Title of Invention: Thermoplastic resin composition and molded article manufactured therefrom
technical field
[One]
[Cross Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0136605 dated October 21, 2020 and Korean Patent Application No. 10-2021-0078390 filed again on June 17, 2021 based thereon. All content disclosed in the literature of the application is incorporated as a part of this specification.
[3]
The present invention relates to a thermoplastic resin composition and a molded article prepared therefrom, and more particularly, to a thermoplastic resin composition excellent in surface resistance, appearance quality, gloss and processability when an antistatic agent and a metal pigment are added and the product is molded, and the It relates to molded articles manufactured from
background
[4]
Recently, due to the demand for product differentiation and product design change, diversification of colors and designs is being attempted. Changes in design require material changes, and research on product development with a metal-like surface is also being actively conducted.
[5]
In order to give a metallic feel to the surface of the product, metal was actually used on the surface of the product or metallic paint was applied to the surface. When applying to the surface, there was a problem that harmful components may be generated from the paint on the surface.
[6]
Accordingly, recently, vinyl cyanide compounds represented by acrylonitrile-butadiene-styrene (hereinafter referred to as 'ABS') resins with good processability, excellent impact strength, and excellent appearance -conjugated diene rubber -aromatics A method of directly introducing a metal pigment into a vinyl compound graft copolymer (hereinafter referred to as 'ABS-based resin') and molding it into a product was introduced, but in this case, an antistatic agent must be included to improve antistatic properties And, when it contains an antistatic agent, there is a disadvantage that the surface defect becomes larger, and while maintaining excellent processability, moldability, impact resistance, strength and gloss of the ABS-based resin, while providing excellent antistatic properties, product quality including surface quality There is still a need for a technology for producing this excellent ABS resin.
[7]
[Prior art literature]
[8]
[Patent Literature]
[9]
Korean Patent Publication No. 2013-0046154
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[10]
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 antistatic properties and excellent injection quality and appearance.
[11]
Another object of the present invention is to provide a molded article having a metallic color prepared from the above thermoplastic resin composition.
[12]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[13]
In order to achieve the above object, the present invention
[14]
A first graft copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer and a vinyl cyan-based monomer; a second graft copolymer comprising an acrylic rubber-based polymer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer; and a thermoplastic copolymer comprising an aromatic vinylic monomer and a vinylcyanic monomer; a base resin comprising;
[15]
thermoplastic polyamide elastomer,
[16]
an ethylene copolymer, and
[17]
containing a metal pigment,
[18]
Let a be the weight of the thermoplastic polyamide elastomer with respect to 100 parts by weight of the base resin, let b be the weight of the ethylene copolymer with respect to 100 parts by weight of the base resin, and the second graph out of 100 parts by weight of the base resin It provides a thermoplastic resin composition, characterized in that b + c ≥ 0.5a when the weight of the copolymer is c.
[19]
The weight ratio of the first graft copolymer to the second graft copolymer may be in the range of 3:1 to 5:1.
[20]
The base resin is 15 to 40% by weight of the first graft copolymer; 3 to 17 wt% of the second graft copolymer and 55 to 80 wt% of the thermoplastic copolymer may be included.
[21]
The ethylene copolymer may be selected from among ethylenevinyl acetate copolymer, ethylenebutyl acrylate copolymer, ethylenemethyl acrylate copolymer, ethyleneethyl acrylate copolymer, ethylenemethyl methacrylate copolymer, ethylenebutene copolymer and ethyleneoctene copolymer. It may be one or more selected.
[22]
The ethylene copolymer may be included in an amount of 1 to 6 parts by weight based on 100 parts by weight of the base resin.
[23]
The ethylene copolymer may include 18 to 30% by weight of vinyl acetate based on 100% by weight of the total ethylene copolymer.
[24]
The thermoplastic polyamide elastomer may have a surface resistance measured in accordance with IEC 60093 in the range of 1 X 10^7 to 1 X 10^9 Ω/sq.
[25]
The thermoplastic polyamide elastomer may include at least one selected from a poly(ether-block-amide) copolymer and a poly(ether ester-block-amide) copolymer in an amount of 5 to 20 parts by weight based on 100 parts by weight of the base resin. have.
[26]
The metal pigment may include at least one selected from an aluminum pigment, a copper pigment, and a silver pigment in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the base resin.
[27]
The first graft copolymer may have an average particle diameter of the conjugated diene-based rubber of 0.01 to 1 μm, and a weight average molecular weight of the shell of 70,000 to 300,000 g/mol.
[28]
The first graft copolymer, 40 to 80% by weight of the conjugated diene-based polymer, 10 to 45% by weight of the aromatic vinyl-based monomer, and 1 to 25% by weight of the vinyl cyanide monomer, among 100% by weight of the total of the first graft copolymer % may be included.
[29]
In the second graft copolymer, the average particle diameter of the acrylic rubber may be 0.01 to 1 μm, and the weight average molecular weight of the shell may be 70,000 to 300,000 g/mol.
[30]
The second graft copolymer comprises 40 to 70% by weight of an acrylic rubber polymer, 10 to 45% by weight of an aromatic vinylic monomer, and 1 to 25% by weight of a vinyl cyanide monomer, based on a total of 100% by weight of the second graft copolymer. may include.
[31]
The acrylic rubber-based polymer may be at least one selected from a butyl (meth)acrylate polymer, a 2-ethylhexyl (meth)acrylate polymer, and a hexyl acrylate polymer.
[32]
The thermoplastic copolymer may include 50 to 90% by weight of an aromatic vinylic monomer and 10 to 50% by weight of a vinylcyanic monomer in 100% by weight of a total of 100% by weight of the thermoplastic copolymer.
[33]
The thermoplastic copolymer may include two or more kinds of thermoplastic copolymers having different vinyl cyan-based monomer contents.
[34]
The thermoplastic resin composition may be a permanent antistatic thermoplastic resin composition.
[35]
[36]
Also, the present invention
[37]
A first graft copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer and a vinyl cyan-based monomer; a second graft copolymer comprising an acrylic rubber-based polymer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer; and a thermoplastic copolymer comprising an aromatic vinylic monomer and a vinylcyanic monomer; melt-kneading and extruding a thermoplastic resin composition comprising a base resin, a thermoplastic polyamide elastomer, an ethylene copolymer, and a metal pigment. including,
[38]
Let a be the weight of the thermoplastic polyamide elastomer with respect to 100 parts by weight of the base resin, let b be the weight of the ethylene copolymer with respect to 100 parts by weight of the base resin, and the second graph out of 100 parts by weight of the base resin When the weight of the copolymer is c, b+c≥0.5a provides a method for producing a thermoplastic resin composition.
[39]
[40]
In addition, the present invention provides a molded article prepared from the above-described thermoplastic resin composition.
[41]
The molded article may have a surface resistance of 1 X 10^12 Ω/sq or less according to IEC 60093, and a glossiness (45°) of 100 or more according to ASTM E97.
