Technical field
[One]
Mutual citation with related applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0171962 filed on December 14, 2017 and Korean Patent Application No. 10-2018-0107120 filed on September 7, 2018, and All contents disclosed in the documents of the Korean patent application are included as part of this specification.
[3]
[4]
Technical field
[5]
The present invention relates to a graft copolymer and a thermoplastic resin composition and a thermoplastic resin molded article comprising the same.
Background
[6]
In general, ABS resins obtained by graft copolymerization of aromatic vinyl monomers and vinyl cyanide monomers to diene rubber polymers prepared by polymerizing conjugated diene monomers are excellent in impact resistance and processability, have excellent mechanical strength and heat distortion temperature, and have good colorability. Therefore, it is widely used in electric and electronic products, automobile parts, and office equipment. However, since the rubber polymer used for manufacturing the ABS resin contains chemically unsaturated bonds, there is a problem in that the rubber polymer is easily aged by ultraviolet rays and weather resistance is very weak.
[7]
In order to improve this disadvantage, a method of adding a stabilizer capable of improving weather resistance when manufacturing a resin composition by extruding an ABS-based resin has been proposed, but there is a problem that the effect is insufficient and is still vulnerable to ultraviolet rays. Accordingly, a method of using a polymer obtained by mixing and polymerizing a diene-based monomer and an acrylic-based monomer or using a chemically more stable acrylic rubber polymer has been proposed instead of a diene-based rubber polymer containing a double bond.
[8]
A typical example of a weather-resistant thermoplastic resin using an acrylic rubber polymer that does not contain an unstable double bond as described above is an acrylate-styrene-acrylonitrile (ASA), which contains an unstable double bond in the polymer. Fields requiring such characteristics as excellent weather resistance, chemical resistance, chemical resistance, and thermal stability, for example, outdoor electric/electronic parts, construction materials, agricultural equipment materials, ASA/ABS double-layer sheets, It is widely used for profile extrusion, road signs, outdoor products, PVC for construction materials, leisure goods, sports goods, and automobile parts.
[9]
The preparation method of ASA polymer excellent in weather resistance and aging resistance is disclosed in German Patent No. 1,260,135, and the core used here is a large diameter latex of crosslinked acrylate having an average particle diameter of 150 to 800 nm and a narrow particle size distribution. Compared to a polymer prepared using a small-diameter polyacrylate latex, a polymer containing a large-diameter polyacrylate latex improves the notch impact strength, increases the hardness, and reduces the shrinkage. However, the large diameter acrylonitrile-acrylate-styrene graft copolymer has a disadvantage in that it is difficult to color compared to the small-diameter acrylonitrile-acrylate-styrene graft copolymer.
[10]
The use of the corresponding ASA polymer to make colored moldings is limited, ie a pale pastel color is obtained rather than a bright color.
[11]
In addition, U.S. Patent No. 4,224,419 discloses, in a weather-resistant, high-impact thermoplastic resin that can be easily colored, a crosslinked acrylate polymer having an average particle diameter of about 50 to 150 nm as a core, and styrene and acrylonitrile as a graft shell. The prepared first acrylonitrile-acrylate-styrene graft copolymer, a crosslinked acrylate polymer having an average particle diameter of about 200 to 500 nm as a core, and a second acrylic separately prepared from styrene and acrylonitrile as a graft shell A hard component including a ronitrile-acrylate-styrene graft copolymer, and a copolymer of acrylonitrile and styrene or α-methyl styrene, and the weight ratio between the core components is 90:10 to 35:65 and 2 A molding material is described wherein the proportion of the sum of the core components of the dogs is about 10 to 35% by weight, based on the mixture.
[12]
Materials known to date have excellent weather resistance and mechanical properties, and have improved colorability. However, it is still insufficient for the level of exterior characteristics and weather resistance that are constantly increasing demanded by customers.
[13]
Accordingly, the present inventors confirmed that appearance properties and weather resistance are improved by using an alkyl methacrylate monomer as a main component when preparing the seed of the ASA graft copolymer, and the particle diameter of the core and the graft rate of the shell are also weather resistance and appearance properties. The present invention was completed by discovering that it may have an effect on.
Detailed description of the invention
Technical challenge
[14]
An object of the present invention is to provide a graft copolymer having excellent weather resistance and colorability, a thermoplastic resin composition including the same, and a thermoplastic resin molded article.
