Title of Invention: Thermoplastic resin composition, manufacturing method thereof, and molded article manufactured therefrom
technical field
[One]
[Cross Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0141893 dated on October 29, 2020 and Korean Patent Application No. 10-2021-0107006 filed again on August 13, 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 producing the same, and a molded article manufactured therefrom, and more particularly, to a thermoplastic resin composition having excellent chemical resistance while having excellent mechanical properties such as fluidity, impact resistance, and tensile strength, a method for producing the same and It relates to a molded article manufactured therefrom.
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') 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, and in particular, it has excellent 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.
[5]
In particular, in the case of a cup holder, which is a kind of interior material for automobiles, there is a problem in that cracks occur due to contact with chemical products such as air fresheners.
[6]
In order to solve this problem, an acrylate-styrene-acrylonitrile copolymer grafted with a styrene-acrylonitrile copolymer having a high molecular weight and a crystalline polymer were applied, but there is a problem of low impact resistance and fluidity.
[7]
Therefore, there is a need for the development of a thermoplastic resin composition having excellent chemical resistance and excellent impact resistance and fluidity.
[8]
[9]
[Prior art literature]
[10]
[Patent Literature]
[11]
Korean Patent Publication No. 2006-0131373
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[12]
In order to solve the problems of the prior art as described above, the present invention is to provide a thermoplastic resin composition excellent in chemical resistance and excellent mechanical properties such as impact resistance and tensile strength and fluidity, a manufacturing method thereof, and a molded article manufactured therefrom. do it with
[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 is (A) 10 to 40% by weight of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; (B) (meth)acrylic acid alkyl ester compound-α-methyl styrenic compound-vinyl cyan compound copolymer 18 to 52% by weight; and (C) 13 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; (D) 7 to 17 parts by weight of a polyether ester elastomer resin and (E) a modified polyester resin in 100 parts by weight of a base resin containing 1.1 to 10 parts by weight, wherein the (C) aromatic vinyl compound-vinyl cyan compound copolymer provides a thermoplastic resin composition comprising 10 to 25 wt % of the vinyl cyan compound.
[15]
[16]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 40% by weight; (B) (meth)acrylic acid alkyl ester compound-α-methyl styrenic compound-vinyl cyan compound copolymer 18 to 52% by weight; (C) 13 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; And (G) block polymerization vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (D) 7 to 17 parts by weight of polyether ester elastomer resin and (E) modified polyester in 100 parts by weight of a base resin containing; Containing 1.1 to 10 parts by weight of the resin, the (C) aromatic vinyl compound-vinyl cyan compound copolymer may provide a thermoplastic resin composition comprising 10 to 25 wt % of the vinyl cyan compound.
[17]
[18]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 40% by weight; (B) (meth)acrylic acid alkyl ester compound-α-methyl styrenic compound-vinyl cyan compound copolymer 18 to 52% by weight; and (C) 13 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; (D) 7 to 17 parts by weight of a polyether ester elastomer resin, (E) a modified polyester resin in 100 parts by weight of a base resin containing 1.1 to 10 parts by weight and (F) 0.3 to 5 parts by weight of the alkylene oxide copolymer, wherein the (C) aromatic vinyl compound-vinyl cyan compound copolymer comprises 10 to 25 weight % of the vinyl cyanide compound It is possible to provide a thermoplastic resin composition comprising
[19]
[20]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 40% by weight; (B) (meth)acrylic acid alkyl ester compound-α-methyl styrenic compound-vinyl cyan compound copolymer 18 to 52% by weight; and (C) 13 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; (D) 7 to 17 parts by weight of a polyether ester elastomer resin and (E) a modified polyester resin in 100 parts by weight of a base resin containing 1.1 to 10 parts by weight, wherein the (C) aromatic vinyl compound-vinyl cyan compound copolymer comprises 10 to 25 wt % of the vinyl cyan compound, and a curvature jig having 2.0% strain. After fixing a 160*10*4mm specimen and applying 0.1cc of Amway's fragrance Aroma Natural (product name), cracks did not occur after 24 hours in the chemical resistance evaluation, which measures the time that cracks occurred on the specimen. A thermoplastic resin composition can be provided.
[21]
[22]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 40% by weight; (B) (meth)acrylic acid alkyl ester compound-α-methyl styrenic compound-vinyl cyan compound copolymer 18 to 52% by weight; and (C) 13 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; (D) 7 to 17 parts by weight of a polyether ester elastomer resin and (E) a modified polyester resin in 100 parts by weight of a base resin containing Including 1.1 to 10 parts by weight, comprising the steps of kneading and extruding under 200 to 300 ℃ and 200 to 700 rpm conditions to prepare pellets, wherein the (C) aromatic vinyl compound-vinyl cyan compound copolymer is a vinyl cyan compound 10 to It provides a method for producing a thermoplastic resin composition, characterized in that it comprises 25% by weight.
[23]
[24]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 40% by weight; (B) (meth)acrylic acid alkyl ester compound-α-methyl styrenic compound-vinyl cyan compound copolymer 18 to 52% by weight; (C) 13 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; And (G) block polymerization vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer; (D) 7 to 17 parts by weight of polyether ester elastomer resin and (E) modified polyester in 100 parts by weight of a base resin containing; Including 1.1 to 10 parts by weight of the resin, comprising the step of kneading and extruding under 200 to 300 ℃ and 200 to 700 rpm conditions to prepare pellets, wherein the (C) aromatic vinyl compound-vinyl cyan compound copolymer is a vinyl cyan compound 10 To provide a method for producing a thermoplastic resin composition, characterized in that it comprises 25% by weight.
