Title of Invention: Thermoplastic resin composition, manufacturing method thereof, and molded article comprising same
technical field
[One]
[Cross Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0135221 dated October 19, 2020 and Korean Patent Application No. 10-2021-0130783, which was re-applied on October 1, 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, a method for manufacturing the same, and a molded article comprising the same, and more particularly, to an ABS-based thermoplastic resin composition that contains an excessive amount of regenerated resin while maintaining existing mechanical properties and chemical resistance. The present invention relates to a thermoplastic resin composition having significantly improved physical property retention by preventing deterioration of physical properties.
background
[4]
The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer represented by acrylonitrile-butadiene-styrene resin (hereinafter referred to as 'ABS-based resin') has excellent processability, mechanical properties, and appearance characteristics, resulting in electrical/electronic It is widely used in product parts, automobiles, small toys, furniture, and construction materials.
[5]
On the other hand, as interest in the environment is growing, regulations to suppress carbon dioxide emissions are being strengthened. In particular, recently, as environmental pollution due to an increase in the use of plastics has emerged as a serious problem, the use of recycled resins is mandatory in the United States, etc. Regulations at the manufacturing stage are being tightened. Accordingly, the manufacturer must add a certain amount of regenerated resin or more when manufacturing a resin molded product, and an eco-friendly grade is given according to the content of the regenerated resin.
[6]
However, since regenerated resins are already processed resins, they contain additives such as colorants, lubricants, and mold release agents, and their properties have already changed while going through a high-temperature processing process. There is a problem in that the chemical properties and thermal stability are poor, and the appearance quality due to foreign substances is deteriorated.
[7]
In order to solve this problem, a method of including the content of the new resin in a composition including the regenerated resin at a certain level or more has been attempted. However, through this, the deterioration of mechanical properties can be alleviated to some extent, but the chemical resistance is still not satisfactory, and the problem of deterioration of appearance quality due to foreign substances on the surface during injection or extrusion processing is still unresolved. Moreover, as the number of processing increases, this problem becomes more serious.
[8]
[Prior art literature]
[9]
[Patent Literature]
[10]
(Patent Document 1) Korean Patent Laid-Open No. 2016-0144185
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[11]
In order to solve the problems of the prior art as described above, the present invention improves the problem of deterioration of physical properties due to repeated molding while maintaining the mechanical properties, chemical resistance and appearance quality inherent to the conventional ABS resin even though it contains an excessive amount of regenerated resin. An object of the present invention is to provide a thermoplastic resin composition.
[12]
Another object of the present invention is to provide a method for producing the thermoplastic resin composition and a molded article including the same.
[13]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[14]
In order to achieve the above object, the present invention provides 100 parts by weight of a base resin comprising (A) 20 to 90% by weight of a non-renewable thermoplastic resin and (B) 10 to 80% by weight of a recycled thermoplastic resin; (C) 1 to 10 parts by weight of an ethylene compound-vinyl acetate compound copolymer; and (D) 0.01 to 10 parts by weight of the inorganic pigment, wherein the (D) inorganic pigment has a refractive index of 1.65 or more and an average particle diameter of 10 to 500 nm.
[15]
[16]
The present invention also provides 100 parts by weight of a base resin comprising (A) 20 to 90% by weight of a non-renewable thermoplastic resin and (B) 10 to 80% by weight of a recycled thermoplastic resin; (C) 1 to 10 parts by weight of an ethylene compound-vinyl acetate compound copolymer; and (D) 0.01 to 10 parts by weight of an inorganic pigment having a refractive index of 1.65 or more, wherein the (A) non-renewable thermoplastic copolymer is (A-1) non-renewable vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft 20 to 70% by weight of the copolymer and (A-2) 30 to 80% by weight of the non-regenerated aromatic vinyl compound-vinyl cyan compound copolymer, wherein the (B) recycled thermoplastic resin is recycled vinyl cyan compound-conjugated diene compound- It provides a thermoplastic resin composition comprising at least one selected from the group consisting of an aromatic vinyl compound copolymer, a recycled polycarbonate resin, and a recycled aromatic vinyl compound-vinyl cyan compound copolymer.
[17]
[18]
The present invention also provides 100 parts by weight of a base resin comprising (A) 20 to 90% by weight of a non-renewable thermoplastic resin and (B) 10 to 80% by weight of a recycled thermoplastic resin; (C) 1 to 10 parts by weight of an ethylene compound-vinyl acetate compound copolymer; and (D) 0.01 to 10 parts by weight of an inorganic pigment; but provides a thermoplastic resin composition, characterized in that the melt index retention rate calculated by the following Equation 1 is 80% or more.
[19]
[Equation 1]
[20]
Melt index retention (%) = [MI n+5 /MI n ] X 100
[21]
(In Equation 1, MI n is a melt index value measured under conditions of 220° C. and 10 kg according to ASTM D1238 after extruding the thermoplastic resin composition n times at 200 to 250° C. and 250 to 400 rpm. , and MI n + 5 means a melt index value measured after repeatedly performing extrusion processing n + 5 times under the same conditions as above, where n is an integer of 1 to 10.)
[22]
[23]
The present invention also provides 100 parts by weight of a base resin comprising (A) 20 to 90% by weight of a non-renewable thermoplastic resin and (B) 10 to 80% by weight of a recycled thermoplastic resin; (C) 1 to 10 parts by weight of an ethylene compound-vinyl acetate compound copolymer; and (D) 0.01 to 10 parts by weight of an inorganic pigment, but provides a thermoplastic resin composition, characterized in that the impact strength retention calculated by the following Equation 2 is 80% or more.
[24]
[Equation 2]
[25]
Impact strength retention (%)= [ImSt n+5 /ImSt n ] X 100
[26]
(In Equation 2, ImSt n is Izod measured under the condition of 1/8" of specimen thickness according to ASTM D256 after extruding the thermoplastic resin composition n times at 200 to 250° C. and 250 to 400 rpm. It is an impact strength value, and ImSt n+5 means the Izod impact strength value measured after repeating n+5 times of extrusion under the same conditions as above, where n is an integer from 1 to 10.)
[27]
[28]
In addition, the present invention provides (A) 20 to 90% by weight of a non-renewable thermoplastic resin and (B) 100 parts by weight of a base resin comprising 10 to 80% by weight of a recycled thermoplastic resin, (C) ethylene compound-vinyl acetate compound copolymer 1 to 10 parts by weight and (D) including 0.01 to 10 parts by weight of an inorganic pigment, and kneading and extruding at 200 to 280°C; provides a method for producing a thermoplastic resin composition comprising.
[29]
The inorganic pigment (D) may preferably have a refractive index of 1.65 or more and an average particle diameter of 10 to 500 nm.
[30]
[31]
In addition, the present invention provides a molded article comprising the thermoplastic resin composition.
Effects of the Invention
[32]
According to the present invention, a thermoplastic resin composition that has excellent mechanical properties, chemical resistance, and appearance quality even though it contains an excessive amount of regenerated resin, and can exhibit excellent physical properties even after multiple processing by preventing deterioration of physical properties due to repeated molding processing process, There is an effect of providing a manufacturing method thereof and a molded article manufactured therefrom.
Brief description of the drawing
[33]
1 shows the chemical resistance test results of Examples and Comparative Examples of the present invention.
[34]
Figure 2 shows the results of recording the surface foreign matter occurrence points of Examples and Comparative Examples of the present invention.
[35]
3 shows the results of observing the surface foreign matter of Examples and Comparative Examples of the present invention with an optical microscope.
Modes for carrying out the invention
[36]
Hereinafter, the thermoplastic resin composition of the present invention will be described in detail.
[37]
The present inventors confirmed that when a specific compound is added together in a predetermined amount when mixing the regenerated resin in the ABS-based resin composition, mechanical properties and chemical resistance are improved, and the problem of deterioration of mechanical properties and appearance quality due to repeated processing is greatly improved. And, based on this, further research was devoted to complete the present invention.
[38]
[39]
The thermoplastic resin composition of the present invention comprises (A) 20 to 90% by weight of a non-renewable thermoplastic resin and (B) 100 parts by weight of a base resin comprising 10 to 80% by weight of a recycled thermoplastic resin; (C) 1 to 10 parts by weight of an ethylene compound-vinyl acetate compound copolymer; and (D) 0.01 to 10 parts by weight of an inorganic pigment, wherein (D) the inorganic pigment has a refractive index of 1.65 or more and an average particle diameter of 10 to 500 nm, in this case, while including an excessive amount of the regenerated resin It has excellent mechanical strength, such as impact strength and tensile strength, molding processability and chemical resistance, and excellent retention of physical properties for repeated molding processing.
