Title of the invention: Method for producing a graft copolymer, a graft copolymer and a thermoplastic resin molded article containing the same
Technical field
[One]
[Mutual citation with related application]
[2]
The present invention claims the benefit of priority based on Korean Patent Application No. 10-2018-0092433 filed on August 08, 2018, and includes all contents disclosed in the documents of the Korean patent application as part of this specification.
[3]
[Technical field]
[4]
The present invention relates to a method for preparing a graft copolymer, a graft copolymer, and a thermoplastic resin molded article including the same, and a method for preparing a graft copolymer further adding an alkyl acrylate polymer among the methods for preparing the graft copolymer , To a graft copolymer and a thermoplastic resin molded article comprising the same.
[5]
Background
[6]
Recently, there is an increasing demand for enhancing not only heat resistance but also weather resistance for a thermoplastic resin composition for automobiles including an ASA graft copolymer.
[7]
Accordingly, a method of using a core having a small particle diameter has been proposed, but there is a problem that mechanical properties and fluidity are deteriorated. In addition, a method of graft polymerization of an alkyl (meth)acrylate-based monomer such as methyl methacrylate together with an aromatic vinyl-based monomer and a vinyl cyano-based monomer has been proposed, but the heat resistance and mechanical properties are deteriorated. Occurred. In addition, a method of adding poly(methyl methacrylate) when compounding the ASA graft copolymer has been proposed, but the weather resistance is improved, but the heat resistance and mechanical properties are deteriorated.
[8]
Accordingly, there is a need for development of a graft copolymer having excellent heat resistance, weather resistance, and impact resistance.
[9]
Detailed description of the invention
Technical challenge
[10]
An object of the present invention is to provide a method for producing a graft copolymer, which improves weather resistance, impact resistance, and fluidity, while maintaining basic physical properties such as heat resistance at the same level as before, a graft copolymer, and a thermoplastic resin molded article comprising the same. will be.
[11]
Means of solving the task
[12]
In order to solve the above-described problem, the present invention is a step of 1) preparing a seed by adding at least one selected from the group consisting of an alkyl (meth)acrylate monomer, an aromatic vinyl monomer, and a vinyl cyano monomer and polymerization ; 2) preparing a core by adding and polymerizing an alkyl (meth)acrylate-based monomer in the presence of the seed; And 3) in the presence of the core, adding and polymerizing an aromatic vinyl-based monomer and a vinyl cyano-based monomer to prepare a shell, and further adding an alkyl acrylate-based polymer to prepare a graft copolymer. .
[13]
In addition, the present invention is a seed comprising at least one selected from the group consisting of an alkyl (meth) acrylate monomer unit, an aromatic vinyl monomer unit, and a vinyl cyano monomer unit; A core including the seed and an alkyl (meth)acrylate-based monomer unit; A shell including the core, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit; And it provides a graft copolymer comprising an alkyl acrylate-based polymer.
[14]
In addition, the present invention is the above-described graft copolymer; And a matrix copolymer comprising an aromatic vinyl monomer unit and a vinyl cyan monomer unit, and has a weather resistance of 1.8 or less and an impact strength of 13 kg·cm/cm or more. .
[15]
Effects of the Invention
[16]
According to the manufacturing method of the graft copolymer of the present invention, it is possible to manufacture a graft copolymer and a thermoplastic resin molded article with improved weather resistance, impact resistance, fluidity and appearance characteristics while maintaining the basic physical properties such as heat resistance at the same level as before. I can.
[17]
Best mode for carrying out the invention
[18]
Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.
[19]
The terms or words used in the specification and claims are not to be construed as limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of ​​the present invention based on the principle that there is.
[20]
[21]
In the present invention, the viscosity of the alkyl acrylate-based polymer can be measured using Brookfield under the following conditions.
[22]
Spindle type-Cone type (CPA-52Z), cone angle = 3°, cone radius = 1.2 cm, gap: 13 ㎛ or less, measurement shear rate: 10 ~ 20 /sec, measurement Temperature: 25 ℃
[23]
[24]
In the present invention, the weight average molecular weight of the alkyl acrylate polymer is a relative value of a standard PS (standard polystyrene) sample using tetrahydrofuran (THF) as an eluent and gel permeation chromatography (GPC, water breeze). Can be measured.
[25]
[26]
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-based monomer unit and the vinyl cyan-based monomer unit grafted to the core.
[27]
In the present invention, the weight average molecular weight of the shell of the graft copolymer is determined by dissolving the graft copolymer in acetone and centrifuging. After dissolving the sol dissolved in acetone in tetrahydrofuran, gel permeation chromatography ( GPC, waters breeze) can be used to measure the relative value of a standard PS (standard polystyrene) sample.
[28]
[29]
In the present invention, the average particle diameter of the seed, core, and graft copolymer can be measured using a dynamic light scattering method, and in detail, it can be measured using Nicomp 380 equipment (product name, manufacturer: PSS). have.
[30]
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. The arithmetic mean particle diameter can be measured as the average particle diameter of the scattering intensity (Intensity Distribution), the average particle diameter of the Volume Distribution, and the average particle diameter of the Number Distribution, of which it is preferable to measure the average particle diameter of the scattering intensity.
[31]
[32]
In the present invention, whether an alkyl acrylate-based polymer is included in the graft copolymer can be analyzed through a liquid chromatography mass spectrometer (LC-MS).
[33]
[34]
In the present invention, the weather resistance is Ci4000 Weather-Ometer (device name, manufacturer: ATLAS, lamp: xenon arc lamp, filter: quartz (inner), S.Boro (outer), irradiance): 0.55 W/m 2 (340 nm) ) Using SAE J1960 conditions for 6,000 hours, it can be calculated by the following equation.
[35]