[25]
[26]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 40% by weight; (B) (meth)acrylic acid alkyl ester compound-α-methyl styrenic compound-vinyl cyan compound copolymer 18 to 52% by weight; and (C) 13 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; (D) 7 to 17 parts by weight of a polyether ester elastomer resin, (E) a modified polyester resin in 100 parts by weight of a base resin containing 1.1 to 10 parts by weight, and (F) including 0.3 to 5 parts by weight of the alkylene oxide copolymer, comprising the steps of kneading and extruding under 200 to 300 ℃ and 200 to 700 rpm conditions to prepare pellets, the (C) The aromatic vinyl compound-vinyl cyan compound copolymer may provide a method for producing a thermoplastic resin composition comprising 10 to 25 wt % of the vinyl cyan compound.
[27]
[28]
In addition, the present invention (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 10 to 40% by weight; (B) (meth)acrylic acid alkyl ester compound-α-methyl styrenic compound-vinyl cyan compound copolymer 18 to 52% by weight; and (C) 13 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; (D) 7 to 17 parts by weight of a polyether ester elastomer resin and (E) a modified polyester resin in 100 parts by weight of a base resin containing Comprising the step of kneading and extruding under the conditions of 200 to 300 ℃ and 200 to 700 rpm including 1.1 to 10 parts by weight to prepare a thermoplastic resin composition, the (C) aromatic vinyl compound-vinyl cyan compound copolymer is a vinyl cyan compound It is made by including 10 to 25% by weight, and the prepared thermoplastic resin composition is obtained by fixing a 160*10*4mm specimen to a curvature jig having 2.0% strain, and Aroma Natural (product name), a fragrance of Amway. It is possible to provide a method for producing a thermoplastic resin composition, characterized in that cracks do not occur after 24 hours in the chemical resistance evaluation of measuring the time that cracks occur on the specimen after applying 0.1 cc.
[29]
[30]
In addition, the present invention provides a molded article comprising the thermoplastic resin composition.
Effects of the Invention
[31]
Advantageous Effects of Invention According to the present invention, there is an effect of providing a thermoplastic resin composition applicable for automotive interior materials, a method for manufacturing the same, and a molded article manufactured therefrom, having excellent mechanical properties and fluidity such as impact resistance and tensile strength, and excellent chemical resistance.
[32]
Specifically, the thermoplastic resin composition of the present invention has the advantage that cracks do not occur even after 24 hours in the chemical resistance test tested with Aroma Natural (product name), a fragrance of Amway.
Modes for carrying out the invention
[33]
Hereinafter, the thermoplastic resin composition of the present disclosure, a method for producing the same, and a molded article prepared therefrom will be described in detail.
[34]
The present inventors have disclosed a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, (meth)acrylic acid alkyl ester compound-α-methyl styrene-based compound-vinyl cyan compound copolymer, and aromatic vinyl containing a vinyl cyan compound in a predetermined content. When the polyether ester elastomer resin and the modified polyester resin are included in a predetermined amount in the base resin including the compound-vinyl cyan compound copolymer in a predetermined amount, the effect of remarkably improving mechanical properties, fluidity and chemical resistance is confirmed, Based on this, further research has been devoted to complete the present invention.
[35]
[36]
The thermoplastic resin composition of the present invention comprises (A) 10 to 40 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; (B) (meth)acrylic acid alkyl ester compound-α-methyl styrenic compound-vinyl cyan compound copolymer 18 to 52% by weight; and (C) 13 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; (D) 7 to 17 parts by weight of a polyether ester elastomer resin and (E) a modified polyester resin in 100 parts by weight of a base resin containing 1.1 to 10 parts by weight, wherein the (C) aromatic vinyl compound-vinyl cyan compound copolymer comprises 10 to 25 weight % of the vinyl cyan compound. In this case, mechanical properties such as impact resistance and tensile strength and fluidity are excellent, and there is an effect of excellent chemical resistance.
[37]
[38]
Hereinafter, the thermoplastic resin composition of the present invention will be described in detail for each configuration.
[39]
[40]
(A) Vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer
[41]
(A) the vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure is, for example, 10 to 40% by weight, preferably 15 to 40% by weight, more preferably 20 to 35% by weight in the base resin %, there is an excellent effect of mechanical strength, fluidity and physical property balance within this range.
[42]
[43]
The (A) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer is preferably 40 to 80 wt% of a conjugated diene rubber comprising a conjugated diene compound, 10 to 40 wt% of an aromatic vinyl compound, and vinyl cyanide It may be a graft copolymer that is graft-polymerized by including 1 to 20% by weight of the compound, and in this case, there is an excellent impact resistance effect.
[44]
More preferably, the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer is 45 to 70 wt% of a conjugated diene rubber including a conjugated diene compound, 20 to 40 wt% of an aromatic vinyl compound, and a vinyl cyan compound 5 It may be a graft copolymer comprising to 20% by weight of the graft polymerization, and in this case, there is an excellent impact resistance effect.
[45]
More preferably, the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer is 50 to 65 wt% of a conjugated diene rubber including a conjugated diene compound, 20 to 35 wt% of an aromatic vinyl compound, and a vinyl cyan compound 5 It may be a graft copolymer polymerized by grafting to 15% by weight, and in this case, there is an excellent impact resistance effect.
[46]
[47]
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 thermoplastic resin composition and physical properties such as colorability are excellent.
[48]
The average particle diameter of the conjugated diene rubber in the present description can be measured using dynamic light scattering, and in detail, in Gaussian mode using a particle measuring instrument (product name: Nicomp 380, manufacturer: PSS). It is measured as an intensity value. At this time, as a specific example of measurement, the sample is prepared by diluting 0.1 g of Latex (TSC 35-50wt%) 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 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.
[49]
[50]
The conjugated diene compound may include, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, isoprene, chloroprene and piperylene. It may be one or more selected from the group.
[51]
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 member 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.
[52]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and derivatives thereof.
[53]
The conjugated diene rubber may be one or more of a butadiene polymer, a butadiene-styrene copolymer, a butadiene-acrylonitrile copolymer, an ethylene-propylene copolymer, and a polymer 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, a 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.
