The present invention claims the benefit of priority based on Korean Patent Application No. 10-2018-0125522 filed on October 19, 2018, and includes all contents disclosed in the literature of the Korean patent application as a part of this specification.
[3]
[Technical field]
[4]
The present invention relates to a method for producing a graft copolymer powder, and to provide a method for producing a graft copolymer powder having improved weather resistance, surface gloss and appearance quality while maintaining basic physical properties.
background
[5]
Recently, there is an increasing demand for strengthening not only heat resistance but also weather resistance of a thermoplastic resin composition for automobiles containing the ASA graft copolymer.
[6]
Accordingly, a method of using a core having a small particle size has been proposed, but there is a problem in 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 with an aromatic vinyl-based monomer and a vinyl cyan-based monomer during the manufacture of the shell has been proposed, but there is a problem in that heat resistance and mechanical properties are lowered. 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 there is a problem in that heat resistance and mechanical properties are deteriorated.
[7]
Accordingly, there is a demand for the development of a graft copolymer having excellent heat resistance, weather resistance and impact resistance.
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[8]
It is an object of the present invention to provide a method for producing a graft copolymer powder having improved weather resistance, surface gloss and appearance quality while maintaining the basic physical properties of the graft copolymer powder.
means of solving the problem
[9]
In order to solve the above problems, the present invention comprises the steps of 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 to a reactor and polymerization ; preparing a core by adding and polymerizing an alkyl (meth)acrylate-based monomer in the presence of the seed; and preparing a graft copolymer latex by adding an aromatic vinyl-based monomer and a vinyl cyanide-based monomer and polymerization in the presence of the core; It provides a method for producing a graft copolymer powder comprising the step of adding an alkyl methacrylate-based polymer to the graft copolymer latex and agglomeration.
[10]
[11]
In addition, the present invention is a first graft copolymer powder prepared by the above-mentioned manufacturing method; And it provides a thermoplastic resin composition comprising a matrix copolymer comprising an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit.
[12]
[13]
Further, the present invention provides a thermoplastic resin molded article made of the above-described thermoplastic resin composition, made of the thermoplastic resin composition, and having ΔE of 3 or less, which is represented by the following formula:
[14]

[15]
Wherein, L 'is L a value measured by the CIE LAB color coordinates after irradiating light to the SAE J1960 conditions for 6000 hours in the thermoplastic resin molded product, L O is the L value measured by the CIE LAB color coordinate system before irradiation with light,
[16]
a' is the a value measured by the CIE LAB color coordinate system after irradiating the thermoplastic resin molded article 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 light irradiation,
[17]
b' is the b value measured with the CIE LAB color coordinate system after irradiating the thermoplastic resin molded article 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.
Effects of the Invention
[18]
According to the production method of the graft copolymer powder of the present invention, it is possible to provide a graft copolymer having significantly improved weather resistance, surface gloss and appearance quality while maintaining basic physical properties such as impact resistance.
Best mode for carrying out the invention
[19]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[20]
The terms or words used in the present specification and claims are not to 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.
[21]
[22]
In the present invention, the weight average molecular weight of the alkyl methacrylate-based polymer is relative to a standard PS (standard polystyrene) sample using tetrahydrofuran (THF) as an eluent, and gel permeation chromatography (GPC, waters breeze). can be measured with
[23]
[24]
In the present invention, the glass transition temperature of the alkyl (meth)acrylate-based crosslinked polymer and the alkyl methacrylate-based polymer can be measured by a Differential Scanning Calorimeter.
[25]
[26]
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.
[27]
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, that is, an average particle diameter of scattering intensity.
[28]
[29]
In the present invention, ΔE value is an accelerated weather resistance test device (weather-o-meter, ATLAS Ci4000, xenon arc lamp, Quartz (inner) / S. Boro (outer) filter, irradiznce 0.55W/m2 at 340 nm) by applying It can be measured by performing the test for 6,000 hours under SAE J1960 condition.
[30]
The following ΔE is an arithmetic mean value before and after the accelerated weather resistance test, and the closer the value is to 0, the better the weather resistance is.
[31]

[32]
In the above formula, L' is the L value measured with the CIE LAB color coordinate system after irradiating the thermoplastic resin molded article 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,
[33]
a' is the a value measured by the CIE LAB color coordinate system after irradiating the thermoplastic resin molded article 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 light irradiation,
[34]
b' is the b value measured with the CIE LAB color coordinate system after irradiating the thermoplastic resin molded article 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.
[35]
[36]
In the present invention, the 'total weight of the monomers added in the method for preparing the graft copolymer powder' refers to 'the seed, the core, and the alkyl (meth) acrylate-based monomer and the aromatic vinyl-based monomer added in the preparation of the graft copolymer latex. and the total weight of the vinyl cyan-based monomer.
[37]
[38]
1. Manufacturing method of graft copolymer powder
[39]
In the method for producing a graft copolymer powder according to an embodiment of the present invention, 1) at least one selected from the group consisting of an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer is added to a reactor and polymerization to prepare a seed; 2) preparing a core by adding and polymerizing an alkyl (meth)acrylate-based monomer in the presence of the seed; and 3) preparing a graft copolymer latex by adding an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of the core and polymerizing; 4) adding an alkyl methacrylate-based polymer to the graft copolymer latex and agglomeration.
[40]
[41]
Meanwhile, steps 1) to 4) included in the method for producing a graft copolymer powder according to an embodiment of the present invention will be described in detail below.
[42]
[43]
1) Step: Seed Preparation Step
[44]
First, 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 is added to a reactor and polymerized to prepare a seed.
[45]
[46]
In order to quickly produce a seed having a small average particle diameter, it is preferable to add an alkyl (meth)acrylate monomer alone and polymerize it. To prepare a seed having a large average particle diameter, an aromatic vinyl monomer and a vinyl cyan monomer are combined It is preferable to add and polymerize.