Effects of the Invention
[42]
The thermoplastic resin composition according to the present invention has excellent compatibility between the styrene-based resin as the base resin and the additive, thereby preventing aggregation of the metal pigment.
[43]
That is, the molded article made of the thermoplastic resin composition according to the present invention has excellent appearance and gloss by improving the flow marks on the metallic surface, and excellent injection quality and antistatic properties, so that it can be used in various industrial fields including electronic products and home appliances. It can be widely applied.
Brief description of the drawing
[44]
1 is a photograph confirming the streaks generated by the aggregation of pearls on the surface of a molded article according to Comparative Example 2 to be described later.
[45]
2 is a photograph confirming that there is no stripe by preventing aggregation of pearls on the surface of the molded article according to Example 1 to be described later.
Modes for carrying out the invention
[46]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[47]
The terms or words used in the present specification and claims should not be construed as being limited to conventional or dictionary meanings, and considering that the inventor may appropriately define the concept of the term in order to best describe the invention. Therefore, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[48]
In the present description, the meaning of "comprising" may be defined as "including polymerization prepared", "polymerized including" or "including as a derived unit" unless otherwise defined.
[49]
In the present description, surface resistance is a variable indicating antistatic property and can be measured in various ways known in the art, and refers to a value (unit Ω/sq) measured according to IEC 60093 unless otherwise specified.
[50]
If the corresponding surface resistance is 1 X 10^12 Ω/sq or less, it can be judged that the effect is excellent as a permanent charging material.
[51]
In the present description, the average particle diameter can be measured using a dynamic light scattering method, and in detail, it can be measured in a Gaussian mode using a particle size distribution analyzer (Nicomp 380) in a latex state, and the dynamic light scattering method It may mean an arithmetic mean particle diameter in the particle size distribution measured by
[52]
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 or distilled water, that is, diluting it appropriately so as not to significantly deviate from the Intensity Setpoint 300kHz, and putting it in a glass tube, and the measurement method is auto-dilution and measured with a flow cell, the measurement mode is dynamic light scattering method/Intensity 300KHz/Intensity-weight Gaussian Analysis, and the setting value is temperature 23 ℃, measurement wavelength 632.8 nm, channel width 10 It can be measured in μsec.
[53]
In the present description, the weight average molecular weight can be measured as a relative value with respect to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent, and specifically, a gel This is a value obtained by applying the polystyrene reduced weight average molecular weight (Mw) by permeation chromatography (GPC: gel permeation chromatography, PL GPC220, Agilent Technologies).
[54]
Specifically, it is dissolved in tetrahydrofuran so as to have a concentration of 1% of the polymer to be measured, and 10 μl is injected into GPC, introduced at a flow rate of 0.3 mL/min, and 30 for a sample concentration of 2.0 mg/mL (100 μl injection). The analysis can be performed at °C. Here, the column may be one in which two PLmixed Bs from Waters are connected in series, and the data is processed using ChemStation after measurement at 40° C. using an RI detector (manufactured by Agilent Waters, 2414) as a detector.
[55]
In the present description, the composition ratio of the (co)polymer may mean the content of units constituting the (co)polymer, or may mean the content of units input during polymerization of the (co)polymer.
[56]
In the present description, "content" means weight unless otherwise defined.
[57]
As used herein, the term “derivative” of a compound refers to a substance in which at least one of hydrogen and a functional group of the compound is substituted with another group such as an alkyl group or a halogen group.
[58]
The graft rate of the present substrate is obtained by adding acetone to 1 g of the graft polymer dry powder, stirring it at room temperature for 24 hr, centrifuging it to collect insoluble fraction not dissolved in acetone, measuring the weight after drying, and using the following Equation 1 can be obtained by calculation.
[59]
[Equation 1]
[60]
Graft rate (%) = [weight of grafted monomer (g) / rubber weight (g)] * 100
[61]
- Weight (g) of grafted monomer: Put the graft copolymer in acetone and vibrate for 24 hours with a vibrator (brand name: SI-600R, manufacturer: Lab.companion) to dissolve the free graft copolymer and centrifuge The weight of the insoluble material (gel) obtained by centrifugation at 14,000 rpm with a vacuum dryer (trade name: DRV320DB, manufacturer: ADVANTEC) and drying for 2 hours at 140°C (product name: DRV320DB, manufacturer: ADVANTEC) minus the weight of rubber (g)
[62]
- Rubber weight (g): The weight of the theoretically added rubber core in the graft copolymer powder
[63]
[64]
The present inventors have found that when molding a material containing an antistatic agent in order to impart antistatic properties to a styrenic resin having good processability, excellent impact strength and excellent appearance, into a metallic color product, the second graft according to the present invention When the copolymer and the ethylene copolymer are used, the surface properties are poor due to the easy aggregation of the metal pigment, but when the second graft copolymer and the ethylene copolymer are added in an appropriate mixing ratio compared to the antistatic agent, the styrene-based resin While maintaining excellent processability, moldability, impact resistance, strength and luster, it provides excellent compatibility between the styrene-based resin and the metal pigment, and furthermore, an antistatic agent to prevent agglomeration of the metal pigment, while maintaining excellent antistatic properties and surface properties. It was confirmed that a material with good basic properties was provided, and based on this, the present invention was completed by further concentrating on research.
[65]
The thermoplastic resin composition of the present invention includes a base resin including the first graft copolymer, the second graft copolymer, and the thermoplastic copolymer, and a metal pigment, an ethylene copolymer, and a thermoplastic polyamide elastomer.
[66]
The thermoplastic resin composition of the present invention includes the above components together, and the weight of the thermoplastic polyamide elastomer with respect to 100 parts by weight of the base resin is a, and the weight of the ethylene copolymer with respect to 100 parts by weight of the base resin is b, When the weight of the second graft copolymer out of 100% by weight of the base resin is c, b+c≥0.5a may be satisfied, and in this case, the desired effects such as antistatic properties, appearance, injection quality, gloss and A molded article having workability can be provided.
[67]
In addition, the present invention can provide a thermoplastic resin composition for permanent antistatic.
[68]
[69]
Hereinafter, each component constituting the thermoplastic resin composition of the present disclosure will be described in detail as follows.
[70]
[71]
base resin
[72]
The base resin may include: a first graft copolymer in consideration of the molding characteristics of the material to which mechanical properties such as processability and impact strength, maintenance of appearance quality, and antistatic properties; a second graft copolymer; and a thermoplastic copolymer.
[73]
[74]
first graft copolymer
[75]
The first graft copolymer of the present disclosure comprises a conjugated diene-based polymer, an aromatic vinyl-based monomer, and a vinylcyanic monomer.
[76]
The first graft copolymer may serve as an impact modifier in the thermoplastic resin molded article as well as imparting excellent processability to the thermoplastic resin composition.
[77]
The conjugated diene-based polymer may include a conjugated diene-based polymer modified by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer to a conjugated diene-based polymer prepared by polymerization of a conjugated diene-based monomer. Here, the conjugated diene-based polymer may be a conjugated diene rubbery polymer.
