Title of Invention: ABS-based 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. 10-2020-0123587 dated September 24, 2020, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
[4]
The present invention relates to an ABS-based resin composition, a method for manufacturing the same, and a molded article comprising the same, and more particularly, when the impact strength is improved in the prior art, the colorability and gloss are poor, and conversely, when the colorability and gloss are improved, the impact strength is increased It relates to an ABS-based resin composition excellent in both impact strength, colorability and gloss, which was difficult to improve at the same time due to the worsening trade-off relationship, a manufacturing method thereof, and a molded article manufactured therefrom.
background
[5]
Vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer (hereinafter referred to as 'ABS-based resin') represented by acrylonitrile-butadiene-styrene resin is a high-impact polystyrene (HIPS) It solves the disadvantages of low heat resistance and rigidity, and it has excellent physical properties such as high impact resistance, chemical resistance, thermal stability, colorability, fatigue resistance, rigidity, and workability. Due to these characteristics, ABS-based resins are used as interior/exterior materials for automobiles, office equipment, parts for various electric/electronic products, or materials for toys.
[6]
However, when an ABS-based resin having higher impact strength is required, an additive such as silicone is mixed to improve the impact strength of the ABS-based resin.
[7]
However, when an additive such as silicone is mixed with ABS-based resin to improve impact strength, impact strength is improved, but colorability and glossiness are deteriorated due to a trade-off relationship between physical properties.
[8]
Accordingly, there is a need to develop an ABS-based resin composition that simultaneously improves impact strength, colorability, and gloss while not lowering the intrinsic physical properties of the ABS-based resin.
[9]
[Prior art literature]
[10]
[Patent Literature]
[11]
Republic of Korea Patent Publication No. 2001-0056186
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[12]
In order to solve the problems of the prior art as described above, the present base material is improved at the same time due to the trade-off relationship in which, when the impact strength is improved, the colorability and glossiness are inferior, and conversely, when the colorability and glossiness are improved, the impact strength is poor. An object of the present invention is to provide an ABS-based resin composition excellent in both impact strength, colorability and gloss, a method for producing the same, and a molded article manufactured therefrom.
[13]
[14]
The above and other objects of the present disclosure can all be achieved by the present disclosure described below.
means of solving the problem
[15]
In order to achieve the above object, the present base material is a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 20 to 40% by weight and aromatic vinyl compound-vinyl cyan compound copolymer 60 to 80% by weight of the base resin comprising 100 parts by weight; And it provides an ABS-based resin composition comprising 0.1 to 5 parts by weight of polyether-modified polysiloxane.
[16]
The polyether-modified polysiloxane may be preferably a polydialkylsiloxane modified with an alkylene oxide.
[17]
The polyether-modified polysiloxane may be at least one selected from the group consisting of branched polyether-modified polysiloxane, terminal polyether-modified polysiloxane, and side-chain-terminated polyether-modified polysiloxane.
[18]
The polyether-modified polysiloxane may preferably have a weight average molecular weight of 10,000 to 50,000 g/mol.
[19]
The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer preferably contains 40 to 80 wt% of a conjugated diene rubber, 10 to 40 wt% of an aromatic vinyl compound, and 1 to 20 wt% of a vinyl cyan compound. It may be a graft copolymer that has been polymerized.
[20]
The aromatic vinyl compound-vinyl cyan compound copolymer may preferably include 60 to 80 wt % of the aromatic vinyl compound and 20 to 40 wt % of the vinyl cyanide compound.
[21]
The aromatic vinyl compound-vinyl cyan compound copolymer may have a weight average molecular weight of 50,000 to 200,000 g/mol.
[22]
The ABS-based resin composition may preferably include 0.1 to 5 parts by weight of an inorganic pigment.
[23]
The inorganic pigment may preferably be carbon black.
[24]
Preferably, the ABS-based resin composition may have a Color L value of 28.5 or less measured using a color difference meter (Color-Eye 7000A, SCI mode).
[25]
Preferably, the ABS-based resin composition may have a gloss (gloss) of 86 or more measured at 45° with a gloss meter VG7000.
