The present invention relates to a thermoplastic resin composition, a method for preparing the same, and a molded product manufactured therefrom, and more particularly, to a thermoplastic resin composition having excellent weather resistance and heat resistance, and greatly improved processability and scratch resistance while minimizing deterioration in colorability and heat resistance. , It relates to a manufacturing method thereof and a molded article manufactured therefrom.
background art
[4]
ABS-based resins, represented by Acrylonitrile-Butadiene-Styrene (hereinafter referred to as 'ABS-based') resins, have strength, chemical resistance, processability, mechanical strength, and beautiful appearance, making them suitable for automotive applications and electrical applications. / It is used in various ways such as electronic products and office equipment. However, since the ABS-based resin uses a butadiene rubber polymer, it has poor weather resistance and is not suitable as an outdoor material.
[5]
In order to solve this problem, in order to obtain a thermoplastic resin with excellent physical properties and excellent weather resistance and aging resistance, a crosslinked alkyl (meth)acrylate rubber in which ethylenically unsaturated polymers that cause aging due to ultraviolet rays do not exist in the graft copolymer An ASA-based resin represented by an acrylonitrile-styrene-acrylate (hereinafter referred to as 'ASA-based') resin using a polymer has been developed. These ASA-based resins have excellent weather resistance and aging resistance, and are used in various fields such as automobiles, ships, leisure goods, building materials, and horticultural purposes.
[6]
Among them, a technology including an alkyl-substituted styrene-based monomer has been developed to provide a heat-resistant ASA-based resin. However, as the glass transition temperature is increased due to the inclusion of alkyl-substituted styrene-based monomers, weather resistance, heat resistance, and scratch resistance are improved, the refractive index is also significantly increased, resulting in a decrease in coloration, which is disadvantageous in implementing Color L.
[7]
In addition, the technology including these alkyl-substituted styrenic monomers is produced by bulk polymerization. In this case, the product yield is low due to high viscosity, and the copolymer is decomposed, resulting in increased production of residual oligomers and rather reduced heat resistance. .
[8]
Therefore, research into a thermoplastic resin composition having a low residual oligomer content and a method for preparing the same while maintaining weatherability and heat resistance while improving colorability, processability, and scratch resistance is being continued.
[9]
[Prior art literature]
[10]
[Patent Literature]
[11]
Korean Registered Patent No. 2035036
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[12]
In order to solve the problems of the prior art as described above, an object of the present invention is to provide a thermoplastic resin composition having excellent weatherability and heat resistance as well as excellent colorability, processability and scratch resistance, and having a small content of residual oligomers.
[13]
In addition, an object of the present invention is to provide a method for producing the above thermoplastic resin composition.
[14]
Another object of the present invention is to provide a molded article manufactured from the above thermoplastic resin composition.
[15]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[16]
In order to achieve the above object, the present invention
[17]
Styrene-based copolymers comprising (meth)acrylate-based monomers, aromatic vinyl-based monomers and maleimide-based monomers;
[18]
a first graft copolymer comprising an acrylic rubber polymer, an aromatic vinyl monomer, and a vinyl cyan monomer; and
[19]
A second graft copolymer comprising an acrylic rubber polymer, an aromatic vinyl monomer, and a vinyl cyan monomer,
[20]
The styrenic copolymer has a residual oligomer content of 0.37% by weight or less,
[21]
The first graft copolymer and the second graft copolymer provide a thermoplastic resin composition in which the average particle diameters of the acrylic rubber polymers are different from each other.
[22]
[23]
In addition, the present invention
[24]
100 parts by weight of a monomer mixture including a (meth)acrylate monomer, an aromatic vinyl monomer, and a maleimide monomer, 100 to 200 parts by weight of a reaction solvent, 0.01 to 1 part by weight of an initiator, 1 to 5 parts by weight of a dispersant, and a molecular weight regulator Suspension polymerization of a polymerization solution mixed with 0.01 to 1 part by weight;
[25]
adjusting the pH of the polymerization slurry produced by the suspension polymerization to 1 to 4 and preparing a styrenic copolymer in the form of beads;
[26]
Mixing 65 to 85% by weight of the styrenic copolymer with 10 to 30% by weight of the first graft copolymer comprising an acrylic rubber polymer and 1 to 15% by weight of the second graft copolymer comprising an acrylic rubber polymer and kneading and extruding under conditions of 200 to 270 ° C,
[27]
The styrenic copolymer has a residual oligomer content of 0.37% by weight or less,
[28]
The first graft copolymer and the second graft copolymer provide a method for preparing a thermoplastic resin composition in which the average particle diameters of the acrylic rubber polymers are different from each other.
[29]
[30]
In addition, the present invention provides a molded article made of the thermoplastic resin composition described above.
Effects of the Invention
[31]
According to the present invention, there is an effect of providing a thermoplastic resin composition having excellent weather resistance and heat resistance, excellent colorability, processability and scratch resistance, and a low residual oligomer content, a manufacturing method thereof, and a molded product including the same.
[32]
Therefore, the thermoplastic resin composition and molded article according to the present invention can be widely applied to various industrial fields that require them.
Mode for Carrying Out the Invention
[33]
Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
[34]
Terms or words used in this specification and claims should not be construed as being limited to their usual or dictionary meanings, and given that the inventors may appropriately define the concept of terms in order to best describe the invention. Therefore, it should be interpreted as meaning and concept consistent with the technical spirit of the present invention.
[35]
In the present description, the meaning of "comprising" may be defined as "containing and polymerizing", "including and polymerizing" or "including as a derived unit" unless otherwise defined.