[40]
[41]
The present invention also provides a thermoplastic resin composition comprising: (A) 20 to 90% by weight of a non-renewable thermoplastic resin and (B) 100 parts by weight of a base resin comprising 10 to 80% by weight of a recycled thermoplastic resin; (C) 1 to 10 parts by weight of an ethylene compound-vinyl acetate compound copolymer; and (D) 0.01 to 10 parts by weight of an inorganic pigment having a refractive index of 1.65 or more, wherein the (A) non-renewable thermoplastic copolymer is (A-1) non-renewable vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft 20 to 70% by weight of the copolymer and (A-2) 30 to 80% by weight of the non-regenerated aromatic vinyl compound-vinyl cyan compound copolymer, wherein the (B) recycled thermoplastic resin is recycled vinyl cyan compound-conjugated diene compound- It is characterized in that it contains at least one selected from the group consisting of an aromatic vinyl compound copolymer, a recycled polycarbonate resin, and a recycled aromatic vinyl compound-vinyl cyan compound copolymer. It has excellent mechanical strength, molding processability, and chemical resistance, such as, and excellent retention of physical properties for repeated molding processing.
[42]
[43]
The thermoplastic resin composition of the present invention also comprises: (A) 20 to 90% by weight of a non-renewable thermoplastic resin and (B) 100 parts by weight of a base resin comprising 10 to 80% by weight of a recycled thermoplastic resin; (C) 1 to 10 parts by weight of an ethylene compound-vinyl acetate compound copolymer; and (D) 0.01 to 10 parts by weight of an inorganic pigment; but it is characterized in that the melt index retention rate calculated by the following Equation 1 is 80% or more, and in this case, the impact strength and tensile strength, etc., while including an excessive amount of the regenerated resin There is an advantage in that the mechanical strength, molding processability, and chemical resistance are excellent, and the property retention rate for repeated molding processing is excellent.
[44]
[Equation 1]
[45]
Melt index retention (%) = [MI n+5 /MI n ] X 100
[46]
(In Equation 1, MI n is 220 ° C., 10 kg conditions according to ASTM D1238 after performing extrusion processing n times for the thermoplastic resin composition at an extrusion temperature of 200 to 250 ° C and a screw rotation speed of 250 to 400 rpm. It is the measured melt index value, and MI n+5 refers to the melt index value measured after repeating the extrusion process n+5 times under the same conditions as above, where n is an integer from 1 to 10.)
[47]
[48]
The thermoplastic resin composition of the present invention also comprises: (A) 20 to 90% by weight of a non-renewable thermoplastic resin and (B) 100 parts by weight of a base resin comprising 10 to 80% by weight of a recycled thermoplastic resin; (C) 1 to 10 parts by weight of an ethylene compound-vinyl acetate compound copolymer; and (D) 0.01 to 10 parts by weight of an inorganic pigment; but it is characterized in that the impact strength retention calculated by the following Equation 2 is 80% or more, and in this case, the impact strength and tensile strength, etc., while including an excessive amount of the regenerated resin There is an advantage in that the mechanical strength, molding processability, and chemical resistance are excellent, and the property retention rate for repeated molding processing is excellent.
[49]
[Equation 2]
[50]
Impact strength retention (%)= [ImSt n+5 /ImSt n ] X 100
[51]
(In Equation 2, ImSt n is 1/8" of the specimen thickness according to ASTM D256 after performing n times of extrusion processing of the thermoplastic resin composition under the conditions of an extrusion temperature of 200 to 250° C. and a screw rotation speed of 250 to 400 rpm. Izod impact strength value measured under the conditions, ImSt n+5 means the Izod impact strength value measured after performing the extrusion process n+5 times repeatedly under the same conditions as above, where n is an integer from 1 to 10 .)
[52]
[53]
The n value of Equation 1 and the n value of Equation 2 may be independently the same as or different from each other.
[54]
[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]
[57]
In the present description, the recycled thermoplastic resin is not particularly limited if it is generally recognized as a recycled thermoplastic resin in the technical field to which the present invention pertains, as long as it follows the definition of the present invention. For example, it means that it is prepared as a usable raw material through screening, washing and pulverization from the collected waste plastics. In addition, if necessary, it can be used in the form of pellets through the extrusion process, in this case, there is an advantage that does not require additional processing such as additional purification. Since the regenerated thermoplastic resin has been processed at least once, it may contain additives such as colorants, lubricants, and/or release agents.
[58]
[59]
In the present description, the non-renewable thermoplastic resin is in contrast to the recycled thermoplastic resin defined above, and may be prepared by directly preparing by polymerizing monomers constituting the thermoplastic resin, or may be an available product corresponding thereto.
[60]
[61]
Hereinafter, each component constituting the thermoplastic resin composition of the present disclosure will be described in detail as follows.
[62]
[63]
(A) non-recycled thermoplastic
[64]
The (A) non-renewable thermoplastic resin is included in an amount of 20 to 90% by weight based on the total weight of the base resin, and in this case, mechanical properties, molding processability, chemical resistance, and appearance quality are excellent. The content of the (A) non-renewable thermoplastic resin included in the total weight of the base resin is preferably 20 to 80% by weight, more preferably 25 to 75% by weight, even more preferably 25 to 70% by weight. and within this range, mechanical properties, molding processability, appearance quality, and physical property balance may be more excellent.
[65]
[66]
The (A) non-renewable thermoplastic resin is, for example, (A-1) non-renewable vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer (hereinafter referred to as '(A-1) graft copolymer') 20 to 70% by weight and (A-2) 30 to 80% by weight of the non-renewable aromatic vinyl compound-vinyl cyan compound copolymer (hereinafter referred to as '(A-2) copolymer'), in this range There are advantages in mechanical properties, molding processability, chemical resistance and appearance quality in the interior.
[67]
The (A) non-renewable thermoplastic resin may preferably include 20 to 60% by weight of the (A-1) graft copolymer and 40 to 80% by weight of the (A-2) copolymer based on the total weight thereof, More preferably, it may contain 20 to 50% by weight of the (A-1) graft copolymer and 50 to 80% by weight of the (A-2) copolymer.
[68]
[69]
The (A-1) graft copolymer is, for example, 50 to 80% by weight of a conjugated diene rubber including a conjugated diene compound, 5 to 20% by weight of a vinyl cyanide compound, and 10 to 40% by weight of an aromatic vinyl compound. It may be one, and there is an advantage in that mechanical properties, molding processability, appearance quality, and physical property balance are excellent within this range.
[70]
The (A-1) graft copolymer may include 50 to 70% by weight of a conjugated diene rubber, 5 to 15% by weight of a vinyl cyanide compound, and 20 to 40% by weight of an aromatic vinyl compound as a preferred example, more preferably Preferably, it may contain 55 to 65% by weight of a conjugated diene rubber, 10 to 15% by weight of a vinyl cyanide compound, and 20 to 30% by weight of an aromatic vinyl compound. have.
[71]
The average particle diameter of the conjugated diene rubber included in the (A-1) graft copolymer may be, for example, 2,000 to 5,000 Å, preferably 2,000 to 4,000 Å, more preferably 2,500 to 3,500 Å, within this range There is a better effect of impact strength without deterioration of other physical properties.
[72]
In this description, the average particle diameter of the conjugated diene rubber can be measured using a dynamic light scattering method unless otherwise specified, and in detail, a particle size distribution analyzer (product name: Nicomp 380, manufacturer: PSS) is used. Thus, it is measured as an intensity value in a Gaussian mode. At this time, as a specific measurement example, the sample is prepared by diluting 0.1 g of Latex (TSC 35 to 50 wt%) 1,000 to 5,000 times with deionized or distilled water, that is, diluting it appropriately so as not to significantly deviate from the Intensity Setpoint 300 kHz, and putting it in a glass tube. , 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, It can be measured with a channel width of 10 μsec.
[73]
[74]
[75]
The (A-1) graft copolymer may have, for example, a graft rate of 20 to 70%, preferably 20 to 55%, more preferably 20 to 45%, and compatibility and molding processability within this range There is an excellent effect of ensuring proper balance with other mechanical properties.