[47]
[48]
The alkyl (meth)acrylate-based monomer is an alkyl (meth)acrylate-based crosslinked polymer having a glass transition temperature of -20°C or less, -70°C to -20°C, or -50°C to -25°C due to a crosslinking reaction, that is, There is no particular limitation as long as the alkyl (meth)acrylate-based rubber can be produced.
[49]
When the alkyl (meth)acrylate-based crosslinked polymer satisfies the above-described glass transition temperature, excellent elasticity and mechanical properties can be maintained even in a harsh environment. When the above-mentioned range is exceeded, sufficient mechanical properties may not be secured.
[50]
[51]
The alkyl (meth) acrylate monomer may be a C 4 to C 10 alkyl (meth) acrylate monomer, preferably a C 4 to C 8 alkyl (meth) acrylate monomer.
[52]
The alkyl (meth) acrylate-based monomer is butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl ( It may be at least one selected from the group consisting of meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, and decyl (meth)acrylate, and among these, butyl acrylate is more preferable.
[53]
[54]
The aromatic vinyl-based monomer may be at least one selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, among which styrene is preferable.
[55]
[56]
The vinyl cyan-based monomer may be at least one selected from acrylonitrile, methacrylonitrile, phenyl acrylonitrile, α-chloroacrylonitrile and ethacrylonitrile, among which acrylonitrile is preferable.
[57]
[58]
The sum of the monomers added in step 1) may be added in an amount of 1 to 20% by weight or 3 to 15% by weight based on the total weight of the monomers added in the method for preparing the graft copolymer powder, of which 3 It is preferably added in an amount of 15 to 15% by weight. When the above-described range is satisfied, a graft copolymer having excellent balance of weather resistance, fluidity, impact resistance, chemical resistance, and coloring property can be prepared.
[59]
[60]
The seed may have an average particle diameter of 20 to 80 nm or 25 to 50 nm, of which 25 to 50 nm is preferable. When the above-mentioned range is satisfied, a graft copolymer having excellent stability during polymerization and excellent weather resistance and impact resistance can be prepared.
[61]
[62]
The polymerization may be emulsion polymerization, and may be carried out at 55 to 85 °C or 60 to 80 °C, of ​​which it is preferably carried out at 60 to 80 °C. When the above-mentioned range is satisfied, emulsion polymerization can be stably performed.
[63]
[64]
In 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 to the reactor.
[65]
The initiator may be a radical initiator, and the initiator may include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, 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 azobisisobutyronitrile (butyric acid) methyl, of which, An inorganic peroxide is preferable and potassium persulfate is more preferable.
[66]
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, based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder. it is preferable When the above-mentioned range is satisfied, polymerization can be easily performed.
[67]
[68]
The emulsifier may be at least one selected from the group consisting of metal salts of alkyl sulfosuccinic acid, metal salts of alkyl sulfates, metal salts of rosin acid, and metal salts of dimer acids, among which metal salts of alkyl sulfates are preferable, and sodium dodecyl sulfate is more preferable. do.
[69]
The alkyl sulfosuccinic acid metal salt is composed of sodium dicyclohexylsulfosuccinate, sodium dihexylsulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, potassium di-2-ethylhexylsulfosuccinate and di-2-ethylhexyl sulfosuccinic acid. It may be at least one selected from the group.
[70]
The alkyl sulfate ester metal salt may be at least one selected from the group consisting of sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate and potassium octadecyl sulfate.
[71]
The metal rosin acid salt may be at least one selected from the group consisting of potassium rosin acid salt and sodium rosin acid salt.
[72]
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, of which 0.05 to 4.5 parts by weight, based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder. it is preferable When the above-mentioned range is satisfied, a seed having a desired average particle diameter, specifically, a seed latex can be easily prepared.
[73]
[74]
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 Late di(meth)acrylate, neopentylglycol 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, vinyltrimethoxysilane It may be one or more, of which ethylene glycol dimethacrylate is preferable.
[75]
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, based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder. it is preferable When the above-mentioned range is satisfied, some of the monomers introduced in step 1) may be cross-linked and polymerized to prepare a cross-linked product, and the remainder may be graft-polymerized to the cross-linked product to prepare seeds having a desired average particle diameter. let there be
[76]
[77]
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 preferable.
[78]
The grafting agent may be added in an amount of 0.001 to 3.0 parts by weight or 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 preparing the graft copolymer powder. It is most preferable to be When the above-mentioned range is satisfied, some of the monomers introduced in step 1) may be cross-linked and polymerized to prepare a cross-linked product, and the remainder may be graft-polymerized to the cross-linked product to prepare seeds having a desired average particle diameter. let there be
[79]
[80]
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 , may be at least one selected from the group consisting of KOH and NaOH, of which KOH is preferred.
[81]
The electrolyte may be added in an amount of 0.001 to 1 parts by weight or 0.01 to 0.8 parts by weight, of which 0.01 to 0.8 parts by weight, based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder. it is preferable When the above-mentioned range is satisfied, a seed having a small average particle diameter, specifically, a seed latex can be stably obtained.
[82]
[83]
The water may be distilled water or ion-exchanged water.
[84]
[85]
2) Step: Core Manufacturing Step
[86]
Then, in the presence of the seed, an alkyl (meth)acrylate-based monomer is added and polymerized to prepare a core.
[87]
[88]
The type of the alkyl (meth) acrylate-based monomer is the same as described above, and butyl acrylate is preferable.
[89]
[90]
The alkyl (meth) acrylate-based monomer may be added in an amount of 25 to 55% by weight or 30 to 50% by weight, of which 30 to 55% by weight, based on the total weight of the monomers added in the method for preparing the graft copolymer powder. It is preferably added in an amount of 50% by weight. When the above-mentioned range is satisfied, a graft copolymer having excellent balance of weather resistance, fluidity and chemical resistance can be prepared.
[91]
[92]
The alkyl (meth) acrylate-based monomer may be continuously added at a constant rate, and when added in the above-described method, runaway due to heat removal and excessive heat during polymerization can be easily suppressed.
