dimethyl styrene. and may be one or more of these, 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 includes: 1) a graft copolymer obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer to an acrylic rubbery polymer; 2) C 1 To C 3 A first matrix copolymer comprising an alkyl (meth)acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; 3) C 1 to C 3 A second matrix copolymer comprising an alkyl (meth)acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; and 4) an additive comprising a polymer including a C 1 to C 3 alkyl (meth)acrylate-based monomer unit, wherein 2) the first matrix copolymer and the 3) second matrix copolymer have a weight average molecular weights are different.
[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.
[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 acrylic rubber polymer may have an average particle diameter of 40.0 to 400.0 nm, 50.0 to 320.0 nm, or 65.0 to 310.0 nm, of which 65.0 to 310.0 nm is preferable. When the above-mentioned range is satisfied, it is possible to provide a graft copolymer having excellent weather resistance and impact resistance.
[62]
On the other hand, in order to significantly improve the weather resistance, colorability, chemical resistance, appearance quality, elongation and whitening properties of the graft copolymer, the average particle diameter of the acrylic rubber polymer is 40.0 to 100.0 nm, 50.0 to 90.0 nm, or 65.0 to 75.0 nm. and 65.0 to 75.0 nm is preferred. Specifically, the smaller the average particle diameter of the acrylic rubber polymer is, the more the specific surface area increases, so 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.
[63]
[64]
In addition, in order to significantly improve the impact resistance, chemical resistance and appearance quality of the graft copolymer, the acrylic rubber polymer may have an average particle diameter of 150.0 to 400.0 nm, 230.0 to 320.0 nm, or 250.0 to 310.0 nm, of which 250.0 to 310.0 nm are preferred.
[65]
[66]
The graft copolymer may be a copolymer obtained by graft copolymerizing butyl acrylate rubbery polymer with styrene and acrylonitrile.
[67]
[68]
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.
[69]
[70]
The graft copolymer may have a weight average molecular weight of 30,000 to 200,000 g/mol or 50,000 to 180,000 g/mol of the shell, of which 80,000 to 150,000 g/mol is preferable. When the above-mentioned range is satisfied, compatibility with the matrix copolymer may be improved, and dispersibility of the graft copolymer, specifically, the acrylic rubber polymer in the thermoplastic resin composition may be improved.
[71]
[72]
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.
[73]
Here, the core may refer to the above-described acrylic rubber polymer.
[74]
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. .
[75]
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.
[76]
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. .
[77]
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.
[78]
The total weight of the monomers added during the preparation of the seed may be 1 to 20% by weight or 5 to 15% by weight, of which 5 to 15% by weight, based on the total weight of the monomers added during the preparation of the graft copolymer. % is preferred.
[79]
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.
[80]
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.
[81]
[82]
The graft copolymer may be included in an amount of 30 to 90 parts by weight or 35 to 85 parts by weight, of which 35 to 90 parts by weight, based on 100 parts by weight of the total of the graft copolymer, the first matrix copolymer, and the second matrix copolymer. It is preferably included in 85 parts by weight. When the above-mentioned range is satisfied, elongation, weather resistance, chemical resistance, colorability, processability, surface gloss characteristics, and whitening characteristics of the thermoplastic resin composition can be remarkably improved.
[83]
[84]
2) first matrix copolymer
[85]
The first matrix copolymer includes a C 1 to C 3 alkyl (meth)acrylate monomer unit, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit.
[86]
[87]
The first matrix copolymer may improve colorability, weather resistance, and hardness of the thermoplastic resin composition.
[88]
[89]
Meanwhile, the first matrix copolymer has a different weight average molecular weight than that of the second matrix copolymer, which will be described later. In addition, due to the difference in weight average molecular weight of the first matrix copolymer and the second matrix copolymer, the elongation of the thermoplastic resin composition may be remarkably improved.
[90]
[91]
The difference between the weight average molecular weight of the first matrix copolymer and the second matrix copolymer may be 50,000 to 150,000 g/mol, 70,000 to 130,000 g/mol, or 90,000 to 110,000 g/mol, of which 90,000 to 110,000 g/mol mol is preferred. When the above-described range is satisfied, the elongation of the thermoplastic resin composition can be remarkably improved.