[76]
In this description, the graft rate is determined by adding 30 g of acetone to 0.5 g of the graft (co)polymer dry powder, stirring at 210 rpm for 12 hours at room temperature (SKC-6075, Lab companion), and centrifuging it (Supra R30, Hanil Science) Insoluble fractions that were not dissolved in acetone were collected by centrifugation at 0°C at 18,000 rpm for 3 hours with Thus, it can be obtained by calculating with the following Equation (1).
[77]
[Equation 1]
[78]
Graft rate (%) = [weight of grafted monomer (g) / rubber weight (g)] * 100
[79]
In Equation 1, the weight (g) of the grafted monomer is the weight obtained by dissolving the graft copolymer in acetone and centrifuging it to the weight of the insoluble matter (gel) obtained by subtracting the rubber weight (g), and the rubber weight ( g) is the weight of the theoretically added rubber component in the graft copolymer powder.
[80]
The drying may proceed until there is no further change in weight.
[81]
[82]
The vinyl cyanide compound-aromatic vinyl compound copolymer included in the (A-1) graft copolymer may have, for example, a weight average molecular weight of 50,000 to 200,000 g/mol, or 65,000 to 180,000 g/mol, within this range. may have good flowability and excellent workability and impact resistance, but is not limited thereto. Here, the vinyl cyan compound-aromatic vinyl compound copolymer included in the (A-1) graft copolymer is a vinyl cyan compound-aromatic vinyl compound grafted onto the conjugated diene rubber of the (A-1) graft copolymer. means a copolymer.
[83]
In the present description, unless otherwise defined, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as the eluent ) can be measured relative to a standard PS (standard polystyrene) sample. At this time, as a specific example of measurement, solvent: THF, column temperature: 40°C, flow rate: 0.3ml/min, sample concentration: 20mg/ml, injection amount: 5 μl, column model: 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI temperature: 35℃, data processing: Agilent ChemStation S/W, test method (Mn, Mw and PDI): It can be measured under OECD TG 118 conditions.
[84]
[85]
The (A-1) graft copolymer may be prepared by a known polymerization method including, for example, emulsion polymerization, suspension polymerization, bulk polymerization, and the like, and preferably may be prepared by emulsion polymerization.
[86]
The (A-1) graft copolymer is, for example, 50 to 80 parts by weight of the conjugated diene rubber latex (solid content) based on 100 parts by weight of the conjugated diene rubber, the aromatic vinyl compound and the vinyl cyan compound included in the graft copolymer. A monomer mixture comprising 5 to 20 parts by weight of a vinyl cyanide compound and 10 to 40 parts by weight of an aromatic vinyl compound in a mixed solution comprising 0.1 to 5 parts by weight of an emulsifier, 0.1 to 3 parts by weight of a molecular weight regulator, and 0.05 to 1 parts by weight of an initiator It may be prepared including the step of continuously or batch input and polymerization.
[87]
In another example, the (A-1) graft copolymer contains 50 to 80 parts by weight of conjugated diene rubber latex (based on solid content) and 60 parts by weight of ion-exchanged water based on 100 parts by weight of a total of 100 parts by weight of the conjugated diene rubber, the aromatic vinyl compound, and the vinyl cyanide compound. to 150 parts by weight, 5 to 20 parts by weight of a vinyl cyanide compound mixed in a separate mixing device, 10 to 40 parts by weight of an aromatic vinyl compound, 10 to 50 parts by weight of ion-exchanged water, 0.09 to 1.5 parts by weight of an initiator, 0.1 to an emulsifier A mixed solution containing 2 parts by weight and 0.05 to 1.5 parts by weight of a molecular weight regulator is added at 65 to 75° C. for 2 to 4 hours, then 0.01 to 0.5 parts by weight of an initiator is added, and the temperature is raised to 75 to 80° C. over 30 to 90 minutes. It can be prepared by terminating the graft polymerization at a polymerization conversion rate of 93 to 99% by weight, and in this case, there is an effect excellent in impact resistance, mechanical strength and molding processability.
[88]
In the present description, the polymerization conversion rate may be defined as the weight% of the monomers converted into the copolymer until the measurement time based on the total of 100% by weight of the monomers input until the end of the polymerization, and the method for measuring the polymerization conversion rate is determined according to this definition. The method for measuring polymerization conversion is not particularly limited, and 1.5 g of the copolymer latex prepared as a specific example is dried in a hot air dryer at 150° C. for 15 minutes, then the weight is measured and the total solid content (Total Solid Content) ; TSC) and can be calculated by substituting it in Equation 5 below. Equation 5 below is based on the total weight of the added monomer being 100 parts by weight.
[89]
[Equation 4]
[90]

[91]
[Equation 5]
[92]
Polymerization conversion (%) = [total solid content (TSC) × (total weight of the added monomer, ion-exchanged water, and auxiliary materials) / 100] - (weight of added additives other than monomer and ion-exchanged water)
[93]
In Equation 5, the auxiliary material refers to an initiator, an emulsifier, and a molecular weight regulator, and includes an electrolyte when an electrolyte is used.
[94]
[95]
The conjugated diene compound is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, isoprene, chloroprene and pyrerylene. It may be at least one selected from the group consisting of.
[96]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and derivatives thereof.
[97]
The aromatic vinyl compound is, for example, styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brobo styrene, ρ-bro It may be at least one selected from the group consisting of parent styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene.
[98]
In a preferred embodiment, the conjugated diene rubber may be at least one selected from the group consisting of butadiene polymer, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and ethylene-propylene copolymer, but is not limited thereto. do.
[99]
In the present description, the derivative is a compound in which a hydrogen atom or an atomic group of the original compound is substituted with another atom or group, for example, refers to a compound substituted with a halogen or an alkyl group.
[100]
[101]
The emulsifier may be, for example, at least one selected from the group consisting of allyl aryl sulfonate, alkali methyl alkyl sulfonate, sulfonated alkyl ester, fatty acid soap, and rosin acid alkali salt, and in this case, excellent stability of polymerization reaction there is
[102]
The molecular weight modifier may be, for example, at least one selected from the group consisting of t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl methcaptan and carbon tetrachloride, preferably t-dodecyl mercaptan. .
[103]
As the initiator, for example, a water-soluble persulfate polymerization initiator, a fat-soluble polymerization initiator, or an oxidation-reduction catalyst system may be used. may be at least one selected from It may be at least one selected from the group consisting of peroxides.
[104]
The latex obtained by the emulsion polymerization is, for example, agglomerated with a coagulant such as sulfuric acid, MgSO 4 , CaCl 2 or Al 2 (SO 4 ) 3 , and then aged, dehydrated and dried to obtain a powder state.
[105]
The (A-1) graft copolymer may be prepared, for example, by further including an oxidation-reduction catalyst, and the oxidation-reduction catalyst is, for example, diumformaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, sulfuric acid. It may be at least one selected from the group consisting of ferrous iron, dextrose, sodium pyrrolate and sodium sulfite, but is not limited thereto, and is not limited as long as it is a type commonly used in the manufacture of an ABS-based graft copolymer. You can choose to use it accordingly.
[106]
[107]
Other additives, such as electrolytes, which are not specifically mentioned in the present description, may be appropriately selected as needed, and are not particularly limited in the range generally applied to polymerization of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer. does not
[108]
[109]
Other reaction conditions such as reaction time, reaction temperature, pressure, time of input of reactants, etc. in the method for preparing the graft copolymer other than the above-described description are not particularly limited as long as they are within the range commonly used in the art to which the present invention belongs, and necessary It can be appropriately selected and implemented according to the
[110]
[111]
As another example, as the graft copolymer (A-1), commercially available products may be used as long as it follows the definition of the present invention.
[112]
[113]
The copolymer (A-2) may include, for example, 20 to 40% by weight of a vinyl cyanide compound and 60 to 80% by weight of an aromatic vinyl compound, and in this case, mechanical properties, molding processability and chemical resistance are better There is this.
[114]
The copolymer (A-2) is preferably 20 to 35 wt% of a vinyl cyan compound and 65 to 80 wt% of an aromatic vinyl compound, more preferably 23 to 33 wt% of a vinyl cyanide compound and 67 to 77 wt% of an aromatic vinyl compound % may be included, and within this range, there is a more excellent effect of chemical resistance and physical property balance.
[115]
[116]
The copolymer (A-2) may have, for example, a weight average molecular weight of 70,000 to 200,000 g/mol, preferably 80,000 to 180,000 g/mol, more preferably 90,000 to 160,000 g/mol, within this range. It has excellent chemical resistance and excellent processability and physical property balance.
