Title of Invention: Thermoplastic resin composition, manufacturing method thereof, and molded article comprising same
technical field
[One]
[Cross Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0132479 dated October 14, 2020, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
The present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article including the same, and more particularly, has no toxicity to the human body, excellent thermal stability, and excellent initial antibacterial as well as antibacterial persistence, and there is no gas defect or peeling phenomenon during injection It relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article comprising the same.
background
[4]
Recently, with the increase of interest in personal health and hygiene and the improvement of income level, the demand for thermoplastic resin products with antibacterial and sanitary functions, although somewhat expensive, is increasing. Accordingly, antibacterial thermoplastic resin products capable of removing or inhibiting bacteria from the surface of household goods and home appliances are increasing, and the development of more stable and reliable functional antibacterial materials is becoming very important.
[5]
In order to prepare an antimicrobial ABS resin, the addition of an antimicrobial agent is absolutely necessary. The antibacterial agent may be divided into an organic antibacterial agent and an inorganic antibacterial agent.
[6]
The organic antibacterial agent has excellent initial antibacterial properties, but there is a risk of toxicity to the human body, and there is a fear that the antibacterial effect may be lost due to decomposition during processing at a high temperature. In addition, the antibacterial durability is short, so the scope of use is extremely limited.
[7]
The inorganic antibacterial agent has excellent thermal stability, but has disadvantages such as dispersion problems and discoloration during processing. In addition, due to the rapid dissolution of antibacterial metal ions, the antibacterial durability is low, and there are many restrictions on its use.
[8]
Therefore, there is an urgent need to develop a thermoplastic resin that is excellent in both initial antibacterial properties and antibacterial durability while well expressing the original function of the thermoplastic resin.
[9]
[10]
[Prior art literature]
[11]
[Patent Literature]
[12]
KR 10-2004-0054985 A
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[13]
In order to solve the problems of the prior art as described above, the present invention is a thermoplastic resin composition having no toxicity to the human body and excellent thermal stability, excellent initial antibacterial property as well as antibacterial persistence, and no gas defect or peeling phenomenon during injection, a manufacturing method thereof, and the same An object of the present invention is to provide a molded article comprising
[14]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[15]
In order to achieve the above object, the present invention includes A) a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer (A-1) and an aromatic vinyl compound-vinyl cyan compound copolymer (A-2) 100 parts by weight of the base resin; B) 0.1 to 32 parts by weight of a polymer comprising a lone pair of electrons with a weight average molecular weight of greater than 500,000 g/mol; C) 0.1 to 5 parts by weight of an inorganic antibacterial agent comprising at least one carrier selected from the group consisting of phosphate glass, silica gel, calcium phosphate, and sodium zirconium phosphate; and D) 0.2 to 10 parts by weight of zinc oxide having a BET surface area of ​​28 m 2 /g or more.
[16]
In addition, the present invention provides 100 parts by weight of a base resin comprising A) a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer (A-1) and an aromatic vinyl compound-vinyl cyan compound copolymer (A-2) ; B) 0.1 to 32 parts by weight of a polymer comprising a lone pair of electrons with a weight average molecular weight of greater than 500,000 g/mol; C) 0.1 to 5 parts by weight of an inorganic antibacterial agent comprising at least one carrier selected from the group consisting of phosphate glass, silica gel, calcium phosphate, and sodium zirconium phosphate; and D) kneading and extruding 0.2 to 10 parts by weight of zinc oxide having a BET surface area of ​​28 m 2 /g or more.
[17]
In addition, the present invention provides a molded article comprising the thermoplastic resin composition of the present invention.
Effects of the Invention
[18]
According to the present invention, there is an effect of providing a thermoplastic resin composition having no human toxicity and excellent thermal stability, excellent initial antibacterial property as well as antibacterial durability, and no gas defect or peeling phenomenon during injection, a manufacturing method thereof, and a molded article including the same.
Modes for carrying out the invention
[19]
Hereinafter, the thermoplastic resin composition of the present disclosure, a manufacturing method thereof, and a molded article including the same will be described in detail.