[36]
In the present substrate, heat resistance can be measured in various ways known in the art, and unless otherwise specified, the glass transition temperature (Tg) measured using a differential calorimetry analyzer (manufacturer: Ta Instruments, product name: DISCOVERY DSC25) refers to
[37]
If the corresponding glass transition temperature (Tg) is 116 ℃ or more, it can be determined as a heat-resistant copolymer.
[38]
In the present description, the average particle diameter can be measured using a dynamic light scattering method, and in detail, measured in Gaussian mode using a particle size distribution analyzer (Nicomp 380) in a latex state
More about this source textSource text required for additional translation information
Send feedback
Side panels
History
Saved
Contribute
5,000 character limit. Use the arrows to translate more.It can be determined, and it can mean the arithmetic mean particle diameter in the particle size distribution measured by the dynamic light scattering method, specifically, the average particle diameter of intensity distribution.
[39]
As a specific measurement example, the sample is prepared by diluting 0.1 g of latex (TSC 35-50wt%) 1,000-5,000 times with deionized water or distilled water, that is, appropriately diluted so as not to deviate greatly from the Intensity Setpoint 300 kHz, put in a glass tube, and measure The method is auto-dilution and measurement with a flow cell, the measurement mode is dynamic light scattering method/Intensity 300KHz/Intensity -weight Gaussian Analysis, and the setting values are temperature 23 ℃, measurement wavelength 632.8 nm, channel width It can be measured as 10 μsec.
[40]
In this description, the weight average molecular weight can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent. It is a value obtained by applying the weight average molecular weight (Mw) in terms of polystyrene by permeation chromatography (GPC: gel permeation chromatography, PL GPC220, Agilent Technologies).
[41]
Specifically, the polymer to be measured was dissolved in tetrahydrofuran to a concentration of 1%, and 10 μl was injected into GPC, flowing at a flow rate of 0.3 mL/min, and 30 μl for a sample concentration of 2.0 mg/mL (100 μl injection). The assay can be performed at °C. Here, the column may be connected in series with two PLmixed B from Waters, and the detector may be measured at 40 ° C using an RI detector (2414, manufactured by Agilent Waters) and then processed using ChemStation.
[42]
In the present description, the composition ratio of the (co)polymer may mean the amount of units constituting the (co)polymer, or the amount of units introduced during polymerization of the (co)polymer.
[43]
In this description, "content" means ideal weight unless otherwise defined.
[44]
[45]
The present inventors formed by polymerizing a (meth)acrylate monomer mixture including a (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a maleimide-based monomer together with two types of graft copolymers having different average particle diameters of rubber. When a styrenic copolymer having a residual oligomer content of less than a specific value is mixed within a predetermined content range, it is confirmed that heat resistance, weather resistance, colorability, processability and scratch resistance are all improved, and based on this, research is continued to complete the present invention. I came to do it.
[46]
[47]
A thermoplastic resin composition according to an embodiment of the present invention includes a styrenic copolymer comprising a (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a maleimide-based monomer; a first graft copolymer comprising an acrylic rubber polymer, an aromatic vinyl monomer, and a vinyl cyan monomer; and a second graft copolymer comprising an acrylic rubber polymer, an aromatic vinyl monomer, and a vinyl cyan monomer, wherein the styrenic copolymer has a residual oligomer content of 0.37% by weight or less, and the first graft copolymer The polymer and the second graft copolymer are characterized in that the average particle diameters of the acrylic rubbery polymers are different from each other, and in this case, weather resistance and heat resistance are maintained while coloring, processability, and scratch resistance are improved.
[48]
[49]
Hereinafter, the thermoplastic resin composition of the present invention will be described in detail for each component.
[50]
[51]

[52]
Styrenic Copolymer
[53]
The styrenic copolymer may be a heat-resistant copolymer formed by polymerizing a monomer mixture including a (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a maleimide-based monomer.
[54]
At this time, each monomer becomes a unit of the heat-resistant copolymer.
[55]
The styrenic copolymer can improve colorability, heat resistance and scratch resistance of the thermoplastic resin composition. In addition, since the styrene-based copolymer includes a (meth)acrylate-based monomer, weather resistance of the thermoplastic resin composition may be improved.
[56]
The monomer mixture, that is, the styrene copolymer may include 62 to 88% by weight of the (meth)acrylate-based monomer, 5 to 26% by weight of the aromatic vinyl monomer, and 1 to 10% by weight of the maleimide-based monomer, and the ( It is preferable to include 64 to 86% by weight of a meth)acrylate-based monomer, 10 to 26% by weight of the aromatic vinyl monomer, and 2 to 10% by weight of a maleimide-based monomer. When the above range is satisfied, a styrenic copolymer having a low refractive index and a high glass transition temperature can be prepared.
[57]
In addition, when such a styrenic copolymer is applied to a thermoplastic resin composition, not only colorability and heat resistance of the thermoplastic resin composition may be improved, but also scratch resistance and weather resistance may be improved.
[58]
At this time, since a styrenic copolymer having a high refractive index is prepared when a small amount of the (meth)acrylate-based monomer is included, when the styrenic copolymer is applied to the thermoplastic resin composition, the colorability of the thermoplastic resin composition may be reduced, When an excessive amount is included, a relatively small amount of aromatic vinyl monomer and maleimide monomer are included, so that a styrenic copolymer having a low glass transition temperature can be prepared, and when the styrenic copolymer is applied to a thermoplastic resin composition, the thermoplastic resin composition Heat resistance and scratch resistance may be deteriorated.