[78]
The conjugated diene rubber polymer may be, for example, a latex in which the conjugated diene rubber is dispersed in water in a colloidal state (however, based on the solid content in the case of weight), and in this case, mechanical strength and processability are excellent.
[79]
The conjugated diene rubbery polymer refers to a (co)polymer polymerized including a conjugated diene compound having a structure in which a double bond and a single bond are arranged across one another, for example, butadiene polymer, butadiene-styrene copolymer and butadiene- acrylonitrile copolymers.
[80]
In addition, the conjugated diene-based monomer may be, for example, at least one selected from 1,3-butadiene, isoprene, chloroprene and piperylene, among which 1,3-butadiene may be preferable.
[81]
The conjugated diene-based polymer may have an average particle diameter of, for example, 0.01 to 1 μm, preferably 0.03 to 0.8 μm, and more preferably 0.05 to 0.5 μm. Within the above-described range, the impact strength, processability, surface properties and surface gloss of the molded article prepared from the thermoplastic resin composition of the present invention may be further improved.
[82]
The conjugated diene-based polymer may be included, for example, in an amount of 40 to 80% by weight, preferably 45 to 75% by weight, more preferably 50 to 70% by weight, based on 100% by weight of the total of the first graft copolymer. And within the above range, the impact strength, workability, surface properties and surface gloss of the molded article prepared from the thermoplastic resin composition of the present invention can be further improved.
[83]
The weight average molecular weight of the shell of the copolymer may be, for example, 70,000 to 300,000 g/mol, preferably 80,000 to 170,000 g/mol, more preferably 90,000 to 150,000 g/mol, and mechanical properties within the above range There is an improvement advantage.
[84]
The shell of the copolymer may include an aromatic vinyl-based monomer graft-polymerized with a conjugated diene-based polymer and a vinyl cyan-based monomer.
[85]
The aromatic vinyl-based monomer may be, for example, at least one selected from among styrene, α-methylstyrene, β-methylstyrene, α-ethylstyrene, β-ethylstyrene, vinyltoluene, and derivatives thereof, and styrene is preferable.
[86]
The aromatic vinyl-based monomer is, for example, 10 to 45% by weight, preferably 20 to 40% by weight, more preferably 20 to 30% by weight, most preferably based on 100% by weight of the total of the first graft copolymer. may be included in an amount of 25 to 30% by weight, and within the above range, mechanical properties of a molded article prepared from the thermoplastic resin composition of the present invention may be further improved.
[87]
The vinyl cyan-based monomer may be, for example, at least one selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile and derivatives thereof, among which acrylonitrile is desirable.
[88]
The vinyl cyan-based monomer may be included, for example, in an amount of 1 to 25% by weight, preferably 5 to 19% by weight, more preferably 7 to 15% by weight, based on 100% by weight of the total of the first graft copolymer, , within the above range, the mechanical properties of the molded article prepared from the thermoplastic resin composition of the present invention may be further improved.
[89]
The copolymer may be prepared by polymerization of an aromatic vinylic monomer and a vinylcyanic monomer in one or more methods selected from emulsion polymerization, suspension polymerization, and bulk polymerization in the presence of a conjugated diene-based polymer, and among them, it is prepared by emulsion polymerization desirable.
[90]
The emulsion polymerization may be graft emulsion polymerization, for example, may be carried out at 50 to 90 ℃, preferably 60 to 85 ℃.
[91]
The emulsion polymerization may be carried out in the presence of an initiator and an emulsifier.
[92]
The initiator may include, as a radical initiator, inorganic peroxides including 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 including oxide, 3,5,5-trimethylhexanol peroxide, t-butylperoxy isobutylate; It may be at least one selected from azo compounds including azobis isobutyronitrile, azobis-2,4-dimethyl valeronitrile, azobis cyclohexanecarbonylnitrile, and azobisisobutyronitrile (butyric acid) methyl.
[93]
An activator may be further added to promote the initiation reaction together with the initiator.
[94]
The activator may be, for example, at least one selected from sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrose sulfate, dextrose, sodium pyrophosphate, sodium pyrophosphate anhydros, and sodium sulfate.
[95]
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 total of the monomers (including conjugated diene-based polymer) constituting the copolymer. can be put into wealth. Within the above range, the residual amount of the initiator in the copolymer can be minimized in units of several tens of ppm while the emulsion polymerization can be easily performed.
[96]
The emulsifier is, for example, a potassium compound of an alkylbenzenesulfonate, a sodium compound of an alkylbenzenesulfonate, a potassium compound of an alkylcarboxylate, a sodium compound of an alkylcarboxylate, a potassium compound of oleic acid, a sodium compound of oleic acid, a potassium compound of an alkylsulfate , sodium compound of alkylsulfate, potassium compound of alkyldicarboxylate, sodium compound of alkyldicarboxylate, potassium compound of alkylethersulfonate, sodium compound of alkylethersulfonate and allyloxynonylphenoxypropan-2-yloxy It may be at least one selected from among the ammonium compounds of methylsulfonate, and sodium dodecylbenzenesulfonate is preferable.
[97]
The emulsifier may use a commercially available material. In this case, one or more selected from SE10N, BC-10, BC-20, HS10, Hitenol KH10 and PD-104 may be used.
[98]
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 total of the monomers (including conjugated diene-based polymers) constituting the copolymer. It can be added in parts, and the emulsion polymerization is easily performed within the above range, and the residual amount of the initiator in the copolymer can be minimized in units of several tens of ppm.
[99]
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, and t-dodecyl mercaptan is preferred.
[100]
The molecular weight modifier is, for example, 0.1 to 1 part by weight, preferably 0.2 to 0.8 part by weight, more preferably 0.4 to 0.6, based on 100 parts by weight of the total of the monomers (including conjugated diene-based polymer) constituting the copolymer. It may be added in parts by weight.
[101]
The emulsion polymerization is initiated after the monomers and the like are put into the reactor in a batch, or some monomers are added to the reactor before the emulsion polymerization is started, and the remainder after the start is continuously added or the monomers are continuously added for a certain period of time to carry out the emulsion polymerization. can
[102]
The obtained first graft copolymer may be recovered in the form of a dry powder through the processes of agglomeration, dehydration and drying in the form of latex.
[103]
As a coagulant used for agglomeration, salts such as calcium chloride, magnesium sulfate, and aluminum sulfate, or acidic substances such as sulfuric acid, nitric acid, hydrochloric acid and the like, and mixtures may be used.
[104]
The first graft copolymer may be included, for example, in an amount of 15 to 40% by weight, preferably 17 to 35% by weight, more preferably 20 to 30% by weight, based on 100% by weight of the total of the base resin. When the above-described range is satisfied, mechanical properties and injection quality of a molded article manufactured by injection from the thermoplastic resin composition of the present invention may be excellent.
[105]
[106]
second graft copolymer
[107]
The thermoplastic resin composition of the present invention includes a second graft copolymer, and the second graft copolymer includes, for example, an acrylic rubber-based polymer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer.