[93]
[94]
The polymerization may be emulsion polymerization, and may be carried out at 55 to 85 °C or 60 to 80 °C, of ​​which it is preferably carried out at 60 to 80 °C. When the above-mentioned range is satisfied, emulsion polymerization can be stably performed.
[95]
[96]
The core may have a larger average particle diameter than the seed, and may have an average particle diameter of 40 to 120 nm or 50 to 80 nm, of which 50 to 80 nm is preferable. When the above-mentioned range is satisfied, it is possible to prepare a graft copolymer having excellent stability during polymerization and excellent weather resistance, colorability and impact strength.
[97]
[98]
In 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, and in order to easily suppress runaway due to heat removal and excessive heat during polymerization, C4 to C10 of the alkyl (meth) acrylate-based monomer may be continuously added at a constant rate.
[99]
[100]
The type of the initiator is as described above, and among these, an inorganic peroxide is preferable, and potassium persulfate is more preferable.
[101]
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, based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder. it is preferable When the above-mentioned range is satisfied, polymerization can be easily performed.
[102]
[103]
The type of the emulsifier is the same as described above, and among these, an alkyl sulfate metal salt is preferably added, and sodium dodecyl sulfate is more preferable.
[104]
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, of which 0.05 to 4.5 parts by weight, based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder. it is preferable When the above-mentioned range is satisfied, a core having a desired average particle diameter can be easily manufactured.
[105]
[106]
The type of the crosslinking agent is the same as described above, and among them, ethylene glycol dimethacrylate is preferable.
[107]
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, based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder. it is preferable If the above-mentioned range is satisfied, some of the monomers introduced in step 2) may be cross-linked and polymerized together with the seed to prepare a cross-linked product, and the remainder may be graft-polymerized to the cross-linked product to form a core having a desired average particle size. make it possible to manufacture
[108]
[109]
The type of the grafting agent is the same as described above, and among them, allyl methacrylate is preferable.
[110]
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, and 0.02 to 2.5 parts by weight of the grafting agent, based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder. It is most preferable to be If the above-mentioned range is satisfied, some of the monomers introduced in step 2) may be cross-linked and polymerized together with the seed to prepare a cross-linked product, and the remainder may be graft-polymerized to the cross-linked product to form a core having a desired average particle size. make it possible to manufacture
[111]
[112]
The water may be distilled water or ion-exchanged water.
[113]
[114]
3) Step: Latex Manufacturing Step
[115]
Then, in the presence of the core, an aromatic vinyl-based monomer and a vinyl cyan-based monomer are added and polymerized to prepare a graft copolymer latex.
[116]
[117]
The types of the aromatic vinyl-based monomer and the vinyl cyan-based monomer are the same as described above.
[118]
The sum of the aromatic vinyl-based monomer and the vinyl cyan-based monomer may be added in an amount of 40 to 60% by weight or 45 to 55% by weight, based on the total weight of the monomers added in the method for preparing the graft copolymer powder, It is preferably added in an amount of 45 to 55% by weight. If the above-mentioned range is satisfied, a graft copolymer having excellent balance of weather resistance, fluidity and chemical resistance may be prepared.
[119]
[120]
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. When the above-mentioned range is satisfied, there is an advantage in that the balance of fluidity and chemical resistance of the graft copolymer powder is excellent.
[121]
[122]
The aromatic vinyl-based monomer and the vinyl cyanide-based monomer may be continuously added at a constant rate, and when added in the above-described manner, runaway due to heat removal and excessive heat during polymerization can be easily suppressed.
[123]
[124]
The polymerization may be emulsion polymerization, and may be carried out at 50 to 85 °C or 60 to 80 °C, of ​​which it is preferably carried out at 60 to 80 °C. When the above-mentioned range is satisfied, emulsion polymerization can be stably performed.
[125]
[126]
The graft copolymer has a larger average particle diameter than the core, and may have an average particle diameter of 60 to 150 nm or 65 to 105 nm, of which 65 to 105 nm is preferable. When the above-mentioned range is satisfied, it is possible to prepare a graft copolymer having excellent stability during polymerization and excellent weather resistance and impact strength.
[127]
[128]
In step 3), at least one selected from the group consisting of an initiator, an activator, an emulsifier, a molecular weight regulator, and water may be further added, and may be continuously added at a constant rate together with an alkyl (meth)acrylate-based monomer. .
[129]
The type of the initiator is the same as described above, and organic peroxide is preferable, and cumene hydroperoxide is more preferable.
[130]
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, based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder. it is preferable When the above-mentioned range is satisfied, polymerization can be easily performed.
[131]
[132]
The activator may be at least one selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, anhydrous sodium pyrophosphate and sodium sulfate, of which sulfuric acid It is preferable that at least one member selected from the group consisting of ferrous iron, dextrose and sodium pyrophosphate.
[133]
The activator may be added in an amount of 0.01 to 1 parts by weight or 0.1 to 0.8 parts by weight, of which 0.1 to 0.8 parts by weight, based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder. It is preferable to be When the above content is satisfied, polymerization initiation can be promoted.
[134]
[135]
The type of the emulsifier is as described above, and among these, a metal rosin acid salt is preferable, and a potassium rosin acid salt is more preferable.
[136]
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 added in the method for preparing the graft copolymer powder. it is preferable When the above-mentioned range is satisfied, a graft copolymer having a desired average particle diameter can be easily prepared.
[137]
[138]
The molecular weight modifier is α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, mercaptans such as n-octyl mercaptan, carbon tetrachloride, halogenated hydrocarbons such as methylene chloride and methylene bromide, tetraethyl thiuram It may be a sulfur-containing compound such as disulfide, dipentamethylene thiuram disulfide, diisopropylxanthogen disulfide. Preferably, it may be t-dodecyl mercaptan.
[139]
The molecular weight regulator may be added in an amount of 0.001 to 1 parts by weight or 0.01 to 0.8 parts by weight, of which 0.01 to 0.8 parts by weight, based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder. It is preferable to be When the above-mentioned range is satisfied, a graft copolymer with improved mechanical properties and surface properties can be prepared by appropriately maintaining the weight average molecular weight of the shell.