Means of solving the task
[15]
One embodiment of the present invention is (A) a seed comprising a unit derived from an alkyl methacrylate monomer; (B) a core formed on the seed and comprising a unit derived from an alkyl acrylate monomer; And (C) a shell formed on the core and comprising at least one derived unit of an aromatic vinyl monomer, a vinyl cyanide monomer, and an alkyl methacrylate monomer; and, the average particle diameter of the core is 40 to 90 nm. , To provide a graft copolymer having a graft rate of 10 to 30% of the shell.
[16]
Another embodiment of the present invention is the graft copolymer; And it provides a thermoplastic resin composition comprising an aromatic vinyl-cyanide vinyl-based copolymer.
[17]
Another embodiment of the present invention provides a thermoplastic resin molded article comprising the thermoplastic resin composition.
Effects of the Invention
[18]
The graft copolymer of the present invention includes an alkyl methacrylate in the seed, and the core particle diameter and the shell graft rate are controlled within a specific range, thereby exhibiting excellent properties in all of weather resistance, colorability, and impact strength.
[19]
Therefore, the thermoplastic resin molded article manufactured by injecting the resin composition containing the graft copolymer of the present invention is also excellent in weather resistance and excellent appearance characteristics.
Best mode for carrying out the invention
[20]
Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
[21]
The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of ​​the present invention based on the principle that there is.
[22]
In the present specification, the average particle diameter (D 50 ) may be defined as a particle diameter corresponding to 50% of the cumulative volume in the particle diameter distribution curve of the particles. The average particle diameter (D 50 ) may be measured using, for example, a laser diffraction method. In general, the laser diffraction method can measure a particle diameter of about several mm from a submicron region, and high reproducibility and high resolution results can be obtained.
[23]
As an exemplary embodiment of the present invention, the graft copolymer comprises (A) a seed comprising a unit derived from an alkyl methacrylate monomer; (B) a core formed on the seed and comprising a unit derived from an alkyl acrylate monomer; And (C) a shell formed on the core and comprising at least one derived unit of an aromatic vinyl monomer, a vinyl cyanide monomer, and an alkyl methacrylate monomer, and the average particle diameter of the core is 40 to 90 nm, The graft rate of the shell is 10 to 30%.
[24]
Hereinafter, the method for preparing the graft copolymer of the present invention will be described in detail step by step.
[25]
Preparation of graft copolymer
[26]
(A) Preparation of seed
[27]
In the step of preparing the seed, an alkyl methacrylate-based monomer, a crosslinking agent, an initiator, and an emulsifier may be polymerized to prepare a seed, and optionally, at least one of an electrolyte, a grafting agent and an oxidation-reduction catalyst is further added to perform polymerization. I can.
[28]
The alkyl methacrylate monomer may be a chain alkyl having 1 to 10 carbon atoms or an alkyl methacrylate including a branched alkyl group, preferably a methacrylate including a chain alkyl group having 1 to 4 carbon atoms. Specifically, it may be at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, and 2-ethylhexyl methacrylate. .
[29]
Further, in the seed preparation step, the alkyl methacrylate monomer may be used alone, but an alkyl acrylate monomer may be additionally used. This can improve the mechanical strength of the graft copolymer.
[30]
The additionally used alkyl acrylate monomer may be an acrylate containing a chain alkyl having 1 to 10 carbon atoms or a branched alkyl group, preferably an acrylate containing a chain alkyl group having 1 to 4 carbon atoms. Specifically, it may be at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate.
[31]
(A) The derived unit of the alkyl methacrylate monomer constituting the seed and optionally the derived unit of the alkyl acrylate monomer is 4 to 30% by weight, preferably 4 to 20% by weight, based on the total weight of the graft copolymer. It may be, more preferably 4 to 15% by weight. In the case of the above content range, a graft copolymer having excellent impact resistance, weather resistance, and physical property balance may be prepared.
[32]
The average particle diameter (D 50 ) of the seed obtained from the seed preparation step may be 30 to 70 nm, preferably 30 to 60 nm. In the above range, the appearance characteristics and impact resistance of the resin molded article using the graft copolymer are excellent.