[117]
The aromatic vinyl compound included in the (A-2) copolymer is, for example, styrene, ethyl styrene, ο-brobo styrene, ρ-bromo styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, It may be at least one selected from the group consisting of m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, and preferably styrene.
[118]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, preferably acrylonitrile.
[119]
[120]
The (A-2) copolymer is, for example, 0 to 30% by weight, preferably 1 to 20% by weight of at least one selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides and maleic monomers; More preferably, it may be further comprised in an amount of 5 to 10% by weight, and in the case of a copolymer polymerized by adding such a comonomer, heat resistance and processability are more excellent.
[121]
The unsaturated carboxylic acid may be, for example, at least one selected from the group consisting of maleic acid, acrylic acid and methacrylic acid, and the unsaturated carboxylic acid anhydride may be, for example, an anhydride of the unsaturated carboxylic acid, and the maleimide-based monomer is For example, it may be a maleimide substituted with N by an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms, and specific examples thereof may be N-phenyl maleimide, maleimide, or a mixture thereof.
[122]
[123]
The (A-2) aromatic vinyl compound-vinyl cyan compound copolymer can be prepared by performing methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and continuous bulk polymerization, and in particular, prepared by emulsion polymerization and suspension polymerization It is preferable to use one, and any commercially available product may be used as long as it follows the definition of the present invention.
[124]
[125]
(B) Recycled thermoplastic resin
[126]
The (B) regenerated thermoplastic resin is included in an amount of 10 to 80% by weight based on the total weight of the base resin, and in this case, mechanical properties, molding processability, chemical resistance and appearance quality are excellent. The content of the (B) regenerated thermoplastic resin included in the total weight of the base resin is preferably 20 to 80 wt%, more preferably 25 to 75 wt%, even more preferably 30 to 75 wt%, , within this range, mechanical properties, molding processability, appearance quality, and physical property balance may be more excellent.
[127]
[128]
The (B) recycled thermoplastic resin is, for example, a recycled vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer (hereinafter referred to as 'regenerated ABS-based resin'), a recycled polycarbonate resin (hereinafter 'regenerated PC-based resin') ) and a recycled aromatic vinyl compound-vinyl cyan compound copolymer (hereinafter, referred to as 'regenerated SAN-based resin') may include at least one selected from the group consisting of, in this case, mechanical properties, molding processability, and chemical resistance and excellent appearance quality, but is not limited thereto.
[129]
[130]
The unit constituting the recycled ABS-based resin and the recycled SAN-based resin may be selected within the same range as mentioned in (A) the non-renewable thermoplastic copolymer as a preferred example.
[131]
[132]
The type of the regenerated PC-based resin is not particularly limited, but may be, for example, a polymer polymerized including a bisphenol-based monomer and a carbonate precursor.
[133]
The bispinol-based monomer is, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis (4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z; BPZ), 2,2-bis(4-hydroxy-3 ,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2 ,2-bis(4-hydroxy-3chlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl) )propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane and α,ω-bis[3-(ο-hydroxyphenyl)propyl] It may be at least one selected from the group consisting of polydimethylsiloxane.
[134]
The carbonate precursor is, for example, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m- cresyl carbonate, dinaphthyl carbonate, bis ( diphenyl) carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, and bishaloformate may be at least one selected from the group consisting of.
[135]
The regenerated PC-based resin may be, for example, at least one selected from the group consisting of a linear polycarbonate resin, a branched polycarbonate resin, and a polyester carbonate copolymer resin, preferably a linear polycarbonate resin, In this case, the fluidity is improved and the appearance characteristics are more excellent.
[136]
A specific example of the linear polycarbonate resin may be a bisphenol-A-based polycarbonate resin, but is not limited thereto.
[137]
[138]
The (B) recycled thermoplastic resin further includes at least one selected from the group consisting of, for example, a recycled polyethylene resin, a recycled polypropylene resin, a recycled polyester resin, a recycled polystyrene-based resin, a recycled polyamide resin, and a recycled polyvinyl chloride resin. In this case, there is an advantage of providing a composition having excellent physical properties by using more various regenerated resins.
[139]
[140]
The (B) regenerated thermoplastic resin may have, for example, a weight average molecular weight of 10,000 to 1,000,000 g/mol, 15,000 to 900,000 g/mol, or 20,000 to 900,000 g/mol, and mechanical properties such as impact strength within this range Although this is excellent, the appearance quality may be excellent, but the present invention is not limited thereto.
[141]
[142]
The (B) regenerated thermoplastic resin may have, for example, a glass transition temperature of 60 to 180° C., preferably 63 to 170° C., and more preferably 65 to 160° C., and mechanical properties and molding within this range. There is an effect superior to the workability.
[143]
In the present substrate, the glass transition temperature (Tg) may be measured at a temperature increase rate of 10° C./min using TA Instruments Q100 Differential Scanning Calorimetry (DSC) according to ASTM D 3418.
[144]
[145]
The (B) recycled thermoplastic resin may be, for example, a commercially available product as long as it follows the definition of the present invention.
[146]
[147]
(C) ethylene compound-vinyl acetate compound copolymer
[148]
The (C) ethylene compound-vinyl acetate compound copolymer (hereinafter referred to as '(C) copolymer') may be included in an amount of 1 to 10 parts by weight, preferably 1 to 8 parts by weight, based on 100 parts by weight of the base resin. parts, more preferably 1 to 6 parts by weight, and in this case, chemical resistance and appearance quality are more excellent, and there is an advantage of excellent retention of physical properties for repeated molding processing. As a particularly preferred example, the (C) copolymer may be included in an amount of 1 to 5 parts by weight, more preferably 1 to 4 parts by weight, and 2 to 4 parts by weight as another preferred example based on 100 parts by weight of the base resin, In this case, the chemical resistance and appearance quality are better, the property retention rate for repeated molding processing is excellent, and there is an advantage that peeling does not occur in the cross section of the molded product.
[149]
[150]
The (C) copolymer may include 50% by weight or more of crystalline units as a preferred example, more preferably 60 to 95% by weight, even more preferably 65 to 90% by weight, Within the range, chemical resistance and appearance quality are excellent, and in particular, there is an advantage in that the property retention rate for repeated molding processing is superior. Here, the crystalline unit refers to a monomer-derived unit capable of forming crystals, and specifically refers to an ethylene compound-derived unit.
[151]
[152]
The (C) copolymer may include, for example, 50 to 95% by weight of an ethylene compound and 5 to 50% by weight of a vinyl acetate compound, preferably 70 to 95% by weight of an ethylene compound and 5 to 30% by weight of a vinyl acetate compound % by weight, more preferably 75 to 95% by weight of an ethylene compound and 5 to 25% by weight of a vinyl acetate compound, even more preferably 80 to 90% by weight of an ethylene compound and 10 to 20% by weight of a vinyl acetate compound Within this range, chemical resistance, appearance quality, and physical property retention for repeated molding processing are superior. In another preferred example, the copolymer (C) contains 60 to 85% by weight of an ethylene compound and 15 to 40% by weight of a vinyl acetate compound, more preferably 60 to 80% by weight of an ethylene compound and 20 to 40% by weight of a vinyl acetate compound, Even more preferably, 65 to 80% by weight of an ethylene compound and 20 to 35% by weight of a vinyl acetate compound may be included, and within this range, the impact strength and appearance quality are better and the retention rate of physical properties for repeated molding processing There is a greater advantage than this.
[153]
[154]
The method for preparing the ethylene compound-vinyl acetate compound copolymer is not particularly limited as long as it is a method commonly used in the art to which the present invention pertains.
[155]
[156]
The (C) copolymer is, for example, based on 100 parts by weight of the sum of the ethylene compound and the vinyl acetate compound, 50 to 95 parts by weight of the ethylene compound, 5 to 50 parts by weight of the vinyl acetate compound, and 0.001 to 0.1 parts by weight of the initiator. It can be prepared including the step of free radical polymerization.
[157]
[158]
The (C) copolymer polymerization reaction may be carried out, for example, under a pressure of 500 bar or more and a temperature of 130 to 300 °C, preferably 700 to 5,000 bar and 150 to 300 °C, more preferably 800 to 4,000 bar and It can proceed under the conditions of 150 to 250 ℃, there is an advantage that a high polymerization conversion can be obtained within this range and the efficiency of the polymerization reaction is more excellent.