[140]
[141]
The water may be distilled water or ion-exchanged water.
[142]
[143]
4) Step: Powder Preparation Step
[144]
Then, an alkyl methacrylate-based polymer is added to the graft copolymer latex and aggregated.
[145]
[146]
Since the alkyl methacrylate-based polymer is added in step 4), it does not affect the polymerization of the graft copolymer, and thereby, without deterioration of basic physical properties such as impact resistance of the graft copolymer powder, weather resistance, surface gloss and It is possible to significantly improve the appearance quality.
[147]
If the alkyl methacrylate-based polymer is added in steps 1) to 3), it may cause a decrease in basic physical properties of the graft copolymer. If the alkyl methacrylate-based polymer is added during compounding, not only the impact resistance is remarkably reduced, but also the effect of improving weather resistance and appearance quality is not significant compared to the case of adding in step 4).
[148]
[149]
On the other hand, the alkyl methacrylate-based polymer is preferably a hard polymer in order to implement excellent surface properties.
[150]
[151]
The alkyl methacrylate-based polymer has a glass transition temperature of 60 to 140 °C or 80 to 130 °C, of ​​which 80 to 130 °C is preferable. If the above-described range is satisfied, a graft copolymer having excellent weather resistance, processability and appearance quality may be prepared. If it is less than the above range, the appearance quality may be reduced, and if it exceeds the above range, the kneading property may be reduced during processing.
[152]
[153]
The alkyl methacrylate-based polymer may have a weight average molecular weight of 30,000 to 2,000,000 g/mol or 40,000 to 1,500,000 g/mol, of which 40,000 to 1,500,000 g/mol is preferable. When the above-mentioned range is satisfied, a graft copolymer having excellent weather resistance, impact resistance and appearance quality can be prepared.
[154]
[155]
The alkyl methacrylate-based polymer is poly(methyl methacrylate), poly(ethyl methacrylate), poly(propyl methacrylate), poly(butyl methacrylate), poly(ethylhexyl methacrylate) and poly(ethylhexyl methacrylate). (decyl methacrylate) may be at least one selected from the group consisting of, poly (methyl methacrylate) is preferred.
[156]
[157]
The alkyl methacrylate-based polymer is preferably added in an amount of 0.5 to 20 parts by weight or 1 to 15 parts by weight based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder, of which 1 to It is more preferable to put in 15 parts by weight. When the above-mentioned range is satisfied, the weather resistance and appearance quality can be improved while preventing the deterioration of the impact resistance.
[158]
[159]
On the other hand, the alkyl methacrylate-based polymer is preferably in the form of a latex in order to be easily mixed with the graft copolymer latex and to aggregate together.
[160]
[161]
The latex-type alkyl methacrylate-based polymer can be prepared by emulsion polymerization using an alkyl methacrylate-based monomer, that is, by adding the alkyl methacrylate-based monomer, initiator, emulsifier, and water, and then emulsion polymerization. have. At this time, the emulsion polymerization may be carried out at 60 to 80 ℃ or 65 to 75 ℃, of which it is preferably carried out at 65 to 75 ℃.
[162]
[163]
The alkyl methacrylate-based monomer is not particularly limited as long as it can prepare an alkyl methacrylate-based polymer having a glass transition temperature of 60 to 140° C. by emulsion polymerization.
[164]
The alkyl methacrylate-based monomer may be a C 1 to C 10 alkyl methacrylate-based monomer. The C 1 to C 10 alkyl methacrylate-based monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethylhexyl methacrylate, and decyl methacrylate and may be one or more of them, of which methyl methacrylate is preferable.
[165]
[166]
The type of the initiator is as described above, among which potassium persulfate is preferable.
[167]
The initiator may be added in an amount of 0.1 to 5 parts by weight or 0.5 to 3 parts by weight based on 100 parts by weight of the alkyl methacrylate-based monomer, of which 0.5 to 1.5 parts by weight is preferred. When the above-mentioned conditions are satisfied, an alkyl methacrylate-based polymer having a desired molecular weight can be prepared.
[168]
[169]
The type of the emulsifier is as described above, and sodium dodecyl benzene sulfate is preferable among them.
[170]
The emulsifier may be added in an amount of 0.1 to 10 parts by weight or 0.5 to 5 parts by weight based on 100 parts by weight of the alkyl methacrylate-based monomer, of which 0.5 to 5 parts by weight is preferable. When the above-mentioned conditions are satisfied, an alkyl methacrylate-based polymer having a desired molecular weight can be prepared.
[171]
[172]
During the emulsion polymerization, an electrolyte and a molecular weight regulator may be additionally added.
[173]
The type of the electrolyte is the same as described above, and Na 2 CO 3 is preferable.
[174]
The electrolyte may be added in an amount of 0.01 to 2 parts by weight or 0.1 to 1 parts by weight based on 100 parts by weight of the alkyl methacrylate-based monomer, of which 0.1 to 1 parts by weight is preferred. When the above conditions are satisfied, latex stability can be secured during polymerization.
[175]
[176]
The type of the molecular weight modifier is the same as described above, and n-octyl mercaptan is preferable among them.
[177]
The molecular weight modifier may be added in an amount of 10 parts by weight or less, or 0.5 to 3 parts by weight, based on 100 parts by weight of the alkyl methacrylate-based monomer, of which 0.5 to 3 parts by weight is preferred. When the above-mentioned conditions are satisfied, an alkyl methacrylate-based polymer having a desired molecular weight can be prepared.
[178]
[179]
In step 4), a stirring process may be added so that the graft copolymer and the alkyl methacrylate-based polymer can be mixed well.
[180]
[181]
In step 4), a coagulant may be added.
[182]
The coagulant may be at least one selected from the group consisting of H 2 SO 4 , MgSO 4 and CaCl 2 , and CaCl 2 is preferred.