[26]
The ABS-based resin composition may have an impact strength of 30 kgf·cm/cm or more, preferably measured at a thickness of 1/8″ of a specimen according to ASTM D256.
[27]
The base material includes 100 parts by weight of a base resin comprising 20 to 40 wt% of a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer and 60 to 80 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; And 0.1 to 5 parts by weight of polyether-modified polysiloxane; provides a method for producing an ABS-based resin composition comprising the step of extruding after melt-kneading under 200 to 250 ℃ and 100 to 400 rpm conditions, including.
[28]
The present substrate provides a molded article comprising the ABS-based resin composition.
Effects of the Invention
[29]
According to the present description, impact strength, colorability and glossiness, which were difficult to improve at the same time due to the trade-off relationship in which conventionally, when the impact strength is improved, the colorability and gloss are inferior, and conversely, when the colorability and gloss are improved, the impact strength is poor. All are effective in providing an excellent ABS-based resin composition, a method for manufacturing the same, and a molded article manufactured therefrom.
Modes for carrying out the invention
[30]
Hereinafter, the ABS-based resin composition of the present disclosure, a method for manufacturing the same, and a molded article manufactured therefrom will be described in detail.
[31]
When the present inventors mix an ABS-based resin and a SAN-based resin in a predetermined ratio, and include a predetermined amount of polyether-modified polysiloxane therein, the trade in impact strength, colorability and gloss that has been conventionally applied to ABS-based resins The -off relationship was not established, and it was confirmed that the impact strength, colorability, and gloss were all unexpectedly improved, and based on this, further research was completed and the present invention was completed.
[32]
[33]
The ABS-based resin composition of the present invention is a base resin comprising 20 to 40 wt% of a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer and 60 to 80 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer. wealth; and 0.1 to 5 parts by weight of polyether-modified polysiloxane, and in this case, when the impact strength is improved in the prior art, the colorability and gloss are inferior, and conversely, when the colorability and gloss are improved, the impact strength is poor. There is an advantage in that all of the impact strength, colorability and glossiness, which were difficult to be improved at the same time due to the off relationship, are improved.
[34]
[35]
Each component constituting the ABS-based resin composition of the present invention is divided and looked at in detail as follows.
[36]
[37]
Vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer
[38]
The vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure is, for example, 20 to 40 wt%, preferably 20 to 35 wt%, more preferably 20 to 30 wt%, more in the base resin Preferably, it may be included in an amount of 23 to 27% by weight, and within this range, there is an excellent effect of mechanical strength, fluidity, and balance of physical properties.
[39]
[40]
The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer preferably contains 40 to 80 wt% of a conjugated diene rubber, 10 to 40 wt% of an aromatic vinyl compound, and 1 to 20 wt% of a vinyl cyan compound. It may be a graft copolymer that has been polymerized, and in this case, there is an effect of excellent impact resistance.
[41]
[42]
More preferably, the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer comprises 45 to 70 wt% of a conjugated diene rubber, 20 to 40 wt% of an aromatic vinyl compound, and 5 to 20 wt% of a vinyl cyan compound It may be a graft-polymerized graft copolymer, and in this case, there is an effect of excellent impact resistance.
[43]
[44]
More preferably, the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer comprises 50 to 65 wt% of a conjugated diene rubber, 20 to 35 wt% of an aromatic vinyl compound, and 5 to 15 wt% of a vinyl cyan compound It may be a graft-polymerized graft copolymer, and in this case, there is an effect of excellent impact resistance.
[45]
[46]
The conjugated diene rubber may preferably have an average particle diameter of 50 to 500 nm, more preferably 100 to 500 nm, still more preferably 150 to 400 nm, still more preferably 200 to 350 nm, most preferably is 250 to 320 nm, and within this range, mechanical properties of the ABS-based resin composition and physical properties such as colorability are excellent.
[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 of the United States by a dynamic laser light scattering method. As a specific example of this, the sample is prepared by diluting 0.1 g of Latex (TSC 35-50wt%) 1,000-5,000 times with deionized water or distilled water, that is, diluting it appropriately so as not to significantly deviate from the Intensity Setpoint 300kHz, and putting it in a glass tube, and prepare and measure The 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℃, measuring wavelength 632.8nm, channel width It can measure as 10 microseconds.