[20]
The present inventors have found that the base resin comprising a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer and an aromatic vinyl compound-vinyl cyan compound copolymer, individually, has poor antibacterial persistence and has poor weight average molecular weight exceeding 500,000 g/mol a polymer containing a lone pair of electrons; an inorganic antibacterial agent comprising at least one carrier selected from the group consisting of phosphate glass, silica gel, calcium phosphate, and sodium zirconium phosphate; And when all zinc oxide having a predetermined BET surface area is included in a predetermined amount, in addition to the synergistic effect due to the organic combination of water-soluble inorganic antibacterial agent and water-insoluble zinc oxide, unshared electron pair of poly(ether ester amide) resin Due to the effect of lowering the elution rate of metal ions according to coordination with metal ions by
[21]
[22]
The thermoplastic resin composition of the present invention is a base resin 100 comprising A) a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer (A-1) and an aromatic vinyl compound-vinyl cyan compound copolymer (A-2) parts by weight; B) 0.1 to 32 parts by weight of a polymer comprising a lone pair of electrons with a weight average molecular weight of greater than 500,000 g/mol; C) 0.1 to 5 parts by weight of an inorganic antibacterial agent comprising at least one carrier selected from the group consisting of phosphate glass, silica gel, calcium phosphate, and sodium zirconium phosphate; and D) BET surface area of ​​28 m 2 /g or more, comprising 0.2 to 10 parts by weight of zinc oxide. There is an effect that there is no peeling phenomenon.
[23]
[24]
Hereinafter, each component constituting the thermoplastic resin composition of the present disclosure will be described in detail as follows.
[25]
[26]
(A-1) Vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer
[27]
(A-1) Vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure may be preferably 20 to 40 wt%, more preferably 20 to 35 wt%, based on the total weight of the base resin. %, more preferably 25 to 35% by weight, even more preferably 25 to 30% by weight.
[28]
The (A-1) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer is preferably graft-polymerized with a vinyl cyan compound and an aromatic vinyl compound to a conjugated diene rubber comprising a conjugated diene compound. It is a copolymer.
[29]
The conjugated diene rubber may preferably have an average particle diameter of 0.05 to 0.5 μm, more preferably 0.2 to 0.5 μm, still more preferably 0.25 to 0.45 μm, and still more preferably 0.3 μm to 0.4 μm.
[30]
In this description, the average particle diameter can be measured using Dynamic Light Scattering, and in detail, it can be measured with Intensity Gaussian Distribution using Nicomp 380 equipment (product name, manufacturer: PSS). have.
[31]
In addition, in the present description, the average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, specifically, an average particle diameter of scattering intensity.
[32]
[33]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof, preferably acrylonitrile.
[34]
In the present description, a derivative of a certain compound may mean a compound in which one or more hydrogens in the compound are substituted with other substituents such as an alkyl group or a halogen group.
[35]
Preferably, the vinyl cyanide compound may be included in an amount of 3 to 25 wt%, more preferably 5 to 20 wt%, based on the total weight of the (A-1) graft copolymer.
[36]
[37]
The conjugated diene compound may be, for example, at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene, preferably 1,3-butadiene.
[38]
[39]
The conjugated diene compound may preferably be included in an amount of 50 to 80% by weight, more preferably 55 to 70% by weight, based on the total weight of the (A-1) graft copolymer.
[40]
The conjugated diene rubber refers to a polymer or copolymer polymerized including a conjugated diene compound having a structure in which a double bond and a single bond are arranged across one, preferably a butadiene polymer, a butadiene-styrene copolymer and It may be at least one selected from the group consisting of butadiene-acrylonitrile copolymers.
[41]
[42]
The aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methylstyrene, ρ-methylstyrene, ο-ethylstyrene, ρ-ethylstyrene, vinyltoluene, and derivatives thereof.
[43]
The aromatic vinyl compound may preferably be included in an amount of 25 to 50 wt%, more preferably 25 to 40 wt%, based on the total weight of the (A-1) graft copolymer.
[44]
[45]
The method for preparing the (A-1) graft copolymer is not limited if it is a manufacturing method commonly used in the art, and may preferably be prepared by emulsion polymerization, and in this case, the grafting efficiency is excellent and the mechanical It has excellent effects such as physical properties and processability.
[46]
[47]
(A-2) Aromatic vinyl compound-vinyl cyan compound copolymer
[48]
(A-2) Aromatic vinyl compound-vinyl cyan compound copolymer of the present description may preferably contain 60 to 80% by weight, more preferably 65 to 80% by weight, still more preferably 65 to 75% by weight , even more preferably from 70 to 75% by weight.
[49]
[50]
The (A-2) aromatic vinyl compound-vinyl cyan compound copolymer may preferably be a copolymer comprising 55 to 85 wt % of an aromatic vinyl compound and 15 to 45 wt % of the vinyl cyan compound, more preferably is a copolymer comprising 55 to 75 wt% of an aromatic vinyl compound and 25 to 45 wt% of a vinyl cyan compound, and more preferably 60 to 70 wt% of an aromatic vinyl compound and 30 to 40 wt% of a vinyl cyanide compound. It is a copolymer made up of
[51]
[52]
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, vinyltoluene, and derivatives thereof, preferably styrene to be.
[53]
The vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof, preferably acrylonitrile.