[183]
The coagulant may be added in an amount of 0.1 to 5 parts by weight or 0.5 to 3 parts by weight, of which 0.5 to 3 parts by weight, based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder. desirable. When the above-mentioned range is satisfied, the graft copolymer latex and the alkyl methacrylate-based polymer may be easily aggregated.
[184]
[185]
Step 4) may be carried out at 75 to 95 °C or 80 to 90 °C, of ​​which it is preferably carried out at 80 to 90 °C. When the above-mentioned range is satisfied, the graft copolymer latex and the alkyl methacrylate-based polymer may be easily aggregated.
[186]
[187]
In the method for producing a graft copolymer powder according to an embodiment of the present invention, when step 4) is completed, aging, dehydration, washing, drying processes, etc. may be further performed to prepare a graft copolymer powder.
[188]
[189]
2. Thermoplastic resin composition
[190]
The thermoplastic resin composition according to another embodiment of the present invention is a graft copolymer powder prepared according to the above-described method for preparing the graft copolymer powder of the present invention (hereinafter referred to as 'first graft copolymer powder' for convenience). ); and a matrix copolymer including an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit.
[191]
[192]
The aromatic vinyl-based monomer unit included in the matrix copolymer may be a unit derived from at least one selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, of which α- Units derived from methyl styrene are preferred.
[193]
[194]
The vinyl cyan-based monomer unit included in the matrix copolymer may be a unit derived from at least one selected from acrylonitrile, methacrylonitrile, phenyl acrylonitrile, α-chloroacrylonitrile and ethacrylonitrile. and, among these, units derived from acrylonitrile are preferred.
[195]
[196]
The matrix copolymer may include an aromatic vinyl-based monomer unit and a vinyl cyan-based 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. When the above content is satisfied, it is possible to provide a thermoplastic resin composition excellent in heat resistance, fluidity and chemical resistance.
[197]
[198]
The thermoplastic resin composition may include the graft copolymer powder (the first graft copolymer powder) and the matrix copolymer in a weight ratio of 60:40 to 10:90 or 55:45 to 10:85, of which It is preferable to include it in a weight ratio of 55:45 to 10:85. When the above-mentioned range is satisfied, a thermoplastic resin composition having excellent weather resistance, heat resistance, fluidity, chemical resistance and appearance characteristics can be prepared.
[199]
[200]
In order to further improve the impact resistance of the thermoplastic resin composition, in addition to the graft copolymer powder prepared according to the method of the present invention, other graft copolymer powder (hereinafter referred to as 'second graft copolymer powder' for convenience) ) may be further included.
[201]
The second graft copolymer powder is prepared without the step of adding the alkyl methacrylate-based polymer, and has a different composition from the first graft copolymer powder including the alkyl methacrylate-based polymer.
[202]
Specifically, the second graft copolymer powder is a graft copolymer obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer to an acrylic rubber polymer.
[203]
The acrylic rubbery polymer may be a polymer of an alkyl (meth)acrylate-based monomer or a polymer of a mixture of an alkyl (meth)acrylate-based monomer and at least one of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.
[204]
The types of the alkyl (meth) acrylate-based monomer, the aromatic vinyl-based monomer and the vinyl cyan-based monomer used for preparing the second graft copolymer powder are the same as described above.
[205]
On the other hand, in the second graft copolymer, it is preferable that the average particle diameter of the acrylic rubber polymer forming the core is about 300 to 450 nm.
[206]
As the second graft copolymer powder as described above, a commercially available acrylic rubber graft copolymer may be used, or it may be prepared through steps 1) to 3) described above. At this time, the step 4), that is, the step of agglomeration with the alkyl methacrylate-based polymer is not performed.
[207]
[208]
The thermoplastic resin composition is based on the total weight of the thermoplastic resin composition, 30 to 50% by weight of the first graft copolymer; 1 to 10% by weight of the second graft copolymer; and 45 to 65% by weight of the matrix copolymer, preferably 35 to 45% by weight of the first graft copolymer; 2 to 7% by weight of the second graft copolymer; and 50 to 60% by weight of the matrix copolymer. When the above-described range is satisfied, it is possible to provide a thermoplastic resin composition having excellent weather resistance, impact resistance, and appearance quality.
[209]
[210]
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 use.
[211]
[212]
3. Thermoplastic resin molded products
[213]
A thermoplastic resin molded article according to another embodiment of the present invention is manufactured from the thermoplastic resin composition according to another embodiment of the present invention, and ΔE expressed by the following formula may be 3 or less, preferably 2.4 or less:
[214]

[215]
Wherein, L 'is L a value measured by the CIE LAB color coordinates after irradiating light to the SAE J1960 conditions for 6000 hours in the thermoplastic resin molded product, L O is the L value measured by the CIE LAB color coordinate system before irradiation with light,
[216]
a' is the a value measured by the CIE LAB color coordinate system after irradiating the thermoplastic resin molded article 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 light irradiation,
[217]
b' is the b value measured with the CIE LAB color coordinate system after irradiating the thermoplastic resin molded article 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.
[218]
[219]
When the above conditions are satisfied, a thermoplastic resin molded article having remarkably excellent weather resistance can be manufactured.
[220]
[221]
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.
[222]
[223]
< Preparation of poly(methyl methacrylate) >
[224]
Preparation Example 1
[225]
100 parts by weight of methyl methacrylate, 200 parts by weight of distilled water, 5 parts by weight of sodium dodecyl benzene sulfate as an emulsifier, 0.2 parts by weight of Na 2 CO 3 as an electrolyte, and 2.5 parts by weight of n-octyl mercaptan as a molecular weight regulator in a nitrogen-substituted reactor After batch input, the internal temperature of the reactor was raised to 70° C., 1.0 parts by weight of potassium persulfate was added to initiate the reaction. Poly(methyl methacrylate) latex having a weight average molecular weight of 40,000 g/mol and a glass transition temperature of 110 °C was prepared by carrying out polymerization for 60 minutes while maintaining the internal temperature of the reactor at 70 °C.