[59]
In addition, when a small amount of the maleimide-based monomer is included, a styrenic copolymer having a high glass transition temperature cannot be prepared, and when the styrenic copolymer is applied to a thermoplastic resin composition, the heat resistance of the thermoplastic resin composition may be reduced. , When an excessive amount is included, since a relatively small amount of (meth)acrylate-based monomer and aromatic vinyl-based monomer are included, a styrenic copolymer having a high refractive index can be prepared, and when applying such a styrenic copolymer to a thermoplastic resin composition , the colorability and scratch resistance of the thermoplastic resin composition may decrease.
[60]
The (meth)acrylate-based monomer included in the styrenic copolymer is, for example, selected from the group consisting of (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate and propyl (meth)acrylate It may be one or more, of which methyl methacrylate is preferred. Here, (meth)acrylate may include both acrylate and methacrylate.
[61]
The aromatic vinyl monomer included as a unit in the styrenic copolymer may be, for example, at least one selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and ρ-methyl styrene, of which styrene is preferred.
[62]
On the other hand, in preparing the styrenic copolymer, the production of the copolymer using an alkyl styrenic monomer requires a slow polymerization rate and a long reaction time, and the resulting copolymer has a low weight average molecular weight and thermal decomposition can easily occur . In addition, since a copolymer having a high glass transition temperature and a remarkably high refractive index can be prepared, it is preferable not to include an alkyl styrene-based monomer in the present invention.
[63]
As the maleimide-based monomer included in the styrenic copolymer, it is preferable to use, for example, N-phenylmaleimide, which has excellent transparency, colorability, heat resistance, and reactivity compared to isopropyl maleimide.
[64]
The styrenic copolymer may include the aromatic vinyl monomer and the (meth)acrylate monomer in a weight ratio of 1:2.25 to 1:3.5 or 1:4.8 to 1:10, of which 1:2.46 to It is preferably included in a weight ratio of 1:3.5 or 1:4.8 to 1:8.6. When the above range is satisfied, a styrenic copolymer having a high glass transition can be prepared, and when the styrenic copolymer is applied to a thermoplastic resin composition, heat resistance of the thermoplastic resin composition can be further improved.
[65]
The styrenic copolymer may be a low refractive index heat-resistant copolymer having a refractive index of, for example, 1.518 or less, preferably 1.499 to 1.517, and more preferably 1.499 to 1.515.
[66]
In the present description, the refractive index can be measured at 25 °C using a known method, that is, an Abbe Refractometer in accordance with ASTM D542.
[67]
In addition, the refractive index of the styrenic copolymer may be calculated according to Equation 1 below using the refractive index and content of each component (or polymer) constituting the styrenic copolymer:
[68]
[Equation 1]
[69]

[70]
In Equation 1, Wti is the weight fraction (%) of each component (or polymer) in the styrenic copolymer, and RIi is the refractive index of the polymer forming the styrenic copolymer.
[71]
As the glass transition temperature of the styrenic copolymer is improved, a thermoplastic resin composition having excellent scratch resistance may be provided.
[72]
The styrenic copolymer may have a glass transition temperature of, for example, 120 °C or higher, preferably 120 to 130 °C, more preferably 120.1 to 124.3 °C.
[73]
In the present substrate, the glass transition temperature can be measured using a differential calorimetry (manufacturer: Ta Instruments, product name: DSC Q20).
[74]
The styrenic copolymer may have a weight average molecular weight of 90,000 to 139,000 g/mol, preferably 96,000 to 133,000 g/mol.
[75]
In this description, the weight average molecular weight is a relative value for a standard PS (Standard Polystyrene) sample using tetrahydrofuran (THF) as a solvent at a temperature of 40 ° C through gel chromatography (GPC) filled with porous silica as a column packing material. to measure
[76]
The styrenic copolymer has a residual oligomer content of 0.
More about this source textSource text required for additional translation information
Send feedback
Side panels
History
Saved
Contribute
5,000 character limit. Use the arrows to translate more.37% by weight or less, preferably 0.32 to 0.36% by weight.
[77]
In this description, the residual oligomer content can be measured by a conventional method in the related field. For example, 1 g of the sample is dissolved in 10 mL of chloroform, then the polymer is precipitated with methanol, and the supernatant of the sample is taken and a 0.2 μm disk syringe filter is used. After filtering, it can be analyzed using ALS-GC/FID.
[78]
As the residual oligomer content in the styrenic copolymer is lower, a copolymer having higher purity can be prepared.
[79]
In the present invention, the styrenic copolymer can achieve a balance between colorability and heat resistance when all of the conditions of refractive index, glass transition temperature, weight average molecular weight and residual oligomer content are satisfied, and when such a copolymer is applied to a thermoplastic resin composition, A thermoplastic resin composition excellent in both colorability and heat deflection temperature can be prepared.
[80]
In addition, as the heat distortion temperature is improved, a thermoplastic resin composition having excellent scratch resistance can be prepared.
[81]
The styrenic copolymer is preferably a methyl methacrylate-styrene-N-phenylmaleimide copolymer.
[82]
The styrenic copolymer may be prepared by suspension polymerization of the above-described monomer mixture as described below. For reference, when prepared by solution polymerization, the yield of the product is low due to high viscosity and the residual oligomer content is high, so heat resistance may be reduced.
[83]
The styrenic copolymer may be, for example, 65 to 85% by weight, preferably 70 to 80% by weight, more preferably 72 to 77% by weight, based on the total weight of the thermoplastic resin composition, within this range heat resistance While being maintained, there is an effect of improving weather resistance, colorability, workability and scratch resistance.