[92]
[93]
The first matrix copolymer may have a weight average molecular weight of 160,000 to 240,000 g/mol, 170,000 to 230,000 g/mol, or 180,000 to 220,000 g/mol, of which 180,000 to 220,000 g/mol is preferable. When the above-described range is satisfied, the colorability, weather resistance, and hardness of the thermoplastic resin composition can be remarkably improved.
[94]
[95]
Meanwhile, the first 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.
[96]
The monomer mixture may include 60 to 90% by weight or 65 to 85% by weight of the C 1 to C 3 alkyl (meth)acrylate-based monomer, and it is preferable to include it in an amount of 65 to 85% by weight. . When the above-mentioned range is satisfied, the colorability, weather resistance, and hardness of the thermoplastic resin can be further improved.
[97]
The monomer mixture may include 8 to 32% by weight or 10 to 25% by weight of the aromatic vinyl-based monomer, preferably 10 to 25% by weight of this. When the above-mentioned range is satisfied, the processability of the thermoplastic resin composition can be further improved.
[98]
The monomer mixture may include 2 to 12 wt% or 1 to 10 wt% of the vinyl cyanide monomer based on the total weight of the first matrix copolymer, of which 1 to 10 wt% is preferable. do. When the above-mentioned range is satisfied, the chemical resistance of the thermoplastic resin composition can be further improved.
[99]
[100]
The first matrix copolymer may be a copolymer of methyl methacrylate, styrene, and acrylonitrile.
[101]
[102]
The first matrix copolymer may be included in an amount of 1 to 65 parts by weight or 5 to 60 parts by weight based on 100 parts by weight of the total of the graft copolymer, the first matrix copolymer, and the second matrix copolymer, 5 of which It is preferably included in an amount of to 60 parts by weight. When the above-mentioned range is satisfied, the colorability, weather resistance, and hardness of the thermoplastic resin composition can be remarkably improved.
[103]
[104]
Meanwhile, the thermoplastic resin composition may include the first matrix copolymer and the second matrix copolymer in a weight ratio of 55:45 to 95:5 or 60:40 to 90:10, of which 60:40 to 90 It is preferable to include it in a weight ratio of :10. When the above-described range is satisfied, elongation, whitening, scratch resistance, and appearance characteristics of the thermoplastic resin composition may be further improved.
[105]
[106]
3) second matrix copolymer
[107]
The second matrix copolymer includes a C 1 to C 3 alkyl (meth)acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit.
[108]
[109]
The second matrix copolymer may improve colorability, weather resistance, and hardness of the thermoplastic resin composition.
[110]
[111]
The second matrix copolymer may have a weight average molecular weight of 60,000 to 140,000 g/mol, 70,000 to 130,000 g/mol, or 80,000 to 120,000 g/mol, of which 80,000 to 120,000 g/mol is preferable.
[112]
When the above-described range is satisfied, the colorability, weather resistance, and hardness of the thermoplastic resin composition can be remarkably improved.
[113]
[114]
Meanwhile, the second 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.
[115]
The monomer mixture may include 60 to 90% by weight or 65 to 85% by weight of the C 1 to C 3 alkyl (meth)acrylate-based monomer, and it is preferable to include it in an amount of 65 to 85% by weight. . When the above-mentioned range is satisfied, the colorability, weather resistance, and hardness of the thermoplastic resin can be further improved.
[116]
The monomer mixture may include 8 to 32% by weight or 10 to 25% by weight of the aromatic vinyl-based monomer, preferably 10 to 25% by weight of this. When the above-mentioned range is satisfied, the processability of the thermoplastic resin composition can be further improved.
[117]
The monomer mixture may include 2 to 12% by weight or 1 to 10% by weight of the vinyl cyanide-based monomer, and preferably includes 1 to 10% by weight of the vinyl cyanide monomer. When the above-mentioned range is satisfied, the chemical resistance of the thermoplastic resin composition can be further improved.
[118]
[119]
The second matrix copolymer may be a copolymer of methyl methacrylate, styrene, and acrylonitrile.