[226]
[227]
Preparation 2
[228]
Poly(methyl methacrylate) having a weight average molecular weight of 60,000 g/mol and a glass transition temperature of 110° C. in the same manner as in Preparation Example 1 except that 1.5 parts by weight of n-octyl mertaptan was added instead of 2.5 parts by weight Latex was prepared.
[229]
[230]
Preparation 3
[231]
Poly(methyl methacrylate) having a weight average molecular weight of 100,000 g/mol and a glass transition temperature of 110 °C in the same manner as in Preparation Example 1 except that 0.1 parts by weight of n-octyl mertaptan was added instead of 2.5 parts by weight Latex was prepared.
[232]
[233]
Preparation 4
[234]
A poly(methyl methacrylate) latex having a weight average molecular weight of 1,000,000 g/mol and a glass transition temperature of 110° C. was prepared in the same manner as in Preparation Example 1 except that n-octyl mertaptan was not added.
[235]
[236]
Example 1
[237]

[238]
6.5 parts by weight of butyl acrylate in a nitrogen-substituted reactor, 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, and 0.1 parts by weight of KOH as an electrolyte Parts and 60 parts by weight of distilled water were batched in, and the temperature was raised to 70° C., and then 0.04 parts by weight of potassium persulfate as an initiator was batched in to initiate the reaction. After polymerization for 1 hour, the polymerization was terminated to obtain seeds (average particle diameter: 34 nm).
[239]
[240]

[241]
In the reactor in 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 of 0.03 parts by weight of potassium persulfate as a part and an initiator was polymerized while continuously added at a constant rate for 2 hours at 70° C., and after further polymerization for 1 hour after completion of the addition, the mixture was terminated and the core (average particle diameter: 65 nm) was obtained.
[242]
[243]

[244]
In the reactor in which the core was obtained, 23 parts by weight of distilled water, 38 parts by weight of styrene, 12 parts by weight of acrylonitrile, 1.8 parts by weight of potassium rosinate as an emulsifier, 0.1 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, and cumene as an initiator A first mixture containing 0.05 parts by weight of hydroperoxide, and a second mixture containing 0.09 parts by weight of sodium pyrophosphate, 0.12 parts by weight of textrose, and 0.002 parts by weight of ferrous sulfate as an activator were each prepared at a constant rate at 75° C. for 2.5 hours. It was polymerized while continuously being added to the After the continuous input was completed, the reaction was further carried out at 75 ° C. for 1 hour, and the polymerization reaction was terminated by cooling to 60 ° C. to prepare a graft copolymer latex (average particle diameter: 85 nm).
[245]
[246]

[247]
5 parts by weight (based on solid content) of the poly(methyl methacrylate) latex of Preparation Example 1 was added to the graft copolymer latex and stirred to prepare a mixture, and then the mixture was mixed with an aqueous calcium chloride solution (distilled water 500 parts by weight, calcium chloride 1 parts by weight) at atmospheric pressure, 85 ° C. for 10 minutes to co-agglomerate, aged at 95 ° C. for 5 minutes, dehydrated and washed, and dried for 30 minutes with hot air at 90 ° C. Then, the graft copolymer powder A was prepared.
[248]
[249]

[250]
40 parts by weight of the graft copolymer powder A prepared as described above as the first graft copolymer powder, 4 parts by weight of SA927 of LG Chem as the second graft copolymer powder, and 100UH of LG Chem as the matrix copolymer A thermoplastic resin composition A was prepared by mixing 56 parts by weight.
[251]
[252]
Example 2
[253]
In the same manner as in Example 1, except that 3 parts by weight (based on solid content) of the poly(methyl methacrylate) latex of Preparation Example 2 was added instead of 5 parts by weight of the poly(methyl methacrylate) latex of Preparation Example 1 A graft copolymer powder B was prepared.
[254]
In addition, a thermoplastic resin composition B was prepared in the same manner as in Example 1, except that the graft copolymer powder B was used instead of the graft copolymer powder A.
[255]
[256]
Example 3
[257]
In the same manner as in Example 1, except that 5 parts by weight (based on solid content) of the poly(methyl methacrylate) latex of Preparation Example 2 was added instead of 5 parts by weight of the poly(methyl methacrylate) latex of Preparation Example 1 A graft copolymer powder C was prepared.
[258]
In addition, a thermoplastic resin composition C was prepared in the same manner as in Example 1, except that the graft copolymer powder C was used instead of the graft copolymer powder A.
[259]
[260]
Example 4
[261]
In the same manner as in Example 1, except that 10 parts by weight (based on solid content) of the poly(methyl methacrylate) latex of Preparation Example 2 was added instead of 5 parts by weight of the poly(methyl methacrylate) latex of Preparation Example 1 A graft copolymer powder D was prepared.
[262]
In addition, a thermoplastic resin composition D was prepared in the same manner as in Example 1, except that the graft copolymer powder D was used instead of the graft copolymer powder A.
[263]
[264]
Example 5
[265]
In the same manner as in Example 1, except that 5 parts by weight (based on solid content) of the poly(methyl methacrylate) latex of Preparation Example 3 was added instead of 5 parts by weight of the poly(methyl methacrylate) latex of Preparation Example 1 A graft copolymer powder E was prepared.
[266]
In addition, a thermoplastic resin composition E was prepared in the same manner as in Example 1, except that the graft copolymer powder E was used instead of the graft copolymer powder A.
[267]
[268]
Example 6
[269]
In the same manner as in Example 1, except that 5 parts by weight (based on solid content) of the poly(methyl methacrylate) latex of Preparation Example 4 was added instead of 5 parts by weight of the poly(methyl methacrylate) latex of Preparation Example 1 A graft copolymer powder F was prepared.
[270]
In addition, a thermoplastic resin composition F was prepared in the same manner as in Example 1, except that the graft copolymer powder F was used instead of the graft copolymer powder A.