[56]
[57]
The vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer can be prepared by a known polymerization method including, for example, emulsion polymerization, suspension polymerization, bulk polymerization, and the like, and is preferably prepared by emulsion polymerization. can
[58]
[59]
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 the monomer mixture containing 40% by weight.
[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, agglomerated with one or more coagulants selected from the group consisting of sulfuric acid, MgSO 4 , CaCl 2 and Al 2 (SO 4 ) 3 It can be obtained in a powder state by aging, dehydration and drying. have.
[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 apparatuses 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]
(B) (meth)acrylic acid alkyl ester compound-α-methyl styrene compound-vinyl cyan compound copolymer
[67]
(B) (meth)acrylic acid alkyl ester compound-α-methyl styrenic compound-vinyl cyan compound copolymer of the present description is, for example, 18 to 52 wt%, preferably 20 to 50 wt%, more preferably in the base resin may be 25 to 45% by weight, and within this range, impact resistance, fluidity and chemical resistance are all excellent.
[68]
The (B) copolymer is, for example, comprising 30 to 55% by weight of a (meth)acrylic acid alkyl ester compound, 25 to 50% by weight of an α-methyl styrenic compound, and 10 to 30% by weight of a vinyl cyanide compound, within this range It has the advantages of excellent impact resistance, heat resistance and fluidity in the interior.
[69]
The copolymer (B) preferably comprises 35 to 50% by weight of a (meth)acrylic acid alkyl ester compound, 30 to 45% by weight of an α-methyl styrene compound, and 12 to 27% by weight of a vinyl cyanide compound. , there is an advantage of excellent impact resistance, heat resistance and fluidity within this range.
[70]
The (B) copolymer is more preferably comprising 40 to 45 wt% of a (meth)acrylic acid alkyl ester compound, 35 to 40 wt% of an α-methyl styrene compound, and 17 to 22 wt% of a vinyl cyanide compound. And within this range, there is an advantage of excellent impact resistance, heat resistance and fluidity.
[71]
[72]
The (B) copolymer may have, for example, a weight average molecular weight of 50,000 to 200,000 g/mol, preferably 70,000 to 150,000 g/mol, more preferably 80,000 to 120,000 g/mol, and impact strength and It has excellent mechanical properties such as tensile strength and excellent injection moldability.
[73]
In the present description, the weight average molecular weight and the number average molecular weight may be measured using GPC (Gel Permeation Chromatography, waters breeze) unless otherwise defined. Chromatography, water breeze) can be measured as a relative value with respect 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.
[74]
[75]
The (meth)acrylic acid alkyl ester polymer may be, for example, at least one selected from methacrylic acid alkyl esters or acrylic acid alkyl esters having 1 to 20 carbon atoms in the alkyl group, preferably 1 to 10 carbon atoms, preferably methyl meth It may be a acrylate.
[76]
The α-methyl styrene-based compound may be, for example, at least one selected from the group consisting of α-methyl styrene and derivatives thereof, and in this case, excellent heat resistance is obtained.
[77]
Preferably, the derivative of α-methyl styrene may be a compound in which one or two or more of its hydrogens are substituted with a substituent such as an alkyl group having 1 to 10 carbon atoms or a halogen group, and more preferably an aromatic ring thereof It may be a compound in which one or two or more of the hydrogens are substituted with a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogen group, or the like.
[78]
The type of the vinyl cyan compound included in the (B) copolymer may be within the same range as the type of the vinyl cyan compound included in the (A) graft copolymer of the present disclosure.
[79]
[80]
The copolymer (B) may be prepared by, for example, solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization, preferably bulk polymerization.
[81]
The solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization are not particularly limited in the case of emulsion polymerization and suspension polymerization methods commonly performed in the art to which the present invention belongs, respectively.
[82]
[83]
(C) Aromatic vinyl compound-vinyl cyan compound copolymer
[84]
(C) aromatic vinyl compound-vinyl cyan compound copolymer of the present disclosure may be included in an example of 13 to 55 wt%, preferably 15 to 50 wt%, more preferably 20 to 45 wt% in the base resin, Within this range, there is an excellent effect of mechanical strength, fluidity and physical property balance.
[85]
The (C) aromatic vinyl compound-vinyl cyan compound copolymer may preferably include 75 to 90 wt % of an aromatic vinyl compound and 10 to 25 wt % of a vinyl cyan compound, in this case, to improve the flowability of the thermoplastic resin composition. It has the advantage of excellent processability and productivity.
[86]
The (C) aromatic vinyl compound-vinyl cyan compound copolymer may more preferably include 75 to 85 wt % of an aromatic vinyl compound and 15 to 25 wt % of a vinyl cyan compound, and in this case, the processability of the thermoplastic resin composition and While excellent in productivity, there are advantages in mechanical properties such as impact strength, heat resistance and colorability.
[87]
The (C) aromatic vinyl compound-vinyl cyan compound copolymer may more preferably contain 75 to 80 wt % of an aromatic vinyl compound and 20 to 25 wt % of a vinyl cyan compound, and in this case, the processability of the thermoplastic resin composition and It has excellent effects such as mechanical properties such as impact strength, heat resistance and colorability while being excellent in productivity.
[88]
[89]
The (C) 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 120,000 to 150,000 g/mol, and obtains the desired fluidity within this range, so that processability, productivity, etc. are excellent, and there are advantages of excellent colorability.
[90]
[91]
The (C) aromatic vinyl compound-vinyl cyan compound copolymer may be prepared by, for example, bulk polymerization or emulsion polymerization, but may be preferably prepared by bulk polymerization in terms of manufacturing cost.
[92]
The method for preparing the (C) aromatic vinyl compound-vinyl cyan compound copolymer is not particularly limited if conditions, methods, and apparatuses commonly used in the art to which the present invention pertains are used as long as the definition of the present invention is followed.