[120]
[121]
The second matrix copolymer may be included in an amount of 1 to 25 parts by weight or 2 to 20 parts by weight based on 100 parts by weight of the total of the graft copolymer, the first matrix copolymer, and the second matrix copolymer, of which 2 It is preferably included in an amount of to 20 parts by weight. When the above-mentioned range is satisfied, the colorability, weather resistance, and hardness of the thermoplastic resin composition can be remarkably improved.
[122]
[123]
4) Additives
[124]
The additive includes a polymer including a C 1 to C 3 alkyl (meth)acrylate-based monomer unit.
[125]
[126]
The additive may improve hardness, surface gloss, scratch resistance and appearance quality of the thermoplastic resin composition.
[127]
[128]
The polymer may have a weight average molecular weight of 30,000 to 90,000 g/mol, 40,000 to 80,000 g/mol, or 50,000 to 70,000 g/mol, preferably 50,000 to 70,000 g/mol. When the above-mentioned range is satisfied, compatibility with the graft copolymer, the first matrix copolymer, and the second matrix copolymer is further improved, and the surface gloss and scratch resistance of the thermoplastic resin composition can be further improved.
[129]
[130]
The polymer may be poly(methyl methacrylate).
[131]
[132]
The polymer to improve the processability and surface gloss and hardness, C 1 to C 3 alkyl (meth) acrylate-based monomer units may be a copolymer comprising two or more thereof, preferably C 1 to C 3 of It may be a copolymer including an alkyl methacrylate-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 90:10 to 99:1 or 92:8 to 97:3 by weight, of which, it is preferable to include it in a weight ratio of 92:8 to 97:3. When the above-mentioned range is satisfied, processability, fluidity, and optical properties may be excellent.
[133]
[134]
The copolymer may be a copolymer of methyl methacrylate and methyl acrylate.
[135]
[136]
The additive may further include an antioxidant.
[137]
The antioxidants include tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphate and pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxy). It may be at least one selected from the group consisting of phenyl) propionate, of which tris (2,4-di-t-butylphenyl) phosphite is preferable.The antioxidant is 0.01 based on 100 parts by weight of the polymer. to 1 part by weight or 0.1 to 0.5 part by weight, and preferably included in 0.1 to 0.5 part by weight of this, if the above-described range is satisfied, weather resistance may be further improved.
[138]
[139]
The additive may be included in an amount of 0.1 to 5.0 parts by weight or 1.0 to 3.0 parts by weight, of which 1.0 to 3.0 parts by weight, based on 100 parts by weight of the total of the graft copolymer, the first matrix copolymer, and the second matrix copolymer. preferably included. When the above-mentioned range is satisfied, the hardness, surface gloss, scratch resistance and appearance quality of the thermoplastic resin composition can be remarkably improved.
[140]
[141]
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.
[142]
[143]
Preparation Example 1
[144]

[145]
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, 0.1 parts by weight of NaHCO 3 as an electrolyte, and 40 parts by weight of distilled water were put in a batch, and the temperature was raised to 65 ° C. After polymerization for 1 hour, the butyl acrylate rubber polymer as a seed was terminated (average particle size) : 52.5 nm) was obtained.
[146]
[147]

[148]
30 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, 0.2 parts by weight of allyl methacrylate, electrolyte A mixture containing 0.1 parts by weight of NaHCO 3 and 20 parts by weight of distilled water, and 0.06 parts by weight of potassium persulfate, each of which is an initiator, were continuously added at a constant rate for 3 hours at 70 ° C. After polymerization, it was completed to obtain a core butyl acrylate rubbery polymer (average particle diameter: 68.5 nm).
[149]
[150]

[151]
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 rosin acid salt 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%.
[152]
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.
[153]
[154]
Preparation 2
[155]

[156]
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).
[157]
[158]

[159]
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).
[160]
[161]

[162]
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%.
[163]
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.