[33]
In the present invention, as a crosslinking agent, an acrylic compound containing an unsaturated vinyl group and capable of serving as a crosslinking agent may be used. For example, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, divinylbenzene, diethylene glycol Dimethacrylate, triethylene glycol dimethacrylate, 1,3-butadiol dimethacrylate, hexanediol propoxylate diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxylate diacrylate , Neopentyl glycol propoxylate diacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, trimethylpropane ethoxylate triacrylate, trimethylpropane propoxylate triacrylate, pentaerythritol ethoxylate It may be one or more selected from the group consisting of triacrylate, pentaerythritol propoxylate triacrylate, and vinyl trimethoxysilane, but is not limited thereto.
[34]
The crosslinking agent is used as 0.01 to 3 parts by weight, 0.01 to 1 parts by weight, 0.05 to 1 parts by weight, 0.01 to 0.5 parts by weight, or 0.1 to 0.5 parts by weight based on 100 parts by weight of the total monomers used in the preparation of the graft copolymer. I can.
[35]
In the present invention, a water-soluble initiator, a fat-soluble initiator, or a mixture of these initiators may be used as the initiator.
[36]
The water-soluble initiator may be one or more selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide, but is not limited thereto.
[37]
The fat-soluble initiator is, for example, t-butyl peroxide, cumene hydroperoxide, p-methane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl Peroxide, dibenzoyl peroxide, diisopropylbenzene hydroperoxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy isobutylate, azobis isobutyronitrile, azobis-2,4 -It may be one selected from the group consisting of dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (butyric acid) methyl, but is not limited thereto.
[38]
It is preferable to use a water-soluble initiator in the seed preparation step. Accordingly, it is possible to easily prepare a polymer having a desired size by controlling the reaction rate, and thus there is an effect of improving the physical properties of the graft copolymer.
[39]
The initiator may be used in an amount of 0.01 to 3 parts by weight, preferably 0.01 to 1 part by weight, based on a total of 100 parts by weight of the monomers used to prepare the graft copolymer.
[40]
In the present invention, a derivative of a C12 to C18 alkyl sulfosuccinate metal salt, a C12 to C20 alkyl sulfate ester or a derivative of a sulfonic acid metal salt may be used as the emulsifier. As the derivative of the C12 to C18 alkyl sulfosuccinate metal salt, dicyclohexyl sulfonate, the sodium or potassium salt of dihexyl sulfosuccinate may be used, and the C12 to C20 sulfuric acid ester or sulfonic acid metal salt is sodium laur Alkyl sulfate metal salts such as ric sulfate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate, and potassium octadecyl sulfate, and the like can be used. In addition, as an emulsifier, derivatives of carboxylic acid metal salts such as C12 to C20 fatty acid metal salts and rosin acid metal salts having a pH of 9 to 13 may be used. Examples of the fatty acid metal salts include petisic acid, lauryl acid, and There are sodium or potassium salts, and the metal salts of rosin acid include sodium rosinate or potassium rosinate. The emulsifier may be used alone or in combination of two or more.
[41]
In the present specification, a derivative of a compound refers to a compound in which one or two or more hydrogen or functional groups of the compound are substituted with other organic or inorganic groups.
[42]
The emulsifier may be used as 0.01 to 5 parts by weight, 0.01 to 3 parts by weight, 0.1 to 2 parts by weight, 0.1 to 1 parts by weight, or 0.5 to 1.5 parts by weight based on 100 parts by weight of the total monomers used in preparing the graft copolymer. I can.
[43]
In the present invention, the electrolyte is KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , K 4 P 2 O 7 , Na 4 P 2 O 7 , K 3 PO 4 , Na 3 PO 4, K 2 HPO 4 , Na 2 HPO 4 , KOH, NaOH, Na 2 S 2 O 7 may be one or more selected from the group consisting of, but is not limited thereto.
[44]
The electrolyte may be used in an amount of 0.0001 to 1 part by weight, 0.001 to 1 part by weight, or 0.05 to 1 part by weight based on a total of 100 parts by weight of the monomers used to prepare the graft copolymer, and the polymerization reaction and the stability of the latex within this range Is improved.
[45]
In the present invention, a compound containing an unsaturated vinyl group having two or more different reactivity may be used as the grafting agent. For example, it may be one or more selected from the group consisting of allyl methacrylate, triallyl isocyanurate, triallyl amine, and diallyl amine, but is not limited thereto.
[46]
The grafting agent may be used in an amount of 0.01 to 3 parts by weight, 0.01 to 1 part by weight, or 0.01 to 0.1 parts by weight based on a total of 100 parts by weight of the monomers used to prepare the graft copolymer, and within this range, the graft ratio of the graft copolymer This can be improved.