[93]
[94]
(D) polyether ester elastomer resin
[95]
(D) polyether ester elastomer resin of the present base may be included in an amount of, for example, 7 to 17 parts by weight, preferably 7 to 15 parts by weight, more preferably 9 to 15 parts by weight, based on 100 parts by weight of the base resin, Within the range, there are excellent effects in mechanical properties, heat resistance, fluidity and chemical resistance.
[96]
The (D) polyether ester elastomer resin has, for example, a melt index of 0.1 to 10 g/10min, preferably 1 to 10 g/10min, more preferably 3, measured at 230°C under 2.16 kg according to ASTM D1238. to 7 g/10min, and within this range, the moldability and processability of the thermoplastic resin composition are excellent, and chemical resistance is improved.
[97]
The (D) polyether ester elastomer resin is, for example, an aromatic dicarboxylic acid or an ester-forming derivative thereof; aliphatic diols; and polyalkylene oxide; after melt polymerization, it may be obtained by solid-state polymerization of the product. Preferably, the resin is a random copolymer of a hard fraction formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol, and a soft fraction mainly composed of polyalkylene oxide.
[98]
[99]
The aromatic dicarboxylic acid is for example terephthalic acid (TPA), isophthalic acid (IPA), 2,6-naphthalene dicarboxylic acid (2,6-naphthalene dicarboxylic acid, 2,6-NDCA), 1,5 -Naphthalene dicarboxylic acid (1,5-naphthalene dicarboxylic acid, 1,5-NDCA), 1,4-cyclohexane dicarboxylic acid (4-cyclohexane dicarboxylic acid, 1,4-CHDA) and diacid are substituted aromatic with a dimethyl group dimethyl terephthalate (DMT), dimethyl isophthalate (DMI), 2,6-dimethyl naphthalene dicarboxylate (2,6-dimethyl naphthalene dicarboxylate, 2,6- NDC) and dimethyl 1,4-cyclohexane dicarboxylate (dimethyl 1,4-cyclohexanedicarboxylate, DMCD) may be at least one selected from the group consisting of, preferably dimethyl terephthalate.
[100]
The aromatic dicarboxylic acid or its ester-forming derivative may be, for example, 25 to 60% by weight, preferably 29 to 55% by weight, more preferably 34 to 45% by weight based on 100% by weight of the total polyether ester elastomer resin, and , there is an effect excellent in the reaction balance within this range.
[101]
[102]
In addition, the aliphatic diol may preferably be a diol having a number average molecular weight (Mn) of 300 g/mol or less, more preferably ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol (1,4-butane diol, 1,4-BG), 1,5-pentanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol (1,4-cycloheanedimethanol; 1,4-CHDM) may be at least one selected from the group consisting of, and more preferably 1,4-butanediol.
[103]
The aliphatic diol may be, for example, 10 to 40% by weight, preferably 15 to 40% by weight, more preferably 20 to 30% by weight, based on 100% by weight of the total polyetherester elastomer resin, and the reaction within this range There is an excellent effect of balance.
[104]
[105]
The polyalkylene oxide is a unit constituting the soft fraction, and may include an aliphatic polyether as a component. The polyalkylene oxide is, for example, polyoxyethylene glycol, polypropylene glycol, poly (tetramethylene ether) glycol (poly (tetramethylene) glycol, PTMEG), polyoxyhexamethylene glycol (polyoxyhexamethylene glycol) ), at least one selected from the group consisting of a copolymer of ethylene oxide and propylene oxide, an ethylene oxide addition polymer of polypropylene oxide glycol, and a copolymer of ethylene oxide and tetrahydrofuran may be a unit derived from, preferably a unit derived from an ethylene oxide addition polymer of polytetramethylene glycol or polypropylene glycol.
[106]
The polytetramethylene glycol-derived unit may have a number average molecular weight of, for example, 600 to 3,000 g/mol, preferably 1,000 to 2,500 g/mol, and more preferably 1,800 to 2,200 g/mol.
[107]
The unit derived from the ethylene oxide addition polymer of the polypropylene glycol may be, for example, a unit derived from polypropylene glycol capped with ethylene oxide, and preferably has a weight average molecular weight of 2,000 to 3,000 g/mol.
[108]
The polyalkylene oxide may be, for example, 10 to 60% by weight, preferably 15 to 55% by weight, more preferably 25 to 45% by weight, based on 100% by weight of the total polyetherester elastomer resin, and within this range There is an excellent effect of the reaction balance.
[109]
The (D) polyether ester elastomer resin may preferably include a branching agent, and in this case, the melt viscosity and melt strength of the elastomer resin may be increased.
[110]
The branching agent is, for example, glycerol, pentaerythritol, trimellitic anhydride, trimellitic acid, trimethylol propane, and neopentyl glycol. ) may be at least one selected from the group consisting of, preferably trimellitic acid anhydride.
[111]
The branching agent may be, for example, 0.05 to 0.1% by weight, preferably 0.05 to 0.09% by weight, more preferably 0.06 to 0.09% by weight, based on 100% by weight of (D) polyetherester elastomer resin in total. There is an advantage in that it is easy to control the intrinsic viscosity during melt polymerization as a result by controlling the melt viscosity of the elastomer resin by increasing the melt viscosity within the elastomeric resin.
[112]
[113]
The (D) polyether ester elastomer resin of the present invention may be obtained by, for example, melt-condensation polymerization and then solid-state polymerization.
[114]
Preferably, BHBT (bis ( 4-hydroxy) butyl terephthalate) oligomer is produced, and then the TBT catalyst is re-injected, and the melt polycondensation reaction is performed at 215 to 245° C. for 100 to 150 minutes, specifically at 700 to 800 torr for 120 minutes, specifically at 760 torr. 0.1 to 1 torr, for example, may be carried out while stepwise pressure reduction to 0.3 torr. The melt polycondensation reaction may be performed until the flow flow index (MFI) measured at 230° C. under a load of 2.16 kg according to ASTM D1238 becomes 20 g/10 min or less. After completion of the reaction, it can be discharged into the reactor under nitrogen pressure to pelletize the strand through pelletizing.