[54]
[55]
The (A-2) aromatic vinyl compound-vinyl cyan compound copolymer preferably has a weight average molecular weight of 50,000 to 200,000 g/mol, more preferably 60,000 to 180,000 g/mol, still more preferably 70,000 to 150,000 g/mol.
[56]
In the present description, the weight average molecular weight is, for example, prepared by dissolving a resin in tetrahydrofuran (THF) at a concentration of 1 mg/ml, then filtering it with a 0.45 μm syringe filter, and using gel chromatography (GPC) can be measured.
[57]
[58]
The method for preparing the (A-2) aromatic vinyl compound-vinyl cyan compound copolymer is not particularly limited, and may be a manufacturing method commonly used in this technical field, preferably a continuous bulk polymerization method, In this case, manufacturing cost is reduced and mechanical properties are excellent.
[59]
[60]
B) a polymer comprising a lone pair of electrons
[61]
B) of the present description, the polymer containing a lone pair may be, for example, 0.1 to 32 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the base resin, and within this range, the inorganic antibacterial agent and zinc oxide It has the effect of greatly increasing the antibacterial persistence by significantly lowering the elution rate of metal ions. At this time, the unshared electron pair of the poly(ether ester amide) resin coordinates the inorganic antibacterial agent and the metal ion of zinc oxide, thereby significantly lowering the elution rate of the metal ion to the outside of the thermoplastic resin composition, thereby improving the antimicrobial persistence.
[62]
[63]
B) the polymer including a lone pair preferably has a weight average molecular weight of more than 500,000 g/mol, as measured by gel permeation chromatography (GPC), more preferably 510,000 g/mol or more, More preferably 600,000 g/mol or more, even more preferably 660,000 g/mol or more, particularly preferably 700,000 g/mol or more, specifically, more than 500,000 g/mol to 1,000,000 g/mol or less, preferably 510,000 to 1,000,000 g / mol, more preferably 600,000 to 1,000,000 g / mol, more preferably 660,000 to 1,000,000 g / mol, within this range, the elution rate of the inorganic antibacterial agent and the metal ion of zinc oxide is greatly reduced to significantly increase the antimicrobial persistence It works.
[64]
[65]
B) The polymer containing a lone pair is preferably the sum of the integral values ​​of the CH 2 peaks A when measured by 13 C NMR and the sum B of the integral values ​​of the peaks of the hydroxyl, ether, ester and amide groups. B/A may be 0.01 to 1.0, more preferably 0.1 to 1.0, still more preferably 0.2 to 0.9, even more preferably 0.3 to 0.9, particularly preferably 0.3 to 0.6, within this range the inorganic It has the advantage of greatly increasing the antimicrobial persistence by significantly lowering the elution rate of metal ions from the antibacterial agent and zinc oxide.
[66]
[67]
B) The polymer containing a lone pair is a generic term for polymers having at least one of ether, ester, amide, amine and hydroxyl functional groups, for example, poly (ether ester amide) resin, poly (ether amide) block copolymer, It may be at least one selected from the group consisting of poly(ester amide) block copolymer, poly(ether ester) block copolymer, polyether resin, polyester resin, and polyamide resin, and within this range, the inorganic antibacterial agent and zinc oxide It has the effect of greatly increasing the antibacterial persistence by significantly lowering the elution rate of metal ions.
[68]
The poly(ether ester amide) resin, poly(ether amide) block copolymer, poly(ester amide) block copolymer, poly(ether ester) block copolymer, polyether resin, polyester resin and polyamide resin are the present invention As long as the definition is followed, it is not particularly limited if it is a resin or copolymer commonly used in the technical field to which the present invention belongs.
[69]
The polyamide resin may be preferably nylon 6, nylon 66, or a mixture thereof.
[70]
[71]
The poly(ether ester amide) resin may be, for example, a poly(ether ester amide) block copolymer, preferably an amino carboxylic acid, lactam or diamine-dicarboxylate having 6 or more carbon atoms; And polyalkylene glycol and, if necessary, may be a block copolymer of a reaction mixture comprising a dicarboxylic acid having 4 to 20 carbon atoms.
[72]
The amino carboxylic acid, lactam or diamine-dicarboxylate having 6 or more carbon atoms is, for example, ω-aminocaproic acid, ω-aminoenantic acid, ω-aminocaprylic acid, ω-aminopelconic acid, ω-aminocar aminocarboxylic acids such as priric acid, 1,1-aminoundecanoic acid, and 1,2-aminododecanoic acid; lactams such as caprolactam, enanthractam, caprylactam and lauryllactam; and diamine-dicarboxylate such as hexamethylenediamine-adipinate, hexamethylenediamine-isophthalate, and the like, and preferably at least one selected from the group consisting of 1,2-aminododecanoic acid, caproic acid, and the like. It may be at least one selected from the group consisting of lactam and hexamethylenediamine-adipinate.