[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 pyrerylene. It may be at least one selected from the group consisting of.
[50]
The aromatic vinyl compound may be, for example, at least one 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, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and derivatives thereof.
[52]
[53]
In a preferred embodiment, the conjugated diene rubber may be at least one of butadiene polymer, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene copolymer, and polymers derived therefrom, but is not limited thereto. specify
[54]
The term "polymer derived" in the present description means copolymerized with other monomers or polymers not originally included in the copolymer, or copolymerized with derivatives of the monomers.
[55]
In the present description, the derivative refers to a compound in which a hydrogen atom or an atomic group of the original compound is substituted with another atom or atomic group, for example, a compound substituted with a halogen or an alkyl group.
[56]
[57]
The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer can be prepared by known polymerization methods including, for example, emulsion polymerization, suspension polymerization, bulk polymerization, and the like, and is preferably prepared by emulsion polymerization. can
[58]
Preferably, the method for preparing the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer by emulsion polymerization is 100 parts by weight of the conjugated diene rubber, the aromatic vinyl compound, and the vinyl cyan compound included in the graft copolymer. Based on 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 regulator, and 0.05 to 1 parts by weight of a polymerization initiator, 1 to 20% by weight of a vinyl cyanide compound and 10 parts by weight of an aromatic vinyl compound It may include the step of polymerizing by continuously or batch input a monomer mixture containing 40% by weight.
[59]
[60]
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 It works.
[61]
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 mercaptan and carbon tetrachloride, and is preferably t-dodecyl mercaptan.
[62]
The polymerization initiator may be, for example, at least one selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate, and in this case, polymerization efficiency and physical properties of the polymer to be prepared are excellent.
[63]
The latex obtained by the emulsion polymerization is, for example, sulfuric acid, MgSO 4 , CaCl 2 or Al 2 (SO 4 ) 3 After agglomeration with a coagulant such as aging, dehydration and drying, it can be obtained in a powder state.
[64]
The method for preparing the vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer is not particularly limited when using conditions, methods, and devices commonly used in the art to which the present invention pertains as long as the definition of the present invention is followed. does not
[65]
[66]
Aromatic vinyl compound-vinyl cyan compound copolymer
[67]
The aromatic vinyl compound-vinyl cyan compound copolymer of the present disclosure is, for example, 60 to 80% by weight, preferably 65 to 80% by weight, more preferably 70 to 80% by weight, still more preferably 73 to 77% by weight in the base resin. It may be included in weight %, and there is an excellent effect of mechanical strength, fluidity and physical property balance within this range.
[68]
In the present description, the aromatic vinyl compound-vinyl cyan compound copolymer is not particularly limited in the case of an aromatic vinyl compound-vinyl cyan compound copolymer (SAN-based resin) generally meaning in this field, and preferably aromatic vinyl compounds 60 to 80 It may include 20 to 40 wt% of a vinyl cyanide compound by weight, and in this case, there is an advantage in excellent processability and productivity due to improved fluidity of the ABS-based resin composition.
[69]
As another example, the aromatic vinyl compound-vinyl cyan compound copolymer may include 70 to 80 wt% of an aromatic vinyl compound and 20 to 30 wt% of a vinyl cyan compound, and in this case, the processability and productivity of the ABS-based resin composition are improved. It has excellent advantages in mechanical properties such as impact strength, heat resistance and colorability.
[70]
As another example, the aromatic vinyl compound-vinyl cyan compound copolymer may include 70 to 75 wt % of an aromatic vinyl compound and 25 to 30 wt % of a vinyl cyan compound, and in this case, the processability and productivity of the ABS-based resin composition While this is excellent, mechanical properties such as impact strength, heat resistance, and colorability are excellent.
[71]
[72]
The aromatic vinyl compound-vinyl cyan compound copolymer may be prepared by, for example, bulk polymerization or emulsion polymerization, but it may be preferable to prepare by bulk polymerization in terms of manufacturing cost.
