Title of the invention: Thermoplastic resin composition, manufacturing method thereof, and molded article including the same
Technical field
[One]
[Mutual citation with application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0006154 filed on January 17, 2019, and all contents disclosed in the documents of the Korean patent application are included as part of this specification.
[3]
[4]
The present invention relates to a thermoplastic resin composition, a method of manufacturing the same, and a molded article including the same, and more particularly, without a decrease in fluidity, mechanical properties, and thermal deformation temperature, chemical resistance to chemical solvents such as thinners is greatly improved, and thus paintability It relates to an excellent thermoplastic resin composition, a method of manufacturing the same, and a molded article including the same.
Background
[5]
Vinylcyan compound represented by acrylonitrile-butadiene-styrene resin-conjugated diene compound-aromatic vinyl compound graft copolymer (hereinafter referred to as'ABS resin') is less harmful to the human body, yet has impact and chemical resistance to the external environment. It is widely used in various technical fields due to its relatively excellent properties such as weather resistance, and excellent moldability and secondary processability such as injection molding and extrusion molding.
[6]
ABS resins generally go through a post-processing process, and a typical post-processing process is a painting process. In the painting process, a chemical solvent such as a thinner is used to properly coat the paint on the ABS resin. ABS resin has a severe curvature of the rubber component due to the chemical solvent component, and after painting, the adhesion surface between the paint and the molded resin becomes uneven, resulting in large and small cracks, which are pinholes that are poorly painted. Leads to the occurrence of.
[7]
To solve this problem, a method of diluting the components of a chemical solvent and a styrene-acrylonitrile (SAN) resin with a high content of acrylonitrile (AN) to prevent damage to the rubber component is used to damage the rubber component. A method to prevent this problem has been proposed, but there is inconvenience of long-term exposure of the diluted solvent to the molded resin, and when using a styrene-acrylonitrile resin (SAN resin) with a high acrylonitrile (AN) content, chemical resistance and gloss There is a problem that characteristics are deteriorated.
[8]
In addition, various studies are being conducted such as increasing the content of butadiene rubber, which is a raw material monomer of ABS resin, increasing the size of the rubber, and increasing the molecular weight, but also in this case, due to the increase in residual stress of the molded article due to the decrease in fluidity, poor painting (pinhole) is improved There is a limit to this.
[9]
Therefore, it is necessary to develop an ABS resin composition having excellent physical properties such as fluidity while improving chemical resistance and paintability by a chemical solvent.
[10]
[11]
〔Prior technical literature〕
[12]
[Patent Literature] Japanese Patent Registration Publication No. Hei 7-47679
Detailed description of the invention
Technical challenge
[13]
In order to solve the problems of the prior art as described above, the present disclosure aims to provide a thermoplastic resin composition.
[14]
In addition, the present description aims to provide a method for producing the above thermoplastic resin composition.
[15]
In addition, the present description aims to provide a molded article made of the above thermoplastic resin composition.
[16]
[17]
The above and other objects of the present description can be achieved by the present description described below.
Means of solving the task
[18]
In order to achieve the above object, the present substrate includes a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 20 to 40% by weight and α-methyl styrene compound-vinyl cyan compound copolymer 60 to 80% by weight 100 parts by weight of the basic resin; And 0.4 to 3 parts by weight of alkoxylated polyethylene imine; It provides a thermoplastic resin composition comprising a.
[19]
[20]
In addition, the base resin 100% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 20 to 40% by weight and α-methyl styrene compound-vinyl cyan compound copolymer 60 to 80% by weight part; And 0.4 to 3 parts by weight of alkoxylated polyethylene imine; It provides a method for producing a thermoplastic resin composition comprising the step of melt-kneading and then extruding under 230 to 270 ℃ and 200 to 400 rpm conditions.
[21]
[22]
In addition, the present description provides a molded article made of the thermoplastic resin composition.
Effects of the Invention
[23]
According to the present disclosure, in the case of including alkoxylated polyethyleneimine in the thermoplastic resin, chemical resistance is improved without deterioration in fluidity, heat resistance, and mechanical strength to provide a thermoplastic resin composition having excellent paintability, a manufacturing method thereof, and a molded article including the same. It works.