[115]
Then, the pellet may be subjected to solid-state polymerization in a solid-state polymerization reactor or a rotatable vacuum dryer at a temperature of 140 to 200° C. for about 10 to 24 hours under an inert air stream such as nitrogen under vacuum. The solid-state polymerization has a flow rate index (MFI) of 10 g/10 min or less, preferably 1 to 10 g/10 min (230° C., 2.16 kg), more preferably 1 to 10 g/10 min (230° C., 2.16 kg), measured at 230° C. and a load of 2.16 kg according to ASTM D1238. High viscosity can be achieved until 3 to 8 g/10 min (230° C., 2.16 kg).
[116]
The vacuum applied during the solid-state polymerization is not particularly limited as long as it is a degree of vacuum generally applied in the technical field to which the present invention pertains.
[117]
[118]
The hardness of the (D) polyether ester elastomer resin is expressed as shore hardness-D (shore D) measured according to ISO 868, and the hardness may be determined by the content of polyalkylene oxide. (D) 10 to 60% by weight of the polyalkylene oxide based on 100% by weight of the total polyetherester elastomer resin so that the shore hardness of the polyetherester elastomer resin is 35 to 50D, preferably 40 to 50D, preferably 15 to 55% by weight, more preferably 25 to 45% by weight may be used. Within the above range, the hardness of the polyether ester elastomer resin is low, so the flexibility is good, and the heat resistance and compatibility of the resin itself are also excellent.
[119]
[120]
(E) modified polyester resin
[121]
The (E) modified polyester resin of the present base may be, for example, 1.1 to 10 parts by weight, preferably 1.5 to 8 parts by weight, more preferably 2 to 7 parts by weight, within this range, based on 100 parts by weight of the base resin. Mechanical properties such as impact strength and tensile strength, chemical resistance, and fluidity all have excellent effects.
[122]
[123]
The (E) modified polyester resin is, for example, an amorphous resin copolymerized by adding 1,4-cyclohexanedimethanol (CHMD) to 50% or more during polymerization of polyethylene terephthalate, a type of polyester resin, and has a transparent characteristic, preferably Preferably, the 1,4-cyclohexanedimethanol-derived unit may be 50% by weight or more, and in this case, it has excellent impact resistance and chemical resistance, can be molded under a wide range of conditions, and has easy secondary processability as well as environmental hormone substances. It has the advantage of not containing
[124]
In the present description, the unit weight % derived from compound A is not particularly limited in the case of unit weight % derived from compound A as commonly defined in the art to which the present invention belongs, for example, the total weight % of the units derived from compound A in the polymer or It may mean the total weight % of the compound A participating in polymerization.
[125]
[126]
The (E) modified polyester resin may be specifically glycol modified polyethylene terephthalate (PETG), and in this case, transparency, fluidity, chemical resistance and mechanical properties are excellent.
[127]
[128]
(F) alkylene oxide copolymer
[129]
The (F) alkylene oxide copolymer may be included, for example, in an amount of 0.3 to 5 parts by weight, preferably 0.5 to 4 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the base resin, in this range There is an effect that the mechanical properties, impact resistance and fluidity are further improved within. If it is less than the above range, tensile strength and chemical resistance are lowered.
[130]
[131]
The (F) alkylene oxide copolymer may be, for example, a block copolymer including a first block including an ethylene oxide-derived unit and a second block including a propylene oxide-derived unit.
[132]
The (F) alkylene oxide copolymer is, for example, the ethylene oxide-derived unit and the propylene oxide-derived unit from 50:50 to 3:97, preferably from 40:60 to 5:95, more preferably from 30:70 to It may be included in a weight ratio of 10:90, and there is an advantage of excellent mechanical properties within this range.
[133]
[134]
The (F) alkylene oxide copolymer may preferably be a triblock copolymer represented by the following formula (1).
[135]
[Formula 1]
[136]

[137]
In Formula 1,
[138]
x, y or z is x + y + z = 100 in mole %, respectively, to a total of 100 mole % of x, y and z, 10 ≤ x ≤ 80, 10 ≤ y ≤ 50 and 10 ≤ z ≤ 80 .
[139]
[140]
The (F) alkylene oxide copolymer may have a weight average molecular weight of, for example, 7,000 to 100,000 g/mol, preferably 7,500 to 9,500 g/mol, more preferably 80,000 to 90,000 g/mol, and within this range There is an effect that the chemical resistance is further improved.
[141]
The (F) alkylene oxide copolymer may have a flow index of 10 to 15 g/10min, preferably 12 to 14 g/10min, measured under conditions of 190°C and 2.16 kg according to ASTM D1238, for example, There is an effect of excellent workability within the range.
[142]
[143]
(G) bulk polymerization vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer
[144]
The base resin is an example of (A) graft copolymer, (B) copolymer, (C) copolymer, (D) resin, and (G) bulk polymerization vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound copolymer. The copolymer (G) may be included in an amount of 1 to 20% by weight, preferably 3 to 15% by weight, more preferably 5 to 10% by weight, based on the total weight, and flowability and tensile strength within this range There is an effect of further improving mechanical properties such as.
[145]
[146]
The (G) block polymerization vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer is, for example, 5 to 20% by weight of a conjugated diene rubber including a conjugated diene compound, 55 to 85% by weight of an aromatic vinyl compound, and a vinyl cyan compound 5 to 25% by weight of the bulk-polymerized bulk copolymer, preferably 8 to 15% by weight of a conjugated diene rubber comprising a conjugated diene compound, 65 to 78% by weight of an aromatic vinyl compound, and 13 to 22% by weight of a vinyl cyanide compound % may be a bulk-polymerized bulk copolymer, and fluidity and tensile strength are more improved within this range.