[108]
The second graft copolymer can impart excellent impact resistance and rigidity to the thermoplastic resin composition, and in particular, the first graft copolymer described above and a metal pigment and thermoplastic polyamide elastomer described below provide compatibility with the present invention. It is possible to improve the appearance characteristics of the molded article manufactured by injecting the thermoplastic resin composition of
[109]
The second graft copolymer may have a seed, core, and shell structure.
[110]
The seed may include an acrylic rubber-based polymer prepared by polymerizing an alkyl (meth) acrylate-based monomer alone or by polymerizing an alkyl (meth) acrylate-based monomer and an aromatic vinyl-based monomer together.
[111]
The core surrounds the seed and may be polymerized including an alkyl (meth)acrylate-based monomer.
[112]
The alkyl (meth) acrylate-based monomer included in the seed and the core is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl acrylate, decyl (meth) acrylate, and may be at least one selected from lauryl (meth) acrylate, double butyl (meth) acrylate monomer, 2-ethylhexyl (meth) acrylate It may be a monomer or a hexyl acrylate monomer.
[113]
The shell surrounds the core and may be polymerized including at least one selected from an aromatic vinyl-based monomer and a vinyl cyan-based monomer.
[114]
The polymerization used in the preparation of the second graft copolymer may be performed by at least one method selected from emulsion polymerization, suspension polymerization, and bulk polymerization, and it is preferable to prepare by double emulsion polymerization.
[115]
The seed of the second graft copolymer is prepared by emulsion polymerization after batch or continuous input of an alkyl (meth) acrylate monomer, or after batch or continuous input of an alkyl (meth) acrylate monomer and an aromatic vinyl monomer. , can be prepared by emulsion polymerization.
[116]
The core of the second graft copolymer may be prepared by adding an alkyl (meth)acrylate-based monomer in a batch or continuously in the presence of the seed, followed by emulsion polymerization.
[117]
The shell of the second graft copolymer may be prepared by adding one or more selected from the group consisting of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer in a batch or continuously in the presence of the core, followed by emulsion polymerization.
[118]
The acrylic rubber-based polymer in the second graft copolymer is, for example, 40 to 70% by weight, preferably 45 to 65% by weight, more preferably 45 to 70% by weight, based on 100% by weight of the total of the second graft copolymer. It may be included in 60% by weight. When the above-mentioned range is satisfied, the surface quality including impact strength, thermal stability and surface gloss of the molded article manufactured from the thermoplastic resin composition of the present invention is excellent.
[119]
The acrylic rubber-based polymer may have an average particle diameter of, for example, 0.01 to 1 μm, preferably 0.03 to 0.8 μm, and more preferably 0.05 to 0.6 μm. When the above-mentioned range is satisfied, the mechanical properties, glossiness, and workability of a molded article prepared from the thermoplastic resin composition of the present invention can be further improved.
[120]
The weight average molecular weight of the shell of the copolymer may be, for example, 70,000 to 300,000 g/mol, preferably 80,000 to 170,000 g/mol, more preferably 90,000 to 150,000 g/mol, and mechanical properties within the above range There is an improvement advantage.
[121]
The aromatic vinyl-based monomer is the same as described in the description of the first graft copolymer.
[122]
The aromatic vinyl-based monomer is, for example, 10 to 45% by weight, preferably 20 to 40% by weight, more preferably 20 to 30% by weight, most preferably based on 100% by weight of the total of the second graft copolymer. may be included in an amount of 25 to 30% by weight, and within the above range, the stiffness and processability of the copolymer may be further improved, and the mechanical properties of the thermoplastic resin composition may be further improved.
[123]
The vinyl cyan-based monomer is the same as described in the description of the first graft copolymer.
[124]
The vinyl cyan-based monomer may be included, for example, in an amount of 1 to 25% by weight, preferably 2 to 20% by weight, more preferably 4 to 17% by weight, based on 100% by weight of the second graft copolymer, and , within the above range, the stiffness and impact resistance of the copolymer may be further improved, and the mechanical properties of the thermoplastic resin composition may be further improved.
[125]
The second graft copolymer may be included, for example, in an amount of 3 to 17% by weight, preferably 5 to 15% by weight, more preferably 5 to 10% by weight, based on 100% by weight of the total of the base resin. When the above-described range is satisfied, mechanical properties and injection quality of a molded article manufactured by injection from the thermoplastic resin composition of the present invention may be excellent.
[126]
The weight ratio of the first graft copolymer to the second graft copolymer may be in the range of 3:1 to 5:1. When the above-described range is satisfied, mechanical properties and injection quality of a molded article manufactured by injection from the thermoplastic resin composition of the present invention may be excellent.
[127]
[128]
thermoplastic copolymer
[129]
The thermoplastic copolymer of the present invention comprises an aromatic vinylic monomer and a vinylcyanic monomer.
[130]
The thermoplastic copolymer may be included in order to serve as a base resin to control the balance of physical properties of the thermoplastic resin composition, that is, mechanical properties including surface impact, processability, paint appearance quality, and post-painting crack prevention.
[131]
The thermoplastic copolymer may be prepared by copolymerizing an aromatic vinyl-based monomer and a vinyl cyan-based monomer.
[132]
Specifically, the thermoplastic copolymer may be prepared by adding an aromatic vinyl-based monomer and a vinyl cyanide-based monomer in a batch or continuously, and polymerization by one or more methods selected from emulsion polymerization, suspension polymerization, and bulk polymerization.
[133]
The aromatic vinyl-based monomer and the type of the vinyl cyan-based monomer are as described in the description of the first graft copolymer.
[134]
The thermoplastic copolymer is 50 to 90% by weight, preferably 55 to 85% by weight, more preferably 60 to 80% by weight of the aromatic vinyl-based monomer, for example, based on 100% by weight of the total of the thermoplastic copolymer. , most preferably 65 to 76% by weight. When the above-described range is satisfied, the balance of physical properties and surface gloss of a molded article prepared from the thermoplastic resin composition of the present invention can be further improved.
[135]
The thermoplastic copolymer is, for example, 10 to 50% by weight of the vinyl cyan-based monomer, preferably 15 to 45% by weight, more preferably 20 to 40% by weight, based on 100% by weight of the total of the thermoplastic copolymer, Most preferably, it may be included in an amount of 24 to 35% by weight. When the above-described range is satisfied, the balance of physical properties and surface gloss of a molded article prepared from the thermoplastic resin composition of the present invention can be further improved.
[136]
The thermoplastic copolymer may have a weight average molecular weight of, for example, 40,000 to 200,000 g/mol, preferably 60,000 to 190,000 g/mol, and more preferably 80,000 to 190,000 g/mol. When the above-mentioned range is satisfied, the balance of the physical properties of the base resin, that is, the balance of mechanical properties, processability, and coating appearance quality can be more easily adjusted.
[137]
As the thermoplastic copolymer, commercially available materials may be used as long as it follows the definition of the present invention.
[138]
The thermoplastic copolymer is, for example, 55 to 80% by weight, preferably 60 to 80% by weight, more preferably 65 to 80% by weight, most preferably 65 to 75% by weight based on 100% by weight of the total weight of the base resin. % may be included. When the above-described range is satisfied, the balance of physical properties and surface gloss of a molded article prepared from the thermoplastic resin composition of the present invention can be further improved.