[47]
The oxidation-reduction catalyst may be at least one selected from the group consisting of sodium pyrophosphate, textrose, ferrous sulfide, sodium sulfite, sodium formaldehyde sulfoxylate, and sodium ethylenediamine tetraacetate, but is not limited thereto.
[48]
The oxidation-reduction catalyst may be used in an amount of 0.01 to 3 parts by weight based on a total of 100 parts by weight of monomers used to prepare the graft copolymer.
[49]
(B) preparation of core
[50]
In the manufacturing step of the core, in the presence of the seed, an alkyl acrylate monomer, a crosslinking agent, an initiator and an emulsifier may be polymerized to prepare a core, and optionally at least one of an electrolyte, a grafting agent and an oxidation-reduction catalyst is used. It can be further added and polymerized.
[51]
The alkyl acrylate monomer of the (B) core is not limited thereto, but the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate It may be one or more selected from.
[52]
The derived unit of the alkyl acrylate monomer constituting the core (B) may be 20 to 60% by weight, 30 to 60% by weight, or 35 to 50% by weight based on the total weight of the graft copolymer. In the above content range, a graft copolymer having excellent impact resistance, weather resistance, and physical property balance can be prepared.
[53]
The core obtained from the core preparation step, that is, the average particle diameter (D 50 ) of the core including the seed is 40 to 90 nm, preferably 40 to 80 nm, more preferably 45 to 80 nm, even more preferably 50 to 70 nm to be. When the core average particle diameter is less than 40 nm, the impact strength is lowered, and when it is larger than 90 nm, there is a limit in improving weather resistance.
[54]
Specific examples and contents of the crosslinking agent, initiator, emulsifier, electrolyte, grafting agent, and oxidation-reduction catalyst used in the core manufacturing step may be the same as described in the seed manufacturing step.
[55]
(C) Preparation of shell
[56]
In the production step of the shell, in the presence of the core, a shell can be prepared by polymerizing at least one monomer, an initiator and an emulsifier among aromatic vinyl monomers, vinyl cyanide monomers and alkyl methacrylate monomers, and optionally a crosslinking agent , An electrolyte, a grafting agent, an oxidation-reduction catalyst, and a molecular weight modifier may be further added to perform polymerization.
[57]
It is preferable that the shell essentially contains an aromatic vinyl monomer and a vinyl cyanide monomer. In addition, it may further include an alkyl methacrylate monomer, whereby the weather resistance and appearance quality of the graft copolymer may be improved.
[58]
The aromatic vinyl-based monomer may be at least one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, and vinyl toluene, and is preferably styrene.
[59]
The vinyl cyanide-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, and is preferably acrylonitrile.
[60]
The alkyl methacrylate monomer of the (C) shell may be an alkyl methacrylate containing a chain alkyl or branched alkyl group having 1 to 10 carbon atoms, preferably a methacrylate containing a chain alkyl group having 1 to 4 carbon atoms. . Specifically, it may be at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, and 2-ethylhexyl methacrylate. .
[61]
The unit derived from one or more of the aromatic vinyl monomers, the cyanide vinyl monomers, and the alkyl methacrylate monomers constituting the shell (C) is 20 to 60% by weight, 30 to 60% by weight based on the total weight of the graft copolymer. It may be 60% by weight or 35 to 50% by weight.
[62]
For example, the graft copolymer may contain 20 to 40% by weight, preferably 25 to 40% by weight, of the derived unit of the aromatic vinyl monomer based on the total weight of the graft copolymer, and the origin of the vinyl cyanide monomer The unit may contain 5 to 20% by weight, preferably 10 to 20% by weight. Within this range, the mechanical strength and appearance quality of the graft copolymer can be improved.
[63]
The average particle diameter (D 50 ) of the graft copolymer particles obtained from the shell preparation step may be 60 to 120 nm, preferably 65 to 120 nm, and more preferably 65 to 110 nm. If it is within the above range, the weather resistance and impact strength of the graft copolymer may be excellent.
[64]
The graft rate of the shell is 10 to 30%, preferably 20 to 30% or 15 to 25%. If the shell graft rate is 10% or less, impact and colorability are deteriorated, and when the shell graft rate is 30% or more, there is a limit to improving weather resistance.
[65]
The grafting rate of the shell may be calculated as the monomer content / seed and core content * 100 (%) of one or more derived units among aromatic vinyl monomers, vinyl cyanide monomers, and alkyl methacrylate monomers bound to the core.