[164]
[165]
Preparation 3
[166]
In a nitrogen-substituted 26-liter first reactor, 80 parts by weight of methyl methacrylate, 15 parts by weight of styrene, 5 parts by weight of acrylonitrile, 25 parts by weight of toluene, and 1,1-bis(t-butylperoxy)- as an initiator- 0.01 parts by weight of 3,3,5-trimethyl cyclohexane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3 as a sterically hindered phenolic antioxidant 0.1 parts by weight of ,5-triazine-2,4,6-(1H,3H,5H)trione and 0.08 parts by weight of n-dodecyl mercaptan as a molecular weight modifier were continuously added for 2 hours at a rate of 12 ℓ/hour Polymerization at 140° C. to obtain a first copolymer, and polymerization at 150° C. while continuously introducing the first copolymer into a nitrogen-substituted 26 L second reactor at a rate of 12 L/hour for 2 hours to obtain a second copolymer water was obtained. At this time, the polymerization conversion rate was 72%. 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 the form of pellets (weight average molecular weight: 200,000 g/mol) was prepared.
[167]
[168]
Preparation 4
[169]
In a nitrogen-substituted 26-liter first reactor, 80 parts by weight of methyl methacrylate, 15 parts by weight of styrene, 5 parts by weight of acrylonitrile, 25 parts by weight of toluene, and 1,1-bis(t-butylperoxy)- as an initiator- 0.01 parts by weight of 3,3,5-trimethyl cyclohexane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3 as a sterically hindered phenolic antioxidant 0.1 parts by weight of ,5-triazine-2,4,6-(1H,3H,5H)trione and 0.08 parts by weight of n-dodecyl mercaptan as a molecular weight modifier were continuously added for 2 hours at a rate of 12 ℓ/hour Polymerization at 140° C. to obtain a first copolymer, and polymerization at 150° C. while continuously introducing the first copolymer into a nitrogen-substituted 26 L second reactor at a rate of 12 L/hour for 2 hours to obtain a second copolymer water was obtained. 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 the form of pellets (weight average molecular weight: 100,000 g/mol) was prepared.
[170]
[171]
Preparation 5
[172]
In a nitrogen-substituted reactor, 96 parts by weight of methyl methacrylate, 4 parts by weight of methyl acrylate, 0.2 parts by weight of t-butylperoxy neodecanate as an initiator, 133 parts by weight of distilled water, and methyl methacrylate-methacrylic acid as a suspending agent 0.82 parts by weight of a saponified aqueous solution in which the coal is saponified with NaOH (concentration: 3% by weight), 0.098 parts by weight of sodium dihydrogen phosphate as a buffer, 0.053 parts by weight of disodium hydrogen phosphate, and 0.33 parts by weight of n-octyl mercaptan as a molecular weight regulator The parts were charged in batches, and the temperature was raised to 60° C., followed by polymerization for 120 minutes. And after raising the temperature to 105 ℃ at a constant rate over 50 minutes, lauryl peroxide as an initiator was batch-injected, and after further polymerization for 40 minutes, it was completed to obtain a copolymer in the form of beads. At this time, the polymerization conversion rate was 99.95%.
[173]
The obtained copolymer was washed with distilled water at 60 °C in a centrifugal separator, and then dried while adding air at 120 °C, filtered of moisture and dust, at 7.5 m3/hr.
[174]
The copolymer had a weight average molecular weight of 60,000 g/mol and a polydispersity index of 1.7.
[175]
100 parts by weight of the copolymer and 0.2 parts by weight of tris(2,4-di-t-butylphenyl)phosphate as an antioxidant were mixed, and then extruded in a twin-screw extruder at 245° C., and then pellets were prepared.
[176]
[177]
Examples and Comparative Examples
[178]
[179]
The specifications of the components used in the following Examples and Comparative Examples are as follows.
[180]
[181]
(A) graft copolymer
[182]
(A-1) First graft copolymer: The graft copolymer of Preparation Example 1 was used.
[183]
(A-2) Second graft copolymer: The graft copolymer of Preparation Example 2 was used.
[184]
[185]
(B) matrix copolymer
[186]
(B-1) First matrix copolymer: The copolymer of Preparation Example 3 was used.
[187]
(B-2) Second matrix copolymer: The copolymer of Preparation Example 4 was used.