[159]
[160]
Other additives not specifically mentioned in the present description, such as initiators or chain transfer agents, may be appropriately selected as needed, and are not particularly limited in the range generally applied to the preparation of the ethylene compound-vinyl acetate compound copolymer.
[161]
[162]
For example, as the copolymer (C), commercially available products may be used as long as it follows the definition of the present invention.
[163]
[164]
The copolymer (C) may have, for example, a weight average molecular weight of 10,000 to 800,000 g/mol or 30,000 to 700,000 g/mol, and may have better molding processability and chemical resistance within this range, but is limited thereto not.
[165]
As an example, the copolymer (C) may have a molecular weight distribution (PDI) of 1.5 to 3.0, preferably 2.0 to 2.5, and may have better molding processability and appearance quality within this range. However, the present invention is not limited thereto.
[166]
In the present description, the molecular weight distribution (PDI) is defined as M w /M n , where M w and M n mean a weight average molecular weight and a number average molecular weight, respectively.
[167]
The weight average molecular weight and number average molecular weight of the copolymer (C) can be measured according to a method commonly practiced in the art to which the present invention pertains, and as a specific example, using a TCB (trichlorobenzene) solvent as an eluent, It can be measured as a relative value with respect to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze). At this time, as a specific example of measurement, solvent: TCB + 0.015 wt% BHT (Butylated hydroxytoluene), column temperature: 160°C, flow rate: 1.0 ml/min, sample concentration: 1.0 mg/ml, injection amount: 200 μl, column model: 3 x PLgel 10㎛ MIXED-B (300x7.5mm), equipment name: Agilent PL-PGC 220, Refractive index detector: Agilent G1362 RID, RI temperature: 160℃, data processing: Agilent ChemStation S/W, test method (Mn, Mw) and PDI): It can be measured under the conditions of OECD TG 118.
[168]
[169]
The (C) copolymer may have a melt index of 2 to 50 g/10min, preferably 15 to 30 g/10min, measured under the conditions of 190°C and 2.16 kg according to ASTM D1238, for example, Within this range, there is an advantage in that the appearance quality is better without deterioration of other physical properties.
[170]
[171]
(D) inorganic pigment
[172]
The (D) inorganic pigment may be included, for example, in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the base resin, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, even more preferably 0.5 to 7 parts by weight, more preferably 1 to 5 parts by weight, even more preferably 1 to 4 parts by weight, there is an advantage in that mechanical properties and appearance quality are more excellent without deterioration of other physical properties within this range .
[173]
[174]
As the (D) inorganic pigment, it is more advantageous in terms of improving appearance quality to use a refractive index of 1.65 or more. The refractive index of the inorganic pigment (D) may be preferably 1.65 to 3.0, more preferably 1.7 to 2.8, and still more preferably 1.75 to 2.75.
[175]
In the present substrate, the refractive index of the inorganic pigment may be measured at 25° C. with REICHERT MARK 2 PLUS according to ASTM D 542-50.
[176]
[177]
It is more advantageous in terms of mechanical properties and appearance quality improvement to use the inorganic pigment (D) having an average particle diameter of 10 to 500 nm. The average particle diameter of the (D) inorganic pigment is preferably 50 to 400 nm, more preferably 50 to 300 nm.
[178]
In this description, the average particle diameter of the inorganic pigment may be a value measured by BET unless otherwise specified, and in detail, using a nitrogen gas adsorption method, BET analysis equipment (Surface Area and Porosity Analyzer ASAP 2020, Micromeritics) is used can be measured by
[179]
[180]
The (D) inorganic pigment may be, for example, at least one selected from the group consisting of titanium dioxide, zinc oxide, zinc sulfide, aluminum hydroxide, iron oxide, magnesium oxide, calcium carbonate, barium sulfate, clay, carbon black and white carbon, Preferably, it may be at least one selected from the group consisting of titanium dioxide, zinc oxide and carbon black, more preferably at least one selected from the group consisting of titanium dioxide and carbon black, and in this case, the appearance quality is improved without deterioration of other physical properties. There are better advantages.
[181]
[182]
Thermoplastic resin composition
[183]
The thermoplastic resin composition of the present invention comprises (A) 20 to 90% by weight of a non-recycled thermoplastic resin and (B) 100 parts by weight of a base resin comprising 10 to 80% by weight of a recycled thermoplastic resin, (C) an ethylene compound-vinyl acetate compound copolymer 1 to 10 parts by weight of the coalescing and (D) 0.01 to 10 parts by weight of the inorganic pigment, in this case, while maintaining the mechanical properties, molding processability and chemical resistance of the conventional ABS-based resin, deterioration of physical properties due to repeated molding processing is prevented. There is an excellent effect of the retention rate.
[184]
[185]
The inorganic pigment (D) preferably has a refractive index of 1.65 or more and an average particle diameter of 10 to 500 nm.
[186]
The thermoplastic resin composition may have, for example, a melt index retention rate of 80% or more, preferably 85% or more, more preferably 90% or more, calculated by Equation 1 below, in a high-temperature molding process such as extrusion processing. It is possible to provide a regenerated resin composition having excellent physical property retention as described above, which is more advantageous for quality uniformity, and excellent in mechanical properties, chemical resistance and appearance quality even when repeatedly performed.
[187]
[Equation 1]
[188]
Melt index retention (%) = [MI n+5 /MI n ] X 100
[189]
(In Equation 1, MI n is a melt index value measured under conditions of 220° C. and 10 kg according to ASTM D1238 after extruding the thermoplastic resin composition n times at 200 to 250° C. and 250 to 400 rpm. (g/10min), and MI n+5 means a melt index value (g/10min) measured after repeating the extrusion process n+5 times under the same conditions as above, where n is an integer from 1 to 10 to be.)
[190]
[191]
The thermoplastic resin composition may have an impact strength retention rate of 80% or more, preferably 85% or more, more preferably 90% or more, calculated by the following Equation 2, for example, in a high-temperature molding process such as extrusion processing. It is possible to provide a regenerated resin composition having excellent physical property retention as described above, which is more advantageous for uniform quality, and excellent in mechanical properties, chemical resistance and appearance quality even when repeatedly performed.
[192]
[Equation 2]
[193]
Impact strength retention (%)= [ImSt n+5 /ImSt n ] X 100
[194]
(In Equation 2, ImSt n is Izod measured under the condition of 1/8" of specimen thickness according to ASTM D256 after extruding the thermoplastic resin composition n times at 200 to 250° C. and 250 to 400 rpm. Impact strength value (kgf cm/cm), ImSt n+5 means Izod impact strength value (kgf cm/cm) measured after repeating n+5 times of extrusion under the same conditions as above, where n is an integer from 1 to 10.)
[195]
In Equations 1 and 2, n may independently be 0 to 10, 0 to 7, 0 to 5, or 0 to 3, and preferably 1 to 8, 1 to 6, 1 to 5, or 1 to can be 4
[196]
In the thermoplastic resin composition of the present invention, by adjusting the composition ratio to a specific range as described above, mechanical properties, chemical resistance and appearance quality are greatly improved even when the regenerated resin is applied in excess, and high-temperature molding processing such as extrusion is repeated 5 times or more. Even so, deterioration of physical properties is prevented, and thus the amount of the recycled resin used and the number of reuse of the recycled resin can be greatly improved.
[197]
[198]
The thermoplastic resin composition is, for example, within the specified composition ratio range, a specimen having a size of 200 mm * 10.0 mm * 3.2 mm is fixed to a curvature jig having a stress of 1%, 1 cc of Nanox detergent is applied, and then the diameter on the surface of the specimen The chemical resistance (Environmental Stress-Cracking Resistance, ESCR), which is measured as the time for cracks of 3 mm or more, is 20 hours or more, which has excellent chemical resistance. When the chemical resistance satisfies the above range, for example, it is possible to prevent the occurrence of cracks due to the use of organic solvents and detergents in post-processing processes such as painting or deposition, and as another example, the use of vehicle air fresheners when used as vehicle air vent parts. It can prevent cracks from occurring, so it can be applied to various fields and has the effect of preventing deterioration of the product even during use.
[199]
As a specific example, chemical resistance in the present disclosure may be measured at 23° C. using a liquid-type Nanox detergent.
