CN116490567A - Thermoplastic resin composition and molded article produced therefrom - Google Patents

Thermoplastic resin composition and molded article produced therefrom Download PDF

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Publication number
CN116490567A
CN116490567A CN202180079671.XA CN202180079671A CN116490567A CN 116490567 A CN116490567 A CN 116490567A CN 202180079671 A CN202180079671 A CN 202180079671A CN 116490567 A CN116490567 A CN 116490567A
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resin composition
thermoplastic resin
weight
parts
silver
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朴东铉
咸玟庆
梁允祯
张相埈
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Lotte Chemical Corp
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Lotte Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The thermoplastic resin composition of the present invention comprises: about 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; about 4 parts by weight to about 23 parts by weight of a polyetheresteramide block copolymer; about 0.03 to 1 part by weight of a silver (Ag) based compound; and about 0.05 to 4 parts by weight of zinc oxide, wherein the zinc oxide is composed of primary particles and secondary particles, the primary particles having an average particle diameter (D50) of about 1nm to 50nm, and the secondary particles having an average particle diameter (D50) of about 0.1 μm to 10 μm. The thermoplastic resin composition has excellent antibacterial properties, transparency, antistatic properties, impact resistance, and the like.

Description

Thermoplastic resin composition and molded article produced therefrom
Technical Field
The present invention relates to thermoplastic resin compositions and molded articles produced therefrom. More particularly, the present invention relates to a thermoplastic resin composition having good characteristics in terms of antibacterial property, transparency, antistatic property, impact resistance and the like, and a molded article produced therefrom.
Background
Recently, as people's attention to personal health and hygiene is gradually increased and income level is gradually increased, demand for thermoplastic resin products having antibacterial and hygienic functions is also gradually increased. Accordingly, there is an increasing demand for thermoplastic resin products that have been subjected to an antibacterial treatment to remove or inhibit bacterial growth on the surfaces of household articles and electronic products. Therefore, it is a very important challenge to develop a functional antibacterial material (antibacterial thermoplastic resin composition) having stability and reliability.
Such an antibacterial thermoplastic resin composition requires an antibacterial agent. The antibacterial agent may be classified into an organic antibacterial agent and an inorganic antibacterial agent.
Although a small amount of the organic antibacterial agent has advantages of being relatively inexpensive and having a good antibacterial effect, the organic antibacterial agent is sometimes toxic to the human body and effective only for some bacteria, and there is a concern that the antibacterial effect of the organic antibacterial agent may be lost by decomposition when processed at high temperature. Moreover, organic antibacterial agents can cause discoloration after processing and have short antibacterial durability due to elution thereof. Therefore, the range of antibacterial agents suitable for antibacterial thermoplastic resin compositions is very limited.
Inorganic antibacterial agents contain metal components such as silver (Ag) and copper (Cu) and exhibit good thermal stability, and are thus often used for preparing antibacterial thermoplastic resin compositions (antibacterial resins). However, the inorganic antibacterial agent must be added in an excessive amount due to insufficient antibacterial properties of the inorganic antibacterial agent as compared with the organic antibacterial agent, and the use of the inorganic antibacterial agent is very limited due to disadvantages such as relatively high price, problems of uniform distribution at the time of processing, and discoloration due to metal components.
Therefore, it is required to develop a thermoplastic resin composition having good characteristics in terms of antibacterial property, transparency, antistatic property, impact resistance, and the like.
The background of the invention is disclosed in korean patent registration No. 10-0696385, etc.
Disclosure of Invention
Technical problem
An object of the present invention is to provide a thermoplastic resin composition having good characteristics in terms of antibacterial property, transparency, antistatic property, impact resistance and the like.
It is another object of the present invention to provide a molded article formed of the above-stated thermoplastic resin composition.
The above and other objects of the present invention will become apparent from the following detailed description of embodiments.
Technical proposal
1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition comprises: about 100 parts by weight of a rubber modified aromatic vinyl copolymer resin; about 4 parts by weight to about 23 parts by weight of a polyether-ester-amide block copolymer; about 0.03 parts by weight to about 1 part by weight of a silver (Ag) compound; and about 0.05 to about 4 parts by weight of zinc oxide, wherein the zinc oxide comprises primary particles having an average particle size (D50) of about 1nm to about 50nm and secondary particles having an average particle size (D50) of about 0.1 μm to about 10 μm.
2. In embodiment 1, the weight ratio of the polyether-ester-amide block copolymer to the sum of the silver compound and zinc oxide (polyether-ester-amide block copolymer: silver compound + zinc oxide) may be in the range of about 1:0.01 to about 1:0.5.
3. In embodiments 1 or 2, the weight ratio of silver compound to zinc oxide (silver compound: zinc oxide) may be in the range of about 1:0.5 to about 1:60.
4. In embodiments 1 to 3, the rubber-modified aromatic vinyl copolymer resin may include about 5wt% to about 50wt% of the rubber-modified vinyl graft copolymer and about 50wt% to about 95wt% of the aromatic vinyl copolymer resin.
5. In embodiments 1 to 4, the rubber-modified vinyl graft copolymer can be obtained by graft-polymerizing an alkyl (meth) acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer to a rubber polymer.
6. In embodiments 1 to 5, the aromatic vinyl copolymer resin may be obtained by polymerization of an alkyl (meth) acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer.