Brief description of the drawing
[24]
1 is a schematic diagram of an alkoxylated polyethylene imine.
Best mode for carrying out the invention
[25]
Hereinafter, the thermoplastic resin composition of the present disclosure will be described in detail.
[26]
The present inventors confirmed the effect of greatly improving chemical resistance and paintability without deteriorating fluidity, heat resistance and mechanical strength when alkoxylated polyethylene imine is included in a thermoplastic resin including ABS resin, and based on this, further research The present invention has been completed.
[27]
[28]
A detailed look at the thermoplastic resin composition according to the present disclosure is as follows.
[29]
[30]
The thermoplastic resin composition of the present disclosure includes a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 20 to 40 wt% and an α-methyl styrene compound-vinyl cyan compound copolymer 60 to 80 wt% 100 parts by weight; And 0.4 to 3 parts by weight of alkoxylated polyethylene imine, and in this case, there is an effect of excellent chemical resistance and paintability without deteriorating fluidity, heat resistance, and mechanical strength.
[31]
[32]
Each component constituting the thermoplastic composition of the present disclosure will be described in detail as follows.
[33]
[34]
(a) Vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer
[35]
The (a) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer is, for example, 20 to 40% by weight, or 20 to 35% by weight, preferably 25 to 32% by weight, more preferably in the base resin. May be contained in an amount of 27 to 30% by weight, and within this range, mechanical strength, fluidity, and physical property balance are excellent.
[36]
[37]
The (a) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer includes, for example, 40 to 80% by weight of a conjugated diene rubber, 10 to 40% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinylcyan compound. Thus, it may be a graft copolymer subjected to graft polymerization, and in this case, the impact resistance is excellent.
[38]
[39]
Preferably, the (a) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer is 45 to 70% by weight of a conjugated diene rubber, 20 to 40% by weight of an aromatic vinyl compound, and 5 to 20% by weight of a vinylcyan compound It may be a graft copolymer including graft polymerization, and in this case, there is an effect of excellent impact resistance.
[40]
[41]
More preferably, the (a) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer is 50 to 65% by weight of conjugated diene rubber, 20 to 35% by weight of aromatic vinyl compound, and 5 to 15% by weight of vinylcyan compound Including %, it may be a graft-polymerized graft copolymer, and in this case, there is an effect of excellent impact resistance.
[42]
[43]
The (a) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer is, for example, a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer having an average particle diameter of 0.05 to 0.2 µm of the conjugated diene rubber. To 40% by weight or 20 to 30% by weight; And 60 to 90% by weight or 70 to 80% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer having an average particle diameter of more than 0.2 μm to 0.5 μm or less of the conjugated diene rubber, and in this case It has excellent heat resistance effect.
[44]
[45]
Preferably, the (a) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer is a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer having an average particle diameter of 0.1 to 0.15 µm of the conjugated diene rubber. 10 to 40% by weight or 20 to 30% by weight of coalescence; And 60 to 90% by weight or 70 to 80% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer having an average particle diameter of 0.3 to 0.4 µm of the conjugated diene rubber, and in this case, heat resistance This has an excellent effect.
[46]
[47]
In the present description, the average particle diameter of the conjugated diene rubber can be measured as an intensity value in Gaussian mode using a Nicomp 370HPL device manufactured by Nicomp in the United States by a dynamic laser light scattering method.
[48]
[49]
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 pyrrerylene. It may be one or more selected from the group consisting of.
[50]
The aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, and vinyltoluene.
[51]
The vinyl cyan compound may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof.
[52]
[53]
The (a) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer may be prepared by a known polymerization method including emulsion polymerization, suspension polymerization, bulk polymerization, and the like, and is not particularly limited.
[54]
[55]
The (a) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer emulsion graft polymerization method is, for example, a conjugated diene rubber contained in the graft copolymer, aromatic vinyl compound and a total of 100 vinyl cyanide compounds Based on parts by weight, in a mixed solution consisting of 40 to 80% by weight of a conjugated diene rubber, 0.1 to 5 parts by weight of an emulsifier, 0.1 to 3 parts by weight of a molecular weight control agent, and 0.05 to 1 parts by weight of a polymerization initiator, 1 to 20% by weight of a vinyl cyan compound and an aromatic vinyl The monomer mixture containing 10 to 40% by weight of the compound may be added continuously or collectively.