[200]
Nanox detergent is a detergent widely known as a highly concentrated detergent compared to commonly used household laundry detergent. In the case of household laundry detergent, the concentration of surfactant is generally about 20 to 30% by weight, whereas Nanox detergent is 50 to 60% by weight. It is known that the concentration of surfactant is very high and the cleaning power is strong. However, when Nanox detergent is used in a general washing machine as an example, chemical deterioration of the plastic material mainly used for home appliances, such as cracks occurring in the part where the plastic (thermoplastic resin) material inside the washing machine comes into direct contact with the Nanox detergent may cause problems, and in severe cases, it may cause malfunction. As an example, the thermoplastic resin composition of the present substrate has the advantage of excellent chemical resistance to Nanox detergent as described above. There is an advantage. In particular, when used as an interior material for a washing machine, a dish washing machine, etc., there is an advantage that more various detergents can be used.
[201]
[202]
The thermoplastic resin composition may have a melt index of 15.0 g/10 min or more, preferably 15.0 to 40 g/10 min, more preferably 17.0 to 40 g/ 10 min, and more preferably 20 to 38 g/10 min, there is an effect of more excellent molding processability and appearance quality without deterioration of other physical properties within this range.
[203]
[204]
The thermoplastic resin composition may have an Izod impact strength of 17 kgf·cm/cm or more, preferably 17 to 50 kgf·cm/cm, measured using a specimen having a thickness of 1/8″ according to ASTM D256, for example, More preferably, it may be 20 to 45 kgf·cm/cm, and within this range, there is an excellent effect of mechanical strength without deterioration of other physical properties.
[205]
[206]
The thermoplastic resin composition may have a tensile strength of 380 kg/cm 2 or more, preferably 380 to 500, measured under a condition of a tensile rate of 50 mm/min using a specimen having a thickness of 1/8” according to ASTM D638, for example. kg/cm 2 , and more preferably 400 to 480 kg/cm 2 , and within this range, mechanical strength is excellent without deterioration of other physical properties.
[207]
[208]
Method for producing a thermoplastic resin composition
[209]
The thermoplastic resin composition of the present invention comprises (A) 20 to 90% by weight of a non-renewable thermoplastic resin and (B) 100 parts by weight of a base resin comprising 10 to 80% by weight of a recycled thermoplastic resin; (C) 1 to 10 parts by weight of an ethylene compound-vinyl acetate compound copolymer; and (D) 0.01 to 10 parts by weight of an inorganic pigment; including, kneading and extruding at 200 to 280°C. In this case, even though the regenerated resin is included in excess, the physical properties inherent to the existing ABS-based resin are maintained, and both the appearance characteristics and the physical property retention rate for repeated molding processing are excellent.
[210]
[211]
The inorganic pigment (D) preferably has a refractive index of 1.65 or more and an average particle diameter of 10 to 500 nm.
[212]
[213]
In the kneading and extruding step, for example, the temperature and the screw rotation speed of the extruder are 200 to 280 ° C. and 250 to 600 rpm, respectively, preferably 210 to 250 ° C. and 300 to 550 rpm. In this case, mechanical properties, It has excellent chemical resistance, heat resistance and appearance quality.
[214]
The kneading and extruding step may be performed by using, for example, at least one selected from the group consisting of a single screw extruder, a twin screw extruder and a Banbury mixer, and uniformly mixing the composition and then extruding the thermoplastic resin in the form of pellets. A composition can be obtained, and in this case, deterioration of mechanical properties and deterioration of heat resistance are prevented and the appearance quality is excellent.
[215]
[216]
The thermoplastic resin composition is optionally a lubricant, a heat stabilizer, a light stabilizer, an antioxidant, an ultraviolet stabilizer, a dye, a colorant, a mold release agent, an antistatic agent, an antibacterial agent, a processing aid, a compatibilizer, a metal inert, if necessary, during the kneading and extrusion process. It may further include one or more additives selected from the group consisting of a fire agent, a flame retardant, a flame retardant, an anti-drip agent, a foaming agent, a plasticizer, a reinforcing agent, a filler, a matting agent, an anti-friction agent, and an anti-wear agent.
[217]
The additive is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the total of (A) non-renewable thermoplastic resin, (B) recycled thermoplastic resin, (C) copolymer, and (D) inorganic pigment. It may be further included in an amount of parts by weight, 0.05 to 5 parts by weight, or 0.05 to 3 parts by weight, and within this range, there is an effect that the required physical properties are well realized without reducing the original physical properties of the thermoplastic resin composition.
[218]
The lubricant may be, for example, at least one selected from ethylene bis steramide, polyethylene oxide wax, magnesium stearate, calcium steramide, stearic acid, and silicone oil, but is not limited thereto.
[219]
The silicone oil may be, for example, at least one selected from the group consisting of dimethyl silicone oil, methyl hydrogen silicone oil, ester-modified silicone oil, hydroxy silicone oil, carbinol-modified silicone oil, vinyl silicone oil, and silicone acrylate.
[220]
The antioxidant may include, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, and the like, but is not limited thereto.
[221]
The antistatic agent may include, for example, one or more anionic surfactants, non-ionic surfactants, and the like, but is not limited thereto.
[222]
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.
[223]
[224]
molded product
[225]
The molded article of the present invention is characterized in that it includes the thermoplastic resin composition of the present invention, and in this case, even though it is manufactured including the regenerated resin, it has excellent mechanical properties, molding processability, chemical resistance and appearance quality, and physical properties for repeated molding processing It has an excellent retention rate.
[226]
[227]
The molded article may be manufactured by, for example, injection processing the thermoplastic resin composition or pellets thereof.
[228]
The injection processing may be performed under injection conditions of, for example, an injection temperature of 220 to 280° C. and a holding pressure of 10 to 200 bar. At this time, the mold temperature may be, for example, 50 to 120 ℃, preferably 55 to 100 ℃.
[229]
[230]
The molded article has excellent mechanical strength, appearance quality, and chemical resistance, and thus can be used, for example, in housings and parts of electronic products such as home appliances or OA devices.
[231]
[232]
The molded article is, for example, the number of foreign substances having a diameter of 100 μm or more observed on the surface through an optical microscope is less than 15 / 100 cm 2 , preferably 10 / 100 cm 2 or less, more preferably 8 / 100 cm 2 or less, more preferably 7 pieces / 100 cm 2 or less, there is an advantage of excellent physical property balance while excellent in appearance quality within this range.
[233]
In this base material, the foreign material of the molded article is 3 mm thick and 10 cm in width and length (observation area 100 cm 2 ) of a specimen with a magnification of 100 times when observed with an optical microscope (OM). It can be obtained by observing the number. The foreign material of the molded article may be expressed as an average value of values ​​observed three or more times as a preferred example, and five times as a specific example.
[234]
The molded article includes the thermoplastic resin composition of the present invention, and thus the amount of foreign matter is greatly reduced compared to a molded article manufactured with a conventional regenerated resin composition. The effect is excellent, and even if there is a foreign material, it is not noticeable, so the appearance quality is more excellent.
[235]
[236]
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.
[237]
[238]
[Example]
[239]
Materials used in the following Examples, Comparative Examples and Reference Examples are as follows.