[36]
In the above formula, L'is the L value measured with the CIE LAB color coordinate system after irradiating the thermoplastic resin molded product with light under SAE J1960 conditions for 6,000 hours, and L O is the L value measured with the CIE LAB color coordinate system before light irradiation,
[37]
a'is the value a measured by the CIE LAB color coordinate system after irradiating the thermoplastic resin molded product with light under SAE J1960 conditions for 6,000 hours, and a O is the a value measured by the CIE LAB color coordinate system before the light irradiation,
[38]
b'is the b value measured by the CIE LAB color coordinate system after irradiating the thermoplastic resin molded product with light under SAE J1960 conditions for 6,000 hours, and b O is the b value measured with the CIE LAB color coordinate system before light irradiation.
[39]
[40]
In the present invention, the impact strength can be measured according to ASTM 256.
[41]
[42]
1. Method for producing graft copolymer
[43]
The method for preparing a graft copolymer according to an embodiment of the present invention is 1) by adding at least one selected from the group consisting of an alkyl (meth)acrylate monomer, an aromatic vinyl monomer, and a vinyl cyan monomer, Preparing a seed; 2) preparing a core by adding and polymerizing an alkyl (meth)acrylate-based monomer in the presence of the seed; And 3) in the presence of the core, adding and polymerizing an aromatic vinyl-based monomer and a vinyl cyan-based monomer to prepare a shell, and an alkyl acrylate-based polymer is further added.
[44]
[45]
When the alkyl acrylate polymer is added, a graft copolymer having improved weather resistance, fluidity, mechanical properties, and surface gloss can be prepared.
[46]
In addition, since the alkyl acrylate-based polymer has excellent compatibility with the graft copolymer and can also serve as a lubricant, it is possible to improve the processability of the graft copolymer, lower the processing temperature, and shorten the processing time.
[47]
[48]
The alkyl acrylate-based polymer may have a weight average molecular weight of 1,000 to 2,500 g/mol or 1,200 to 2,300 g/mol, of which 1,200 to 2,300 g/mol is preferable. If the above-described conditions are satisfied, a graft copolymer having more improved appearance properties such as weather resistance, fluidity, mechanical properties, and surface gloss can be prepared.
[49]
[50]
The alkyl acrylate-based polymer may have a polydispersity index (Mw/Mn) of 1 to 2 or 1.2 to 1.8, of which it is preferably 1.2 to 1.8. If the above-described conditions are satisfied, a graft copolymer having more improved fluidity and impact resistance can be prepared.
[51]
[52]
The alkyl acrylate-based polymer may have a viscosity of 20 to 1,000 cps or 100 to 900 cps at 25° C., of which 100 to 900 cps is preferable. If the above-described conditions are satisfied, a graft copolymer having more improved appearance properties such as weather resistance, fluidity, mechanical properties, and surface gloss can be prepared.
[53]
[54]
It is preferable that the alkyl acrylate polymer has an APHA color of 60 or less so as not to affect the color of the graft copolymer.
[55]
[56]
The alkyl acrylate-based polymer may be introduced in one or more of steps 1) to 3), and may be added after step 3). Of these, it is preferable to add the input at any one or more of the 3) step and the 3) step.
[57]
If the alkyl (meth) acrylate-based polymer is added in step 3), a graft copolymer having improved weather resistance, impact strength, and tensile strength can be prepared.
[58]
In addition, if the alkyl acrylate-based polymer is added in step 3), it is preferable to continuously add the aromatic vinyl-based monomer and the vinyl cyan-based monomer at a constant rate. When the alkyl acrylate-based polymer is continuously added at a constant rate, the dispersibility of the alkyl acrylate-based polymer is improved, so that weather resistance and impact strength are excellent, and the solid coagulum content after polymerization may be reduced.
[59]
[60]
If the alkyl acrylate-based polymer is added after step 3), a graft copolymer having improved fluidity can be prepared.
[61]
In addition, after the step 3) may mean before the step 3) is completed and the agglomeration process is performed.
[62]
[63]
If the alkyl acrylate-based polymer is added at one or more points after step 3) and after step 3), the polymerization stability is improved and the solid coagulum content is reduced compared to that in step 1) or 2). And, it is possible to prepare a graft copolymer having improved fluidity and impact resistance.
[64]
[65]
The alkyl acrylate-based polymer may be added in an amount of 0.1 to 3 parts by weight or 0.5 to 2.0 parts by weight, of which 0.5 to 2.0 parts by weight, based on 100 parts by weight of the total of monomers introduced in the method for preparing the graft copolymer. It is preferable to be added as a part. If the above-described conditions are satisfied, a graft copolymer having more improved appearance properties such as weather resistance, fluidity, mechanical properties, and surface gloss can be prepared.
[66]
[67]
The alkyl acrylate polymer may be one or more selected from the group consisting of poly(methyl acrylate), poly(ethyl acrylate), and poly(butyl acrylate), of which poly(butyl acrylate) is preferable. .
[68]
[69]
The alkyl acrylate-based polymer may be prepared directly, or ADP1200 (trade name, manufacturer: BASF) among commercially available materials may be used.
[70]
[71]
Meanwhile, steps 1) to 3) included in the method for preparing a graft copolymer according to an embodiment of the present invention will be described in detail below.
[72]
[73]
Level 1
[74]
First, at least one selected from the group consisting of an alkyl (meth)acrylate monomer, an aromatic vinyl monomer, and a vinyl cyan monomer is added and polymerized to prepare a seed.
[75]
[76]
In step 1), in order to quickly prepare a seed having a small average particle diameter, it is preferable to add an alkyl (meth)acrylate monomer alone and polymerize it. In order to prepare a seed having a large average particle diameter in consideration of impact resistance, aromatic It is preferable to add a vinyl-based monomer and a vinyl cyan-based monomer together and perform polymerization.
[77]
When the average particle diameter of the seed is small, the weather resistance and colorability of the graft copolymer may be improved, and when the average particle diameter of the seed is large, the impact resistance of the graft copolymer may be improved.
[78]
[79]
The alkyl (meth) acrylate monomers are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl ( It may be one or more selected from the group consisting of meth)acrylate and lauryl (meth)acrylate, of which butyl acrylate is preferred.
[80]
[81]
The aromatic vinyl-based monomer may be at least one selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, p-methyl styrene, and vinyl toluene, among which styrene is preferable.
[82]
[83]
The vinyl cyan-based monomer may be one or more selected from acrylonitrile, methacrylonitrile, phenyl acrylonitrile, α-chloroacrylonitrile, and ethacrylonitrile, of which acrylonitrile is preferable.
[84]
[85]
At least one selected from the group consisting of the alkyl (meth)acrylate monomer, the aromatic vinyl monomer, and the vinyl cyan monomer is 4 to 25 based on the total weight of the monomers introduced in the method for preparing the graft copolymer. It may be added in wt% or 5 to 24 wt%, of which 5 to 24 wt% is preferably added. If the above-described range is satisfied, there is an advantage in that the graft copolymer has excellent balance of weather resistance, fluidity, impact resistance, chemical resistance, and colorability.
[86]
[87]
Here, the monomers introduced in the method for preparing the graft copolymer may refer to an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer introduced in the step of preparing a seed, a core, and a shell. .
[88]
[89]
The seed may have an average particle diameter of 20 to 60 nm or 25 to 55 nm, of which 25 to 55 nm is preferable. If the above-described range is satisfied, a graft copolymer having excellent stability during polymerization and excellent weather resistance and impact resistance can be prepared.
[90]
[91]
The polymerization may be emulsion polymerization, may be carried out at 50 to 85 ℃ or 60 to 80 ℃, of which is preferably carried out at 60 to 80 ℃. If the above-described range is satisfied, emulsion polymerization can be stably performed.
[92]
[93]
In the step 1), at least one selected from the group consisting of an initiator, an emulsifier, a crosslinking agent, a grafting agent, an electrolyte, and water may be further added.
[94]
The initiator may be a radical initiator, and the initiator may include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium superphosphate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxide, 3,5,5-trimethylhexanol peroxide, and t-butyl peroxy isobutylate; It may be at least one selected from the group consisting of azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobis isobutyric acid (butyric acid) methyl, among which, Inorganic peroxide is preferable, and potassium persulfate is more preferable.
[95]