[73]
The aromatic vinyl compound-vinyl cyan compound copolymer may have a weight average molecular weight of preferably 50,000 to 200,000 g/mol, more preferably 80,000 to 180,000 g/mol, still more preferably 100,000 to 150,000 g/mol, More preferably, it is 120,000 to 150,000 g/mol, and within this range, the desired fluidity is obtained, so that processability, productivity, etc. are excellent, and there is an advantage of excellent colorability.
[74]
The weight average molecular weight may be measured by a gel permeation chromatography (GPC) method, and as a specific example, it may be measured as a value converted to standard polystyrene measured by GPC.
[75]
In this description, the weight average molecular weight is a detailed measurement example, and it can be measured as a relative value with respect to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent. . At this time, as an example of specific measurement conditions, 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.
[76]
[77]
The method for preparing the aromatic vinyl compound-vinyl cyan compound copolymer is not particularly limited when using conditions, methods, and devices commonly used in the art to which the present invention pertains as long as the definition of the present invention is followed.
[78]
[79]
Polyether-modified polysiloxane
[80]
The polyether-modified polysiloxane of the present base may be included, for example, in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the base resin, preferably 0.2 to 3 parts by weight, more preferably 0.3 to 3 parts by weight, even more preferably 0.4 to 2.5 parts by weight, even more preferably 0.5 to 2.5 parts by weight, particularly preferably 1 to 2.5 parts by weight, particularly more preferably 1.5 to 2.5 parts by weight, within which impact strength, colorability and glossiness are All of them are excellent, and there is an advantage that is particularly excellent in chemical resistance.
[81]
The polyether-modified polysiloxane may be preferably a polysiloxane modified with an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide or tetramethylene oxide, more preferably modified with ethylene oxide and/or propylene oxide It is a polydialkyl siloxane, and in this case, it has the advantages of excellent impact strength, colorability and glossiness.
[82]
The polyether-modified polysiloxane may preferably be at least one selected from the group consisting of polydimethyl siloxane, polydiethyl siloxane, polydipropyl siloxane, polydibutyl siloxane and polydipentyl siloxane, in which case impact strength, colorability and Both have the advantage of being excellent in glossiness.
[83]
[84]
The polyether-modified polysiloxane is preferably at least one selected from the group consisting of branched polyether-modified polysiloxane, terminal-type polyether-modified polysiloxane, and side-chain-terminated polyether-modified polysiloxane, and more preferably, branched-chain polyether-modified polyether-modified polysiloxane It may be at least one selected from the group consisting of polydialkyl siloxane, terminal-type polyether-modified polydialkyl siloxane, and branched-terminated polyether-modified polydialkyl siloxane, and in this case, the impact strength, colorability and glossiness are all excellent. have.
[85]
The branched polyether modification means that the polyether residue is bonded to the side chain with respect to the polysiloxane main chain, and the terminal polyether modification means that the polyether residue is bonded to the end (chain end), The side chain-terminated polyether modification means that the polyether residue is bonded to both the side chain and the terminal.
[86]
[87]
The branched-chain polyether-modified polydialkyl siloxane may more preferably be a polymer represented by the following formula (1), and in this case, all of the impact strength, colorability and glossiness are excellent.
[88]
[Formula 1]
[89]

[90]
PE in Formula 1 represents a polyether moiety; R 1 represents an alkyl group; R 2 represents an alkylene group; x, y, and z are arbitrary numbers, specifically, an integer of 50 to 1,000.
[91]
[92]
In the present description, the alkyl group is, for example, an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 16 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 8 carbon atoms, even more preferably may be an alkyl group having 1 to 4 carbon atoms.
[93]
The alkyl group may be, for example, linear, branched or cyclic.
[94]
Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, It may be at least one selected from the group consisting of an n-hexyl group, an n-heptyl group, an n-octyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
[95]
In addition, the alkyl group may be optionally substituted with one or more substituents.
[96]
[97]
In the present description, the alkylene group is, for example, an alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 16 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, and still more preferably an alkylene group having 1 to 8 carbon atoms. , and more preferably an alkylene group having 1 to 4 carbon atoms.