[139]
The thermoplastic copolymer may preferably include two or more kinds of thermoplastic copolymers having different vinyl cyan-based monomer contents.
[140]
That is, the thermoplastic copolymer may include a first copolymer in which the vinyl cyan-based monomer has a first content and a second copolymer in which the vinyl cyan-based monomer has a second content greater than the first content.
[141]
Here, the first copolymer may contain, for example, 21 to 31 wt% (corresponding to the first content) of the vinyl cyan-based monomer, and the second copolymer may contain, for example, more than 31 wt% and 35 wt% of the vinyl cyan-based monomer. % or less (corresponding to the second content), it is possible to further improve the mechanical properties, injection quality and processability of the molded article manufactured by injection from the thermoplastic resin composition of the present invention within this range.
[142]
The thermoplastic copolymer can be prepared by polymerizing an aromatic vinylic monomer and a vinylcyanic monomer by at least one method selected from bulk polymerization, emulsion polymerization, and suspension polymerization, and when prepared by double bulk polymerization, the manufacturing cost is reduced only However, there is an effect of excellent mechanical properties.
[143]
In the case of the bulk polymerization, since no additives such as an emulsifier or a suspending agent are added, a high-purity copolymer with a minimized amount of impurities in the copolymer can be prepared. Accordingly, it may be advantageous to include a copolymer prepared by bulk polymerization in the thermoplastic resin composition for maintaining transparency.
[144]
The bulk polymerization may be, for example, a method of polymerization by adding an organic solvent as a reaction medium to the monomer mixture and, if necessary, an additive including a molecular weight regulator and a polymerization initiator.
[145]
As a specific example, in the method for preparing the thermoplastic copolymer, 20 to 40 parts by weight of a reaction medium and 0.05 to 0.5 parts by weight of a molecular weight regulator are mixed with 100 parts by weight of a monomer mixture comprising an aromatic vinyl compound and a vinyl cyanide compound, and the reaction temperature It may include the step of polymerization for 2 to 4 hours while maintaining 130 to 170 ℃.
[146]
The reaction medium is not particularly limited if it is a solvent commonly used in the art, and may be, for example, an aromatic hydrocarbon-based compound such as ethylbenzene, benzene, toluene, and xylene.
[147]
The method for producing the thermoplastic copolymer is, for example, a raw material input pump, a continuous stirring tank into which the reaction raw materials are continuously introduced, a preheating tank for preliminarily heating the polymerization solution discharged from the continuous stirring tank, unreacted monomers and/or reaction It can be carried out in a continuous processing machine consisting of a volatilization tank for volatilizing the medium, a polymer transfer pump and an extruder for producing the polymer in the form of pellets.
[148]
At this time, the extrusion processing conditions may be, for example, 210 to 240 ℃, but is not limited thereto.
[149]
As the thermoplastic copolymer, commercially available materials may be used as long as it follows the definition of the present invention.
[150]
The thermoplastic copolymer may be, for example, 55 to 80% by weight, preferably 60 to 80% by weight, more preferably 65 to 75% by weight, based on 100% by weight of the total weight of the base resin. When the above-mentioned range is satisfied, the balance of the physical properties of the base resin, that is, the balance of mechanical properties, processability, and coating appearance quality can be more easily adjusted.
[151]
[152]
Thermoplastic polyamide elastomer
[153]
In the present substrate, the thermoplastic polyamide elastic body serves as an antistatic agent.
[154]
The thermoplastic polyamide elastomer may have, for example, a surface resistance measured in accordance with IEC 60093 in the range of 1 X 10^7 to 1 X 10^9 Ω/sq.
[155]
The thermoplastic polyamide elastomer may be, for example, at least one selected from a poly(ether-block-amide) copolymer and a poly(etherester-block-amide) copolymer.
[156]
The thermoplastic polyamide elastomer is, for example, 5 to 20 parts by weight, preferably 6 to 19 parts by weight, based on 100 parts by weight of the base resin (first graft copolymer + second graft copolymer + thermoplastic copolymer); Most preferably, it may be included in an amount of 8 to 17 parts by weight. When used in combination with a metal pigment to be described later by satisfying the above range, a molded article exhibiting a metallic appearance having excellent antistatic properties may be injected from the thermoplastic resin composition of the present invention.
[157]
[158]
ethylene copolymer
[159]
When used in an appropriate amount in combination with the above-described second graft copolymer, the ethylene copolymer of the present substrate solves surface quality defects including streaks that appear when the above-described thermoplastic polyamide elastomer and metal pigment are used in combination, and provides an improved injection appearance has the effect of
[160]
The ethylene copolymer comprises i) ethylene; and ii) C 3 -C 10 alphaolefins, C 1 -C 12 alkylesters of unsaturated C 3 -C 20 monocarboxylic acids, anhydrides of unsaturated C 3 -C 20 mono or dicarboxylic acids, unsaturated C 4 -C 8 dicarboxylic acids and It may be a copolymer of at least one ethylenically unsaturated monomer selected from the vinyl ester of saturated C 2 -C 18 carboxylic acid or an ionomer of the copolymer.
[161]
The ethylene copolymer is, for example, an ethylenevinyl acetate copolymer, an ethylenebutyl acrylate copolymer, an ethylenemethyl acrylate copolymer, an ethyleneethyl acrylate copolymer, an ethylenemethyl methacrylate copolymer, an ethylenebutene copolymer, and an ethyleneoctene copolymer. It may be one or more types selected from coalescing.
[162]
The ethylene copolymer may include 18 to 30% by weight of vinyl acetate, specifically, 21 to 30% by weight of the total 100% by weight of the ethylene copolymer. When the above-mentioned range is satisfied, there is an effect of resolving defects in surface quality, including stripes, which appear when the thermoplastic polyamide elastomer and the metal pigment are used together, and providing an improved appearance of injection.
[163]
The ethylene copolymer is, for example, 1 to 6 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the base resin (first graft copolymer + second graft copolymer + thermoplastic copolymer), More preferably, it may be 2 to 5 parts by weight. When the above-described range is satisfied, a molded article exhibiting excellent metallic color appearance and physical properties may be injected from the thermoplastic resin composition of the present invention.
[164]
When the content of the aforementioned thermoplastic polyamide-based elastomer is a, the content of the ethylene copolymer is b, and the content of the second graft copolymer is c, b+c is 0.5 times or more of a It is possible to provide a molded article having excellent antistatic properties, appearance, injection quality, glossiness and workability, which are desired effects.
[165]
[166]
metal pigment
[167]
The metal pigment serves to form a metallic appearance.
[168]
The metal pigment may be, for example, an aluminum pigment, a copper pigment, or a silver pigment, preferably an aluminum pigment.
[169]
The metal pigment may be prepared and used directly or a commercially available material may be used.