The initiator may be added in an amount of 0.01 to 3 parts by weight or 0.02 to 2.5 parts by weight, of which 0.02 to 2.5 parts by weight is added, based on 100 parts by weight of the total of the monomers introduced in the method for preparing the graft copolymer. desirable. If the above range is satisfied, polymerization can be easily performed.
[96]
[97]
The emulsifier may be one or more selected from the group consisting of metal salts of alkyl sulfosuccinic acid, metal salts of alkyl sulfates, metal salts of rosin acids, and metal salts of dimer acids, and among them, metal salts of alkyl sulfates are preferably added.
[98]
The alkyl sulfosuccinic acid metal salt is composed of dicyclohexyl sulfosuccinate sodium, dihexyl sulfosuccinate sodium, di-2-ethylhexyl sulfosuccinate sodium, di-2-ethylhexyl sulfosuccinate potassium salt and di-2-ethylhexyl sulfosuccinic acid. It may be one or more selected from the group.
[99]
The alkyl sulfate ester metal salt is at least one selected from the group consisting of sodium dodecyl sulfate, sodium lauric sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate, and potassium octadecyl sulfate. I can.
[100]
The metal rosin acid salt may be at least one selected from the group consisting of a potassium rosin acid salt and a sodium rosin acid salt.
[101]
As the metal salt of the dimer acid, FS200 (brand name, manufacturer: LG Household & Health Care) among commercially available materials may be used.
[102]
The emulsifier may be added in an amount of 0.01 to 5 parts by weight or 0.05 to 4.5 parts by weight based on 100 parts by weight of the total of the monomers introduced in the method for preparing the graft copolymer, of which 0.05 to 4.5 parts by weight is added. desirable. If the above-described range is satisfied, a seed having a desired average particle diameter, specifically, a seed latex can be easily prepared.
[103]
[104]
The crosslinking agent is ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, divinylbenzene, diethylene glycol di (meth) acrylate, triethylene glycol di ( Meth)acrylate, 1,3-butadiol dimethacrylate, hexanediol ethoxylate diacrylate, hexanediol propoxylate di(meth)acrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxy Rate di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, trimethylolmethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylpropane ethoxylate tri(meth) From the group consisting of acrylate, trimethylpropane propoxylate tri(meth)acrylate, pentaerythritol ethoxylate tri(meth)acrylate, pentaerythritol propoxylate tri(meth)acrylate, and vinyl trimethoxysilane It may be one or more, of which ethylene glycol dimethacrylate is preferred.
[105]
The crosslinking agent may be added in an amount of 0.01 to 1 parts by weight or 0.02 to 0.8 parts by weight, of which 0.02 to 0.8 parts by weight is added, based on 100 parts by weight of the total of the monomers introduced in the method for producing the graft copolymer. desirable. If the above-described range is satisfied, the seed may have an appropriate degree of crosslinking, and the seed may be properly piled up during core production to prepare a core having a desired average particle diameter.
[106]
[107]
The grafting agent may be at least one selected from the group consisting of allyl methacrylate, triallyl isocyanurate, diallylamine, and triallylamine, among which allyl methacrylate is preferred.
[108]
The grafting agent may be added in an amount of 0.001 to 3.0 parts by weight, 0.005 to 2.5 parts by weight, of which 0.005 to 2.5 parts by weight, based on 100 parts by weight of the total of the monomers added in the method for producing the graft copolymer. It is most preferable. If the above-described range is satisfied, the seed may have an appropriate degree of crosslinking, and the seed may be properly stacked during core production to prepare a core having a desired average particle diameter.
[109]
[110]
The electrolyte is KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 4 , Na 2 S 2 O 7 , K 4 P 2 O 7 , K 3 PO 4 , Na 3 PO 4 or Na 2 HPO 4 , It may be one or more selected from the group consisting of KOH and NaOH, of which KOH is preferred.
[111]
The electrolyte may be added in an amount of 0.001 to 1 part by weight or 0.01 to 0.8 part by weight based on 100 parts by weight of the total of the monomers introduced in the method of preparing the graft copolymer, of which 0.01 to 0.8 parts by weight desirable. If the above-described range is satisfied, a seed having a small particle diameter, specifically, a seed latex can be stably obtained.
[112]
[113]
The water may be distilled water or ion-exchanged water.
[114]
[115]
2) step
[116]
Then, in the presence of the seed, an alkyl (meth)acrylate-based monomer is added and polymerized to prepare a core.
[117]
[118]
The kind of the alkyl (meth)acrylate-based monomer is as described above.
[119]
[120]
The alkyl (meth)acrylate-based monomer may be added in an amount of 25 to 55% by weight or 30 to 50% by weight based on the total weight of the monomers introduced in the method for preparing the graft copolymer, of which 30 to 50 It is preferably added in weight percent. If the above-described range is satisfied, there is an advantage in that the graft copolymer has excellent balance of weather resistance, fluidity and chemical resistance.
[121]
[122]
The alkyl (meth)acrylate-based monomer may be continuously added at a constant rate, and when added in the above-described manner, it is possible to easily suppress runaway due to heat removal and excessive heat generation during polymerization.
[123]
[124]
The polymerization may be emulsion polymerization, may be carried out at 50 to 85 ℃ or 60 to 80 ℃, of which is preferably carried out at 60 to 80 ℃. If the above-described range is satisfied, emulsion polymerization can be stably performed.
[125]
[126]
The core may have a larger average particle diameter than the seed and may have an average particle diameter of 40 to 80 nm or 45 to 75 nm, of which 45 to 75 nm is preferable. If the above-described range is satisfied, a graft copolymer having excellent stability during polymerization and excellent weather resistance, colorability, and impact strength can be prepared.
[127]
[128]
In the step 2), at least one selected from the group consisting of an initiator, an emulsifier, a crosslinking agent, a grafting agent, and water may be further added.In order to easily suppress runaway due to heat removal and excessive heat during polymerization, alkyl (meth ) It can be continuously added with an acrylate-based monomer at a constant rate.
[129]
[130]
The types of the initiators are as described above, of which inorganic peroxides are preferable, and potassium persulfate is more preferable.
[131]
The initiator may be added in an amount of 0.01 to 3 parts by weight or 0.02 to 2.5 parts by weight, of which 0.02 to 2.5 parts by weight is added, based on 100 parts by weight of the total of the monomers introduced in the method for preparing the graft copolymer. desirable. If the above range is satisfied, polymerization can be easily performed.
[132]
[133]
The kind of the emulsifier is as described above, of which an alkyl sulfate ester metal salt is preferably added.
[134]
The emulsifier may be added in an amount of 0.01 to 5 parts by weight or 0.05 to 4.5 parts by weight based on 100 parts by weight of the total of the monomers introduced in the method for preparing the graft copolymer, of which 0.05 to 4.5 parts by weight is added. desirable. If the above-described range is satisfied, a core having a desired average particle diameter can be easily manufactured.
[135]
[136]
The type of the crosslinking agent is as described above.
[137]
The crosslinking agent may be added in an amount of 0.01 to 1 parts by weight or 0.02 to 0.8 parts by weight, of which 0.02 to 0.8 parts by weight is added, based on 100 parts by weight of the total of the monomers introduced in the method for producing the graft copolymer. desirable. If the above range is satisfied, the core may have an appropriate degree of crosslinking.
[138]
[139]
The kind of the grafting agent is as described above.
[140]
The grafting agent may be added in an amount of 0.01 to 3.0 parts by weight, 0.02 to 2.5 parts by weight, of which 0.02 to 2.5 parts by weight, based on 100 parts by weight of the total of the monomers added in the method for producing the graft copolymer. It is most preferable. If the above range is satisfied, the core may have an appropriate degree of crosslinking.
[141]
[142]
The water may be distilled water or ion-exchanged water.
[143]
[144]
3) step
[145]
Then, in the presence of the core, an aromatic vinyl monomer and a vinyl cyan monomer are added and polymerized to prepare a shell.
[146]
[147]
The types of the aromatic vinyl-based monomer and the vinyl cyan-based monomer are as described above.
[148]
The sum of the aromatic vinyl-based monomer and the vinyl cyan-based monomer may be added in an amount of 30 to 60% by weight or 35 to 55% by weight, based on the total weight of the monomers introduced in the method for preparing the graft copolymer, of which It is preferably added in 35 to 55% by weight. If the above-described range is satisfied, there is an advantage in that the graft copolymer has excellent balance of weather resistance, fluidity and chemical resistance.
[149]
[150]
The aromatic vinyl-based monomer and the vinyl cyan-based monomer may be added in a weight ratio of 65:35 to 85:15 or 70:30 to 80:20, of which it is preferably added in a weight ratio of 70:30 to 80:20. Do. If the above-described range is satisfied, there is an advantage in that the graft copolymer has excellent balance of fluidity and chemical resistance.