[84]
[85]
First Graft Copolymer
[86]
The first graft copolymer may be obtained by graft polymerization of an acrylic rubber, an aromatic vinyl monomer, and a vinyl cyan monomer, and for example, a graft copolymer including an acrylic rubber polymer having an average particle diameter of 50 to 200 nm In this case, the mechanical properties such as impact strength and tensile strength are excellent, while heat resistance, colorability and weather resistance are excellent.
[87]
The acrylic rubber included in the first graft copolymer may have, for example, an average particle diameter of 50 to 200 nm, preferably 70 to 150 nm, and more preferably 100 to 130 nm. If the above range is satisfied, mechanical properties, heat resistance and weather resistance are all excellent. If the range is less than the above range, mechanical properties such as impact strength and tensile strength may deteriorate. If the above range is exceeded, thermal stability is deteriorated. Problems can arise.
[88]
The acrylic rubber included in the first graft copolymer is, for example, 20 to 60% by weight, preferably 30 to 55% by weight, more preferably 40 to 50% by weight based on the total weight of the first graft copolymer It can be, and within this range, there is an effect of excellent weather resistance, impact strength and scratch resistance.
[89]
In the present description, the average particle diameter is measured using an intensity gaussian distribution (Nicomp 380) by a dynamic laser light scattering method.
[90]
For example, the acrylic rubber may be prepared by emulsion polymerization of (meth)acrylate monomers, and as a specific example, emulsion polymerization by mixing a (meth)acrylate monomer, an emulsifier, an initiator, a graft agent, a crosslinking agent, an electrolyte, and water, In this case, the grafting efficiency is excellent, and there is an effect of excellent physical properties such as impact resistance.
[91]
The (meth)acrylate-based monomer may be, for example, at least one selected from the group consisting of alkyl (meth)acrylates having 2 to 8 carbon atoms, preferably an alkyl acrylate having 4 to 8 carbon atoms in an alkyl group, More preferably, it may be butyl acrylate or ethylhexyl acrylate.
[92]
Emulsion polymerization may be graft emulsion polymerization, and may be carried out at, for example, 50 to 85 °C, preferably 60 to 80 °C.
[93]
The emulsion polymerization may be carried out in the presence of an initiator and an emulsifier.
[94]
The initiator may preferably be a radical initiator, and specific examples include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium persulfate, 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 oxide, organic peroxides including 3,5,5-trimethylhexanol peroxide, t-butylperoxy isobutyrate; It may be at least one selected from among azo compounds including azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonylnitrile, and azobisisobutyrate (butyrate)methyl.
[95]
An activator may be further added to promote an initiation reaction together with the initiator.
[96]
The activator may be, for example, at least one selected from sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, sodium pyrophosphate anhydrous, and sodium sulfate.
[97]
The initiator is, for example, 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, more preferably 0.02 to 0.1 part by weight, based on 100 parts by weight of the sum of rubber and monomers constituting the first graft copolymer. can be put in Within this range, emulsion polymerization can be easily performed and the residual amount of the initiator in the first graft copolymer can be minimized by several tens of ppm.
[98]
The emulsifier is, for example, a potassium compound of alkylbenzenesulfonate, a sodium compound of alkylbenzenesulfonate, a potassium compound of alkylcarboxylate, a sodium compound of alkylcarboxylate, a potassium compound of oleic acid, a sodium compound of oleic acid, a potassium compound of alkylsulfate , sodium compound of alkyl sulfate, potassium compound of alkyl dicarboxylate, sodium compound of alkyl dicarboxylate, potassium compound of alkyl ether sulfonate, sodium compound of alkyl ether sulfonate, and allyloxynonylphenoxypropan-2-yloxy It may be at least one selected from among ammonium compounds of methyl sulfonate, of which sodium dodecylbenzenesulfonate is preferred.
[99]
Commercially available materials may be used as the emulsifier, and in this case, at least one selected from SE10N, BC-10, BC-20, HS10, Hitenol KH10 and PD-104 may be used.
[100]
The emulsifier is, for example, 0.15 to 2.0 parts by weight, preferably 0.3 to 1.5 parts by weight, more preferably 0.5 to 1.2 parts by weight, based on 100 parts by weight of the sum of rubber and monomers constituting the first graft copolymer. Within the above range, emulsion polymerization is easily performed, and the residual amount of the initiator in the first graft copolymer can be minimized by several tens of ppm.
[101]
During the emulsion polymerization, a molecular weight modifier may be further added. The molecular weight modifier may be, for example, at least one selected from t-dodecyl mercaptan, N-dodecyl mercaptan, and alphamethylstyrene dimer, among which t-dodecyl mercaptan is preferred.
[102]
The molecular weight modifier is, for example, 0.1 to 1 part by weight, preferably 0.2 to 0.8 parts by weight, more preferably 0.4 to 0.6 parts by weight, based on 100 parts by weight of the sum of rubber and monomers constituting the first graft copolymer. can be put into wealth.
[103]
The emulsion polymerization may be started after a batch of monomers are added to the reactor, or a portion of the monomers, etc. may be added to the reactor before the start of the emulsion polymerization, and the rest may be continuously added after the start, or the emulsion polymerization may be performed while the monomers are continuously added for a certain period of time. can
[104]
The first graft copolymer obtained in this way is in the form of latex and can be recovered in the form of dry powder through a process of aggregation, dehydration and drying.
[105]
As the coagulant used for the coagulation, salts such as calcium chloride, magnesium sulfate, and aluminum sulfate, or acidic substances and mixtures such as sulfuric acid, nitric acid, and hydrochloric acid may be used.