[170]
The metal pigment may be, for example, in an amount of 0.05 to 5 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.5 to 5 parts by weight, and more preferably 1 to 4 parts by weight based on 100 parts by weight of the base resin. . When the above-described range is satisfied, a molded article having an excellent metallic appearance may be injected from the thermoplastic resin composition of the present invention.
[171]
The metal pigment preferably has an average particle diameter of 1 to 50 μm, more preferably 5 to 40 μm, still more preferably 10 to 30 μm, still more preferably 15 to 25 μm, and excellent metallic within this range. Color and appearance quality can be secured.
[172]
In this substrate, the average particle diameter of the metal pigment can be measured according to a known method for measuring the particle size, and in detail, BET analysis equipment (Micromeritics Surface Area and Porosity Analyzer ASAP 2020 equipment) using nitrogen gas adsorption method. It can be measured using
[173]
[174]
other additives
[175]
The thermoplastic resin composition may include at least one additive selected from a lubricant, a light stabilizer, an antistatic agent, a mold release agent, an impact modifier, and a plasticizer within a range that does not affect the quality of the coating appearance and physical properties.
[176]
The additive may be included, for example, in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total weight of the base resin. When the above-mentioned range is satisfied, there is an effect of realizing the function of the additive without reducing the inherent basic properties of the thermoplastic resin composition of the present invention.
[177]
The lubricant may be, for example, at least one selected from ethylene bis steramide, oxidized polyethylene wax, magnesium stearate, calcium steramide, and stearic acid, but is not limited thereto.
[178]
The light stabilizer may include, for example, a Hals light stabilizer, a benzophenone light stabilizer, a benzotriazole light stabilizer, and the like, but is not limited thereto.
[179]
The antistatic agent may include, for example, one or more anionic surfactants, nonionic surfactants, and the like, but is not limited thereto.
[180]
The release agent may be used, for example, at least one selected from glycerin sterate, polyethylene tetra sterate, and the like, but is not limited thereto.
[181]
As a specific example, the additive may include 0.1 to 5 parts by weight of a lubricant and 0.1 to 1 parts by weight of an antioxidant, and within this range, the properties of the lubricant and antioxidant are expressed without affecting the physical properties of the thermoplastic resin composition. It works.
[182]
[183]
Method for producing a thermoplastic resin composition
[184]
Hereinafter, a method for producing the thermoplastic resin composition of the present invention will be described. In describing the method for producing the thermoplastic resin composition of the present invention, all contents of the above-described thermoplastic resin composition are included.
[185]
The method for producing the thermoplastic resin composition of the present disclosure includes, for example, a first graft copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer, and a vinylcyanic-based monomer; a second graft copolymer comprising an acrylic rubber-based polymer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer; and a thermoplastic copolymer comprising an aromatic vinylic monomer and a vinylcyanic monomer; melt-kneading and extruding a thermoplastic resin composition comprising a base resin, a thermoplastic polyamide elastomer, an ethylene copolymer, and a metal pigment. include
[186]
In this case, a is the weight of the thermoplastic polyamide elastomer with respect to 100 parts by weight of the base resin, b is the weight of the ethylene copolymer with respect to 100 parts by weight of the base resin, and the second When the weight of the graft copolymer is c, the relation b+c≥0.5a is satisfied.
[187]
As another example, in the method for preparing the thermoplastic resin composition, the first graft copolymer, the second graft copolymer, the thermoplastic copolymer, the thermoplastic polyamide elastomer, the ethylene copolymer and the metal pigment are put into an extruder at 210 to 240 ° C. melt-kneading.
[188]
The melt-kneading step may include, for example, other additives described above.
[189]
The melt-kneading and extruding may be performed by using, for example, at least one selected from a single screw extruder, a twin screw extruder, and a Banbury mixer, preferably using a twin screw extruder to uniformly mix and then extrude pellets as an example A thermoplastic resin composition of the form can be obtained, and in this case, mechanical properties, thermal properties, plating adhesion and appearance quality are excellent.
[190]
As another example, the method for preparing the thermoplastic resin composition comprises mixing the first graft copolymer, the second graft copolymer, the thermoplastic copolymer and the thermoplastic polyamide elastomer, the ethylene copolymer, and the metal pigment, followed by a single screw extruder, It may include the step of uniformly dispersing and extruding using a twin screw extruder or Banbury mixer, and then passing the extrudate through a water bath and cutting it to prepare pellets.
[191]
The step of preparing the pellets using the extrusion kneader may be, for example, carried out under 210 to 240 ℃ and 150 to 250 rpm, as a specific example 220 to 235 ℃ and 170 to 230 rpm, wherein the temperature is the temperature set in the cylinder means
[192]
The thermoplastic resin composition pellets may be manufactured as injection-molded articles using an injection machine, for example, at an injection barrel temperature of 210 to 250 °C, preferably at 220 to 240 °C.
[193]
[194]
Further, a molded article including the thermoplastic resin composition of the present invention will be described. In describing a molded article including the thermoplastic resin composition of the present invention, all of the contents of the above-described thermoplastic resin composition are included.
[195]
[196]
molded product
[197]
The molded article of the present substrate may be made of, for example, the thermoplastic resin composition of the present substrate, and in this case, there is an effect of providing a molded article having a metallic color excellent in injection quality and appearance while excellent in mechanical properties and antistatic properties.
[198]
The molded article of the present disclosure may have a surface resistance of 1 X 10^12 Ω/sq or less according to IEC 60093, for example.
[199]
The molded article of the present disclosure may have, for example, a gloss (45°) of 100 or more according to ASTM E97, and may be 100 to 102 as a specific example.
[200]
[201]
The use of the molded article is not particularly limited, but may preferably be a housing for electronic products and home appliances, and in this case, it is possible to prevent problems such as processing problems and dust adsorption due to static electricity generation by providing antistatic properties to the product. have. In addition, since the surface quality is excellent, there is an advantage in that the processing yield of products according to processing is increased.
[202]
In describing the thermoplastic resin composition of the present invention, its manufacturing method and molded article, other conditions or equipment not explicitly described can be appropriately selected within the range commonly practiced in the art, and it is specified that it is not particularly limited. .
[203]
[204]
Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that such changes and modifications fall within the scope of the appended claims.
[205]
[206]
[Example]
[207]
Materials used in Examples 1 to 5, Comparative Examples 1 to 7, and Reference Examples 1 to 4 below were as follows.