[56]
[57]
The emulsifier may be one or more selected from the group consisting of allyl aryl sulfonate, alkali methyl alkyl sulfonate, sulfonated alkyl ester, fatty acid soap, and alkali salt of rosin acid, and in this case, the stability of the polymerization reaction is excellent. It works.
[58]
The molecular weight modifier may be one or more selected from the group consisting of t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan and carbon tetrachloride as an example, and preferably t-dodecyl mercaptan.
[59]
The polymerization initiator may be, for example, one or more selected from the group consisting of potassium persulfate, sodium persulfate, and ammonium persulfate, and in this case, emulsion polymerization can be efficiently performed.
[60]
The latex obtained by the graft emulsion polymerization can be obtained in a powder state by aging, dehydrating and drying after agglomeration with a coagulant such as sulfuric acid, MgSO 4 , CaCl 2 or Al 2 (SO 4 ) 3 .
[61]
[62]
α-methyl styrene compound-vinyl cyan compound copolymer
[63]
The α-methyl styrene compound-vinyl cyan compound copolymer is, for example, 60 to 80% by weight, or 65 to 80% by weight, preferably 68 to 75% by weight, more preferably 70 to 73% by weight in the base resin It may be included as, in this case, there is an excellent effect of heat resistance and physical property balance.
[64]
[65]
The α-methyl styrene-based compound-vinyl cyan compound copolymer may have a weight average molecular weight of 70,000 to 150,000 g/mol, preferably 80,000 to 140,000 g/mol, more preferably 90,000 to 130,000 g/mol, for example, , Within this range, there is an effect of excellent heat resistance and physical property balance.
[66]
In this description, the weight average molecular weight is a relative value for a standard PS (Standard polystyrene) sample using tetrahydrofuran (THF) as a solvent at a temperature of 40°C through gel chromatography (GPC) filled with porous silica as a column packing material. Can be measured.
[67]
[68]
The α-methyl styrene-based compound-vinyl cyan compound copolymer is, for example, a copolymer polymerized including 60 to 80% by weight of an α-methyl styrene compound and 20 to 40% by weight of a vinyl cyanide compound; Preferably, it may be a polymerized copolymer including 65 to 75% by weight of an α-methyl styrene compound and 25 to 35% by weight of a vinyl cyan compound, and in this case, there is an effect of excellent heat resistance.
[69]
[70]
The α-methyl styrene-based compound may be one or more selected from the group consisting of α-methyl styrene and derivatives thereof, for example, and in this case, there is an effect of excellent heat resistance.
[71]
The α-methyl styrene derivative may be, for example, a compound in which 1 or 2 or more of its hydrogens are substituted with a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogen group, etc., and preferably hydrogen in its aromatic ring One or two or more of them may be a compound substituted with a substituent such as an alkyl group having 1 to 10 carbon atoms or a halogen group.
[72]
The vinyl cyan compound copolymer may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof.
[73]
[74]
The α-methyl styrene-based compound-vinyl cyanide compound copolymer may be, for example, a copolymer of α-methyl styrene and acrylonitrile as shown in Formula 1 below.
[75]
[Formula 1]
[76]

[77]
[78]
The α-methyl styrene compound-vinyl cyan compound copolymer is, for example, a polymerization initiator 0.01 to 0.5 in 100 parts by weight of a monomer mixture containing 60 to 80% by weight of an α-methyl styrene compound and 20 to 40% by weight of a vinyl cyanide It can be prepared by bulk polymerization including parts by weight, preferably 0.01 to 0.3 parts by weight.