[106]
The aromatic vinyl monomer included in the first graft copolymer may be, for example, 10 to 50% by weight, preferably 20 to 45% by weight, based on the total weight of the first graft copolymer. It has excellent mechanical properties such as strength and impact strength and processability.
[107]
The aromatic vinyl monomer is, for example, styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-bromo styrene, ρ -Chloro styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyl toluene, vinyl xylene, fluoro styrene and vinyl naphthalene may be at least one selected from the group consisting of, in this case It has excellent processability due to appropriate fluidity and excellent mechanical properties such as tensile strength and impact strength.
[108]
The vinylcyanic monomer included in the first graft copolymer is, for example, 5 to 30% by weight, preferably 5 to 25% by weight, more preferably 10 to 20% by weight based on the total weight of the first graft copolymer %, and within this range, there are excellent effects such as impact resistance and workability.
[109]
The vinyl cyan-based monomer may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof, and in this case, impact resistance and processability are excellent.
[110]
The first graft copolymer may be 10 to 30% by weight, preferably 15 to 25% by weight, more preferably 20 to 25% by weight, based on the total weight of the thermoplastic resin composition, within this range the impact strength, It has excellent mechanical properties such as tensile strength and excellent heat resistance, weather resistance, scratch resistance and colorability, and when it is less than the above range, impact resistance
More about this source textSource text required for additional translation information
Send feedback
Side panels
History
Saved
Contribute
5,000 character limit. Use the arrows to translate more., t-butylcumyl peroxide, di-t-butyl peroxide, and di-t-amine peroxide.
[147]
In this case, there is an effect of facilitating the polymerization reaction to maintain excellent mechanical properties, weather resistance, heat resistance and scratch resistance.
[148]
The initiator may be, for example, 0.01 to 1 part by weight, preferably 0.01 to 0.5 part by weight, and more preferably 0.01 to 0.2 part by weight, based on 100 parts by weight of the monomer mixture, and within this range, the polymerization reaction is facilitated and mechanical It has the effect of maintaining excellent physical properties, weather resistance, heat resistance and scratch resistance.
[149]
The dispersant in the step of preparing the styrenic copolymer may be, for example, a phosphate salt, preferably a metal phosphate salt, and more preferably tricalcium phosphate. In this case, it is possible to prepare a copolymer having a high polymerization conversion rate by improving polymerization stability.
[150]
The dispersant may be, for example, 1 to 5 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the monomer mixture, and within this range, the polymerization reaction can be facilitated and uniform particles can be produced, which is advantageous for processing. It works.
[151]
Suspension polymerization in the step of preparing the styrenic copolymer may be carried out, for example, by maintaining the polymerization solution at 80 to 130 ° C. under a stirring speed of 400 to 600 rpm for 3 to 10 hours, in which case the copolymer It can improve the polymerization conversion rate and has the effect of improving mechanical properties, weather resistance, heat resistance, scratch resistance and colorability by reducing residual monomers and residual oligomers in the particles.
[152]
As a specific example, polymerization at 80 to 100 ° C. for 3 to 6 hours and then polymerization at 100 to 130 ° C. for 1 to 3 hours was most preferable in terms of conversion rate, colorability and residual oligomer content of the styrenic copolymer. When polymerization is performed for a long time exceeding the above range, the difference in conversion rate is insignificant and coloring and residual oligomer content may increase. When polymerization is performed for a short time below the above range, not only the conversion rate decreases, but also coloration and residual monomer content may increase.
[153]
Then, the pH of the polymerization slurry produced by the suspension polymerization may be adjusted to 1 to 4, and a styrenic copolymer in the form of beads may be prepared. When the above pH range is satisfied, the dispersant included in the reaction can be effectively removed and the product is highly purified.
[154]
In the present disclosure, pH may be measured by a method commonly used in the related field, and may be measured using, for example, a pH meter.
[155]
At this time, the pH of the polymerization slurry can be adjusted using an acidic solution, for example, formic acid or hydrochloric acid can be used.
[156]
The kneading and extrusion may be performed, for example, through a single-screw extruder, a twin-screw extruder, or a Banbury mixer, and in this case, the composition is uniformly dispersed, resulting in excellent compatibility.
[157]
The kneading and extrusion may be carried out, for example, at a barrel temperature of 200 to 270 ° C, preferably 220 to 270 ° C, and in this case, melt-kneading may be sufficiently performed with an appropriate amount per unit time, and the resin component There is an effect of not causing problems such as thermal decomposition.
[158]
The kneading and extruding may be performed, for example, under the condition that the number of rotations of the screw is 200 to 300 rpm, preferably 250 to 300 rpm, and in this case, the processing amount per unit time is appropriate, so that the process efficiency is excellent and the effect of suppressing excessive cutting is there is.
[159]
The molded article of the present substrate may, for example, be manufactured from the thermoplastic resin composition of the present substrate, and in this case, the weather resistance, colorability, processability, and scratch resistance are improved while heat resistance is maintained.
[160]
The molded article may be, for example, at least one selected from the group consisting of automobile parts, electrical and electronic parts, or building materials.
[161]
In describing the thermoplastic resin composition of the present description, its manufacturing method and molded article, it is stated that other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art and are not particularly limited. do.
[162]
[163]
Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.
[164]
[Example]
[165]
Materials used in the following Examples and Comparative Examples are as follows.