[73]
[74]
The polyalkylene glycol is, for example, polyethylene glycol, poly (1,2- and 1,3-propylene glycol), polytetramethylene glycol, polyhexamethylene glycol, block or random copolymers of ethylene glycol and propylene glycol, and ethylene It may be at least one selected from the group consisting of a copolymer of glycol and tetrahydrofuran, and the like, preferably polyethylene glycol, a copolymer of ethylene glycol and propylene glycol, or a mixture thereof.
[75]
[76]
The dicarboxylic acid having 4 to 20 carbon atoms may be, for example, at least one selected from the group consisting of terephthalic acid, 1,4-cyclohexacarboxylic acid, sebacic acid, adipic acid and dodecanocarboxylic acid.
[77]
[78]
In another example, the bond between the amino carboxylic acid, lactam or diamine-dicarboxylate having 6 or more carbon atoms and the polyalkylene glycol is an ester bond, and the amino carboxylic acid, lactam or diamine-dicarboxyl acid having 6 or more carbon atoms is an ester bond. The bond between the acid salt and the dicarboxylic acid having 4 to 20 carbon atoms is an amide bond, and the bond between the polyalkylene glycol and the dicarboxylic acid having 4 to 20 carbon atoms is an ester bond.
[79]
[80]
The poly(ether ester amide) resin is, for example, a block copolymer comprising 5 to 95 wt% of an amino carboxylic acid having 6 or more carbon atoms, a lactam or diamine-dicarboxylate, and 5 to 95 wt% of a polyalkylene glycol can
[81]
As another example, the poly(ether ester amide) resin is a block copolymer comprising 5 to 65% by weight of an amino carboxylic acid having 6 or more carbon atoms, lactam or diamine-dicarboxylate, and 35 to 65% by weight of polyalkylene glycol may be synthetic.
[82]
[83]
The poly (ether ester amide) resin is, for example, a total of 100 weight by adding a dicarboxylic acid having 4 to 20 carbon atoms, an amino carboxylic acid having 6 or more carbon atoms, lactam or diamine-dicarboxylate, and the polyalkylene glycol. Based on parts, it may be included in an amount of 70 parts by weight or less, more preferably 5 to 65 parts by weight.
[84]
[85]
B) The polymer including a lone pair may be prepared by a known synthesis method commonly used in the art to which the present invention pertains, and is not particularly limited as long as it follows the definition of the present invention.
[86]
[87]
C) inorganic antibacterial agents
[88]
C) inorganic antibacterial agent of the present disclosure may be included in preferably 0.1 to 5 parts by weight based on 100 parts by weight of the base resin, more preferably 0.1 to 3 parts by weight, still more preferably 0.1 to 1 parts by weight, even more preferably preferably 0.1 to 0.9 parts by weight, particularly preferably 0.1 to 0.5 parts by weight, particularly more preferably 0.2 to 0.5 parts by weight, most preferably 0.2 to 0.4 parts by weight.
[89]
[90]
In the present substrate, the inorganic antibacterial agent is preferably an inorganic antibacterial agent comprising at least one carrier selected from the group consisting of phosphate glass, silica gel, calcium phosphate, and sodium zirconium phosphate, and the ion exchangeable ions in the carrier are partially or entirely antibacterial. Metal ions (active ingredients) are substituted with silver, zinc, copper, mercury or tin ions.
[91]
[92]
The C) inorganic antibacterial agent is preferably a silver (Ag)-based inorganic antibacterial agent; zinc (Zn)-based inorganic antibacterial agent; and at least one selected from the group consisting of silver and zinc mixed inorganic antibacterial agents.
[93]
The silver (Ag)-based inorganic antibacterial agent is not particularly limited in the case of an inorganic antibacterial agent containing a silver component, but is preferably a carrier containing a silver component.
[94]
The zinc (Zn)-based inorganic antibacterial agent is not particularly limited if it is an inorganic antibacterial agent containing a zinc component, but is preferably a support containing a zinc component.
[95]
The silver-zinc mixed inorganic antibacterial agent is not particularly limited if it is an inorganic antibacterial agent containing a silver component and a zinc component, but is preferably a carrier containing a silver component and a zinc component.
[96]
[97]
The silver component and the zinc component are active ingredients of the inorganic antibacterial agent, and the active ingredient is preferably 0.1 to 5% by weight, more preferably 1 to 5% by weight, more preferably 2 to 5% by weight based on the total weight of the inorganic antibacterial agent. It may be included in weight %.
[98]
The active ingredient is preferably ionizable in the carrier.