[151]
[152]
The aromatic vinyl-based monomer and the vinyl cyan-based monomer may be continuously added at a constant rate, and when added in the above-described manner, it is possible to easily suppress runaway due to heat removal and excessive heat generation during polymerization.
[153]
[154]
The polymerization may be emulsion polymerization, may be carried out at 50 to 85 ℃ or 60 to 80 ℃, of which is preferably carried out at 60 to 80 ℃. If the above-described range is satisfied, emulsion polymerization can be stably performed.
[155]
[156]
The graft copolymer including the shell may have an average particle diameter larger than that of the core and may have an average particle diameter of 60 to 110 nm or 65 to 105 nm, of which 65 to 105 nm is preferred. If the above-described range is satisfied, a graft copolymer having excellent stability during polymerization and excellent weather resistance and impact strength can be prepared.
[157]
[158]
In the step 3), at least one selected from the group consisting of an initiator, an activator, an emulsifier, a molecular weight modifier, and water may be further added, and may be continuously added with an alkyl (meth)acrylate-based monomer at a constant rate. .
[159]
The kind of the initiator is as described above, of which organic peroxide is preferable, and cumene hydroperoxide is more preferable.
[160]
The initiator may be added in an amount of 0.01 to 3 parts by weight or 0.02 to 2.5 parts by weight, of which 0.02 to 2.5 parts by weight is added, based on 100 parts by weight of the total of the monomers introduced in the method for preparing the graft copolymer. desirable. If the above range is satisfied, polymerization can be easily performed.
[161]
[162]
The activator may be one or more selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, anhydrous sodium pyrophosphate, and sodium sulfate, among which sulfuric acid It is preferably at least one selected from the group consisting of ferrous iron, dextrose and sodium pyrophosphate.
[163]
The activator may be added in an amount of 0.01 to 1 part by weight or 0.1 to 0.8 part by weight, based on 100 parts by weight of the total of the monomers introduced in the method for preparing the graft copolymer, of which 0.1 to 0.8 parts by weight. It is desirable. If the above-described content is satisfied, polymerization initiation can be accelerated.
[164]
[165]
The type of the emulsifier is as described above, of which a metal salt of rosin acid is preferably added.
[166]
The emulsifier may be added in an amount of 0.1 to 3 parts by weight or 0.5 to 2.5 parts by weight, of which 0.5 to 2.5 parts by weight, based on 100 parts by weight of the total of the monomers introduced in the method for preparing the graft copolymer. desirable. If the above-described range is satisfied, a graft copolymer having a desired average particle diameter can be easily prepared.
[167]
[168]
The molecular weight modifier is α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, mercaptans such as octyl mercaptan, carbon tetrachloride, methylene chloride, halogenated hydrocarbons such as methylene bromide, tetraethyl thiuram disulfide , Dipentamethylene thiuram disulfide, diisopropylxanthogen disulfide. Preferably it may be t-dodecyl mercaptan.
[169]
The molecular weight modifier may be added in an amount of 0.001 to 1 part by weight or 0.01 to 0.8 part by weight, based on 100 parts by weight of a total of monomers introduced in the method for preparing the graft copolymer, of which 0.01 to 0.8 parts by weight. It is desirable. If the above-described range is satisfied, the weight average molecular weight of the shell is appropriately maintained to further improve the mechanical properties and surface properties of the graft copolymer.
[170]
[171]
The water may be distilled water or ion-exchanged water.
[172]
[173]
In the method for producing a graft copolymer according to an embodiment of the present invention, when the step 3) is completed, coagulation, aging, dehydration, washing, drying processes, etc. are further performed to prepare a graft copolymer powder. .
[174]
[175]
2. Graft Copolymer
[176]
The graft copolymer according to another embodiment of the present invention includes a seed comprising at least one selected from the group consisting of an alkyl (meth)acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; A core including the seed and an alkyl (meth)acrylate-based monomer unit; A shell including the core, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit; And alkyl acrylate polymers.
[177]
[178]
The alkyl (meth)acrylate-based polymer may improve weather resistance, impact strength, and tensile strength of the graft copolymer.
[179]
[180]
The alkyl acrylate-based polymer may have a weight average molecular weight of 1,000 to 2,500 g/mol or 1,200 to 2,300 g/mol, of which 1,200 to 2,300 g/mol is preferable. If the above-described conditions are satisfied, appearance properties such as weather resistance, fluidity, mechanical properties, and surface gloss of the graft copolymer can be further improved.
[181]
[182]
The alkyl acrylate-based polymer may have a viscosity of 20 to 1,000 cps or 100 to 900 cps at 25° C., of which 100 to 900 cps is preferable. If the above-described conditions are satisfied, appearance properties such as weather resistance, fluidity, mechanical properties, and surface gloss of the graft copolymer can be further improved.
[183]
[184]
In addition, for the description of the alkyl acrylate polymer, see '1. As described above in'Method of producing a graft copolymer'.
[185]
[186]
Since the alkyl (meth)acrylate-based polymer is hydrophobic and has excellent compatibility with the core, it may be located at one or more of the interface between the core and the shell and the shell, and the interface between the core and the shell compared to the cell Can be located in excess.
[187]
When the alkyl acrylate-based polymer is located in the above-described region, weather resistance, impact strength, and tensile strength of the graft copolymer may be further improved.
[188]
[189]
The core may have a larger average particle diameter than the seed and may have an average particle diameter of 40 to 80 nm or 45 to 75 nm, of which 45 to 75 nm is preferable. If the above-described range is satisfied, a graft copolymer having excellent stability during polymerization and excellent weather resistance, colorability, and impact strength can be prepared.
[190]
[191]
On the other hand, the description of the seed, core, and shell in addition to this is '1. As described above in'Method of Producing Graft Copolymer', the graft copolymer according to another embodiment of the present invention may be prepared according to the method of producing a graft copolymer according to an embodiment of the present invention.
[192]
[193]
3. Thermoplastic resin composition
[194]
The thermoplastic resin composition according to another embodiment of the present invention is a graft copolymer according to an embodiment of the present invention; And a matrix copolymer comprising an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit.
[195]
[196]
The aromatic vinyl-based monomer unit included in the matrix copolymer may be one or more units selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, p-methyl styrene, and vinyl toluene, among which α- Methyl styrene units are preferred.
[197]
[198]
The vinyl cyan-based monomer unit included in the matrix copolymer may be one or more units selected from acrylonitrile, methacrylonitrile, phenyl acrylonitrile, α-chloroacrylonitrile, and ethacrylonitrile, and this Among them, acrylonitrile units are preferred.
[199]
[200]
The matrix copolymer may include an aromatic vinyl monomer unit and a vinyl cyan monomer unit in a weight ratio of 60:40 to 80:20 or 65:35 to 75:25, of which 65:35 to 75:25 It is preferable to include it in a weight ratio. If the above-described content is satisfied, it is possible to provide a thermoplastic resin composition having excellent heat resistance, fluidity, and chemical resistance.
[201]
[202]
The thermoplastic resin composition may include the graft copolymer and the matrix copolymer in a weight ratio of 60:40 to 10:90 or 55:45 to 10:85, of which 55:45 to 10:85 It is preferable to include. If the above-described range is satisfied, a thermoplastic resin composition having excellent weather resistance, heat resistance, fluidity, chemical resistance, and appearance characteristics can be prepared.
[203]
[204]
The thermoplastic resin composition may further include additives such as dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, plasticizers or matting agents, depending on the application.
[205]
[206]
4. Thermoplastic molded product
[207]
The thermoplastic resin molded article made of the thermoplastic resin composition according to another embodiment of the present invention has a weather resistance of 1.8 or less, an impact strength of 13 kg·cm/cm or more, preferably a weather resistance of 1.7 or less, and an impact strength of 13.5. It is more than kg·cm/cm.
[208]
If the above-described conditions are satisfied, it may be suitable to be applied as an exterior material for automobiles and a sheet for furniture requiring high weather resistance.
[209]
[210]
Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in a number of different forms and is not limited to the embodiments described herein.
[211]
[212]
Example 1
[213]