[66]
For example, the graft rate of the shell was determined by dissolving 1 g of the graft copolymer in acetone, separating the gel and the sol with a centrifuge (15000 rpm), and drying the gel portion in a vacuum oven to measure the weight, and then (gel content-seed and Core content) / seed and core content * It may be a value obtained by calculating 100 (%). The seed and core content may be calculated by multiplying the graft copolymer by the fraction of seeds and cores in the graft copolymer.
[67]
Specific examples of the crosslinking agent, initiator, emulsifier, electrolyte, grafting agent, and oxidation-reduction catalyst used in the shell manufacturing step may be the same as described in the seed manufacturing step.
[68]
Preferably, a fat-soluble initiator may be used in the shell preparation step. By using a fat-soluble initiator, a high degree of polymerization can be achieved, and thus the productivity of the resin can be achieved.
[69]
In addition, the shell preparation step may be performed by further including a molecular weight control agent. As an example, a mercaptan compound such as tertiary dodecyl mercaptan may be used, but is not limited thereto.
[70]
The molecular weight modifier may be used in an amount of 0.01 to 2 parts by weight, 0.05 to 2 parts by weight, or 0.05 to 1 part by weight based on 100 parts by weight of the total monomers used for preparing the graft copolymer, and a polymer having a desired size within this range Can be easily manufactured.
[71]
The graft copolymer latex obtained through the seed, core and shell manufacturing steps may be subjected to conventional processes such as agglomeration, washing, and drying to obtain a powdery graft copolymer. For example, a metal salt or an acid may be added to the graft copolymer latex, agglomerated at a temperature of 60 to 100°C, and then subjected to aging, dehydration, washing and drying processes, but is not limited thereto.
[72]
Other conditions not specified in the method for preparing the graft copolymer, such as polymerization conversion rate, reaction pressure, reaction time, gel content, etc., are not particularly limited if they are within the ranges commonly used in the technical field to which the present invention belongs, and is necessary. It is stated that it can be appropriately selected and carried out according to.
[73]
Thermoplastic resin composition
[74]
Another embodiment of the present invention is the graft copolymer; And it provides a thermoplastic resin composition comprising an aromatic vinyl-cyanide vinyl-based copolymer.
[75]
The thermoplastic resin composition may be prepared by mixing the graft copolymer and the aromatic vinyl-vinyl cyanide-based copolymer and then extruding and kneading.
[76]
The extrusion may be performed under conditions of 200 to 300 °C and 30 to 100 rpm, or 200 to 280 °C and 30 to 70 rpm, for example, and within this range, a thermoplastic resin composition having excellent processability and desired physical properties Can be manufactured.
[77]
The added aromatic vinyl-vinyl cyanide copolymer may be a conventional one. For example, the aromatic vinyl-based monomer is at least one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, and vinyl toluene, and is preferably styrene.
[78]
The vinyl cyanide-based monomer is at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, and preferably acrylonitrile.
[79]
In addition, the aromatic vinyl-cyanide vinyl-based copolymer may further include a unit derived from an alkyl (meth)acrylate monomer. The alkyl (meth) acrylate monomer may be an alkyl (meth) acrylate including a chain alkyl having 1 to 10 carbon atoms or a branched alkyl group, preferably a (meth) acrylate including a chain alkyl group having 1 to 4 carbon atoms. have.
[80]
Preferably, the alkyl (meth)acrylate monomer is methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate. It may be one or more selected from the group consisting of.
[81]
In addition, the added alkyl (meth) acrylate monomer may be provided as a copolymer of the aromatic vinyl monomer and the vinyl cyanide monomer, or may be added as a single polymer.
[82]
The aromatic vinyl-vinyl cyanide copolymer may include 60 to 85% by weight of the derived unit of the aromatic vinylic monomer and 15 to 40% by weight of the derived unit of the vinyl cyanide monomer, based on the total weight of the copolymer. In the case, the final thermoplastic resin composition has excellent mechanical strength, weather resistance, and appearance quality.
[83]
In addition, the thermoplastic resin composition of the present invention contains 20 to 60% by weight, preferably 30 to 60% by weight, more preferably 40 to 50% by weight of the graft copolymer based on the total weight of the resin composition, and the aromatic vinyl- The vinyl cyanide copolymer may be included in an amount of 40 to 80% by weight, preferably 40 to 70% by weight, and more preferably 50 to 60% by weight. There are advantages of excellent mechanical properties, appearance quality, and processability within the above range.