[98]
The alkylene group may be, for example, linear, branched or cyclic.
[99]
In addition, the alkylene group may be optionally substituted with one or more substituents.
[100]
The substituent substituted for the alkyl group or the alkylene group is, for example, an alkyl group, an alkoxy group, an alkenyl group, an epoxy group, a cyano group, a thiol group, a carboxyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group Or it may be an aryl group, etc., but is not limited thereto.
[101]
[102]
The polyether-modified polysiloxane may preferably have a surface tension of 15 to 30 mN/m, and within this range, impact strength, colorability, and gloss are all excellent.
[103]
In the present disclosure, the surface tension is not particularly limited when measured by a method commonly used in the art to which the present invention pertains, but may be measured by a droplet method as a specific example.
[104]
[105]
The polyether-modified polysiloxane preferably has a weight average molecular weight of 10,000 to 50,000 g/mol, more preferably 20,000 to 35,000 g/mol, and has excellent impact strength, colorability and glossiness within this range. have.
[106]
The weight average molecular weight may be measured as a value converted to standard polystyrene measured by Gel Permeation Chromatograph (GPC).
[107]
[108]
The method for preparing the polyether-modified polysiloxane is not particularly limited when using conditions, methods, and devices commonly used in the art to which the present invention pertains as long as the definition of the present invention is followed.
[109]
[110]
inorganic pigment
[111]
The inorganic pigment of the present disclosure may preferably be carbon black, titanium dioxide (TiO 2 ), or a mixture thereof, and in this case, it has excellent colorability and low discoloration while maintaining mechanical properties.
[112]
The carbon black is preferably at least one selected from the group consisting of ketjen black, acetylene black, furnace black and channel black, and in this case, mechanical properties are It has excellent colorability while maintaining it, and has the effect of having a low degree of discoloration.
[113]
The carbon black may be a masterbatch mixed with an aromatic vinyl compound-vinyl cyan compound copolymer, and in this case, mechanical properties are maintained while excellent colorability and a low degree of discoloration are obtained.
[114]
The carbon black masterbatch may preferably contain 30 to 70 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer and 30 to 70 wt% of carbon black, more preferably an aromatic vinyl compound-vinyl cyan compound copolymer. It may contain 50 to 70% by weight and 30 to 50% by weight of carbon black, and has excellent colorability and low discoloration while maintaining mechanical properties within this range.
[115]
[116]
The inorganic pigment is preferably used in an amount of 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, still more preferably 0.5 to 2 parts by weight, even more preferably 0.5 to 1.5 parts by weight based on 100 parts by weight of the base resin. It may be included, and while maintaining mechanical properties within this range, there is an effect of excellent colorability and a low degree of discoloration.
[117]
[118]
ABS-based resin composition
[119]
The ABS-based resin composition of the present disclosure may preferably have a melt index (MFR) of 15 to 25 g/10min under 220° C. and 10 kg conditions, more preferably 18 to 25 g/10min, more preferably 18 to 23 g/10 min, there is an advantage of excellent workability and excellent balance of properties within this range.
[120]
[121]
The ABS-based resin composition may preferably have a Color L value measured using a color difference meter (Color-Eye 7000A, SCI mode) of 28.5 or less, more preferably 28 or less, more preferably 27.5 or less, and this There is an advantage of being excellent in colorability within the range and excellent in the balance of physical properties.
[122]
[123]
The ABS-based resin composition preferably has a gloss (gloss) measured at 45° with a gloss meter VG7000 of 86 or more, more preferably 87 or more, more preferably 88 or more, and glossiness within this range is excellent, and there is an advantage of excellent balance of physical properties.
[124]
[125]
The ABS-based resin composition preferably fixes a specimen of 200 mm X 12.7 mm X 3.2 mm to a curvature jig having 1.1% strain, and after applying 1 cc of thinner, cracks occur in the specimen. The chemical resistance as measured by the time taken may be 400 seconds or more, more preferably 450 seconds or more, still more preferably 480 seconds or more, still more preferably 500 seconds or more, particularly preferably 550 seconds or more, most preferably is 600 seconds or more, and has excellent chemical resistance and excellent physical property balance within this range.