[271]
[272]
Comparative Example 1
[273]

[274]
6.5 parts by weight of butyl acrylate in a nitrogen-substituted reactor, 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, and 0.1 parts by weight of KOH as an electrolyte Parts and 60 parts by weight of distilled water were batched in, and the temperature was raised to 70° C., and then 0.04 parts by weight of potassium persulfate as an initiator was batched in to initiate the reaction. After polymerization for 1 hour, the polymerization was terminated to obtain seeds (average particle diameter: 34 nm).
[275]
[276]

[277]
In the reactor in 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 of 0.03 parts by weight of potassium persulfate as a part and an initiator was polymerized while continuously added at a constant rate for 2 hours at 70° C., and after further polymerization for 1 hour after completion of the addition, the mixture was terminated and the core (average particle diameter: 65 nm) was obtained.
[278]
[279]

[280]
In the reactor in which the core was obtained, 23 parts by weight of distilled water, 38 parts by weight of styrene, 12 parts by weight of acrylonitrile, 1.8 parts by weight of potassium rosinate as an emulsifier, 0.1 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, and cumene as an initiator A first mixture containing 0.05 parts by weight of hydroperoxide, and a second mixture containing 0.09 parts by weight of sodium pyrophosphate, 0.12 parts by weight of textrose, and 0.002 parts by weight of ferrous sulfate as an activator were each prepared at a constant rate at 75° C. for 2.5 hours. It was polymerized while continuously being added to the After the continuous input was completed, the reaction was further carried out at 75 ° C. for 1 hour, and the polymerization reaction was terminated by cooling to 60 ° C. to prepare a graft copolymer latex (average particle diameter: 85 nm).
[281]
[282]

[283]
The graft copolymer latex prepared as described above was put into an aqueous calcium chloride solution (500 parts by weight of distilled water, 1 part by weight of calcium chloride) at atmospheric pressure, 85 ° C. for 10 minutes to coagulate, aged at 95 ° C. for 5 minutes, dehydrated and washed and after drying for 30 minutes with hot air at 90 ° C., a graft copolymer powder G was prepared.
[284]
[285]

[286]
40 parts by weight of the graft copolymer powder G prepared as above as the first graft copolymer powder, 4 parts by weight of SA927 of LG Chem as the second graft copolymer powder, and 100UH 56 of LG Chem as the matrix copolymer A thermoplastic resin composition G was prepared by mixing parts by weight.
[287]
[288]
Comparative Example 2
[289]
In the preparation of the graft copolymer latex, 35 parts by weight of styrene, 12 parts by weight of acrylonitrile, and 3 parts by weight of methyl methacrylate were added instead of 38 parts by weight of styrene and 12 parts by weight of acrylonitrile. A graft copolymer powder H was prepared by the method.
[290]
In addition, a thermoplastic resin composition H was prepared in the same manner as in Comparative Example 1, except that the graft copolymer powder H was used instead of the graft copolymer powder G.
[291]
[292]
Comparative Example 3
[293]
40 parts by weight of the graft copolymer powder G prepared in Comparative Example 1 as the first graft copolymer powder, 4 parts by weight of LG Chem's SA927 as the second graft copolymer powder, and 100UH of LG Chem as the matrix copolymer A thermoplastic resin composition I was prepared by mixing 53 parts by weight and 3 parts by weight of poly(methyl methacrylate) (trade name: BA611 grade, manufacturer: LGMMA).
[294]
[295]
Comparative Example 4
[296]
40 parts by weight of the graft copolymer powder G prepared in Comparative Example 1 as the first graft copolymer powder, 4 parts by weight of LG Chem's SA927 as the second graft copolymer powder, and 100UH of LG Chem as the matrix copolymer A thermoplastic resin composition J was prepared by mixing 53 parts by weight and 3 parts by weight of poly(methyl methacrylate (trade name: IH830, manufacturer: LGMMA)).
[297]
[298]
Meanwhile, in Table 1 below, the shell composition of the graft copolymers A to H and the specifications and contents of the alkyl methacrylate-based polymer used in the preparation are described.
[299]
[300]
[Table 1]
division Monomer added during shell production (parts by weight) poly(methyl methacrylate)
styrene Acrylonitrile methyl methacrylate Weight average molecular weight (g/mol) Content (parts by weight)
A 38 12 - 40,000 5
B 38 12 - 60,000 3
C 38 12 - 60,000 5
D 38 12 - 60,000 10
E 38 12 - 100,000 5
F 38 12 - 1,000,000 5
G 38 12 - - -
H 35 12 3 - -
[301]
[302]
Experimental Example 1
[303]
After uniformly mixing 1.5 parts by weight of lubricant, 1.0 parts by weight of antioxidant and 1.0 parts by weight of UV stabilizer to 100 parts by weight of the thermoplastic resin composition of Examples and Comparative Examples, a pellet was prepared using a 36 pie extrusion kneader at 220 ° C., and injection Thus, a specimen was prepared. The physical properties of the specimen were measured in the following way, and the results are shown in Table 2.
[304]
[305]
① Weather resistance (ΔE)- SAE with accelerated weather resistance test device (weather-o-meter, ATLAS Ci4000, xenon arc lamp, Quartz(inner)/S.Boro(outer) filter, irradiznce 0.55W/m 2 at 340nm) It was tested under J1960 condition for 6,000 hours, and ΔE below 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.
[306]

[307]
Wherein, L 'is L a value measured by the CIE LAB color coordinates after irradiating light to the SAE J1960 conditions for 6000 hours in the thermoplastic resin molded product, L O is the L value measured by the CIE LAB color coordinate system before irradiation with light,
[308]
a' is the a value measured by the CIE LAB color coordinate system after irradiating the thermoplastic resin molded article 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 light irradiation,
[309]
b' is the b value measured with the CIE LAB color coordinate system after irradiating the thermoplastic resin molded article 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.
[310]
② Izod impact strength (kg·cm/cm): The thickness of the specimen was 1/4 In, and it was measured according to ASTM 256.
[311]
③ Ejection gloss (45 °): Measured according to ASTM D528.