[84]
When preparing the thermoplastic resin composition, at least one selected from the group consisting of a flame retardant, a lubricant, an antibacterial agent, a release agent, a nucleating agent, a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, a dye, and a compatibilizer may be further added.
[85]
The additive may be added as 0.1 to 10 parts by weight, preferably 1 to 7 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total thermoplastic resin composition. Within the above range, the effect of the additive may be exhibited without deteriorating the inherent physical properties of the resin.
[86]
The thermoplastic resin composition may have a chromaticity change value (ΔE) of 3 or less, preferably 1 to 2.5, measured after standing for 5000 hours according to WOM SAE J1960 for evaluating weather resistance.
[87]
In addition, the value of blackness (L) measured using a spectroscopic colorimeter for the thermoplastic resin composition may be 26.6 or less, preferably 26.0 or less.
[88]
In addition, the Izod impact strength measured according to ASTM 256 for the thermoplastic resin composition may be 7 to 9 kgf·cm/cm, preferably 8 to 9 kgf·cm/cm.
[89]
Thermoplastic molded product
[90]
The thermoplastic resin composition of the present invention may be manufactured into a thermoplastic resin molded article through a thermoforming process such as injection.
[91]
For example, injection may be performed at a temperature of 190 to 300 °C or 200 to 250 °C and a pressure of 30 to 80 bar or 30 to 70 bar, and within this range, it may have excellent processability and desired mechanical properties and appearance properties. have.
[92]
Other conditions that are not explicitly described in the thermoplastic graft copolymer resin composition and the molded article are not particularly limited if they are within the range commonly practiced in the technical field to which the present invention belongs, and may be appropriately selected as necessary.
[93]
Hereinafter, preferred embodiments are presented to aid in the understanding of the present invention, but the following examples are only illustrative of the present invention, and that various changes and modifications are possible within the scope of the present invention and the scope of the technical idea will be apparent to those skilled in the art, It is natural that such modifications and modifications fall within the appended claims.
Mode for carrying out the invention
[94]
Example
[95]
Example 1
[96]

[97]
20 parts by weight of methyl methacrylate, 2.0 parts by weight of sodium dodecyl sulfate, 0.1 parts by weight of ethylene glycol dimethacrylate, 0.1 parts by weight of allyl methacrylate, and 0.1 parts by weight of potassium hydroxide were collectively administered to a nitrogen-substituted reactor, and 70° C. After raising the temperature to, 0.1 parts by weight of potassium persulfate was added to initiate the reaction. After that, polymerization was performed for 1 hour.
[98]
The average size of the rubber polymer particles obtained after completion of the reaction was measured by the following method, and was found to be 48 nm.
[99]
-Measurement of average particle diameter: 1 g of polymer latex was mixed with 100 g of distilled water, and then measured in Gaussian mode using Nicomp 380HPL (USA, PSS Nicomp) by dynamic laser light scattering.
[100]

[101]
A mixture of 40 parts by weight of butyl acrylate, 0.5 parts by weight of sodium dodecyl sulfate, 0.25 parts by weight of ethylene glycol dimethacrylate, 0.25 parts by weight of allyl methacrylate and 0.1 parts by weight of potassium persulfate was mixed with the polymer seed at 70° C. It was continuously added for 2.0 hours, and polymerization was further performed for 1 hour after completion of the addition.
[102]
The average size of the rubber polymer particles obtained after completion of the reaction was confirmed to be 70 nm.
[103]

[104]
In the presence of the polymer core, a monomer mixture containing 28 parts by weight of styrene, 12 parts by weight of acrylonitrile, 0.5 parts by weight of sodium dodecyl sulfate, 0.1 parts by weight of tertiary dodecyl mercaptan (TDDM), and 0.05 parts by weight of cumene hydroperoxide A polymerization reaction was carried out by continuously adding the emulsion containing 0.09 parts by weight of sodium pyrophosphate, 0.12 parts by weight of textrose, and 0.002 parts by weight of ferrous sulfide for 3 hours at 75°C, respectively. In order to increase the polymerization conversion rate, after the addition of the emulsion and the mixed solution was completed, the mixture was further reacted at 75° C. for 1 hour and cooled to 60° C. to terminate the polymerization reaction to prepare a graft copolymer latex.