[166]
*(B) First graft copolymer: Graft copolymer having an average rubber particle diameter of 120 nm (SA130 from LG Chem)
[167]
*(C) Second graft copolymer: Graft copolymer having an average rubber particle diameter of 400 nm (SA927 from LG Chem)
[168]
*Lubricant: Ethylene Bis Stearamide (EBA)
[169]
*Antioxidant: Songnox 11B from Songwon Industry Co., Ltd.
[170]
*Dye: LG Chem’s BK-39
[171]
[172]
Example 1
[173]
<(A) Preparation of styrenic copolymer>
[174]
In a reactor, 140 parts by weight of ion-exchanged water, 86 parts by weight of methyl methacrylate (hereinafter referred to as 'MMA'), 4 parts by weight of N-phenylmaleimide (hereinafter referred to as 'PMI') and styrene (hereinafter referred to as 'SM') ) 0.06 parts by weight of t-butylperoxybenzoate as an initiator, 1.3 parts by weight of tricalcium phosphate as a dispersant, and 0.2 parts by weight of t-dodecylmercaptan as a molecular weight modifier were added to 10 parts by weight of 10 parts by weight, and the temperature was raised to 100 ° C. under 500 rpm to initiate polymerization. Initiated, and maintained for 6 hours to complete polymerization.
[175]
Formic acid was added to the prepared polymerization slurry to adjust the pH of the slurry to 2.5 to remove the dispersant, followed by washing with water, dehydration, and drying to prepare a bead-type styrenic copolymer. The prepared copolymer had a refractive index of 1.499 and a glass transition temperature of 121.8. °C and a weight average molecular weight of 113,000 g/mol.
[176]
[177]

[178]
100 parts by weight of a copolymer composition composed of 75 parts by weight of the above-prepared (A) styrenic copolymer, (B) 20 parts by weight of the first graft copolymer, and 5 parts by weight of (C) the second graft copolymer, 1 lubricant After adding 0.5 parts by weight of an antioxidant and 0.5 parts by weight of a dye, the mixture was put into a 240° C. extruder (28Φ) to prepare a resin in pellet form, and then injected to prepare a specimen.
[179]
[180]
Examples 2 to 6
[181]
Specimens were prepared by repeating the same method as in Example 1, except for using the ingredients and contents in Table 1 below when preparing the (A) styrenic copolymer.
[182]
[183]
Comparative Examples 1 to 6
[184]
Specimens were prepared by repeating the same method as in Example 1, except for using the ingredients and contents in Table 2 below when preparing the (A) styrenic copolymer. For reference, in Comparative Example 6, α-methyl styrene (hereinafter referred to as 'AMS') was added instead of SM.
[185]
[186]
Comparative Example 7
[187]
The same process as in Example 1 was repeated except that the (A) styrenic copolymer manufacturing process was replaced as follows.
[188]
Specifically, a polymerization solution in which 0.03 part by weight of dicumyl peroxide was added to 100 parts by weight of a monomer solution composed of 25% by weight of toluene, 67.5% by weight of methyl methacrylate, 2.25% by weight of N-phenylmaleimide and 5.25% by weight of styrene was added to 12 The mixture was added to a 145° C. continuous reactor at a rate of kg/hr, polymerized, and then passed through a volatilization tank at 250° C. to remove unreacted monomers and reaction solvents to prepare a heat-resistant copolymer in the form of pellets.
[189]
[190]
Comparative Example 8
[191]
(A) styrenic copolymer of Example 1, methyl methacrylate (hereinafter referred to as 'MMA') 60 parts by weight, acrylonitrile (hereinafter referred to as 'AN') 7 parts by weight and styrene 33 parts by weight Example 1, except that (A-1) was replaced with a styrenic copolymer and (B) the first graft copolymer and (C) the second graft copolymer were added in the content ranges shown in Table 2 below. The same process as above was repeated to prepare a copolymer in the form of pellets.
[192]
[193]
[Test Example]
[194]
The physical properties of the specimens prepared in Examples 1 to 6 and Comparative Examples 1 to 8 were measured in the following manner, and the results are shown in Tables 1 and 2 below.
[195]
Physical property measurement
[196]
* Refractive index: measured at 25 °C using an Abbe refractometer according to ASTM D542.
[197]
* Weight average molecular weight (g/mol): Through gel chromatography (GPC) filled with porous silica as a column packing material, a standard PS (Standard Polystyrene) sample using tetrahydrofuran (THF) as a solvent at a temperature of 40 ° C. Relative values were measured for
[198]
* Glass transition temperature (℃): measured using a differential calorimetry (manufacturer Ta Instruments, product name DISCOVERY DSC25).
[199]
* Conversion rate (% by weight): A portion of the polymer in the reactor is taken out, the moisture content is measured, the actual sample weight is obtained by Equation 3 below, dissolved with THF / MeOH, precipitated, and the suspended matter is dried. Calculated using 4.
[200]
[Equation 3]
[201]
Actual sample weight = (reactant sampled) - (reactant sampled × moisture content / 100)
[202]
[Equation 4]
[203]
Polymerization conversion rate (%) = (sample after drying) / (sample before drying) × 100
[204]
* Residual oligomer content (% by weight): 1 g of sample was dissolved in 10 mL of chloroform, then the polymer was precipitated with methanol, and the supernatant of the sample was taken and filtered using a 0.2 μm disk syringe filter, and then analyzed using ALS-GC/FID. .
[205]
* Izod impact strength (kgf cm/cm): Measured according to ASTM D256 using a 1/4" specimen thickness.
[206]
* Fluidity (g/10min): Measured at 220° C. for 10 minutes under a 10 kg load in accordance with ASTM D1238.