[79]
The polymerization initiator is, for example, 1,1-bis(t-butyl peroxy)cyclohexane, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butyl peroxyisobutyrate, 2,2- Bis(4,4-di-t-butylperoxycyclohexane)propane, t-hexylperoxyisopropyl monocarbonate, t-butyl peroxylaurate, t-butylperoxy isopropyl monocarbonate, t-butylper Oxy2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, t-butyl peroxyacetate, 2,2-bis(t-butyl peroxy)butane, t-butyl peroxybenzoate, dicumyl peroxide, At least one selected from the group consisting of 2,5-dimethyl-2,5-bis(t-butyl peroxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide and di-t-amyl peroxide May be, preferably 1,1-bis (t-butyl peroxy) cyclohexane.
[80]
[81]
Alkoxylated polyethylene imine
[82]
The alkoxylated polyethylene imine is contained in an amount of 0.4 to 3 parts by weight, preferably 0.5 to 2.7 parts by weight, more preferably 0.5 to 2.5 parts by weight, and even more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the base resin. In this case, there is an effect excellent in chemical resistance and paintability without deterioration in fluidity, heat resistance and mechanical strength.
[83]
[84]
The alkoxylated polyethyleneimine may include, for example, a polymer portion having a repeating unit including an amine group and an ethylene group. The polymer moiety may serve as a polyethyleneimine backbone of an alkoxylated polyethyleneimine, for example. In the alkoxylated polyethyleneimine, for example, one or more nitrogen atoms of an amine group may be modified with one or more alkoxy moieties to form an alkoxylated polyethyleneimine.
[85]
The amine group of the polyethyleneimine backbone may be, for example, one or more selected from the group consisting of a primary amine group of Formula 2, a secondary amine group of Formula 3, and a tertiary amine group of Formula 4, but is not limited thereto.
[86]
The polyethyleneimine backbone may have a linear, branched, dendrimer type, or comb-like structure.
[87]
[88]
[Formula 2]
[89]

[90]
[91]
[Chemical Formula 3]
[92]

[93]
[94]
[Formula 4]
[95]

[96]
[97]
In the polyethyleneimine backbone structure, for example, one or more of the hydrogen atoms of the amine group may be replaced with one or more alkoxy moieties.
[98]
The alkoxy moiety of the alkoxylated polyethyleneimine may be, for example, an ethoxy moiety, a propoxy moiety, or a butoxy moiety. The alkoxylated polyethyleneimine may include, for example, one or more selected from the group consisting of an ethoxy moiety, a propoxy moiety, and a butoxy moiety.
[99]
In the present description, a moiety refers to a part of a molecule.
[100]
[101]
Specifically, the alkoxylated polyethylene imine may be, for example, one or more selected from the group consisting of ethoxylated polyethyleneimine, propoxylated polyethyleneimine, ethoxylated-butoxylated polyethyleneimine, and ethoxylated-propoxylated-butoxylated polyethyleneimine. , In this case, there is an effect excellent in chemical resistance and paintability without deteriorating fluidity, heat resistance and mechanical strength.
[102]
[103]
The alkoxylated polyethylene imine may, for example, have an alkoxylation rate of 60% by weight or more, preferably 60 to 90% by weight, more preferably 60 to 80% by weight, and decrease in fluidity, heat resistance and mechanical strength within this range. It has excellent chemical resistance and paintability.
[104]
In the present description, the alkoxylation rate can be measured by nuclear magnetic resonance spectral analysis (NMR method).
[105]
[106]
The alkoxylated polyethylene imine has a dynamic viscosity measured at 40°C with a Brookfield viscometer of 700 to 1500 mPa·s, preferably 800 to 1400 mPa·s, more preferably 1000 to 1200 mPa·s. It may be, and within this range, there is an effect of excellent fluidity and physical property balance.
[107]
[108]
The alkoxylated polyethyleneimine may preferably be an ethoxylated polyethyleneimine having a plurality of nitrogen atoms, and the number of ethoxy moieties bonded to each nitrogen atom of the polyethyleneimine backbone is 1 to 40, 5 to 35, for example. , 10 to 30, or 15 to 25, preferably 17 to 23, more preferably may be 18 to 22.
[109]
[110]
The branched ethoxylated polyethyleneimine may be, for example, a compound represented by Formula 5 below, and in this case, while maintaining fluidity, it has excellent chemical resistance and paintability.