[99]
[100]
The carrier is preferably at least one selected from the group consisting of zeolite, phosphate glass, silica gel, calcium phosphate, zirconium phosphate and zirconium sodium phosphate, and more preferably phosphate glass, silica gel, or a mixture thereof.
[101]
[102]
D) Zinc oxide with a BET surface area of ​​28 m 2 /g or more
[103]
D) Zinc oxide having a BET surface area of ​​28 m 2 /g or more of the present substrate may be included, for example, in an amount of 0.2 to 10 parts by weight, preferably 0.4 to 10 parts by weight, more preferably based on 100 parts by weight of the base resin. is 0.4 to 5 parts by weight, more preferably 0.4 to 4.5 parts by weight, and still more preferably 0.5 to 4 parts by weight.
[104]
[105]
The above D) zinc oxide may preferably have a BET surface area of ​​28 to 50 m 2 /g, more preferably 30 to 50 m 2 /g, still more preferably 30 to 45 m 2 /g, even more preferably preferably 35 to 45 m 2 /g,
[106]
In this description, the BET surface area can be measured using a nitrogen gas adsorption method with a BET analysis equipment (Micromeritics Surface Area and Porosity Analyzer ASAP 2020 equipment).
[107]
[108]
D) The zinc oxide having a BET surface area of ​​28 m 2 /g or more is not particularly limited if it is zinc oxide commonly used in the art to which the present invention pertains as long as it follows the definition of the present invention.
[109]
[110]
Thermoplastic resin composition
[111]
The thermoplastic resin composition of the present disclosure may have an antimicrobial persistence of 2.0 or more after pretreatment according to the JIS Z 2801 antibacterial evaluation method, for example, preferably 2.5 or more, more preferably 2.8 or more, and specific examples 2.5 to 7, preferred examples 2.8 to 7.
[112]
[113]
The thermoplastic resin composition may have an antimicrobial persistence of 2.0 or more, for example, after acid treatment according to the JIS Z 2801 antibacterial evaluation method, preferably 2.4 or more, and preferably 2.4 to 7.
[114]
[115]
The thermoplastic resin composition may have an antimicrobial persistence of 2.0 or more, for example, after alkali treatment according to JIS Z 2801 antibacterial evaluation method, preferably 2.2 or more, more preferably 2.3 or more, and preferably 2.2 to 7, more preferably Examples are 2.3 to 7.
[116]
[117]
The thermoplastic resin composition may be preferably used as a material for home appliances or household goods, and more preferably as a material for home appliances.
[118]
The thermoplastic resin composition is optionally selected from the group consisting of a heat stabilizer, a light stabilizer, a dye, a colorant, a mold release agent, an antistatic agent, a processing aid, a metal deactivator, a flame retardant, a flame retardant, an anti-drip agent, an anti-friction agent, and an anti-wear agent One or more may be further included in an amount of 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.5 to 1 parts by weight, and within this range, if the original properties of the thermoplastic resin composition of the present substrate are not reduced There is an advantage that the necessary physical properties are well realized.
[119]
[120]
Method for producing a thermoplastic resin composition
[121]
The method for producing the thermoplastic resin composition of the present invention is preferably A) a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer (A-1) and an aromatic vinyl compound-vinyl cyan compound copolymer (A-2) 100 parts by weight of a base resin comprising; B) 0.1 to 32 parts by weight of a polymer comprising a lone pair of electrons with a weight average molecular weight of greater than 500,000 g/mol; C) 0.1 to 5 parts by weight of an inorganic antibacterial agent comprising at least one carrier selected from the group consisting of phosphate glass, silica gel, calcium phosphate, and sodium zirconium phosphate; and D) kneading and extruding including 0.4 to 10 parts by weight of zinc oxide having a BET surface area of ​​28 m 2 /g or more. There is an advantage of providing a thermoplastic resin composition having excellent durability and no gas defect or peeling phenomenon during injection.
[122]
The kneading and extruding may preferably be carried out under 210 to 280 ℃, more preferably under 220 to 250 ℃, wherein the temperature means the temperature set in the cylinder.
[123]
The extruder used for the kneading and extrusion is not particularly limited if it is an extruder commonly used in the art to which the present invention belongs, and may preferably be a twin screw extruder.
[124]
The extrudate that has undergone the kneading and extruding steps is preferably in the form of pellets.
[125]
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.
[126]
[127]
molded article
[128]
The molded article of the present substrate is preferably characterized in that it contains the thermoplastic resin composition of the present substrate, and in this case, it is not toxic to the human body and has excellent thermal stability, but also has excellent initial antibacterial properties as well as antibacterial persistence, and gas defect or peeling phenomenon during injection There is an advantage of providing a molded article without.
[129]
The molded article may be, for example, an extrusion-molded article or an injection-molded article, preferably an injection-molded article, and more preferably a household article, a home appliance case, or a home appliance housing.