[214]
In a nitrogen-substituted reactor, 6.5 parts by weight of butyl acrylate, 1.5 parts by weight of sodium dodecyl sulfate as an emulsifier, 0.04 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, 0.015 parts by weight of allyl methacrylate as a grafting agent, 0.1 parts by weight of KOH as an electrolyte Parts and 60 parts by weight of distilled water were added at once, the temperature was raised to 70° C., and 0.04 parts by weight of potassium persulfate as an initiator was added at once to initiate the reaction. After the polymerization was completed for 1 hour, the seed was obtained.
[215]
[216]

[217]
In the reactor from which the seed was obtained, 43.5 parts by weight of butyl acrylate, 0.7 parts by weight of sodium dodecyl sulfate as an emulsifier, 0.25 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, 0.09 parts by weight of allyl methacrylate as a grafting agent, 35 parts by weight of distilled water A mixture in which 0.03 parts by weight of potassium persulfate was mixed as a part and an initiator was continuously added at a constant rate for 2 hours at 70° C. for polymerization, and polymerization was further performed for 1 hour after completion of the addition, and then a core was obtained.
[218]
[219]

[220]
In the reactor from which the core was obtained, distilled water 23 parts by weight, styrene 38 parts by weight, acrylonitrile 12 parts by weight, and poly(butyl acrylate) (brand name: ADP1200, manufacturer: BASF) 1.0 parts by weight, potassium rosinate 1.8 as an emulsifier A first mixture containing 0.1 parts by weight of t-dodecyl mercaptan as a molecular weight modifier and 0.05 parts by weight of cumene hydroperoxide as an initiator, 0.09 parts by weight of sodium pyrophosphate as an activator, 0.12 parts by weight of textrose, and 1 The second mixture containing 0.002 parts by weight of iron was polymerized while continuously adding at a constant rate at 75° C. for 2.5 hours, respectively. After the continuous addition was completed, the reaction was further reacted at 75° C. for 1 hour and cooled to 60° C. to terminate the polymerization reaction, thereby preparing a graft copolymer latex including a shell.
[221]
[222]