[111]
[112]
[Formula 5]
[113]

[114]
The alkoxylated polyethyleneimine may be formed from, for example, an acid-catalyzed ring opening reaction of ethyleneimine or aziridine.
[115]
[116]
Referring to FIG. 1 below, an alkoxylated polyethylene imine in which a hydrophilic group (EO) and a hydrophobic group (AO) are connected through an amino group is schematically shown.The hydrophilic group and the hydrophobic group of the alkoxylated polyethylene imine are modified Thus, there is an effect of improving chemical resistance.
[117]
[118]
The thermoplastic resin composition has a chemical resistance measured by the following method, for example, 300 seconds or more, preferably 300 seconds to 800 seconds, more preferably 350 seconds to 700 seconds, while maintaining fluidity within this range There is an effect that pinholes do not occur due to improved paintability.
[119]
In the present description, the chemical resistance is measured by fixing the specimen size 200 × 12.7 × 3.2 mm to a curvature jig having 1.7% strain, applying 200 µl of thinner, and measuring the time the crack occurs in the specimen.
[120]
The thinner may be a mixture of 45% by weight of naphtha, 25% by weight of xylene, 20% by weight of propylene glycol monomethyl ether, and 10% by weight of n-butyl acetic acid.
[121]
[122]
As an example, the thermoplastic resin composition does not generate pinholes on the painted surface measured by the following coating property evaluation method. In this case, the chemical resistance to chemical solvents is improved and can be applied to a painted product.
[123]
In this description, the method for evaluating paintability is to degrease a specimen size of 10cm × 10cm with isopropyl alcohol, spray with 50ml of black paint, and then spray with 50ml of clear paint after 5 minutes, and dry in an oven at 85℃ for 30 minutes. Observe the number of pinholes.
[124]
The black paint may be, for example, a paint including methyl methacrylate, butyl acrylate-2-hydroxyethyl methacrylate copolymer, thermosetting acrylic resin, carbon black, and a solvent.
[125]
Examples of the clear paint are butyl 2-methylprop-2-enoate, 2-hydroxyethyl 2-methylprop-2-enoate, methyl 2-methylprop-2-enoate, styrene, thermosetting acrylic It may be a paint containing a resin, an organic solvent, or the like.
[126]
[127]
The thermoplastic resin composition has an impact strength measured at 1/4" of the specimen thickness according to ASTM D256, for example, 20 kgf·cm/cm or more, preferably 20.5 to 30 kgf·cm/cm, more preferably 21.5 It may be 26.8 kgf·cm/cm, and within this range, there is an excellent effect of fluidity, heat resistance and balance of physical properties.
[128]
[129]
The thermoplastic resin composition includes, for example, one or more selected from the group consisting of lubricants, flame retardants, heat stabilizers, antioxidants, light stabilizers, compatibilizers, pigments, dyes and inorganic additives, 1 to 5 parts by weight per 100 parts by weight of the base resin , Preferably 1.5 to 4 parts by weight, more preferably 2 to 3 parts by weight, and in this case, there is an effect of excellent chemical resistance and paintability and excellent physical property balance.
[130]
The lubricant may be, for example, one or more selected from the group consisting of wax, silicone oil, and steramid.
[131]
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.
[132]
The heat stabilizer is, for example, tris (nonylphenyl) phosphite (tris (nonylphenyl) phosphite), tris (2,4-di-t-butylphenyl) phosphite (tris (2,4-di-t-butyl phenyl) phosphite; TBPP), 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite (2,4,6-tri-tert-butylphenyl-2-butyl -2-ethyl-1,3-propanediol phosphite), diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,4-di -t-butylphenyl) pentaerythritol diphosphite (bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite; PEP24), bis (2,4-di-cumylphenyl) pentaerythritol diphosphite (bis (2,4-di-cumylphenyl) pentaerythritol diphosphite), and tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl]-4,4'-diyl bisphosphonite (tetrakis ( 2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diyl bisphosphonate) may be one or more selected from the group consisting of.
[133]
The antioxidant may be, for example, a hindered phenolic antioxidant, a phosphide-based antioxidant, or a mixture thereof.