[147]
The (G) bulk polymerization vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer may have an average particle diameter of, for example, 1,000 to 2,000 nm, preferably 1,000 to 1,500 nm, within this range. has excellent mechanical properties.
[148]
[149]
The thermoplastic resin composition optionally includes at least one selected from the group consisting of a flame retardant, a hydrolysis stabilizer, a dye, a pigment, a colorant, an antistatic agent, a crosslinking agent, an antibacterial agent, a processing aid, and a black masterbatch in 100 parts by weight of the base resin. Each of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, even more preferably 0.5 to 1 parts by weight may further include, within this range, There is an effect that necessary physical properties are well realized without reducing the original physical properties of the thermoplastic resin composition.
[150]
[151]
Thermoplastic resin composition
[152]
For the thermoplastic resin composition, for example, a 160 * 10 * 4 mm specimen is fixed to a curvature jig having 2.0% strain, and 0.1 cc of Aroma Natural (product name), which is Amway's fragrance, is applied and cracked on the specimen. No cracks occur after 24 hours in the chemical resistance evaluation for measuring the time that this occurs, and in this case, the physical property balance is excellent and the chemical resistance is excellent, so that it can be applied as an automobile interior material.
[153]
In the present description, "cracks do not occur after 24 hours" means that no cracks are generated until the time point after 24 hours has elapsed.
[154]
[155]
The thermoplastic resin composition has, for example, a Charpy impact strength of 26 kJ/m 2 or more, preferably 28 kJ/m 2 or more, measured by cutting a notch in a specimen having a thickness of 4 mm according to ISO 179/1eA , more preferably Preferably 30 kJ/m 2 or more, more preferably 30 to 35 kJ/m 2 , and within this range, the physical property balance is excellent and there is an effect applicable for automobile interiors.
[156]
[157]
The thermoplastic resin composition has, for example, a melt flow index (MFR) of 15 g/10 min or more, preferably 20 g/10 min or more, more preferably 20 to 25 g, measured at 220°C under 10 kg according to ISO 1133. It may be /10 min, and it has excellent fluidity within this range and has the advantage of easy molding into various shapes.
[158]
[159]
The thermoplastic resin composition may have, for example, a tensile strength of 38 MPa or more, preferably 40 MPa or more, more preferably 40 to 45 MPa, measured with a specimen thickness of 4 mm under a condition of 500 mm/min according to ISO 527, There is an effect excellent in the physical property balance within this range.
[160]
[161]
Method for producing a thermoplastic resin composition
[162]
The method for preparing the thermoplastic resin composition of the present disclosure includes (A) 10 to 40 wt% of a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, (B) (meth)acrylic acid alkyl ester compound-α-methyl styrene-based (D) Polyether ester elastomer resin 7 in 100 parts by weight of a base resin comprising 18 to 52 wt% of the compound-vinyl cyan compound copolymer, and (C) 13 to 55 wt% of the aromatic vinyl compound-vinyl cyan compound copolymer to 17 parts by weight and (E) including 1.1 to 10 parts by weight of the modified polyester resin, and kneading and extruding under the conditions of 200 to 300° C. and 200 to 700 rpm to prepare pellets, the (C) aromatic vinyl compound - The vinyl cyan compound copolymer is characterized in that it comprises 10 to 25 wt % of the vinyl cyan compound. In this case, there is an advantage of excellent chemical resistance while having excellent mechanical properties such as fluidity, impact resistance, and tensile strength.
[163]
The kneading and extrusion may be performed by, for example, a single-screw extruder, a twin-screw extruder, or a Banbury mixer, in which case the composition is uniformly dispersed to have excellent compatibility.
[164]
[165]
The kneading and extrusion is, for example, a barrel temperature of, for example, 200 to 300 ℃, preferably 210 to 290 ℃, more preferably 220 to 280 ℃, even more preferably 230 to 260 ℃ It can be carried out within the range In this case, the amount of processing per unit time may be adequate and sufficient melt-kneading may be possible, and there is an effect that does not cause problems such as thermal decomposition of the resin component.
[166]
[167]
The kneading and extrusion, for example, may be performed under the condition that the screw rotation speed is 200 to 700 rpm, preferably 220 to 650 rpm, more preferably 300 to 600 rpm. While excellent, it has an effect of suppressing excessive cutting.
[168]
[169]
The method for producing the thermoplastic resin composition shares all the technical characteristics of the aforementioned thermoplastic resin composition. Therefore, a description of the overlapping portion will be omitted.
[170]
[171]
molded product
[172]
The molded article of the present substrate may include the thermoplastic resin composition of the present substrate, and in this case, there is an advantage in that it has excellent mechanical properties such as fluidity, impact resistance, and tensile strength and excellent chemical resistance.
[173]
The molded article may be preferably an injection molded article, and more preferably an automobile interior or exterior material or a home appliance exterior material.
[174]
[175]
The manufacturing method of the molded article of the present invention is not particularly limited if the conditions, methods and apparatuses commonly used in the technical field to which the present invention pertains are used as long as the definition of the present invention is followed.
[176]
[177]
In describing the thermoplastic resin composition of the present invention, its manufacturing method and molded article, other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art, and it is specified that there is no particular limitation. do.
[178]
[179]
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 variations and modifications fall within the scope of the appended claims.