[130]
[131]
The molded article may preferably be manufactured including the step of injecting the thermoplastic resin composition of the present invention at a molding temperature of 200 to 260 ℃, preferably 210 to 250 ℃, within this range, gas failure or peeling during injection There is an advantage in providing a molded article free of phenomena.
[132]
The thermoplastic resin composition used for the injection may preferably be in the form of pellets.
[133]
[134]
In describing the thermoplastic resin composition of the present disclosure, its manufacturing method and the exterior material, 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.
[135]
[136]
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.
[137]
[138]
[Example]
[139]
Materials used in Examples 1 to 6 and Comparative Examples 1 to 14 below were as follows.
[140]
(A-1) ABS resin (DP270M of LG Chem) having a rubber particle diameter of 0.3 μm was used as the ABS graft copolymer.
[141]
(A-2) A SAN copolymer (81HF of LG Chem) was used.
[142]
(B-1) The weight average molecular weight is 800,000 g/mol, and the sum A of CH 2 peak integral values ​​measured by 13 C NMR and hydroxyl, ether, ester and amide groups A poly(ether ester amide) resin having a ratio (B/A) of the sum of the peak integral values ​​of (groups) B of 0.4 was used.
[143]
(B-2) A poly(ether amide) resin having a weight average molecular weight of 4,500 g/mol and a B/A of 0.3 was used.
[144]
(B-3) A polyvinyl alcohol (PVA) resin having a weight average molecular weight of 500,000 g/mol and B/A of 1 was used.
[145]
(C-1) As the inorganic antibacterial agent, a silver (Ag)-based inorganic antibacterial agent in which the Ag component was supported in an amount of 3 wt% on a phosphoric acid glass carrier was used.
[146]
(C-2) As an inorganic antibacterial agent, a silver (Ag)-based inorganic antibacterial agent (Toagosei, AGZ330) was used in which 2 wt% of Ag was supported on a zirconium phosphate carrier.
[147]
(C-3) As an inorganic antibacterial agent, a silver (Ag)-based inorganic antibacterial agent (manufactured by SHINANEN, DAW502) in which Ag component was supported at 5 wt% on a zeolite carrier was used.
[148]
(D-1) Zinc oxide having a BET surface area of ​​40 m 2 /g was used.
[149]
(D-2) BET Zinc oxide (manufactured by Taekyung SBC, KS-1) having a surface area of ​​15 m 2 /g was used.
[150]
Here, in the 13 C NMR measurement of (B-1), (B-2) and (B-3), the sum A of the integral values ​​of the CH 2 peaks and the peaks of the hydroxy group, ether group, ester group, and amide group The ratio B/A of the sum B of the integral values ​​was measured using 13 C NMR.
[151]
[152]
Examples 1 to 6 and Comparative Examples 1 to 14
[153]
Each component was put into a twin-screw extruder to have the composition and content shown in Table 1 below, melted and kneaded at 230 ° C. to prepare a resin composition in the form of pellets, and the resin composition in the form of pellets was injected at 230 ° C. Specimens for measurement were prepared.
[154]
[155]
[Test Example]
[156]
The properties of the specimens prepared in Examples 1 to 6 and Comparative Examples 1 to 14 were measured by the following method, and the results are shown in Table 2 below.
[157]
* Antibacterial activity: Based on the JIS Z 2801 antibacterial evaluation method, E. coli and Staphylococcus aureus were inoculated into 5 cm × 5 cm specimens, respectively, and after 24 hours of incubation at 35 ° C., RH 90% conditions, the antibacterial activity was measured.
[158]
* Antibacterial persistence after pretreatment: In accordance with the JIS Z 2801 antibacterial evaluation method, E. coli was inoculated into a 5 cm × 5 cm specimen immersed in 50 ° C water for 32 hours, and cultured at 35 ° C, RH 90% for 24 hours, Antibacterial activity values ​​after pretreatment were measured.
[159]
* Antibacterial persistence after acid treatment: According to the JIS Z 2801 antibacterial evaluation method, E. coli was inoculated into a 5 cm × 5 cm specimen immersed in 5% citric acid solution for 16 hours, and cultured at 35°C, RH 90% for 24 hours. Then, the antibacterial activity value after acid treatment was measured.
[160]
* Antibacterial persistence after alkali treatment: According to the JIS Z 2801 antibacterial evaluation method, inoculated with E. coli to a 5 cm × 5 cm specimen immersed in 5% caustic soda solution for 16 hours, 35 ℃, RH 90% condition for 24 hours After incubation, the antibacterial activity value after alkali treatment was measured.
[161]
* Injection characteristics: If there is no peeling phenomenon or gas failure, it was evaluated as good.