[134]
[135]
The production method of the thermoplastic resin composition of the present disclosure includes a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 20 to 40% by weight and an α-methyl styrene compound-vinyl cyan compound copolymer 60 to 80% by weight 100 parts by weight of the basic resin; And 0.4 to 3 parts by weight of alkoxylated polyethylene imine; melt-kneading and extruding under conditions of 230 to 270° C. and 200 to 400 rpm, and in this case, without deterioration in fluidity, heat resistance, and mechanical strength, There is an effect excellent in paintability.
[136]
[137]
The melt-kneading and extruding step may be performed under 230 to 245 °C and 200 to 370 rpm, preferably 230 to 240 °C and 250 to 350 rpm, in this case, and in this case, excellent chemical resistance and excellent mechanical properties It works.
[138]
During the melt-kneading, for example, at least one selected from the group consisting of lubricants, flame retardants, heat stabilizers, anti-drip agents, antioxidants, light stabilizers, compatibilizers, pigments, dyes and inorganic additives is 0.1 to 100 parts by weight of the base resin. 5 parts by weight, preferably 0.3 to 4 parts by weight, more preferably 0.5 to 3 parts by weight. In this case, while chemical resistance is imparted, there is an effect of excellent physical property balance.
[139]
[140]
The extrudate through the melt-kneading and extrusion step may be, for example, a thermoplastic resin composition having a pellet form.
[141]
[142]
The pellet-shaped extrudate may be manufactured as an injection molded article including the step of injection molding as an example, and the injection molding is 210 to 250°C, preferably 215 to 240°C, more preferably 220 to 230°C, for example ℃; And injection speed of 7 to 13 mm/sec, more preferably 75 to 85 mm/sec; and within this range, there is an effect of excellent chemical resistance and paintability without deterioration of fluidity.
[143]
[144]
The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, the α-methyl styrene compound-vinyl cyan compound copolymer, and the alkoxylated polyethylene imine contained in the thermoplastic resin composition follow the above description. Is omitted.
[145]
[146]
The molded article of the present disclosure is characterized by comprising the thermoplastic resin composition, and in this case, there is an effect of excellent chemical resistance and paintability without deterioration in fluidity, heat resistance and mechanical strength.
[147]
The molded article may be, for example, an injection molded article for an automobile, and specifically may be a radiator grill, a spoiler, a trunk garnish, and a switch panel.
[148]
[149]
Hereinafter, preferred embodiments are presented to aid in the understanding of the present description, but the following examples are only illustrative of the present description, and that various changes and modifications are possible within the scope of the present description and the scope of the technical idea will be apparent to those skilled in the art, It is natural that such modifications and modifications fall within the appended claims.
[150]
[151]
[Example]
[152]
Components used in the following Examples and Comparative Examples are as follows.
[153]
* ABS resin (vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer): DP270 (conjugated diene rubber 60% by weight, styrene 30% by weight, and acrylonitrile 10% by weight graft polymer)
[154]
* AMS heat-resistant resin (α-methyl styrene-based compound-vinyl cyan compound copolymer): 100 UH of LG Chem, a copolymer of 69% by weight of α-methyl styrene and 31% by weight of acrylonitrile
[155]
* APEI (alkoxylated polyethylene imine): BASF's PN80 (alkoxylation rate: 60% by weight or more, dynamic viscosity measured by a Brookfield viscometer (Dynamic viscosity; 50 ℃): 1000 to 1200 mPa·s)
[156]
* PEI (polyethylene imine): Non-alkoxylated polyethylene imine, BASF's Lupasol G20 (weight average molecular weight 1300 g/mol, dynamic viscosity measured by Brookfield viscometer (Dynamic viscosity; 50 ℃) 400 mPa·s)
[157]
[158]
Example 1
[159]
0.5 parts by weight of alkoxylated polyethylene imine was melt-kneaded and extruded at 250° C. and 300 rpm using a twin-screw extruder using a twin screw extruder to 100 parts by weight of the base resin containing 27% by weight of ABS resin and 73% by weight of AMS heat-resistant resin. It was prepared in the form. The pellet-shaped extrudate was dried at 80° C. for 4 hours, and then injection-molded in an injection machine under conditions of an injection temperature of 240° C., a mold temperature of 60° C., and an injection speed of 10 mm/sec to prepare a specimen for measuring various physical properties.