[180]
[181]
[Example]
[182]
* (A-1) ABS graft copolymer: DP270 from LG Chem
[183]
* (A-2) ASA graft copolymer: SA927 from LG Chem
[184]
* (B-1) MMA-α-methyl styrene-acrylonitrile copolymer: 290UH from LG Chem
[185]
* (B-2) α-methyl styrene-acrylonitrile copolymer: 200UH from LG Chem
[186]
* (B-3) PMI heat-resistant resin: MSNI of DENKA
[187]
* (C-1) SAN copolymer: 81HF of LG Chem (acrylonitrile content 24 wt%)
[188]
* (C-2) SAN copolymer: 97HC of LG Chem (acrylonitrile content 30.5 wt%)
[189]
* (C-3) SAN copolymer: 92RF of LG Chem (acrylonitrile content 28% by weight)
[190]
* (D) Polyether ester elastomer (TPEE): LG Chem’s KEYFLEX BT2140D (melting index (230℃, 2.16kg): 5 g/10min, Shore D hardness: 40D)
[191]
* (E) Modified polyester resin (PETG): SK Chemical's JIN100
[192]
* (F) PEO/PPO/PEO copolymer: Pluronic F68 from BASF
[193]
* (G) Block-polymerized ABS copolymer: ER400 from LG Chem
[194]
[195]
Examples 1 to 7 and Comparative Examples 1 to 14
[196]
Pellets were prepared by kneading and extruding the components and contents shown in Tables 1 to 3, respectively, in an extruder (SM Twin screw extruder, 25Φ) at an extrusion temperature of 250° C., a feed rate of 25 kg/hr, and a screw speed of 600 rpm. The flow index was measured with the prepared pellets. In addition, injection specimens were prepared using the pellets produced under the conditions of an injection temperature of 240°C, a mold temperature of 60°C, and an injection speed of 30 mm/min using an injection machine (ENGEL, 120MT).
[197]
[198]
[Test Example]
[199]
The properties of the pellets and injection specimens prepared in Examples 1 to 7 and Comparative Examples 1 to 14 were measured by the following method, and the results are shown in Tables 1 to 3 below.
[200]
* Charpy impact strength (kJ/m 2 ): In accordance with ISO 179/1eA, a notch was cut in a specimen having a thickness of 4 mm to measure the Charpy impact strength.
[201]
* Melt flow rate (MFR, g/10min): measured under 10 kg at 220 °C in accordance with ISO 1133.
[202]
* Tensile strength (MPa): It was measured with a specimen thickness of 4 mm under a condition of 50 mm/min according to ISO 527.
[203]
* Chemical resistance: The time for cracking the specimen after fixing a 160*10*4mm specimen on a curvature jig with 2.0% strain and applying 0.1cc of Aroma Natural (product name), Amway's fragrance was measured. If cracks did not occur after 24 hours, it was recorded as 1 day.
[204]
[205]
[Table 1]
division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
(A-1) DP270 25 25 20 25 30 20 30
(A-2) SA927
(B-1) 290UH 25 40 25 25 25 35 50
(B-2) 200UH
(B-3) MSNI
(C-1) 81HF 40 25 45 40 45 35 20
(C-2) 97HC
(C-3) 92RF
(G) ER400 10 10 10 10 10
(D) KEYFLEX BT2140D 13 13 10 13 13 10 13
(E) PETG 5 5 5 2 5 5 5
(F) Pluronic F68 One One One One One One One
Properties
Charpy impact strength 32 30 28 28 34 26 32
MFR 23 16 24 24 20 22 15
The tensile strength 41 40 41 41 39 40 38
chemical resistance 1 day 1 day 1 day 1 day 1 day 1 day 1 day
[206]
[Table 2]
division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6
(A-1) DP270 25 25 25 25
(A-2) SA927 25 30
(B-1) 290UH 25 25
(B-2) 200UH 25 25 40
(B-3) MSNI 10
(C-1) 81HF 40 35 25 55
(C-2) 97HC 40
(C-3) 92RF 40
(G) ER400 10 10 10 10 10 10
(D) KEYFLEX BT2140D 13 13 13 13 13 13
(E) PETG 5 5 5 5 5 5
(F) Pluronic F68 One One One One One One
Properties
Charpy impact strength 25 24 16 19 33 27
MFR 11 17 15 13 21 23
The tensile strength 43 41 43 41 42 41
chemical resistance 1 min 1 min 1 min 15 min 1 min 1 min
[207]
[Table 3]
division Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14
(A-1) DP270 25 30 20 35 25 25 25 25
(A-2) SA927
(B-1) 290UH 25 10 55 45 25 25 25 25
(B-2) 200UH
(B-3) MSNI
(C-1) 81HF 40 45 15 5 40 40 40 40
(C-2) 97HC
(C-3) 92RF
(G) ER400 10 15 10 15 10 10 10 10
(D) KEYFLEX BT2140D 4 13 13 13 22 13 0 13
(E) PETG 5 5 5 5 5 0.1 5 0
(F) Pluronic F68 One One One One One One One One
Properties
Charpy impact strength 28 36 30 40 40 27 26 28
MFR 20 25 12 17 13 23 24 22
The tensile strength 40 41 40 37 35 40 41 40
chemical resistance 1 min 10 min 1 day 15 min 1 day 10 min 1 min 10 min
[208]
(In Tables 1 to 3, (A-1), (A-2), (B-1), (B-2), (B-3), (C-1), (C-2), ( Each content of C-3) and (G) is a weight % based on their total weight, and each content of (D), (E) and (F) is the above (A-1), (A-2) , (B-1), (B-2), (B-3), (C-1), (C-2), (C-3) and (G) total weight based on 100 parts by weight As shown in Tables 1 to 3, the thermoplastic resin compositions (Examples 1 to 7) according to the present invention have excellent chemical resistance and excellent Charpy impact strength, flow index, and tensile strength compared to Comparative Examples 1 to 14. This excellent effect was confirmed.
[209]
Specifically, (C) Comparative Examples 1 and 2 in which the acrylonitrile content of the SAN copolymer was 30.5 wt% and 28 wt%, respectively, deteriorated in chemical resistance.
[210]
In addition, Comparative Examples 3 and 4 including (A-2) ASA graft copolymer and (B-2) α-methyl styrene-acrylonitrile copolymer had poor Charpy impact strength, melt flow index and chemical resistance.