[126]
[127]
The ABS-based resin composition may preferably have an impact strength of 30 kgf·cm/cm or more, more preferably 32 kgf·cm/cm or more, even more preferably, measured at a thickness of 1/8″ of a specimen according to ASTM D256. preferably at least 33 kgf cm/cm, preferably 30 to 35 kgf cm/cm, more preferably 32 to 35 kgf cm/cm, even more preferably 33 to 35 kgf cm/cm, Within this range, there are advantages of excellent impact strength and excellent balance of properties.
[128]
[129]
The ABS-based resin composition, if necessary, contains at least one selected from the group consisting of lubricants, flame retardants, heat stabilizers, antioxidants, light stabilizers, compatibilizers, pigments (except inorganic pigments), dyes, and inorganic additives as the base resin 100 For example, 0.5 to 5 parts by weight, preferably 1 to 4 parts by weight, more preferably 1.5 to 3 parts by weight based on parts by weight, within this range, without impairing the desired effect of the present invention There is an advantage that the intrinsic effect of the additive is well expressed.
[130]
The lubricant may be, for example, at least one selected from the group consisting of wax, silicone oil and steramide.
[131]
The silicone oil may be, for example, at least one selected from the group consisting of dimethyl silicone oil, methyl hydrogen 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 (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-diphosphite) -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 at least one selected from the group consisting of.
[133]
The antioxidant may be, for example, a hindered phenol-based antioxidant, a phosphide-based antioxidant, or a mixture thereof.
[134]
[135]
Method for producing ABS-based resin composition
[136]
The method for preparing the ABS-based resin composition of the present invention preferably comprises 20 to 40 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer and 60 to 80 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer. 100 parts by weight of the base resin including; And 0.1 to 5 parts by weight of polyether-modified polysiloxane; characterized in that it comprises a step of melt-kneading under conditions of 200 to 250 ° C and 100 to 400 rpm, including the step of extruding, and in this case, when the impact strength is improved in the prior art, the colorability It has the effect of providing an ABS-based resin composition excellent in both impact strength, colorability and gloss, which was difficult to improve at the same time due to the trade-off relationship in which impact strength is poor when colorability and gloss are improved. .
[137]
[138]
The melt-kneading and extruding steps are preferably 210 to 250 ° C. and 200 to 350 rpm, more preferably 210 to 240 ° C. and 250 to 350 rpm. Within this range, the desired effect of the present invention has the advantage of being well expressed.
[139]
At the time of 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 (however, inorganic pigments are excluded), dyes and inorganic additives. Based on 100 parts by weight of the resin, 0.1 to 5 parts by weight, preferably 0.3 to 4 parts by weight, more preferably 0.5 to 3 parts by weight can be further added, and within this range, if the desired effect of the present invention is not impaired This has the advantage that the original effect of the additive is well expressed.
[140]
The extrudate through the melt-kneading and extrusion steps may preferably be pellets.
[141]
[142]
The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, the aromatic vinyl compound-vinyl cyan compound copolymer, the polyether-modified polysiloxane and the inorganic pigment included in the ABS-based resin composition are the same as those described above. omit the description.
[143]
[144]
molded article
[145]
The molded article of the present substrate is characterized in that it contains the ABS-based resin composition, and in this case, when the impact strength is improved in the prior art, the colorability and gloss are inferior, and conversely, when the colorability and gloss are improved, the impact strength is poor. There is an advantage in providing a molded article with improved impact strength, colorability and gloss, which were difficult to improve at the same time due to the -off relationship.
[146]
The molded article may be preferably an injection molded article, and more preferably may be an automobile interior or exterior material or a home appliance exterior material, and in this case, there is an advantage that greatly satisfies all of the physical properties required for the product.