[160]
[161]
Examples 2 to 5 and Comparative Examples 1 to 8
[162]
Example 1 was carried out in the same manner as in Example 1, except that alkoxylated polyethylene imine or polyethylene imine was mixed with the base resin including the ABS resin and the AMS heat-resistant resin at the composition ratios of Tables 1 and 2.
[163]
[164]
[Test Example]
[165]
The properties of the specimens prepared in Examples 1 to 5 and Comparative Examples 1 to 8 were measured by the following method, and the results are shown in Tables 1 and 2 below.
[166]
[167]
How to measure
[168]
* Izod impact strength (kgf·cm/cm): Measured according to ASTM D256 using 1/4" specimen thickness.
[169]
* Flowability (g/10min): Measured under conditions of 220° C. and 10 kg according to ASTM D256.
[170]
* HDT (heat deflection temperature; ℃): was measured under the load condition of 18.6kgf / cm 2 according to ASTM D648 using a specimen thickness of 1/4" .
[171]
* Chemical resistance: The time for cracks to occur in the specimen after fixing the specimen size 200 × 12.7 × 3.2 mm on a curvature jig with 1.7% strain and applying 200 µl of thinner (Norubi Chemical, T803) Was measured.
[172]
* Paintability: After degreasing a sample size of 10 cm × 10 cm with isopropyl alcohol, spray with 50 ml of black paint (KCC's UT578(A)-EB(PC)), then clear paint (KCC's UT5015-A-) after 5 minutes CLEAR) was sprayed in 50 ml, dried in an oven at 85° C. for 30 minutes, and then the number of pinholes on the painted surface was observed, and evaluated based on the following criteria.
[173]
○: No pinhole occurrence
[174]
△: 1 to 5 pinholes generated in the corners
[175]
X: 6 or more pinholes in the corner
[176]
[177]
[Table 1]
division Example 1 Example 2 Example 3 Example 4 Example 5
ABS resin (parts by weight) 27 27 27 30 30
AMS heat-resistant resin (parts by weight) 73 73 73 70 70
APEI (parts by weight) 0.5 One 2 0.5 One
PEI (parts by weight) - - - - -
Izod impact strength (kgfㆍcm/cm) 22.0 21.5 20.5 26.8 26.0
Fluidity (g/10min) 7 7.1 7.5 5.2 5.6
HDT(℃) 101.6 101.3 100.8 98.5 98.0
Chemical resistance (second) 350 500 700 550 700
Paintability ○ ○ ○ ○ ○
[178]
[Table 2]
division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8
ABS resin (parts by weight) 27 27 27 27 27 30 50 10
AMS heat-resistant resin (parts by weight) 73 73 73 73 73 70 50 90
APEI (parts by weight) - - 0.2 5 10 - One One
PEI (parts by weight) One 4 - - - - - -
Izod impact strength (kgfㆍcm/cm) 21.0 18.0 22.1 15.0 11.5 27.0 30 6
Fluidity (g/10min) 7.5 8.0 7.4 8.5 11.0 6.0 3.0 15
HDT(℃) 98.3 95.7 100.0 98.0 101.7 98.0 85 106
Chemical resistance (second) 40 60 100 800 800 300 900 150
Paintability X X △ ○ ○ X X X
[179]
As shown in Tables 1 and 2, in Examples 1 to 5 according to the present disclosure, the impact strength, fluidity, and heat distortion temperature compared to Comparative Examples 1 to 8 are maintained at equal or higher levels, while having excellent chemical resistance and coating properties Comparative Example 6 containing no alkoxylated polyethylene imine and Comparative Examples 1 and 2 containing non-alkoxylated polyethyleneimine had poor chemical resistance and poor paintability.
[180]
In addition, Comparative Example 3 containing a small amount of alkoxylated polyethyleneimine decreased chemical resistance and paintability, and Comparative Examples 4 and 5 containing an excessive amount of alkoxylated polyethyleneimine had a sharp decrease in impact strength.