[105]
The final particle average size of the prepared graft copolymer latex was 88 nm, and the graft rate was 25%.
[106]
The graft rate was measured by dissolving 1 g of the graft copolymer in acetone, separating the gel from the sol with a centrifuge (15000 rpm), and then drying the gel portion well in a vacuum oven to measure the weight. The grafted amount of the shell was calculated by subtracting the seed and core contents from the measured gel content, and the grafting rate was calculated as a percentage by dividing this by the total amount of seeds and cores.
[107]

[108]
After applying 0.8 parts by weight of an aqueous calcium chloride solution to the prepared graft copolymer latex and performing atmospheric pressure coagulation at 70°C, aged at 93°C, dehydrated and washed, dried for 30 minutes with a hot air at 90°C, and then graft copolymer A powder was obtained.
[109]

[110]
50 parts by weight of the graft copolymer powder, 50 parts by weight of a hard matrix styrene-acrylonitrile copolymer (30% by weight of acrylonitrile and 70% by weight of styrene), 1.5 parts by weight of lubricant, 1.0 part by weight of antioxidant, 1.0 part by weight of UV stabilizer Add parts by weight and mix. The mixture was prepared in the form of pellets using a 36 pie extrusion kneader at a cylinder temperature of 220°C, and the pellet-shaped resin was injected (injection temperature 200 to 230°C, injection pressure 40 to 60 bar) to prepare a specimen for measuring physical properties. Prepared.
[111]
Example 2
[112]
In the polymer seed preparation step of Example 1, a graft copolymer having an average particle diameter of (B) of 50 nm was prepared using 3.0 parts by weight of sodium dodecyl sulfate.
[113]
Example 3
[114]
In Example 1, (A) and (B) were performed in the same manner as in Example 1, except that the contents shown in Table 1 were used.
[115]
Example 4
[116]
In Example 1, (C) was carried out in the same manner as in Example 1, except that the components and contents shown in Table 1 were used.
[117]
Example 5
[118]
In Example 1, (A) was carried out in the same manner as in Example 1, except that the components and contents shown in Table 1 were used.
[119]
Example 6
[120]
Except for using 20 parts by weight of a methyl methacrylate polymer in 30 parts by weight of the hard matrix styrene-acrylonitrile copolymer (30% by weight of acrylonitrile, 70% by weight of styrene) in the preparation step of the thermoplastic resin composition of Example 1 Was carried out in the same manner as in Example 1.
[121]
Comparative Example 1
[122]
In the polymer seed preparation step of Example 1, 0.5 parts by weight of sodium dodecyl sulfate was used to prepare a graft copolymer having an average particle diameter of (B) of 100 nm, and the same procedure as in Example 1 was performed.
[123]
Comparative Example 2
[124]
In the polymer seed preparation step of Example 1, 5 parts by weight of sodium dodecyl sulfate was used, and each component (A), (B), and (C) was used in the amounts shown in Table 1 below, so that the average particle size of (B) was It was carried out in the same manner as in Example 1, except that a 35 nm graft copolymer was prepared.
[125]
Comparative Example 3
[126]
In the polymer seed preparation step of Example 1, 3 parts by weight of sodium dodecyl sulfate was used, and each component (B) and (C) was used in the amounts shown in Table 1 below, and the graft ratio of the shell was 5%. Except for preparing a coalescence, it was carried out in the same manner as in Example 1.
[127]
Comparative Example 4
[128]
In the polymer seed preparation step of Example 1, (A), (B), and (C) were used in the amounts shown in Table 1 below, except that a graft copolymer having a grafting ratio of 40% was prepared. It was carried out in the same manner as in Example 1.
[129]
Comparative Example 5
[130]
In Example 1, (A) was carried out in the same manner as in Example 1, except that the component shown in Table 1 was used.
[131]
[Table 1]
[132]

[133]
Experimental example
[134]
The physical properties of the ASA-based graft copolymer and the thermoplastic resin composition including the same prepared according to the Examples and Comparative Examples were measured in the following manner, and the results are shown in Table 2 below.
[135]
1) Weather resistance (△E)
[136]
After leaving for 5000 hours in accordance with SAE J1960 with a weather-o-meter (Ci35A from ATLAS), the color value was measured and compared with the initial color value according to Equation 1 below to determine the degree of discoloration (△E). Obtained. Here, ΔE is an arithmetic average value of CIE Lab values ​​before and after the weather resistance experiment, and the closer the value is to 0, the smaller the degree of color change and indicates excellent weather resistance.