[162]
[163]
[Table 1]
(parts by weight) Example
One 2 3 4 5 6
(A-1) 27 27 27 27 27 27
(A-2) 73 73 73 73 73 73
(B-1) 5 20 30 20 20 20
(B-2) - - - - - -
(B-3) - - - - - -
(C-1) 0.4 0.4 0.4 0.4 0.4 0.2
(C-2) - - - - - -
(C-3) - - - - - -
(D-1) One One One 0.5 4 One
(D-2) - - - - - -
[164]
[Table 2]
(parts by weight) comparative example
One 2 3 4 5 6 7 8 9 10 11 12 13 14
(A-1) 27 27 27 27 27 27 27 27 27 27 27 27 27 27
(A-2) 73 73 73 73 73 73 73 73 73 73 73 73 73 73
(B-1) One 35 20 - 20 20 - - - - 20 5 5 5
(B-2) - - - - - - - - 20 - - - - -
(B-3) - - - - - - - - - 20 - - - -
(C-1) 0.4 0.4 0.4 0.4 - One One - 0.4 0.4 0.4 0.4 -
(C-2) - - - - - - - - - - - - 0.4 -
(C-3) - - - - - - - - - - - - - 0.4
(D-1) One One 0.3 One 2 - - 2 One One - 10 One One
(D-2) - - - - - - - - - - One - - -
[165]
[Table 3]
division Example
One 2 3 4 5 6
Antibacterial activity level
(E. coli) 3.8 6.1 6.4 5.6 6.4 5.8
Antibacterial activity level (Staphylococcus aureus) 4.2 6 6.1 5.3 6.4 5.2
Antibacterial persistence (after pretreatment)-E. coli 2.8 3.7 4.9 4.1 6.4 3.8
Antibacterial persistence (after acid treatment)-E. coli 2.4 3.8 4.9 4.3 6.4 3.6
Antibacterial persistence (after alkali treatment)-E. coli 2.3 3.9 4.6 3.9 6.4 3.5
Injection characteristics Good Good Good Good Good Good
impact strength 20 17 15 17 10 15
[166]
[Table 4]
division comparative example
One 2 3 4 5 6 7 8 9 10 11 12 13 14
Antibacterial activity level
(E. coli) 4.1 X 2.8 4.5 2.8 3.3 3.1 2.9 3.5 X 3.1 6.1 1.8 1.5
Antibacterial activity level (Staphylococcus aureus) 4.5 X 2.6 4.1 2.4 3.1 3.0 3.2 3.8 X 2.3 6.1 1.6 1.3
Antibacterial persistence (after pretreatment)-E. coli 2.1 X 2.1 1.8 1.2 1.9 0.8 0.9 1.8 X 1.5 6.1 0.8 0.5
Antibacterial persistence (after acid treatment)-E. coli 1.5 X 1.4 1.6 1.1 2.3 0.6 1.2 1.5 X 1.2 6.1 0.4 0.2
Antibacterial persistence (after alkali treatment)-E. coli 1.2 X 1.5 1.5 1.3 2.1 0.6 1.1 1.6 X 0.8 6.1 0.5 0.6
Injection characteristics Good peeling Good Good Good Good Good Good Good Degassing and peeling Good Good Good Good
impact strength 22 12 16 22 16 17 18 17 17 10 17 5 19 19
[167]
As shown in Tables 3 and 4 above, the thermoplastic resin composition (see Examples 1 to 6) according to the present invention has excellent impact strength while having no gas defect or peeling phenomenon during injection, and has excellent initial antibacterial properties and antibacterial persistence after pretreatment , it was confirmed that the antimicrobial persistence after acid treatment and antibacterial persistence after alkali treatment were both excellent. However, Comparative Example 1, which was less than the content range of the poly(ether ester amide) resin according to the present invention, had poor antibacterial persistence, and the present invention In Comparative Example 2, which exceeds the content range of the poly(ether ester amide) resin, peeling occurred due to compatibility deterioration, and the antibacterial activity value could not be measured.
[168]
In addition, Comparative Example 3, which was less than the content range of zinc oxide according to the present invention, had poor initial antibacterial properties and antibacterial persistence, and Comparative Example 4 did not contain the poly(ether ester amide) resin, inorganic antibacterial agent or zinc oxide according to the present invention. All of the initial antibacterial properties and antibacterial persistence of 8 to 8 were poor.
[169]
Furthermore, Comparative Example 9 in which a poly(ether amide) resin was used instead of the poly(ether ester amide) resin according to the present invention had poor initial antibacterial properties and antimicrobial persistence, and was replaced with the poly(ether ester amide) resin according to the present invention. In Comparative Example 10 using a polyvinyl alcohol resin, it was confirmed that a gas defect and peeling phenomenon appeared on the exterior of the injection product due to a large number of hydroxyl groups.