[208]
A) First graft copolymer (ABS): 60 wt% of butadiene polymer having an average particle diameter of 300 nm, 30 wt% of styrene, 10 wt% of acrylonitrile
[209]
B) Second graft copolymer (ASA): 50 wt% of butyl acrylate polymer having an average particle diameter of 300 nm, 35 wt% of styrene, 15 wt% of acrylonitrile
[210]
C-1) Thermoplastic copolymer (bulk polymerized SAN): styrene 70% by weight, acrylonitrile 30% by weight, Mw 120,000 g/mol
[211]
C-2) Thermoplastic copolymer (bulk polymerized SAN): styrene 68% by weight, acrylonitrile 32% by weight, Mw 150,000 g/mol
[212]
D-1) Thermoplastic polyamide elastomer (poly(ether-block-amide) copolymer) melting point 200 °C, density 1.14, surface resistance measured according to IEC 60093: 1 X 10^7 Ω/sq
[213]
D-2) Thermoplastic polyamide elastomer (poly(etherester-block-amide) copolymer) melting point 202 °C, surface resistance measured according to IEC 60093: 1 X 10^9 Ω/sq
[214]
E-1) Ethylene copolymer: 28% by weight of vinyl acetate and 72% by weight of ethylene
[215]
E-2) Ethylene copolymer: 15% by weight of vinyl acetate and 85% by weight of ethylene
[216]
E-3) Ethylene copolymer: 35% by weight of vinyl acetate and 65% by weight of ethylene
[217]
F-1) Metal pigment (aluminum pigment, manufactured by Silverline, average particle diameter 20 ㎛)
[218]
F-2) Non-metallic inorganic pigment (Product name: BAYFERROX 120, Manufacturer: Lanxess)
[219]
[220]
Examples 1 to 5, Comparative Examples 1 to 7, and Reference Examples 1 to 3
[221]
Each of the components and contents shown in Tables 1 to 3 below was put into a twin-screw extruder set at 230 °C, melt-kneaded and extruded to prepare pellets. Melt index was measured with the prepared pellets.
[222]
Specimens with a size of 100 mm X 100 mm X 3.2 mm were prepared by injecting the produced pellets at a molding temperature of 230 ° C. measured.
[223]
[224]
[Test Example]
[225]
The physical properties of the pellets and specimens prepared in Examples 1 to 5, Comparative Examples 1 to 7, and Reference Examples 1 to 3 were measured by the method described below, and the results are shown together in Tables 1 to 3 below.
[226]
* Flow index (MI, g/10 min): Measure the flow index according to ASTM D1238 by setting the manufactured pellets to a weight of 10 kg and a reference time of 10 minutes at 220 ° C using a melt index measuring device of DYNISCO. did.
[227]
* Surface resistance (Ω/sq): An injection specimen manufactured in the size of 100 mm X 100 mm was measured using a surface resistance measuring instrument with two types of probes in accordance with IEC 60093 .
[228]
* Injection appearance (flow mark and exterior dot evaluation): The conditions for improving flow marks and appearance dots appearing along the wall of the injection product with the gate as the center on the surface of the molded product were evaluated based on the following three criteria. In other words, when the injection temperature is within 10 ℃ and the injection speed is less than 30%, there are no stripes and external dot defects. △, when the injection temperature is controlled over 30 °C, and the injection speed is adjusted to 70% or more, there are many or clear streaks and a large number of bad appearance dots, divided by X.
[229]
* Injection gloss (gloss): The glossiness of the specimen having a thickness of 1/8 inch (3.2 mm) was measured at 45 ° with a glossmeter VG7000 according to ASTM E97.
[230]
[Table 1]
division Example 1 Example 2 Example 3 Example 4 Example 5
A 22 21 22 20 22
B (content c) 5 7 6 8 5
C-1 73 72 72 72 30
C-2 - - - - 43
D-1 (content a) 7 10 - - 10
D-2 (content a) - - 10 12 -
E-1 (content b) 2 3 3 5 2
E-2 (content b) - - - - -
E-3 (content b) - - - - -
F-1 2 2 2 2 2
F-2 - - - - -
b+c/0.5a 7/3.5 10/5 9/5 13/6 7/5
melt index 24.0 23.5 21.3 23.6 22.1
surface resistance <10^12 <10^12 <10^12 <10^12 <10^12
Extrusion exterior ○ ○ ○ ○ ○
ejection gloss 101 102 102 101 102
[231]
(The content of D-1, D-2, E-1, E-2, E-3, F-1, and F-2 is based on a total of 100 parts by weight of A, B, C-1, and C-2 one part by weight.)
[232]
[Table 2]
division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7
A 22 26 26 22 22 22 22
B (content c) 5 5 - 5 5 5 5
C-1 73 74 74 73 73 73 73
C-2 - - - - - - -
D-1 (content a) - 7 7 3 3 3 25
D-2 (content a) - - - - - - -
E-1 (content b) 2 - 3 2 - - 2
E-2 (content b) - - - - 2 - -
E-3 (content b) - - - - - 2 -
F-1 2 2 2 2 2 2 2
F-2 0.1 0.1 - - - - -
b+c/0.5a 7/0 0/3.5 3/3.5 7/1.5 7/3.5 7/3.5 7/12.5
melt index 23.0 23.2 23.5 22.9 22.0 25.0 NA
surface resistance <10^13 <10^12 <10^12 <10^13 <10^12 <10^12 NA
Extrusion exterior ○ Ⅹ △ ○ Ⅹ △ NA
ejection gloss 102 101 100 101 101 85 NA
[233]
(The content of D-1, D-2, E-1, E-2, E-3, F-1, and F-2 is based on a total of 100 parts by weight of A, B, C-1, and C-2 one part by weight.)
[234]
[Table 3]
division Reference Example 1 Reference Example 2 Reference Example 3
A 26 18 22
B (content c) 2 9 5
C-1 72 73 73
C-2 - - -
D-1 (content a) 5 3 7
D-2 (content a) - - -
E-1 (content b) 2 2 2
E-2 (content b) - - -
E-3 (content b) - - -
F-1 2 2 -
F-2 - - 0.2
b+c/0.5a 7/5 11/1.5 7/3.5
melt index 21.0 26.0 24.0
surface resistance <10^13 <10^12 <10^12
Extrusion exterior △ ○ ○
ejection gloss 100 95 100
[235]
(The content of D-1, D-2, E-1, E-2, E-3, F-1, and F-2 is based on a total of 100 parts by weight of A, B, C-1, and C-2 one part by weight.)
[236]
As shown in Tables 1 to 3, in the case of Examples 1 to 5 of the present invention, the first graft copolymer, the second graft copolymer, the thermoplastic copolymer, the thermoplastic polyamide elastomer, the ethylene copolymer and the metal By including the pigment in the optimal composition, it was confirmed that the melt index and injection gloss were maintained at the same or higher than Comparative Examples 1 to 7 and Reference Examples 1 to 3, which were out of the composition of the present invention, while maintaining excellent surface resistance and injection appearance. .
[237]
In Comparative Example 1, which did not contain the thermoplastic polyamide elastomer, the surface resistance did not remarkably fall short of the effect of the present invention, and in the case of Comparative Example 4 in which a small amount was used, the surface resistance did not remarkably fall short of the effect of the present invention, and an excessive amount In Comparative Example 7 used, the workability deteriorated due to aggregation of the metal pigment and the resin, resulting in severe processing defects, and thus physical properties could not be measured.
[238]
In addition, it was confirmed that Comparative Examples 2 and 3, in which the sum ratio of the ethylene copolymer and the second graft copolymer were small, had poor appearance of the injection, respectively.
[239]
In addition, in Comparative Examples 5 to 6, in which the content of vinyl acetate constituting the ethylene copolymer was not appropriate, it was confirmed that the injection appearance and surface quality were not good, respectively.