[188]
(B-3) Third matrix copolymer: 92HR manufactured by LG Chem was used.
[189]
[190]
(C) Additive: The pellets of Preparation Example 5 were used.
[191]
[192]
A thermoplastic resin composition was prepared by mixing and stirring the above-mentioned components according to the contents described in [Table 1] and [Table 2] below.
[193]
[194]
Experimental Example 1
[195]
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] and [Table 2] below.
[196]
[197]
① Impact strength (kg·cm/cm): Measured according to ASTM 256.
[198]
② Hardness: Measured according to ASTM 785.
[199]
③ Elongation (%): Measured according to ASTM D638.
[200]
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 3,000 hours, and the following ΔE is the arithmetic mean value before and after accelerated weather resistance test, and the closer the value is to 0, the better the weather resistance is.
[201]

[202]
In the above formula, L', a' and b' are L, a, and b values ​​measured by the CIE LAB color coordinate system after irradiating the specimen with light under SAE J1960 conditions for 3,000 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.
[203]
[204]
Experimental Example 2
[205]
The thermoplastic resin composition of Examples and Comparative Examples was used to prepare a sheet having a width of 10 cm and a thickness of 0.2 mm using a sheet extruder, and the sheet and a galvanized steel sheet were adhered at 200° C. using an adhesive to prepare a specimen. The physical properties of the specimen were evaluated by the method described below, and the results are described in [Table 1] and [Table 2] below.
[206]
On the other hand, in the case of Comparative Example 2, the specimen was manufactured in a damaged state due to poor processing, and thus physical properties could not be evaluated.
[207]
[208]
⑤ Scratch resistance: In accordance with ASTM D3360, it was measured using scratch resistance equipment (brand name: QMESYS, manufacturer: QM450A).
[209]
○: HB or more, ×: B or less
[210]
[211]
⑥ Baekhwa: A ball drop tester (trade name: FDI-01, manufacturer: Labthink) was used to drop a 1 kg iron ball on the specimen from a height of 1 m, and then measured.
[212]
○: Whitening did not occur, ×: Whitening occurred or the sheet was torn or cracked
[213]
[214]
⑦ Surface gloss: Gloss was measured at 60 ° using a gloss meter (trade name: VG7000, manufacturer: NIPPON DENSHOKU) in accordance with ASTM D523.
[215]
[216]
⑧ Appearance quality: After the bending press, the appearance of the specimen was visually observed.
[217]
○: overall gloss difference, no surface curvature or float
[218]
×: local gloss difference, surface curvature and lifting or tearing
[219]
[220]
[Table 1]
division Example
One 2 3 4 5 6
(A) Graft copolymer (parts by weight) (A-1) 40 60 80 45 65 -
(A-2) - - - - - 40
(B) matrix copolymer (parts by weight) (B-1) 54 36 12 22 20 54
(B-2) 6 4 8 3 15 6
(B-3) - - - - - -
(C) Additives (parts by weight) 2.0 2.0 3.0 1.0 3.0 2.0
impact strength 7.10 9.80 15.00 8.20 10.20 13.30
Hardness 103 87 68 94 85 105
elongation 83 105 171 85 110 112
weather resistance 0.52 0.60 0.79 0.69 0.61 1.67
scratch resistance ○ ○ ○ ○ ○ ○
all sorts of flowers ○ ○ ○ ○ ○ △
surface gloss 125 118 105 124 119 98
appearance quality ○ ○ ○ ○ ○ ○
[221]
[Table 2]
division comparative example
One 2 3 4 5 6 7
(A) Graft copolymer (parts by weight) (A-1) 50 90 - 65 60 60 60
(A-2) - - 55 - - - -
(B) matrix copolymer (parts by weight) (B-1) 25 - - - 36 40 -
(B-2) 25 10 - - 4 - 40
(B-3) - - 45 35 - - -
(C) Additives (parts by weight) - 3.0 - 3.0 - 2.0 2.0
impact strength 8.70 20.10 35.40 13.20 11.60 11.20 6.50
Hardness 95 50 79 63 78 91 82
elongation 58 121 83 31 95 38 35
weather resistance 1.68 2.35 13.75 10.96 2.24 0.58 0.63
scratch resistance × poor processing × × × ○ ○
all sorts of flowers ○ × × ○ × ×
surface gloss 80 50 78 87 100 121
appearance quality ○ ○ × ○ × ○
[222]