[223]
After applying 0.8 parts by weight of the graft copolymer latex to an aqueous calcium chloride solution (concentration: 23% by weight) at 70° C., it is subjected to atmospheric pressure aggregation, aged at 93° C., dehydrated and washed, and dried for 30 minutes with hot air at 90° C. To prepare a copolymer powder.
[224]
[225]

[226]
40 parts by weight of the graft copolymer powder, 4 parts by weight of the large-diameter graft copolymer powder (brand name: SA927, manufacturer: LG Chem, average particle diameter of the graft copolymer: 400 nm) and a rigid matrix copolymer (brand name: 100 UH, Manufacturer: LG Chem) to prepare a thermoplastic resin composition containing 56 parts by weight.
[227]
[228]
Example 2
[229]
Graft copolymer powder and thermoplastic resin composition in the same manner as in Example 1, except that 1 part by weight of poly(butyl acrylate) (brand name: ADP1200, manufacturer: BASF) was added after polymerization in the production of the shell. Was prepared.
[230]
[231]
Example 3
[232]

[233]
In a nitrogen-substituted reactor, 10 parts by weight of butyl acrylate, 1.8 parts by weight of sodium dodecyl sulfate as an emulsifier, 0.06 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, 0.035 parts by weight of allyl methacrylate as a grafting agent, 0.1 parts by weight of KOH as an electrolyte Parts and 65 parts by weight of distilled water were added at once, the temperature was raised to 70° C., and 0.04 parts by weight of potassium persulfate as an initiator was added at once to initiate the reaction. After polymerization for 1 hour and then terminated to prepare a seed.
[234]
[235]

[236]
In the reactor from which the seed was obtained, 40 parts by weight of butyl acrylate, 0.5 parts by weight of sodium dodecyl sulfate as an emulsifier, 0.15 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, 0.075 parts by weight of allyl methacrylate as a grafting agent, 32 parts by weight of distilled water 0.05 parts by weight of potassium persulfate as a part and initiator was polymerized while continuously adding at a constant rate for 2.0 hours at 70° C., and polymerization was further performed for 1 hour after completion of the addition, and the core was obtained.
[237]
[238]

[239]
In the reactor from which the core was obtained, distilled water 20 parts by weight, styrene 38 parts by weight, acrylonitrile 12 parts by weight, and poly(butyl acrylate) (brand name: ADP1200, manufacturer: BASF) 1.0 parts by weight, potassium rosinate 1.8 as an emulsifier A first mixture containing 0.1 parts by weight of t-dodecyl mercaptan as a molecular weight modifier and 0.05 parts by weight of cumene hydroperoxide as an initiator, 0.09 parts by weight of sodium pyrophosphate as an activator, 0.12 parts by weight of textrose, and 1 The second mixture containing 0.002 parts by weight of iron was polymerized while continuously added at a constant rate for 2.5 hours at 75°C. After the continuous addition was completed, the reaction was further reacted at 75° C. for 1 hour and cooled to 60° C. to terminate the polymerization reaction, thereby preparing a graft copolymer latex including a shell.
[240]
[241]

[242]
After applying 0.8 parts by weight of the graft copolymer latex to an aqueous calcium chloride solution (concentration: 23% by weight) at 70° C., it is subjected to atmospheric pressure aggregation, aged at 93° C., dehydrated and washed, and dried for 30 minutes with hot air at 90° C. To prepare a copolymer powder.
[243]
[244]

[245]
40 parts by weight of the graft copolymer powder, 4 parts by weight of the large-diameter graft copolymer powder (brand name: SA927, manufacturer: LG Chem, average particle diameter of the graft copolymer: 400 nm) and a rigid matrix copolymer (brand name: 100 UH, Manufacturer: LG Chem) to prepare a thermoplastic resin composition containing 56 parts by weight.
[246]
[247]
Example 4
[248]
Graft copolymer powder and thermoplastic resin composition in the same manner as in Example 3, except that 1 part by weight of poly(butyl acrylate) (brand name: ADP1200, manufacturer: BASF) was added after polymerization in the production of the shell. Was prepared.
[249]
[250]
Example 5
[251]
In the preparation of the shell, a graft copolymer powder and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 0.5 parts by weight of poly(butyl acrylate) (brand name: ADP1200, manufacturer: BASF) was added.
[252]
[253]
Example 6
[254]
In the preparation of the shell, a graft copolymer powder and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 1.5 parts by weight of poly(butyl acrylate) (trade name: ADP1200, manufacturer: BASF) was added.
[255]
[256]
Comparative Example 1
[257]
In the preparation of the shell, a graft copolymer powder and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that poly(butyl acrylate) (brand name: ADP1200, manufacturer: BASF) was not added.
[258]
[259]
Comparative Example 2
[260]

[261]
In a nitrogen-substituted reactor, 6 parts by weight of butyl acrylate, 0.8 parts by weight of sodium dodecyl sulfate as an emulsifier, 0.04 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, 0.02 parts by weight of allyl methacrylate as a grafting agent, 0.1 parts by weight of KOH as an electrolyte Parts and 45 parts by weight of distilled water were added at once, the temperature was raised to 70° C., and 0.04 parts by weight of potassium persulfate as an initiator was added at once to initiate the reaction. After polymerization for 1 hour and then terminated to prepare a seed.
[262]
[263]

[264]
In the reactor from which the seed was obtained, 44 parts by weight of butyl acrylate, 0.5 parts by weight of sodium dodecyl sulfate as an emulsifier, 0.2 parts by weight of ethylene glycol dimethacrylate as a crosslinking agent, 0.2 parts by weight of allyl methacrylate as a grafting agent, 30 parts by weight of distilled water Polymerization was carried out while continuously adding 0.05 parts by weight of potassium persulfate as a part and initiator at a constant rate for 2.5 hours at 70° C., and polymerization was further performed for 1 hour after completion of the addition, and then a core was obtained.
[265]
[266]