[240]
(A-1) Vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer: the average particle diameter of the conjugated diene rubber including the conjugated diene compound is 3,200 Å, and the content of the conjugated diene rubber is 60% by weight ABS graft copolymer (DP270 of LG Chem)
[241]
(A-2) Aromatic vinyl compound-vinyl cyan compound copolymer: SAN resin containing 23 wt% of acrylonitrile-derived units and 77 wt% of styrene-derived units (weight average molecular weight of 110,000 g/mol; 83SF of LG Chem)
[242]
(B-1) Regenerated vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound copolymer: Melt index (220°C, 10 kg) is 22 g/10 min, measured with a colorimeter (Ci7860, X-Rite) Recycled ABS resin with color L value* of 31 (C&Tech Korea's A204)
[243]
(B-2) Regenerated vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound copolymer: Melt index (220° C., 10 kg) of 16 g/10 min, measured with a colorimeter (Ci7860, X-Rite) Recycled ABS resin with color L value* of 85 (C&Tech Korea's A205LC)
[244]
(B-3) Regenerated aromatic vinyl compound-vinyl cyan compound copolymer: Regenerated SAN resin having a melt index (220°C, 10 kg) of 37 g/10 min (S601 by C&Tech Korea)
[245]
(B-4) Regenerated polycarbonate resin: Bisphenol A-type recycled polycarbonate resin having a melt index (300°C, 1.2 kg) of 20 g/10min (PC PW 20HT from Easychem)
[246]
(C-1) Ethylene compound-vinyl acetate compound copolymer: melt index (190° C., 2.16 kg) of 25 g/10 min, comprising 72 wt% of ethylene compound-derived units and 28 wt% of vinyl acetate compound-derived units EVA resin (EVEA28025 by LG Chem)
[247]
(C-2) Ethylene compound-methyl acrylate compound copolymer: melt index (190° C., 2.16 kg) of 2 g/10 min, containing 76 wt% of ethylene compound-derived units and 24 wt% of methyl acrylate compound-derived units EMA resin (Elvaloy AC 1224 from Dupont)
[248]
(D-1) Inorganic pigment: titanium dioxide having a refractive index of 2.73 and an average particle diameter of 250 nm (R350 manufactured by Dupont)
[249]
(D-2) Inorganic pigment: carbon black having a refractive index of 1.75 and an average particle diameter of 58 nm (HIBLACK 170 manufactured by Orion Engineered Carbons)
[250]
(D-3) Inorganic pigment: diatomaceous earth with a refractive index of 1.46 and an average particle diameter of 45㎛ (Si02n H2O from Dong-Sin, 325 mesh)
[251]
*Color L value: It means the L value of the color coordinates based on the CIE1976 L*a*b* color system, where L has a value of 0 to 100, the closer to 0, the more black, and the closer to 100, the more white. indicates
[252]
[253]
Examples 1 to 7, Comparative Examples 1 to 11 and Reference Examples
[254]
(A-1) a non-regenerated graft copolymer; (A-2) non-regenerated copolymer; Recycled thermoplastic resins of (B-1) to (B-4); (C-1) or (C-2) copolymers; and (D-1) or (D-2) inorganic pigments; mixed using a super mixer at the amounts shown in Tables 1 and 2 below, and then a twin-screw extruder (screw diameter 26mm, L) /D=40), extrusion temperature of 230 ℃ and screw rotation speed of 320 rpm were extruded under the extrusion conditions to prepare pellets.
[255]
After drying the prepared thermoplastic resin composition in the form of pellets at 80° C. for 4 hours or more, injection molding was performed in an injection machine under the conditions of an injection temperature of 240° C., a mold temperature of 60° C., and an injection speed of 30 mm/sec to prepare a specimen, which was obtained at room temperature (20 to 26° C.) for 48 hours or more, and the initial physical properties were measured with the prepared specimen.
[256]
In addition, after repeating the extrusion process additionally 5 times under the same extrusion conditions as the above-prepared pellets to prepare pellets that have undergone the extrusion process for a total of 6 times, it is injection molded under the same injection conditions as above, and this is at room temperature ( 20 to 26 ℃) was left at least 48 hours to measure the retention of physical properties with the prepared specimen.
[257]
[258]
[Test Example]
[259]
The physical properties of the specimens prepared in Examples, Comparative Examples and Reference Examples were measured in the following manner, and the results are shown in Table 2 below.
[260]
[261]
* Melt flow index (g/10min): In accordance with ASTM D1238, it was measured at 220°C under a load of 10 kg for 10 minutes.
[262]
* Izod impact strength (kgfcm/cm): According to ASTM D256, it was measured at 23°C using a 1/8″-thick specimen.
[263]
* Tensile strength (kg/cm 2 ): According to ASTM D638, it was measured at a test speed of 50 mm/min and a temperature of 23° C. using a specimen having a thickness of 1/8″.
[264]
* Surface foreign matter (piece / 100cm 2 ): Prepare a specimen with a thickness of 3 mm and a width and length of 10 cm each with the prepared pellets, and examine the surface of the specimen with an optical microscope (device name: VHX-5000, KEYENCE CORPORATION) at a magnification X100 It was observed 5 times under the conditions and the number of foreign substances having a diameter of 100 μm or more was measured as an average value.
[265]
* Chemical resistance (h): Prepare a specimen with a size of 200 mm * 10.0 mm * 3.2 mm with the prepared pellets, fix it on a curvature jig with a stress of 1%, and apply 1 cc of Nanox detergent (LION) After this, the time (hour) for which a crack of 3 mm in size was generated on the surface of the specimen was measured.
[266]
* Peeling: Using a cutter knife in the width direction in the center of the upper surface of the 200 mm*10.0 mm*3.2 mm size specimen, break it and visually check whether peeling has occurred, and X, depending on the degree of peeling. Δ and O were evaluated. At this time, when peeling occurs, it was observed whether the peeling occurred easily torn by pulling the peeled skin by hand. (X: no peeling, △: peeling is observed in a part of the cross section, but peeling is not easily torn, O: multiple peeling is observed in the cross section and peeling is easily torn)
[267]
* Physical property retention: For each physical property, the physical property (physical property after adding 5 times of extrusion) measurement after the extrusion process is added 5 times to the measured value of the physical property (initial property) after going through the extrusion process once, and subjected to a total of 6 extrusion steps Values ​​are expressed as percentages (%).
[268]
More specifically, it was calculated using Equation A below as the measured values ​​of each physical property.
[269]
[Equation A]
[270]
Retention of physical properties (%) = [(Physical properties after adding 5 extrusions)/(Initial properties)] X 100
[271]
In Equation A, the physical property may be a flow index, impact strength, or tensile strength.
[272]
As another example, the property retention rate may be calculated using Equations 1 and 2 above.
[273]
[274]
[Table 1]
Category
(parts by weight) Example Reference example
One 2 3 4 5 6 7 One
A-1 g-ABS 18 15 12 19 17 19 18 27
A-2 SAN 49 30 13 26 28 26 49 73
Non-renewable resin sum 67 45 25 45 45 45 67 100
B-1 Recycled ABS
(Black) 33 55 75 - - - 33 -
B-2 Recycled ABS
(Gray) - - - 40 25 40 - -
B-3 Replay SAN - - - 15 - 15 - -
B-4 Play PC - - - - 30 - - -
Recycled resin sum 33 55 75 55 55 55 33 -
C-1 EVA One 2 4 2 2 2 8 -
C-2 EMA - - - - - - - -
D-1 TiO 2 0.5 1.0 1.0 2.0 4.0 7.0 0.5 -
D-2 carbon black 0.5 1.0 2.0 - - - 0.5 -
D-3 diatomaceous earth - - - - - - - -
Initial physical properties
(n=1) MI 25.8 26.5 25.7 35.9 17.2 35.5 27.0 41.1
impact strength 24.8 26.0 25.0 25.8 43.6 19.7 27.4 31.1
The tensile strength 428.0 404.0 384.0 402.0 476.0 413.0 410.0 412.0
alien substance 4.0 5.0 8.0 3.0 3.0 2.0 2.0 0
chemical resistance 32.0 41.0 38.5 38.0 25.0 38.0 51.0 20.5
Whether peeling X X X X X X △ X
Physical properties after 5 additional extrusions MI 24.1 24.8 23.6 36.6 17.1 36.3 26.0 40.2
impact strength 24.1 25.6 22.7 25.3 43.0 18.6 26.9 29.4
The tensile strength 423.0 393.0 368.0 399.0 470.0 407.0 401.0 423.0
Property retention rate
(%) MI 93.4 93.6 91.8 101.9 99.4 102.3 96.3 97.8
Property retention rate (%) impact strength 97.2 98.5 90.8 98.1 98.6 94.4 98.2 94.5
Property retention rate (%) The tensile strength 98.8 97.3 95.8 99.3 98.7 98.5 97.8 102.7
[275]
[Table 2]
Category
(parts by weight) comparative example
One 2 3 4 5 6 7 8 9 10 11
A-1 g-ABS 18 15 12 19 19 19 17 19 18 19 18
A-2 SAN 49 30 13 26 26 26 28 26 49 26 49
Non-renewable resin sum 67 45 25 45 45 45 45 45 67 45 67
B-1 Recycled ABS
(Black) 33 55 75 - - - - - 33 - 33
B-2 Recycled ABS
(Gray) - - - 40 40 40 25 40 - 40 -
B-3 Replay SAN - - - 15 15 15 15 - 15 -
B-4 Play PC - - - - - 30 - - - -
Recycled resin sum 33 55 75 55 55 55 55 55 33 55 33
C-1 EVA - - - - - 0.5 - - 12 2 One
C-2 EMA - - - - - - - 2 - - -
D-1 TiO 2 - - - - 2 - - 7 0.5 12 -
D-2 carbon black - - - - - - - - 0.5 - -
D-3 diatomaceous earth - - - - - - - - - - 4
Initial physical properties
(n=1)
MI 26.0 27.3 26.0 39.0 38.0 38.0 15.7 31.5 28.0 21.0 25.0
impact strength 23.1 23.0 21.0 23.7 22.5 23.0 43.1 15.8 26.3 16.0 22.0
The tensile strength 431.0 410.0 396.0 412.0 405.0 405.0 480.0 418.0 405.0 411.0 423.0
alien substance 19.0 24.0 31.0 18.0 13.0 15.0 15.0 7.0 15.0 6.0 17.0
Chemical resistance (h) 16.0 12.5 8.5 16.5 17.5 22.0 10.5 43.0 56.0 14.0 15.8
Whether peeling X X X X X X X X O X X
Physical properties after 5 additional extrusions MI 23.1 22.8 23.4 35.1 35.5 36.0 13.7 29.0 25.0 18.0 22.4
impact strength 18.8 18.3 17.7 19.1 19.0 21.0 37.5 14.4 22.2 13.8 16.4
The tensile strength 410.0 397.0 350.0 387.0 390.0 396.0 460.0 408.0 392.0 395.0 412.0
Property retention rate
(%) MI 88.8 83.5 90.0 90.0 93.4 94.7 87.3 92.1 89.3 85.7 89.6
impact strength 81.4 79.6 84.3 80.6 84.4 91.3 87.0 91.1 84.4 86.3 74.5
The tensile strength 95.1 96.8 88.4 93.9 96.3 97.8 95.8 97.6 96.8 96.1 97.4
[276]
As shown in Tables 1 and 2, in the case of Examples 1 to 7 prepared according to the present invention, fluidity, impact strength, tensile strength, chemical resistance, and peeling properties were higher than Comparative Examples 1 to 11, which was out of the scope of the present invention. It was excellent, and the number of foreign substances observed on the surface was reduced by more than half, and in particular, it was confirmed that the retention of physical properties compared to the initial physical properties was significantly improved even after the extrusion process was additionally repeated 5 times. Moreover, even compared with Reference Example 1 to which the regenerated resin was not applied, it was confirmed that the decrease in physical properties due to the application of the regenerated resin compared to Comparative Examples 1 to 11 was greatly improved.