[211]
In addition, (B-2) α-methyl styrene-acrylonitrile copolymer or (B-3) Comparative Examples 5 and 6 containing the PMI-based heat-resistant resin had lowered chemical resistance.
[212]
In addition, (D) polyether ester elastomer resin, (B-1) MMA-α-methyl styrene-acrylonitrile copolymer, (C-1) SAN copolymer, and (E) modified polyester resin each of the present invention Comparative Examples 7, 8, 10 and 12 including less than the range of the chemical resistance became poor.
[213]
In addition, (D) Comparative Example 11 including the polyether ester elastomer resin exceeding the scope of the present invention had lowered melt flow index and tensile strength.
[214]
In addition, (D) Comparative Example 13 not including the polyether ester elastomer resin and Comparative Example 14 not including (E) the modified polyester resin had poor chemical resistance.
[215]
[216]
In conclusion, the vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, (meth)acrylic acid alkyl ester compound-α-methyl styrene-based compound-vinyl cyan compound copolymer, and vinyl cyan compound according to the present invention are predetermined. When the polyether ester elastomer resin and the modified polyester resin are adjusted in a predetermined content ratio to the base resin containing the aromatic vinyl compound-vinyl cyan compound copolymer included as a predetermined content, it is confirmed that the mechanical properties, fluidity and chemical resistance are excellent. could
Claims
[Claim 1]
(A) 10 to 40 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; (B) (meth)acrylic acid alkyl ester compound-α-methyl styrenic compound-vinyl cyan compound copolymer 18 to 52% by weight; and (C) 13 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; (D) 7 to 17 parts by weight of a polyether ester elastomer resin and (E) a modified polyester resin in 100 parts by weight of a base resin containing The thermoplastic resin composition comprising 1.1 to 10 parts by weight, wherein the (C) aromatic vinyl compound-vinyl cyan compound copolymer comprises 10 to 25 weight % of the vinyl cyan compound.
[Claim 2]
The method according to claim 1, wherein the (A) graft copolymer comprises 45 to 75 wt% of a conjugated diene rubber having an average particle diameter of 0.2 to 0.5 μm including a conjugated diene compound, 15 to 45 wt% of an aromatic vinyl compound, and a vinyl cyan compound Thermoplastic resin composition, characterized in that it comprises 1 to 25% by weight.
[Claim 3]
According to claim 1, wherein the (B) (meth) acrylic acid alkyl ester compound-α-methyl styrenic compound-vinyl cyan compound copolymer comprises 35 to 60 wt % of the (meth) acrylic acid alkyl ester compound, α-methyl styrenic compound A thermoplastic resin composition comprising 30 to 50 wt% and 10 to 20 wt% of a vinyl cyanide compound.
[Claim 4]
The thermoplastic resin composition according to claim 1, wherein the (D) polyether ester elastomer resin has a melt index of 0.1 to 10 g/10min, measured at 230°C under 2.16 kg in accordance with ASTM D1238.
[Claim 5]
According to claim 1, wherein the (D) polyether ester elastomer resin is aromatic dicarboxylic acid or an ester-forming derivative thereof; aliphatic diols; and polyalkylene oxide; after melt polymerization, the thermoplastic resin composition is a resin obtained by solid-state polymerization of the product.
[Claim 6]
The thermoplastic resin composition according to claim 1, wherein the (E) modified polyester resin contains 50 wt% or more of 1,4-cyclohexanedimethanol-derived units.
[Claim 7]
According to claim 1, wherein the base resin is (A) graft copolymer, (B) copolymer, (C) copolymer, and (G) block polymerization vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound copolymer A thermoplastic resin composition comprising 1 to 20% by weight of the (G) copolymer based on the total weight.
[Claim 8]
The method according to claim 7, wherein the (G) block-polymerized vinyl cyan compound-conjugated diene compound-aromatic vinyl compound copolymer comprises 5 to 20 wt% of a conjugated diene rubber including a conjugated diene compound, 55 to 85 wt% of an aromatic vinyl compound and 5 to 25 wt% of a vinyl cyanide compound, and a thermoplastic resin composition characterized in that it is a bulk-polymerized bulk copolymer.
[Claim 9]
The thermoplastic resin composition according to claim 1, wherein 0.3 to 5 parts by weight of the (F) alkylene oxide copolymer is included with respect to 100 parts by weight of the base resin.
[Claim 10]
According to claim 1, wherein the thermoplastic resin composition is a 160 * 10 * 4 mm specimen fixed to a curvature jig having a 2.0% strain, and 0.1cc of Aroma Natural (product name), an Amway fragrance, is applied. Thermoplastic resin composition, characterized in that cracks do not occur after 24 hours in the chemical resistance evaluation for measuring the time at which cracks occur in the specimen.
[Claim 11]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a Charpy impact strength of 26 kJ/m 2 or more , measured by cutting a notch in a specimen having a thickness of 4 mm according to ISO 179/1eA .
[Claim 12]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a melt flow rate (MFR) of 15 g/10min or more, measured at 220°C under 10 kg in accordance with ISO 1133.
[Claim 13]
(A) 10 to 40 wt% of a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer; (B) (meth)acrylic acid alkyl ester compound-α-methyl styrenic compound-vinyl cyan compound copolymer 18 to 52% by weight; and (C) 13 to 55 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer; (D) 7 to 17 parts by weight of a polyether ester elastomer resin and (E) a modified polyester resin in 100 parts by weight of a base resin containing Including 1.1 to 10 parts by weight, comprising the steps of kneading and extruding under 200 to 300 ℃ and 200 to 700 rpm conditions to prepare pellets, wherein the (C) aromatic vinyl compound-vinyl cyan compound copolymer is a vinyl cyan compound 10 to Method for producing a thermoplastic resin composition, characterized in that it comprises 25% by weight.
[Claim 14]
A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 12.