[207]
More about this source textSource text required for additional translation information
Send feedback
Side panels
History
Saved
Contribute
5,000 character limit. Use the arrows to translate more.* Heat deflection temperature (℃): Measured under a load of 18.6 kgf/cm 2 using a specimen having a thickness of 6.4 mm in accordance with ASTM D648.
[208]
* Pencil hardness: After fixing a pencil at a load of 0.5 kg and an angle of 45 ° in accordance with ASTM D3363 using a pencil hardness tester (Cometech), the surface of the specimen is graded by hardness (in order of 2B, B, HB, F, H) It was scratched to determine whether or not it was scratched visually.
[209]
* Colorability (blackness: Color L): Based on the CIE1976 L*a*b* colorimetric system, the color L value was measured using a color meter (product name: Color Eye 7000A). At this time, when L is 100, it means pure white, and when L is 0, it means pure black, respectively, and the lower the L value, the better the black feeling.
[210]
* Weatherability (ΔE): Measured with a weatherability measuring device (QUV), measurement conditions: UV lamp illuminance 0.77 W/m 2 , humidity 50%, BLACK PANEL temperature 60 ℃, after staying for 20 hours, △E is the following equation It is the arithmetic average of the Hunter Lan values before and after the stay calculated as 2, and the closer the value is to 0, the better the weather resistance.
[211]
[Equation 2]
[212]
ΔE= √{(L-L') 2 + (a-a') 2 + (b-b') 2} (√: root sign)
[213]
[Table 1]
Classification Ex1 Ex2 Ex3 Ex4 Ex5 Ex6
Composition A (MMA) 86 82 78 74 69 64
Composition A (PMI) 4 2 6 8 8 10
Composition A (SM) 10 16 16 18 23 26
A physical property (refractive index) 1.499 1.504 1.509 1.515 1.517 1.518
A Property (Mw) 113,000 96,000 103,000 122,000 115,000 133,000
A property (Tg) 121.8 120.1 122.8 124 123.1 124.3
A property (conversion rate) 97 96 96 97 96 96
A property (residual oligomer) 0.33 0.36 0.33 0.32 0.34 0.35
Composition of thermoplastic resin composition (A) 75 75 75 75 75 75
(B) 20 20 20 20 20 20
(C) 5 5 5 5 5 5
thermoplastic
Properties of resin composition Impact strength 6 5 5 6 6 7
Liquidity 15 16 15 14 15 13
Heat deflection temperature 93 91 94 95 95 96
Pencil Hardness 2H 2H 2H 2H 2H 2H
Colorability (L) 24.1 24.2 24.4 24.6 24.7 24.8
Weather resistance 1.5 1.6 1.7 1.7 1.7 1.8
[214]
(A in the above table refers to a styrenic copolymer.)
[215]
[Table 2]
Classification Com Ex1 Com Ex2 Com Ex3 Com Ex4 Com Ex5 Com Ex6 Com Ex7 Com Ex8
Composition A (MMA) 94 80 75 70 60 74 90 60
Composition A (PMI) 4 3 5 3 10 8 3 -
Composition A (SM) 1 17 20 27 30 - 7 33
Composition A (AN) - - - - - - - 7
Composition A (AMS) - - - - - 18 - -
APhysical properties (refractive index) 1.499 1.517 1.521 1.525 1.531 1.521 1.5 1.53
A Property (Mw) 73,000 96,000 140,000 149,000 142,000 112,000 84,000 80,000
A property (Tg) 120.1 118.7 117.7 111.8 115.3 124.5 120.5 102.3
A property (conversion rate) 96 97 96 96 96 93 70 96
A property (residual oligomer) 0.38 0.40 0.41 0.46 0.42 0.61 0.48 0.39
Composition of thermoplastic resin composition (A) 75 75 75 75 75 75 75 65
(B) 20 20 20 20 20 20 20 30
(C) 5 5 5 5 5 5 5 5
thermoplastic
Properties of resin composition Impact strength 3 6 9 10 10 5 6 5
Liquidity 16 14 10 9 10 15 14 19
Heat deflection temperature 93 90 87 83 87 91 96 83.5
Pencil hardness H H H F F 2H 2H 2H
Colorability (L) 24 24.7 25 25.3 25.5 25.3 23.8 26
Weatherability 1.5 1.7 1.8 1.9 1.9 1.5 1.8 1.4
[216]
(A in the above table refers to a styrenic copolymer.)
[217]
As shown in Tables 1 and 2, Examples 1 to 6 prepared according to the present invention are excellent in impact strength, heat resistance and weather resistance compared to Comparative Examples 1 to 8 outside the scope of the present invention, but also have fluidity, heat deflection temperature, It was confirmed that the effect of excellent pencil hardness (scratch resistance) and colorability was confirmed.
[218]
In addition, in Table 1, the (A) styrenic copolymers of Examples 1 to 6 prepared according to the present invention had a lower refractive index and an increased glass transition temperature, thereby improving the colorability and heat deflection temperature of the resin composition. It worked.
[219]
On the other hand, according to Comparative Examples 1 to 8 in Table 2, all residual oligomer contents were 0.38% by weight or more.
[220]
In addition, (A) Comparative Examples 2 and 3 in which the weight ratio of SM/MMA in the styrenic copolymer does not satisfy 1:2.46 to 1:3.5 or 1:4.8 to 1:8.6 are commonly pencil hardness (scratch resistance) This was poor, and in particular, in the case of Comparative Example 3, in which the MMA content used was smaller than that of Comparative Example 2, it was confirmed that the fluidity, heat deflection temperature, and colorability were all poor.