[181]
In addition, Comparative Example 7 in which an excessive amount of ABS resin was included in the base resin was poor in fluidity, heat deflection temperature and paintability, and Comparative Example 8 in which a small amount of ABS resin was included was poor in impact strength, chemical resistance and paintability. .
Claims
[Claim 1]
100 parts by weight of a basic resin comprising 20 to 40% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer and 60 to 80% by weight of an α-methyl styrene compound-vinyl cyan compound copolymer; And alkoxylated polyethylene imine 0.4 to 3 parts by weight; A thermoplastic resin composition comprising a.
[Claim 2]
The thermoplastic resin composition according to claim 1, wherein the alkoxylated polyethylene imine has an alkoxylation rate of 60% by weight or more.
[Claim 3]
The method of claim 1, wherein the alkoxylated polyethylene imine is at least one selected from the group consisting of ethoxylated polyethyleneimine, propoxylated polyethyleneimine, ethoxylated-butoxylated polyethyleneimine, and ethoxylated-propoxylated-butoxylated polyethyleneimine. A thermoplastic resin composition, characterized in that.
[Claim 4]
The thermoplastic resin composition of claim 1, wherein the alkoxylated polyethylene imine has a dynamic viscosity of 700 to 1500 mPa·s measured at 40° C. with a Brookfield viscometer.
[Claim 5]
The method of claim 1, wherein the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer comprises 40 to 80% by weight of a conjugated diene rubber, 10 to 40% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinylcyan compound. A thermoplastic resin composition comprising a graft-polymerized graft copolymer.
[Claim 6]
The method of claim 1, wherein the α-methyl styrene compound-vinyl cyan compound copolymer is a polymerized copolymer comprising 50 to 80 wt% of an α-methyl styrene compound and 20 to 50 wt% of a vinyl cyan compound. The thermoplastic resin composition.
[Claim 7]
The thermoplastic resin composition according to claim 1, wherein the α-methyl styrene-based compound is at least one selected from the group consisting of α-methyl styrene and derivatives thereof.
[Claim 8]
The method of claim 1, wherein the thermoplastic resin composition fixes a specimen size of 200 × 12.7 × 3.2 mm to a curvature jig having 1.7% strain, and thinner (naphtha 45% by weight, xylene 25% by weight, propylene A thinner in which 20% by weight of glycol monomethyl ether and 10% by weight of n-butyl acetic acid are mixed), and the chemical resistance is 300 seconds or more in the chemical resistance evaluation that measures the time for cracks to occur in the specimen after applying 200 µl. Thermoplastic resin composition.
[Claim 9]
The method of claim 1, wherein the thermoplastic resin composition is a black paint (methyl methacrylate, butyl acrylate-2-hydroxyethyl methacrylate copolymer, thermosetting acrylic resin, after degreasing a specimen size of 10 cm × 10 cm with isopropyl alcohol, A paint containing carbon black and a solvent) was sprayed with 50 ml, and after 5 minutes, a clear paint (butyl 2-methylprop-2-enoate, 2-hydroxyethyl 2-methylprop-2-enoate, methyl After spraying with 50 ml of 2-methylprop-2-enoate, styrene, a paint containing a thermosetting acrylic resin and an organic solvent), drying it in an oven at 85° C. for 30 minutes, and then counting the number of pinholes on the painted surface. A thermoplastic resin composition, characterized in that no pinholes are generated in the observed coating property evaluation.
[Claim 10]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an impact strength of 20 kgf·cm/cm or more, measured at 1/4" of a specimen thickness according to ASTM D256.
[Claim 11]
100 parts by weight of a basic resin comprising 20 to 40% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer and 60 to 80% by weight of an α-methyl styrene compound-vinyl cyan compound copolymer; And 0.4 to 3 parts by weight of alkoxylated polyethylene imine; melt-kneading and extruding under conditions of 230 to 270° C. and 200 to 400 rpm.
[Claim 12]
A molded article, characterized in that it is made of the thermoplastic resin composition according to any one of claims 1 to 10.