[240]
On the other hand, according to Reference Example 1 in which the weight ratio of the first graft copolymer to the second graft copolymer exceeds 3: 1, it was confirmed that the gloss was reduced, and in Reference Example 2 of 1:0.5, the dispersibility of the metal pigment It can be seen that the quality of the appearance of the injection product deteriorates due to deterioration.
[241]
Furthermore, in Reference Example 3 using a non-metallic inorganic pigment instead of a metal pigment, physical properties and injection appearance may be secured, but the surface quality provided by the metallic pigment may not be provided.
[242]
In addition, referring to FIGS. 1 and 2 below, Comparative Example 2, which is outside the scope of the present invention, caused streaks due to aggregation of the metal pigment, so that it was possible to directly confirm with the naked eye that the appearance of the injection was poor. According to Example 1, it can be seen that the aggregation phenomenon of the metal pigment was prevented because no streaks were generated.
[243]
[244]
In conclusion, the present invention solves the problem of surface defects that occurred when a metal pigment containing an antistatic agent was introduced into an ABS-based resin and molded into a product. By adding the coalescer at an appropriate mixing ratio, the compatibility between the ABS resin and the metal pigment and the thermoplastic polyamide elastomer injected as an antistatic agent is improved while maintaining the excellent processability, moldability, impact resistance, strength and gloss of the ABS resin. It was confirmed that it was suitable for molded products by providing a metallic color material with excellent antistatic properties, injection appearance, injection gloss and processability, as well as preventing aggregation of metal pigments and remarkably improving surface defects.
Claims
[Claim 1]
A first graft copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer and a vinyl cyan-based monomer; a second graft copolymer comprising an acrylic rubber-based polymer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer; and a thermoplastic copolymer comprising an aromatic vinyl-based monomer and a vinyl cyan-based monomer; a thermoplastic polyamide based on 100 parts by weight of the base resin, including a base resin, a thermoplastic polyamide elastomer, an ethylene copolymer, and a metal pigment. When the weight of the amide elastomer is a, the weight of the ethylene copolymer with respect to 100 parts by weight of the base resin is b, and the weight of the second graft copolymer out of 100 wt% of the base resin is c , b + c ≥ 0.5a, characterized in that the thermoplastic resin composition.
[Claim 2]
The thermoplastic resin composition according to claim 1, wherein the weight ratio of the first graft copolymer to the second graft copolymer is in the range of 3:1 to 5:1.
[Claim 3]
According to claim 1, wherein the base resin is 15 to 40% by weight of the first graft copolymer; A thermoplastic resin composition comprising 3 to 17% by weight of the second graft copolymer and 55 to 80% by weight of the thermoplastic copolymer.
[Claim 4]
According to claim 1, wherein the ethylene copolymer is ethylenevinyl acetate copolymer, ethylenebutyl acrylate copolymer, ethylenemethyl acrylate copolymer, ethyleneethyl acrylate copolymer, ethylenemethyl methacrylate copolymer, ethylenebutene copolymer and at least one selected from among ethylene octene copolymers.
[Claim 5]
The thermoplastic resin composition according to claim 1, wherein the ethylene copolymer is included in an amount of 1 to 6 parts by weight based on 100 parts by weight of the base resin.
[Claim 6]
The thermoplastic resin composition according to claim 1, wherein the ethylene copolymer comprises 18 to 30 wt% of vinyl acetate.
[Claim 7]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic polyamide elastomer has a surface resistance measured in accordance with IEC 60093 in the range of 1 X 10^7 to 1 X 10^9 Ω/sq.
[Claim 8]
According to claim 1, wherein the thermoplastic polyamide elastomer is at least one selected from a poly(ether-block-amide) copolymer and a poly(ether ester-block-amide) copolymer, 5 to 100 parts by weight of the base resin A thermoplastic resin composition comprising 20 parts by weight.
[Claim 9]
The thermoplastic resin composition according to claim 1, wherein the metal pigment comprises at least one selected from an aluminum pigment, a copper pigment, and a silver pigment, in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the base resin.
[Claim 10]
The thermoplastic resin composition according to claim 1, wherein the first graft copolymer has an average particle diameter of the conjugated diene-based rubber of 0.01 to 1 μm, and a weight average molecular weight of the shell of 70,000 to 300,000 g/mol.
[Claim 11]
According to claim 1, wherein the first graft copolymer, of the total of 100% by weight of the first graft copolymer, 40 to 80% by weight of the conjugated diene-based polymer, 10 to 45% by weight of the aromatic vinyl-based monomer, and vinyl A thermoplastic resin composition comprising 1 to 25 wt% of an aliphatic monomer.
[Claim 12]
The thermoplastic resin composition according to claim 1, wherein the second graft copolymer has an average particle diameter of the acrylic rubber of 0.01 to 1 μm, and a weight average molecular weight of the shell of 70,000 to 300,000 g/mol.
[Claim 13]
According to claim 1, wherein the second graft copolymer, 40 to 70% by weight of the acrylic rubber-based polymer, 10 to 45% by weight of the aromatic vinyl-based monomer and the vinyl cyanide based on 100% by weight of a total of 100% by weight of the second graft copolymer. A thermoplastic resin composition comprising 1 to 25% by weight of a monomer.
[Claim 14]
The thermoplastic resin composition of claim 1, wherein the acrylic rubber-based polymer is at least one selected from a butyl (meth)acrylate polymer, a 2-ethylhexyl (meth)acrylate polymer, and a hexyl acrylate polymer.
[Claim 15]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic copolymer comprises 50 to 90% by weight of an aromatic vinylic monomer and 10 to 50% by weight of a vinylcyanic monomer based on 100% by weight of a total of 100% by weight of the thermoplastic copolymer. .
[Claim 16]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic copolymer comprises two or more thermoplastic copolymers having different vinyl cyan-based monomer contents.
[Claim 17]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a permanent antistatic thermoplastic resin composition.
[Claim 18]
A first graft copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer and a vinyl cyan-based monomer; a second graft copolymer comprising an acrylic rubber-based polymer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer; and a thermoplastic copolymer comprising an aromatic vinylic monomer and a vinylcyanic monomer; melt-kneading and extruding a thermoplastic resin composition comprising a base resin, a thermoplastic polyamide elastomer, an ethylene copolymer, and a metal pigment. Including, wherein the weight of the thermoplastic polyamide elastomer with respect to 100 parts by weight of the base resin is a, and the weight of the ethylene copolymer with respect to 100 parts by weight of the base resin is b, and the total weight of the base resin is 100% by weight. When the weight of the second graft copolymer is c, b+c≥0.5a, a method for producing a thermoplastic resin composition.
[Claim 19]
A molded article made of the thermoplastic resin composition of any one of claims 1 to 17.
[Claim 20]
The molded article according to claim 19, wherein the molded article has a surface resistance of 1 X 10^12 Ω/sq or less according to IEC 60093, and a gloss (45°) of 100 or more according to ASTM E97.