[221]
In addition, in Comparative Example 5 in which the weight ratio of SM/MMA is less than 1:2.46 and in Comparative Example 1 in which the weight ratio of SM/MMA is greater than 1:8.6, the weight average molecular weight of the styrenic copolymer is poor, resulting in poor pencil hardness (scratch resistance) was poor.
[222]
In addition, in Comparative Example 4, in which the PMI content was significantly lower than that of SM, the Tg and heat deflection temperature were low, and the pencil hardness (scratch resistance) was poor.
[223]
In addition, in Comparative Example 6 using an alkyl-substituted aromatic vinyl compound instead of styrene, the polymerization conversion rate was lowered, the residual oligomer content was increased, and the colorability was lowered due to the increase in refractive index.
[224]
On the other hand, in Comparative Example 7 using bulk polymerization, the weight average molecular weight of the styrenic copolymer was poor, resulting in poor pencil hardness (scratch resistance) or increased residual oligomer content.
[225]
Furthermore, in Comparative Example 8 using a transparent styrenic copolymer not containing a heat-resistant monomer, even if the transparent residual oligomer content was within an appropriate range, heat resistance was very low, and pencil hardness (scratch resistance) and colorability were remarkably poor.
[226]
[227]
In conclusion, when a styrenic copolymer having a specific refractive index, molecular weight, glass transition temperature, and residual oligomer content is included in graft copolymers having different rubber particle sizes, weather resistance and heat resistance are excellent, and colorability, processability, and scratch resistance are all excellent. It was confirmed that a thermoplastic resin composition suitable for molded articles was provided.

WE claims
[Claim 1]
Styrene-based copolymers comprising (meth)acrylate-based monomers, aromatic vinyl-based monomers and maleimide-based monomers; a first graft copolymer comprising an acrylic rubber polymer, an aromatic vinyl monomer, and a vinyl cyan monomer; and a second graft copolymer comprising an acrylic rubber polymer, an aromatic vinyl monomer, and a vinyl cyan monomer, wherein the styrenic copolymer has a residual oligomer content of 0.37% by weight or less, and the first graft copolymer The thermoplastic resin composition, characterized in that the polymer and the second graft copolymer have different average particle diameters of the acrylic rubber polymer.
[Claim 2]
The styrenic copolymer of claim 1, wherein the styrenic copolymer comprises 62 to 88% by weight of a (meth)acrylate-based monomer, 1 to 10% by weight of a maleimide-based monomer, and 5 to 26% by weight of an aromatic vinyl-based monomer. A thermoplastic resin composition to be.
[Claim 3]
The thermoplastic resin composition according to claim 1, wherein the maleimide-based monomer is N-phenylmaleimide.
[Claim 4]
The thermoplastic resin composition according to claim 1, wherein the styrenic copolymer has a refractive index of 1.518 or less.
[Claim 5]
The thermoplastic resin composition according to claim 1, wherein the styrenic copolymer has a glass transition temperature of 120 °C or higher.
[Claim 6]
The thermoplastic resin composition according to claim 1, wherein the styrenic copolymer has a weight average molecular weight of 90,000 to 139,000 g/mol.
[Claim 7]
The method of claim 1, wherein the first graft copolymer comprises 20 to 60% by weight of an acrylic rubber polymer having an average particle diameter of 50 to 200 nm, 10 to 50% by weight of an aromatic vinyl monomer, and 5 to 30% by weight of a vinylcyanic monomer. A thermoplastic resin composition comprising
[Claim 8]
The method of claim 1, wherein the second graft copolymer contains 20 to 60% by weight of an acrylic rubber polymer having an average particle diameter of 300 to 600 nm, 10 to 50% by weight of an aromatic vinyl monomer, and 5 to 30% by weight of a vinylcyanic monomer. A thermoplastic resin composition, characterized in that made by.
[Claim 9]
The method of claim 1, wherein the thermoplastic resin composition, in a total of 100% by weight, 65 to 85% by weight of the styrenic copolymer, 10 to 30% by weight of the first graft copolymer and 1 to 15% by weight of the second graft copolymer A thermoplastic resin composition comprising %.
[Claim 10]
100 parts by weight of a monomer mixture including a (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a maleimide-based monomer, 100 to 200 parts by weight of a reaction solvent, 0.01 to 1 part by weight of an initiator, 1 to 5 parts by weight of a dispersant, and a molecular weight regulator Suspension polymerization of a polymerization solution mixed with 0.01 to 1 part by weight; adjusting the pH of the polymerization slurry produced by the suspension polymerization to 1 to 4 and preparing a styrenic copolymer; Mixing 65 to 85% by weight of the styrenic copolymer with 10 to 30% by weight of the first graft copolymer comprising an acrylic rubber polymer and 1 to 15% by weight of the second graft copolymer comprising an acrylic rubber polymer and kneading and extruding under conditions of 200 to 270 ° C.
the styrenic copolymer has a residual oligomer content of 0.37% by weight or less, and the first graft copolymer and the second graft copolymer have different average particle diameters of acrylic rubber polymers Thermoplastic, characterized in that A method for producing a resin composition.
[Claim 11]
11. The method of claim 10, wherein the reaction solvent is water, the initiator is a peroxide, and the dispersant is a phosphate salt.
[Claim 12]
11. The method of claim 10, wherein the suspension polymerization is performed at 80 to 130 °C at 400 to 600 rpm.
[Claim 13]
11. The method of claim 10, wherein the pH of the polymerization slurry is adjusted using an acidic solution.
[Claim 14]
A molded article made of the thermoplastic resin composition according to any one of claims 1 to 9.