[267]
In the reactor from which the core was obtained, 23 parts by weight of distilled water, 38 parts by weight of styrene, 12 parts by weight of acrylonitrile and 0.8 parts by weight of FS200 (brand name, manufacturer: LG Household & Health Care) as an emulsifier, 0.1 t-dodecyl mercaptan as a molecular weight regulator A first mixture containing 0.05 parts by weight of cumene hydroperoxide as an initiator and 0.09 parts by weight of sodium pyrophosphate as an activator, 0.12 parts by weight of textrose, and 0.002 parts by weight of ferrous sulfate were each prepared at 75° C. Polymerization was carried out while continuously added at a constant rate for 2.5 hours. After the continuous addition was completed, the reaction was further reacted at 75° C. for 1 hour and cooled to 60° C. to terminate the polymerization reaction, thereby preparing a graft copolymer latex including a shell.
[268]
[269]

[270]
The graft copolymer latex was subjected to atmospheric pressure aggregation at 70° C. by applying 0.8 parts by weight of an aqueous calcium chloride solution, aged at 93° C., dehydrated and washed, and dried for 30 minutes with hot air at 90° C. to prepare a graft copolymer powder. .
[271]
[272]

[273]
40 parts by weight of the graft copolymer powder, 4 parts by weight of the large-diameter graft copolymer powder (brand name: SA927, manufacturer: LG Chem, average particle diameter of the graft copolymer: 400 nm) and a rigid matrix copolymer (brand name: 100 UH, Manufacturer: LG Chem) to prepare a thermoplastic resin composition containing 56 parts by weight.
[274]
[275]
Comparative Example 3
[276]

[277]
40 parts by weight of the graft copolymer powder of Comparative Example 2, 4 parts by weight of the large-diameter graft copolymer powder (brand name: SA927, manufacturer: LG Chem, average particle diameter of the graft copolymer: 400 nm), rigid matrix copolymer (brand name : 100 UH, manufacturer: LG Chem) 51 parts by weight and poly(methyl methacrylate) (trade name: BA611 grade, manufacturer: LGMMA) to prepare a thermoplastic resin composition containing.
[278]
[279]
Comparative Example 4
[280]

[281]
39 parts by weight of the graft copolymer powder of Comparative Example 1, poly(butyl acrylate) (brand name: ADP1200, manufacturer: BASF) 1 part by weight, large diameter graft copolymer powder 4 parts by weight (brand name: SA927, manufacturer: LG Chemical, the average particle diameter of the graft copolymer: 400 nm) and a rigid matrix copolymer (brand name: 100 UH, manufacturer: LG Chem) to prepare a thermoplastic resin composition comprising 56 parts by weight.
[282]
[283]
Experimental Example 1
[284]
The physical properties of the graft copolymers of Examples and Comparative Examples were measured in the following manner, and the results are shown in Tables 1 and 2 below.
[285]
[286]
① Average particle diameter (nm): It was measured with a particle size analyzer (NICOMP 380) using a dynamic light scattering method.
[287]
[288]
② Polymerization conversion rate: (solid content weight of the graft copolymer actually obtained) / solid content weight of the monomer added in the prescription) × 100
[289]
[290]
③ Graft rate (%): Weight of grafted monomer (g)/rubber weight (g) × 100
[291]
[292]
Weight of grafted monomer (g): Weight of insoluble substance (gel) after dissolving 1 g of graft copolymer in 30 g of acetone and centrifuging
[293]
Rubber weight (g): The weight part of the theoretically added butyl acrylate in the graft copolymer powder
[294]
[295]
④ Weight average molecular weight of the shell (g/mol): When measuring the graft rate, the sol dissolved in acetone is dissolved in a THF solution, and then measured as a relative value to a standard PS (standard polystyrene) sample using GPC.
[296]
[Table 1]
division Average particle diameter (nm) Polymerization conversion rate (%) Graft rate (%) Shell weight average molecular weight (g/mol)
Seed core Graft copolymer
Example 1 34 65 85 99.5 26 120,000
Example 2 34 65 86 99.2 26 121,000
Example 3 45 66 88 99.5 27 120,000
Example 4 34 65 87 99.2 27 120,000
Example 5 34 65 86 99.3 26.5 122,000
Example 6 34 65 88 99.4 26.5 115,000
Comparative Example 1 34 65 86 99.2 28 110,000
Comparative Example 2 60 105 145 98.0 33 100,000
[297]
Looking at Table 1, it was confirmed that the graft copolymers of Examples 1 to 6 realized the same level of average particle diameter and polymerization conversion rate as compared to the graft copolymer of Comparative Example 1, but the graft rate decreased and the weight average molecular weight increased. . From these results, it was confirmed that the alkyl acrylate-based polymer did not affect the average particle diameter and polymerization conversion rate of the graft copolymer, but did affect the graft rate and the weight average molecular weight.
[298]
On the other hand, in the graft copolymer of Comparative Example 2, a small amount of the emulsifier was added during seed production compared to the examples, so that seeds and cores having a large average particle diameter were prepared. In addition, since the amount of initiator relative to the number of cores increases during the manufacture of the shell, the weight average molecular weight of the shell decreases, and thus more styrene units and acrylonitrile units are grafted to the core, thereby increasing the grafting rate. Could.
[299]
[300]
Experimental Example 2
[301]
In the thermoplastic resin compositions of Examples and Comparative Examples, a lubricant (brand name: EBS, manufacturer: LG Household & Health Care) 1.5 parts by weight, antioxidant (brand name: IR1076, manufacturer: BASF) 1.0 parts by weight and UV stabilizer (brand name: Tinuvin770, manufacturer: BASF) ) After uniformly mixing 1.0 parts by weight, pellets were prepared using a 36 pie extrusion kneader at 220°C. The flowability of the pellets was measured in the following manner, and the results are shown in Tables 2 and 3 below.
[302]
[303]
⑤ Flow index (MI: melt flow index, g/10 mins): In accordance with ASTM D-1238, it was measured under 220°C and 10 kg.
[304]
[305]
Experimental Example 3
[306]
The pellet prepared in Experimental Example 2 was injected to prepare a specimen. The physical properties of the specimen were measured in the following manner, and the results are shown in Tables 2 and 3.
[307]
[308]
⑥ Weatherability (△E): Applied accelerated weathering test equipment (weather-o-meter, ATLAS Ci4000, xenon arc lamp, Quartz(inner)/S.Boro(outer) filter, irradiznce 0.55W/m 2 at 340nm) applied SAE The test was conducted for 6,000 hours under the condition of J1960, and the following ΔE is an arithmetic mean value before and after the accelerated weathering test, and the closer the value is to 0, the better the weather resistance is.
[309]