Referring to Tables 1 and 2, it was confirmed that Examples 1 to 6 were excellent in elongation, weather resistance, scratch resistance, surface gloss, and appearance quality. However, it was confirmed that the whitening phenomenon occurred in Example 6 including the graft copolymer having a large particle size. On the other hand, comparing Example 2 and Comparative Example 5, Comparative Example 5 without an additive had elongation and weather resistance. , it was confirmed that scratch resistance and surface gloss properties were lowered. Comparing Example 2, Comparative Examples 6 and 7, Comparative Example 6 not including the second matrix copolymer and Comparative Example 7 not including the first matrix copolymer had significantly lower elongation, weather resistance, and appearance quality. and it was confirmed that the whitening phenomenon occurred. In addition, comparing Example 5 and Comparative Example 4, Comparative Example 4 not including the first and second matrix copolymers significantly reduced elongation, weather resistance, scratch resistance, surface gloss and appearance quality, and whitening phenomenon could also be confirmed.
[223]
On the other hand, since Comparative Examples 1 and 3 did not contain an additive, elongation, scratch resistance, and surface gloss were deteriorated. Comparative Example 2 contained an excessive amount of the small particle diameter graft copolymer and did not include the first matrix copolymer, and thus, the specimen was prepared in a damaged state due to the amount of processing, and thus physical properties could not be evaluated.
Claims
[Claim 1]
a graft copolymer obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer to an acrylic rubbery polymer; C 1 To C 3 A first matrix copolymer comprising an alkyl (meth) acrylate-based monomer unit, an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit; C 1 To C 3 A second matrix copolymer comprising an alkyl (meth) acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; and an additive comprising a polymer comprising a C 1 to C 3 alkyl (meth)acrylate-based monomer unit, wherein the first matrix copolymer and the second matrix copolymer have different weight average molecular weights Thermoplastic resin composition.
[Claim 2]
The thermoplastic resin composition of claim 1, wherein a difference in weight average molecular weight of the first matrix copolymer and the second matrix copolymer is 50,000 to 150,000 g/mol.
[Claim 3]
The thermoplastic resin composition of claim 1, wherein the first matrix copolymer has a weight average molecular weight of 160,000 to 240,000 g/mol.
[Claim 4]
The thermoplastic resin composition of claim 1, wherein the second matrix copolymer has a weight average molecular weight of 60,000 to 140,000 g/mol.
[Claim 5]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition comprises the first matrix copolymer and the second matrix copolymer in a weight ratio of 55:45 to 95:5.
[Claim 6]
The thermoplastic resin composition of claim 1, wherein the graft copolymer has an average particle diameter of 40.0 to 400.0 nm of the acrylic rubber polymer.
[Claim 7]
The thermoplastic resin composition of claim 1, wherein the graft copolymer has an average particle diameter of 40.0 to 100.0 nm of the acrylic rubber polymer.
[Claim 8]
The thermoplastic resin composition of claim 1, wherein the graft copolymer has an average particle diameter of 150.0 to 400.0 nm of the acrylic rubber polymer.
[Claim 9]
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 10]
The thermoplastic resin composition of claim 1, wherein the polymer has a weight average molecular weight of 30,000 to 90,000 g/mol.
[Claim 11]
The method according to claim 1, wherein the thermoplastic resin composition is based on 100 parts by weight of the total of the graft copolymer, the first matrix copolymer, and the second matrix copolymer, 30 to 90 parts by weight of the graft copolymer; 1 to 65 parts by weight of the first matrix copolymer; and 1 to 25 parts by weight of the second matrix copolymer.
[Claim 12]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition comprises 0.1 to 5.0 parts by weight of the additive based on 100 parts by weight of the total of the graft copolymer, the first matrix copolymer, and the second matrix copolymer. .