[137]
[Equation 1]
[138]

[139]
(In Equation 1, L, a, and b are initial color values ​​measured immediately after injection, and L', a', and b'are color values ​​measured after 5000 hours have passed.)
[140]
2) Resin colorability (L)
[141]
When processing the resin composition, 1 wt% carbon black was added, and the L value of the colorimetric test specimen was measured using a color difference meter. The lower the L value is, the darker it is, which means that the pigment colorability is good.
[142]
3) Izod impact strength (kgf·cm/cm)
[143]
The impact strength was measured on a specimen of a thermoplastic resin composition having a thickness of 1/4" according to the standard measurement ASTM 256.
[144]
[Table 2]
[145]

[146]
In Table 2, it can be seen that the thermoplastic resin compositions including the AN-MMA-SN graft copolymers of Examples 1 to 6 have excellent impact strength, appearance characteristics, and weather resistance. On the other hand, in the case of Comparative Example 1 in which the average particle diameter of the core exceeded 90 nm, the weather resistance was deteriorated, and in the case of Comparative Example 2 in which the average particle diameter of the core was less than 30 nm, the weather resistance and colorability were maintained, but the impact strength was greatly reduced. In addition, in the case of Comparative Example 3 in which the graft rate of the shell was less than 10%, the coloring properties and impact strength were decreased, and in the case of Comparative Example 4 in which the graft rate was more than 30%, the weather resistance was decreased.
[147]
In addition, in the case of Comparative Example 5 in which butyl acrylate was used instead of methyl methacrylate as the seed, it was confirmed that both weather resistance and colorability were deteriorated.
Claims
[Claim 1]
(A) a seed containing a unit derived from an alkyl methacrylate monomer; (B) a core formed on the seed and comprising a unit derived from an alkyl acrylate monomer; And (C) a shell formed on the core and comprising at least one derived unit of an aromatic vinyl monomer, a vinyl cyanide monomer, and an alkyl methacrylate monomer; and, the average particle diameter of the core is 40 to 90 nm. , Graft copolymer, characterized in that the graft rate of the shell is 10 to 30%.
[Claim 2]
The graft copolymer of claim 1, wherein the seed has an average particle diameter of 30 to 70 nm.
[Claim 3]
The graft copolymer according to claim 1, wherein the core has an average particle diameter of 50 to 70 nm.
[Claim 4]
The graft copolymer of claim 1, wherein the shell has a graft rate of 15 to 25%.
[Claim 5]
The method of claim 1, wherein the alkyl methacrylate monomer of the seed (A) is methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, 2- Graft copolymer, characterized in that at least one selected from the group consisting of ethylhexyl methacrylate.
[Claim 6]
The graft copolymer according to claim 1, wherein the seed (A) further comprises a unit derived from an alkyl acrylate monomer.
[Claim 7]
The method of claim 6, wherein the alkyl acrylate monomer of the seed (A) is a group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate. Graft copolymer, characterized in that at least one selected from.
[Claim 8]
The group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate according to claim 1, wherein the alkyl acrylate monomer of the (B) core Graft copolymer, characterized in that at least one selected from.
[Claim 9]
The method of claim 1, wherein the copolymer comprises (A) 4 to 30% by weight of seeds based on the total weight of the copolymer; (B) 20 to 60% by weight of the core; And (C) a graft copolymer comprising a shell 20 to 60% by weight.
[Claim 10]
The graft copolymer of any one of claims 1 to 9; And an aromatic vinyl-cyanide vinyl-based copolymer.
[Claim 11]
The thermoplastic resin composition of claim 10, wherein the aromatic vinyl-vinyl cyanide copolymer further comprises a unit derived from an alkyl (meth)acrylate monomer.
[Claim 12]
The method of claim 10, wherein the thermoplastic resin composition comprises 20 to 60% by weight of the graft copolymer based on the total weight of the resin composition; And 40 to 80% by weight of an aromatic vinyl-vinyl cyanide copolymer.
[Claim 13]
The thermoplastic resin according to claim 10, wherein the chromaticity change value (ΔE) measured after leaving it for 5000 hours in accordance with SAE J1960 with a weather-o-meter (ATLAS Corporation Ci35A) is 3 or less. Composition.
[Claim 14]
A thermoplastic resin molded article comprising the thermoplastic resin composition of claim 10.