[170]
In addition, it was confirmed that Comparative Example 11 using zinc oxide having a BET surface area of ​​15 m 2 /g instead of zinc oxide according to the present invention had poor initial antibacterial properties and antimicrobial persistence.
[171]
In addition, Comparative Example 12 using an excessive amount of zinc oxide was not suitable for use as a product because the impact strength was significantly lowered, and Comparative Examples 13 and 14 including a silver-based inorganic antibacterial agent to which zirconium phosphate or zeolite was applied as a carrier had initial antibacterial properties, Antimicrobial persistence after pretreatment, antibacterial persistence after acid treatment, and antibacterial persistence after alkali treatment were all poor.
Claims
[Claim 1]
A) 100 parts by weight of a base resin including a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer (A-1) and an aromatic vinyl compound-vinyl cyan compound copolymer (A-2); B) 0.1 to 32 parts by weight of a polymer comprising a lone pair of electrons with a weight average molecular weight of greater than 500,000 g/mol; C) 0.1 to 5 parts by weight of an inorganic antibacterial agent comprising at least one carrier selected from the group consisting of phosphate glass, silica gel, calcium phosphate, and sodium zirconium phosphate; and D) 0.2 to 10 parts by weight of zinc oxide having a BET surface area of ​​28 m 2 /g or more.
[Claim 2]
According to claim 1, wherein the base resin is (A-1) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 20 to 40% by weight and (A-2) aromatic vinyl compound-vinyl cyan compound copolymer A thermoplastic resin composition comprising 60 to 80% by weight.
[Claim 3]
The method according to claim 1, wherein the (A-1) vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer has an average particle diameter of the conjugated diene rubber including the conjugated diene compound of 0.05 to 0.5 μm. A thermoplastic resin composition.
[Claim 4]
The thermoplastic resin composition according to claim 1, wherein the (A-2) aromatic vinyl compound-vinyl cyan compound copolymer comprises 65 to 80 wt % of the aromatic vinyl compound and 20 to 35 wt % of the vinyl cyanide compound. .
[Claim 5]
The poly(ether ester) block copolymer of claim 1, wherein B) the polymer containing unshared electron pairs is a poly(ether ester amide) resin, a poly(ether amide) block copolymer, a poly(ester amide) block copolymer, a poly(ether ester) block copolymer. , a thermoplastic resin composition, characterized in that at least one selected from the group consisting of polyether resins, polyester resins and polyamide resins.
[Claim 6]
According to claim 1, wherein B) the polymer containing a lone pair is the sum of the integral values ​​of the peaks of CH 2 as measured by 13 C NMR A and the sum of the integral values ​​of the peaks of hydroxy groups, ether groups, ester groups and amide groups A thermoplastic resin composition characterized in that the ratio B/A of B is 0.01 to 1.0.
[Claim 7]
The method of claim 1, wherein C) the inorganic antibacterial agent is a silver (Ag)-based inorganic antibacterial agent; zinc (Zn)-based inorganic antibacterial agent; and at least one selected from the group consisting of silver and zinc mixed inorganic antibacterial agents.
[Claim 8]
The thermoplastic resin composition according to claim 7, wherein C) the inorganic antibacterial agent contains silver and zinc as active ingredients in an amount of 0.1 to 5% by weight based on the total weight of the inorganic antibacterial agent.
[Claim 9]
The thermoplastic resin composition according to claim 1, wherein D) zinc oxide has a BET surface area of ​​28 to 50 m 2 /g.
[Claim 10]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an antibacterial persistence of 2.5 or more after pretreatment according to the JIS Z 2801 antibacterial evaluation method.
[Claim 11]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an antibacterial persistence of 2.4 or more after acid treatment according to the JIS Z 2801 antibacterial evaluation method.
[Claim 12]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an antibacterial persistence of 2.2 or more after alkali treatment according to the JIS Z 2801 antibacterial evaluation method.
[Claim 13]
A) 100 parts by weight of a base resin including a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer (A-1) and an aromatic vinyl compound-vinyl cyan compound copolymer (A-2); B) 0.1 to 32 parts by weight of a polymer comprising a lone pair of electrons with a weight average molecular weight of greater than 500,000 g/mol; C) 0.1 to 5 parts by weight of an inorganic antibacterial agent comprising at least one carrier selected from the group consisting of phosphate glass, silica gel, calcium phosphate, and sodium zirconium phosphate; and D) including 0.2 to 10 parts by weight of zinc oxide having a BET surface area of ​​28 m 2 /g or more, and kneading and extruding the method.
[Claim 14]
A molded article comprising the thermoplastic resin composition of any one of claims 1 to 12.