[310]
In the above formula, L'is the L value measured with the CIE LAB color coordinate system after irradiating the thermoplastic resin molded product with light under SAE J1960 conditions for 6,000 hours, and L O is the L value measured with the CIE LAB color coordinate system before light irradiation,
[311]
a'is the value a measured by the CIE LAB color coordinate system after irradiating the thermoplastic resin molded product with light under SAE J1960 conditions for 6,000 hours, and a O is the a value measured by the CIE LAB color coordinate system before the light irradiation,
[312]
b'is the b value measured by the CIE LAB color coordinate system after irradiating the thermoplastic resin molded product with light under SAE J1960 conditions for 6,000 hours, and b O is the b value measured with the CIE LAB color coordinate system before light irradiation.
[313]
[314]
⑦ Izod impact strength (kg/cm2): The specimen was measured according to ASTM 256 with a thickness of 1/4 In.
[315]
⑧ Tensile strength (kg/㎠): Measured according to ASTM D638.
[316]
⑨ Heat deflection temperature (℃): Measured according to ASTM D648.
[317]
[318]
[Table 2]
division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
Fluidity (g/10mins) 8.0 8.1 8.2 7.9 7.2 8.8
Weather resistance (△E) 1.4 1.6 1.4 1.6 1.7 1.3
Impact strength (kg·cm/cm, 1/4 In) 14.0 13.8 14.2 14.0 13.0 15.0
Tensile strength (㎏/㎠) 510 507 508 508 515 505
Heat deflection temperature (℃) 90.5 91.0 90.5 90.5 91.1 90.0
[319]
[Table 3]
division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
Fluidity (g/10mins) 5.2 5.5 7.5 7.0
Weather resistance (△E) 2.5 6.0 2.0 2.1
Impact strength (kg·cm/cm, 1/4 In) 10.0 13.0 11.0 11
Tensile strength (㎏/㎠) 510 480 490 500
Heat deflection temperature (℃) 91.0 89.0 86.0 90
[320]
Looking at Tables 2 and 3, the thermoplastic resin specimens of Examples 1 to 6 have excellent workability (flowability), weather resistance and impact strength compared to the specimens of Comparative Example 1, and the tensile strength and heat resistance (heat deflection temperature) are equivalent. I could see that it was a level.
[321]
In addition, the thermoplastic resin specimens of Examples 1 to 6 had an impact resistance equal to or higher than that of the thermoplastic resin specimen of Comparative Example 2 containing a graft copolymer having a large average particle diameter, but the workability, weather resistance, tensile strength and heat resistance were It was confirmed that it was remarkably excellent.
[322]
In addition, the thermoplastic resin specimens of Examples 1 to 6 were equal to or higher than the thermoplastic specimen of Comparative Example 3 containing a graft copolymer having a large average particle diameter and poly(methyl methacrylate), but weather resistance and impact It was confirmed that the strength, tensile strength and heat resistance were remarkably excellent.
[323]
In addition, since the thermoplastic resin composition of Comparative Example 4 containing the same amount of poly (butyl acrylate) as in Examples 1 to 4 did not add poly (butyl acrylate) in the manufacturing process of the graft copolymer, It was confirmed that workability, weather resistance, and impact strength were reduced.
[324]
From these results, the graft copolymer according to an embodiment of the present invention increases the average particle diameter in order to improve impact resistance, or does not further include poly(methyl methacrylate) in order to improve processability and weather resistance, It was confirmed that impact resistance, processability and weather resistance could be implemented. In addition, it was confirmed that only when poly(butyl acrylate) was added during the manufacturing process of the graft copolymer, the effect of improving processability, weather resistance, and impact strength was large.
[325]
Claims
[Claim 1]
1) preparing a seed by adding at least one selected from the group consisting of an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer and polymerizing it; 2) preparing a core by adding and polymerizing an alkyl (meth)acrylate-based monomer in the presence of the seed; And 3) adding and polymerizing an aromatic vinyl-based monomer and a vinyl cyan-based monomer in the presence of the core to prepare a shell, and further adding an alkyl acrylate-based polymer.
[Claim 2]
The method of claim 1, wherein the alkyl acrylate-based polymer has a weight average molecular weight of 1,000 to 2,500 g/mol.
[Claim 3]
The method of claim 1, wherein the alkyl acrylate-based polymer has a viscosity of 20 to 1,000 cps at 25°C.
[Claim 4]
The method of claim 1, wherein the alkyl acrylate polymer is added in at least one of the steps 1) to 3).
[Claim 5]
The method of claim 1, wherein the alkyl acrylate-based polymer is added after step 3).
[Claim 6]
The method according to claim 1, wherein the alkyl acrylate-based polymer is added in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of a total of monomers introduced in the method for preparing the graft copolymer.
[Claim 7]
The method of claim 1, wherein the alkyl acrylate-based polymer is at least one selected from the group consisting of poly(methyl acrylate), poly(ethyl acrylate), and poly(butyl acrylate). .
[Claim 8]
The method of claim 1, wherein the core has an average particle diameter of 40 to 80 nm.
[Claim 9]
A seed comprising at least one selected from the group consisting of an alkyl (meth)acrylate monomer unit, an aromatic vinyl monomer unit, and a vinyl cyano monomer unit; A core including the seed and an alkyl (meth)acrylate-based monomer unit; A shell including the core, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit; And a graft copolymer comprising an alkyl acrylate polymer.
[Claim 10]
The graft copolymer of claim 9, wherein the alkyl acrylate-based polymer has a weight average molecular weight of 1,000 to 2,500 g/mol and a viscosity of 20 to 1,000 cps at 25°C.
[Claim 11]
The graft copolymer of claim 9, wherein the alkyl acrylate-based polymer is located in at least one region of an interface between the core and the shell and a shell.
[Claim 12]
The graft copolymer of claim 9, wherein the core has an average particle diameter of 40 to 80 nm.
[Claim 13]
The graft copolymer according to any one of claims 9 to 12; And a matrix copolymer comprising an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit, and having a weather resistance of 1.8 or less and an impact strength of 13 kg·cm/cm or more.