[277]
In addition, in the case of Example 3, although the total content of the regenerated resin was as high as 75 parts by weight, mechanical properties, chemical resistance, and the number of foreign substances were remarkably improved, as well as the retention of physical properties for molding processing. In the case of Example 6, although the content of the inorganic pigment was as high as 7 parts by weight, it was confirmed that the deterioration of the physical properties due to the excessive inclusion of the inorganic pigment was greatly improved. Moreover, in the case of Examples 1 to 7, peeling properties were also excellent, and in particular, in Examples 1 to 6, peeling did not occur at all, confirming that the peeling properties were more excellent.
[278]
[279]
1 shows the chemical resistance test results of Examples and Comparative Examples of the present invention, and is a photograph taken 38 hours after application of Nanox detergent on the surface of the specimen. Referring to FIG. 1 below, in the case of the example of the present invention, cracks were not observed until 38 hours had elapsed after detergent application, whereas in the case of the comparative example, cracks were clearly observed with the naked eye. In the case of the example, it can be seen that the chemical resistance is greatly improved.
[280]
2 shows the results of recording the surface foreign matter occurrence points in Examples and Comparative Examples of the present invention, and FIG. 3 shows the results of observing the surface foreign substances in Examples and Comparative Examples of the present invention with an optical microscope. 2 and 3, in the case of the example prepared according to the present invention, compared to the comparative example, not only the number of foreign matter generated was significantly reduced, but also the foreign matter was observed to be blurred even when the foreign material was generated due to the excellent effect of covering the foreign material. It can be seen that the quality is greatly improved.
Claims
[Claim 1]
(A) 100 parts by weight of a base resin comprising 20 to 90% by weight of a non-renewable thermoplastic resin and (B) 10 to 80% by weight of a recycled thermoplastic resin; (C) 1 to 10 parts by weight of an ethylene compound-vinyl acetate compound copolymer; and (D) 0.01 to 10 parts by weight of an inorganic pigment, wherein the (D) inorganic pigment has a refractive index of 1.65 or more and an average particle diameter of 10 to 500 nm.
[Claim 2]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a melt index retention rate of 80% or more calculated by the following Equation (1). [Equation 1] Melt index retention (%) = [MI n+5 /MI n ] X 100 (in Equation 1, MI n is the extruded thermoplastic resin composition at 200 to 250 ℃ and 250 to 400 rpm conditions After processing n times, it is a melt index value (g/10min) measured under the conditions of 220 °C and 10 kg according to ASTM D1238, and MI n + 5 is the extrusion processing performed n + 5 times under the same conditions as above. It means the melt index value (g/10min) measured later, where n is an integer from 1 to 10.)
[Claim 3]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an impact strength retention of 80% or more, calculated by the following Equation (2). [Equation 2] Impact strength retention (%) = [ImSt n+5 /ImSt n ] X 100 (In Equation 2, ImSt n is the thermoplastic resin composition extruded at 200 to 250 ℃ and 250 to 400 rpm conditions It is the Izod impact strength value (kgf cm/cm) measured under the condition of 1/8" thickness of the specimen according to ASTM D256 after processing n times, and ImSt n+5 is n+ for extrusion processing under the same conditions as above. It means the Izod impact strength value (kgf·cm/cm) measured after repeating 5 times, where n is an integer from 1 to 10.)
[Claim 4]
According to claim 1, wherein the thermoplastic resin composition is a specimen having a size of 200 mm * 10 mm * 3.2 mm fixed to a curvature jig having a stress of 1% and 1 cc of Nanox detergent (LION) is applied, and then the specimen The thermoplastic resin composition, characterized in that the chemical resistance (ESCR) measured as the time that cracks are generated on the surface of the 20 hours (hour) or more.
[Claim 5]
The method according to claim 1, wherein the (A) non-renewable thermoplastic copolymer comprises (A-1) 20 to 70 wt% of the non-renewable vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer and (A-2) ratio A thermoplastic resin composition comprising 30 to 80 wt% of a recycled aromatic vinyl compound-vinyl cyan compound copolymer.
[Claim 6]
The method of claim 5, wherein the (A-1) graft copolymer comprises 50 to 80% by weight of a conjugated diene rubber, 5 to 20% by weight of a vinyl cyanide compound, and 10 to 40% by weight of an aromatic vinyl compound. A thermoplastic resin composition.
[Claim 7]
The thermoplastic resin composition according to claim 5, wherein the copolymer (A-2) comprises 20 to 40 wt% of a vinyl cyanide compound and 60 to 80 wt% of an aromatic vinyl compound.
[Claim 8]
The method of claim 1, wherein the (B) recycled thermoplastic resin is one selected from the group consisting of a recycled vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer, a recycled polycarbonate resin, and a recycled aromatic vinyl compound-vinyl cyan compound copolymer. A thermoplastic resin composition comprising more than one species.
[Claim 9]
The thermoplastic resin composition according to claim 1, wherein (B) the regenerated thermoplastic resin has a glass transition temperature of 60 to 180°C.
[Claim 10]
The thermoplastic resin composition according to claim 1, wherein the copolymer (C) comprises 50 to 95 wt% of an ethylene compound and 5 to 50 wt% of a vinyl acetate compound.
[Claim 11]
According to claim 1, wherein the (D) inorganic pigment is one selected from the group consisting of titanium dioxide, zinc oxide, zinc sulfide, aluminum hydroxide, iron oxide, magnesium oxide, calcium carbonate, barium sulfate, clay, carbon black and white carbon. Thermoplastic resin composition, characterized in that the above.
[Claim 12]
(A) 100 parts by weight of a base resin comprising 20 to 90% by weight of a non-renewable thermoplastic copolymer and (B) 10 to 80% by weight of a recycled thermoplastic resin, (C) 1 to 10 parts by weight of an ethylene compound-vinyl acetate compound copolymer , And (D) comprising 0.01 to 10 parts by weight of the inorganic pigment, kneading and extruding at 200 to 280 ° C; including, wherein the (D) inorganic pigment has a refractive index of 1.65 or more, and an average particle diameter of 10 to 500 nm A method for producing a thermoplastic resin composition, characterized in that
[Claim 13]
A molded article comprising the thermoplastic resin composition of any one of claims 1 to 11.
[Claim 14]
The molded article according to claim 13, wherein the number of foreign substances having a diameter of 100 μm or more observed on the surface through an optical microscope of the molded article is less than 15/100 cm 2 .