[147]
[148]
The molded article may preferably be manufactured including the step of injection molding the ABS-based resin composition of the present base or its pellets, and the injection molding is preferably performed at an injection temperature of 210 to 250° C., more preferably 215 to 240 ℃, more preferably 220 to 230 ℃; And preferably, it can be carried out under the conditions of the injection speed of 7 to 13 mm / sec, more preferably 75 to 85 mm / sec, there is an advantage that the desired effect of the present invention is well expressed within this range.
[149]
[150]
The manufacturing method of the molded article is not particularly limited as long as it follows the definition of the present invention, if conditions, methods, and apparatuses commonly used in the technical field to which the present invention pertains are used.
[151]
[152]
Hereinafter, preferred examples are presented to help the understanding of the present disclosure, but the following examples are merely illustrative of the present disclosure, 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 disclosure, It goes without saying that such variations and modifications fall within the scope of the appended claims.
[153]
[154]
[Example]
[155]
The components used in the following Examples and Comparative Examples are as follows.
[156]
(A) Emulsion polymerization vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer: LG Chem's DP270 containing 60% by weight of butadiene polymer having an average particle diameter of 300 nm, 10% by weight of acrylonitrile and 30% by weight of styrene was used.
[157]
(B) Aromatic vinyl compound-vinyl cyan compound copolymer: LG Chem's 92HR containing 27 wt% of acrylonitrile and having a weight average molecular weight of 130,000 g/mol was used.
[158]
(C-1) Polyether-modified polysiloxane: Polyether-modified polydimethylsiloxane (BYK-333) was used.
[159]
(C-2) Polyether-modified polysiloxane: Polyether-modified polydimethylsiloxane (BYK-378) was used.
[160]
(C-3) Unmodified polysiloxane: polydimethylsiloxane (Shin-Etsu Silicone, KF-96-100cs) was used.
[161]
(D) Inorganic pigment: A carbon black masterbatch (non-chemical, product name: BK50) was used.
[162]
[163]
Examples 1 to 4 and Comparative Examples 1 to 3
[164]
The components and contents described in Table 1 were put into a twin-screw extruder, melt-kneaded and extruded at 220° C. and 600 rpm to prepare ABS-based resin composition pellets. After drying the ABS-based resin composition pellets at 80 °C for 3 hours, injection molding was performed in an injection machine under the conditions of an injection temperature of 220 °C, a mold temperature of 60 °C, and an injection speed of 30 mm/sec to prepare a specimen for measuring physical properties.
[165]
[166]
[Test Example]
[167]
The properties of the specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were measured by the following method, and the results are shown in Table 1 below.
[168]
[169]
* Izod impact strength (kgf·cm/cm): It was measured according to ASTM D256 using a specimen thickness of 1/4″.
[170]
* Fluidity (g/10min): Melt viscosity was measured at 220°C and 10 kg according to ASTM D256.
[171]
* Gloss: Measured at 45° with a gloss meter VG7000 (1/8 inch exit gloss).
[172]
* Color L: Color L, a, and b values ​​of the specimen were measured using a colorimeter (Colar-Eye 7000A, SCI mode). For reference, the L value is a numerical value indicating brightness, and the lower the value, the stronger the blackness, the a value is a numerical value indicating the degree of red and green. It is a numerical value indicating the degree of blue, and the lower the value, the stronger the degree of blue.
[173]
* Chemical resistance (ESCR, seconds): A 200mm X 12.7mm X 3.2mm specimen is fixed to a curvature jig with 1.1% strain, and after applying 1cc of thinner, cracks occur in the specimen. time was measured. If cracks did not occur until 600 seconds, it was judged that the chemical resistance evaluation was passed. Those that passed the chemical resistance evaluation were described as >600.