[312]
[313]
Experimental Example 2
[314]
The thermoplastic resin compositions of Examples and Comparative Examples were co-extruded with PVC to confirm the surface properties.
[315]
Specifically, the PVC layer was melt-kneaded at 170° C. through a 130 pi L/D 20 twin-screw extrusion kneader. The thermoplastic resin composition was melt-kneaded at 180° C. through a 60-pi L/D 20 single-screw extrusion kneader. During co-extrusion, PVC and the thermoplastic resin composition were supplied to a co-extrusion die in a weight ratio of 9:1, and then passed through a water-cooled calibrator to prepare a final co-extrusion specimen. The physical properties of the specimen were measured in the following way, and the results are shown in Table 2.
[316]
[317]
④ Co-extrusion gloss: Measured by the method described in '③ Injection gloss."
[318]
[Table 2]
division Thermoplastic resin composition weather resistance impact strength ejection gloss co-extrusion gloss
Example 1 A 1.4 14.1 100 97
Example 2 B 2.1 15.5 92 87
Example 3 C 1.6 14.6 97 93
Example 4 D 1.4 13.8 99 95
Example 5 E 1.7 14.9 93 89
Example 6 F 1.9 15.7 89 85
Comparative Example 1 G 6.0 15.9 73 65
Comparative Example 2 H 2.8 9.8 75 64
Comparative Example 3 I 3.5 10.8 82 78
Comparative Example 4 J 3.8 11.5 78 75
[319]
[320]
Referring to Table 2, in Examples 1, 3, 5 and 6, in which the poly(methyl methacrylate) latex was added in the same amount, the weight average molecular weight of the poly(methyl methacrylate) latex was It was confirmed that the lower the temperature, the better the weather resistance, the injection gloss, and the coextrusion gloss, and the higher the weight average molecular weight of poly(methyl methacrylate), the better the impact strength.
[321]
In the case of Examples 2 to 4, in which poly(methyl methacrylate) latex having the same weight average molecular weight was added, the weather resistance, injection gloss, and coextrusion gloss were improved as the amount increased, and the impact strength was excellent as the amount decreased. could confirm that
[322]
And, Examples 1 to 6, compared to Comparative Example 1 in which poly(methyl methacrylate) latex was not added, it was confirmed that all of the weather resistance, injection gloss and coextrusion gloss were excellent.
[323]
In Examples 1 to 6, the weather resistance, impact strength, injection gloss, and coextrusion gloss were improved compared to Comparative Example 2 in which methyl methacrylate was added during the manufacture of the shell without adding poly(methyl methacrylate) latex. All were confirmed to be excellent.
[324]
On the other hand, it was confirmed that Comparative Examples 3 and 4, in which poly(methyl methacrylate) was added during the compounding process, were all lowered in weather resistance, impact strength, injection gloss, and coextrusion gloss compared to Examples 1 to 6.
[325]
Claims
[Claim 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 to a reactor and polymerization; preparing a core by adding and polymerizing an alkyl (meth)acrylate-based monomer in the presence of the seed; and preparing a graft copolymer latex by adding an aromatic vinyl-based monomer and a vinyl cyanide-based monomer and polymerization in the presence of the core; A method for producing a graft copolymer powder comprising the step of adding an alkyl methacrylate-based polymer to the graft copolymer latex and agglomeration.
[Claim 2]
The method according to claim 1, wherein the alkyl methacrylate-based polymer is added in a latex form.
[Claim 3]
The method according to claim 2, wherein the alkyl methacrylate-based polymer in the form of latex is prepared by emulsion polymerization.
[Claim 4]
The method according to claim 1, wherein the alkyl methacrylate-based polymer has a weight average molecular weight of 30,000 to 2,000,000 g/mol.
[Claim 5]
The method of claim 1, wherein the alkyl methacrylate-based polymer has a weight average molecular weight of 40,000 to 1,500,000 g/mol.
[Claim 6]
The method of claim 1, wherein the alkyl methacrylate-based polymer has a glass transition temperature of 60 to 140 °C.
[Claim 7]
The method according to claim 1, wherein the alkyl methacrylate-based polymer is poly(methyl methacrylate), poly(ethyl methacrylate), poly(propyl methacrylate), poly(butyl methacrylate), poly(ethylhexyl methacrylate) acrylate) and poly (decyl methacrylate) a method for producing a graft copolymer powder of at least one selected from the group consisting of.
[Claim 8]
The method according to claim 1, wherein 0.5 to 20 parts by weight of the alkyl methacrylate-based polymer is added in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder. Way.
[Claim 9]
The method according to claim 1, wherein 1 to 15 parts by weight of the alkyl methacrylate-based polymer is added in an amount of 1 to 15 parts by weight based on 100 parts by weight of the total of the monomers added in the method for preparing the graft copolymer powder. Way.
[Claim 10]
The method of claim 1, wherein the core has an average particle diameter of 40 to 120 nm.
[Claim 11]
A first graft copolymer powder prepared by the method according to any one of claims 1 to 10; and a matrix copolymer including an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit.
[Claim 12]
The thermoplastic resin composition of claim 11 , wherein the thermoplastic resin composition further comprises a second graft copolymer powder obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer to an acrylic rubber polymer.
[Claim 13]
A thermoplastic resin molded article prepared from the thermoplastic resin composition according to claim 11 and having ΔE of 3 or less, expressed by the following formula: where L' is the CIE LAB color coordinate system after irradiating the thermoplastic resin molded article with light under SAE J1960 conditions for 6,000 hours is the L value measured with , L O is the L value measured with the CIE LAB color coordinate system before light irradiation, and a' is the CIE LAB color coordinate system after irradiating the thermoplastic resin molded article with light under the SAE J1960 condition for 6,000 hours. value, a O is the a value measured with the CIE LAB color coordinate system before light irradiation, b' is the b value measured with the CIE LAB color coordinate system after irradiating the thermoplastic resin molded article with light under the SAE J1960 condition for 6,000 hours, b O is the b value measured in the CIE LAB color coordinate system before light irradiation.