[174]
[175]
[Table 1]
(parts by weight) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3
A 25 25 25 25 25 25 25
B 75 75 75 75 75 75 75
C-1 0.5 2
C-2 0.5 2
C-3 0.5 2
D One One One One One One One
impact strength 34.3 33.4 30.4 34.1 27.6 28.0 28.0
melt viscosity 18.8 21.8 19.8 22.1 19.0 19.2 21.5
glossiness 88.2 86.9 88.7 88.1 87.4 86.1 82.4
color L 27.47 28.15 27.41 27.89 27.32 28.11 29.41
a 0.00 -0.08 -0.03 -0.06 -0.01 -0.09 0.20
b -0.93 -1.14 -0.92 -1.15 -0.93 -0.73 -0.13
ESCR
(seconds) One >600 >600 480 >600 245 458 >600
2 571 >600 522 >600 227 428 574
3 559 >600 411 >600 247 510 544
[176]
As shown in Table 1, the ABS-based resin composition (Examples 1 to 4) according to the present invention does not include the polyether-modified polysiloxane according to the present invention or the ABS-based resin composition (Comparative Examples 1 to) 3) In contrast, it was confirmed that the fluidity was maintained within the range of easy processing, while the impact strength, glossiness and colorability were all excellent.
[177]
[178]
In summary, as in the prior art, when polydimethylsiloxane is mixed as in Comparative Examples 2 to 3 to improve the impact strength of the ABS-based resin composition of Comparative Example 1, the impact strength is improved, but on the contrary, the gloss and colorability are poor trade-off relationship However, as in Examples 1 to 4, when the polyether-modified polysiloxane according to the present invention is mixed in a predetermined amount, the trade-off relationship as described above disappears and impact strength, colorability, and glossiness are all improved at the same time.
Claims
[Claim 1]
100 parts by weight of a base resin comprising 20 to 40 wt% of a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer and 60 to 80 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; and 0.1 to 5 parts by weight of polyether-modified polysiloxane.
[Claim 2]
The ABS-based resin composition according to claim 1, wherein the polyether-modified polysiloxane is polydialkylsiloxane modified with alkylene oxide.
[Claim 3]
The ABS-based resin composition according to claim 1, wherein the polyether-modified polysiloxane is at least one selected from the group consisting of branched polyether-modified polysiloxane, terminal polyether-modified polysiloxane, and side-chain-terminated polyether-modified polysiloxane.
[Claim 4]
The ABS-based resin composition according to claim 1, wherein the polyether-modified polysiloxane has a weight average molecular weight of 10,000 to 50,000 g/mol.
[Claim 5]
According to claim 1, wherein the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer comprises 40 to 80 wt% of a conjugated diene rubber, 10 to 40 wt% of an aromatic vinyl compound, and 1 to 20 wt% of a vinyl cyanide compound ABS-based resin composition, characterized in that it is a graft copolymer comprising a graft polymerization.
[Claim 6]
The ABS-based resin composition according to claim 1, wherein the aromatic vinyl compound-vinyl cyan compound copolymer comprises 60 to 80 wt% of an aromatic vinyl compound and 20 to 40 wt% of a vinyl cyanide compound.
[Claim 7]
The ABS-based resin composition according to claim 1, wherein the aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight of 50,000 to 200,000 g/mol.
[Claim 8]
The ABS-based resin composition according to claim 1, wherein the ABS-based resin composition comprises 0.1 to 5 parts by weight of an inorganic pigment.
[Claim 9]
The ABS-based resin composition according to claim 8, wherein the inorganic pigment is carbon black.
[Claim 10]
The ABS-based resin composition of claim 1, wherein the ABS-based resin composition has a Color L value of 28.5 or less measured using a color difference meter (Color-Eye 7000A, SCI mode).
[Claim 11]
The ABS-based resin composition according to claim 1, wherein the ABS-based resin composition has a gloss measured at 45° using a gloss meter VG7000 of 86 or more.
[Claim 12]
The ABS-based resin composition according to claim 1, wherein the ABS-based resin composition has an impact strength of 30 kgf·cm/cm or more when measured at a thickness of 1/8″ of a specimen according to ASTM D256.
[Claim 13]
100 parts by weight of a base resin comprising 20 to 40 wt% of a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer and 60 to 80 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; And 0.1 to 5 parts by weight of polyether-modified polysiloxane; Method for producing an ABS-based resin composition comprising the step of extruding after melt-kneading under the conditions of 200 to 250 ℃ and 100 to 400 rpm.
[Claim 14]
A molded article comprising the ABS-based resin composition of any one of claims 1 to 13.