7. In embodiments 1 to 6, the polyether-ester-amide block copolymer may be a block copolymer including a reaction mixture of: aminocarboxylic acids, lactams or diamine-dicarboxylic acid salts having 6 or more carbon atoms; polyalkylene glycols; and dicarboxylic acids having 4 to 20 carbon atoms.
8. In embodiments 1 to 7, the silver compound may include at least one of metallic silver, silver oxide, silver halide, and a carrier containing silver ions.
9. In embodiments 1 to 8, after inoculating 5cm×5cm samples with staphylococcus aureus and escherichia coli, respectively, according to JIS Z2801, and culturing for 24 hours at 35 ℃ and 90% rh (relative humidity), the thermoplastic resin composition has an antibacterial activity against each of staphylococcus aureus and escherichia coli of about 2 to about 7 when calculated according to formula 1:
[ formula 1]
Antibacterial activity = log (M1/M2)
Wherein M1 represents the number of bacteria when measured on a blank sample after culturing for 24 hours, and M2 represents the number of bacteria when measured on each of samples of the thermoplastic resin composition after culturing for 24 hours.
10. In embodiments 1 to 9, the thermoplastic resin composition may have a haze of about 1% to about 13% and a light transmittance of about 82% to about 95% when measured on a 0.1mm thick sample according to ASTM D1003.
11. In embodiments 1 to 10, the thermoplastic resin composition may have a thickness of about 1X 10 as measured on a 3.2mm thick injection molded sample according to ASTM D257 8 Up to about 5X 10 12 Surface resistance of omega/sq。
12. In embodiments 1 to 11, the thermoplastic resin composition may have a notched Izod impact strength of about 5kgf cm/cm to about 20kgf cm/cm, as measured on a 1/8' thick sample according to ASTM D256.
13. Another aspect of the invention relates to a molded article. The molded article is formed of the thermoplastic resin composition according to any one of embodiments 1 to 12.
14. In embodiment 13, the molded article may be an antibacterial film having a thickness of about 0.1mm to about 3 mm.
Advantageous effects
The present invention provides a thermoplastic resin composition having good characteristics in terms of antibacterial property, transparency, antistatic property, impact resistance, and the like.
Detailed Description
Hereinafter, exemplary embodiments of the present invention will be described in detail.
The thermoplastic resin composition according to the present invention comprises: (a) a rubber-modified aromatic vinyl copolymer resin; (B) a polyether-ester-amide block copolymer; (C) silver (Ag) compounds; and (C) zinc oxide.
As used herein, "a to b" is defined as ". Gtoreq.a and. Ltoreq.b" for the purpose of indicating a particular numerical range.
(A) Rubber modified aromatic vinyl copolymer resin
The rubber-modified aromatic vinyl copolymer resin according to the present invention may be selected from any rubber-modified aromatic vinyl copolymer resin used in typical transparent thermoplastic resin compositions, and may include, for example, (A1) rubber-modified vinyl graft copolymer and (A2) aromatic vinyl copolymer resin.
(A1) Rubber modified vinyl graft copolymer
The rubber-modified vinyl graft copolymer according to an embodiment of the present invention is used to improve transparency, impact resistance, flowability, and the like of a thermoplastic resin composition, and is obtainable by graft-polymerizing an alkyl (meth) acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer to a rubber polymer. For example, the rubber-modified vinyl graft copolymer may be obtained by graft polymerization of a monomer mixture including an alkyl (meth) acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer with a rubber polymer, wherein the monomer mixture may further include a monomer for imparting processability and heat resistance, as required. Here, the polymerization may be performed by any suitable polymerization method known in the art (such as emulsion polymerization, suspension polymerization, bulk polymerization, and the like).
In some embodiments, the rubber polymer may include: diene rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene), and the like; a saturated rubber obtained by adding hydrogen to a diene rubber; an isoprene rubber; acrylic rubbers such as poly (butyl acrylate) and the like; and ethylene-propylene-diene terpolymers (EPDM). These may be used alone or as a mixture thereof. For example, the rubber polymer may include diene rubber, particularly butadiene rubber.
In some embodiments, the rubber polymer (rubber particles) may have an average (z-average) particle size of about 0.1 to about 0.5 μm, for example, about 0.2 to about 0.4 μm. Within this range, the thermoplastic resin composition can have good characteristics in terms of impact resistance, flowability, and the like, without deteriorating transparency. Here, the average (z-average) particle diameter of the rubber polymer (rubber particles) can be measured by a light scattering method in a latex state. Specifically, the rubber polymer latex is filtered through a mesh screen to remove coagulum generated during polymerization of the rubber polymer. Then, a mixed solution of 0.5g of latex and 30ml of distilled water was put into a1,000 ml flask, which was then filled with distilled water to prepare a sample. Then, 10ml of the sample was transferred to a quartz cell, followed by measuring the average particle diameter of the rubber polymer using a light scattering particle size analyzer (Malvern co., ltd., nano-zs).
In some embodiments, the rubber polymer may be present in an amount of about 5wt% to about 65wt%, for example, about 10wt% to about 60wt%, based on 100wt% of the rubber modified vinyl graft copolymer, and the monomer mixture (including alkyl (meth) acrylate, aromatic vinyl monomer, and vinyl cyanide monomer) may be present in an amount of about 35wt% to about 95wt%, for example, about 40wt% to about 90wt%, based on 100wt% of the rubber modified vinyl graft copolymer. Within this range, the thermoplastic resin composition may have good characteristics in terms of impact resistance, transparency, flowability, and the like.
In some embodiments, the alkyl (meth) acrylate may be graft-copolymerized with the rubber polymer or may be graft-copolymerized with the aromatic vinyl monomer, and may include, for example, C (meth) acrylic acid 1 To C 10 Alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like, particularly methyl (meth) acrylate, and the like. The alkyl (meth) acrylate may be present in an amount of about 55wt% to about 85wt%, for example, about 60wt% to about 80wt%, based on 100wt% of the monomer mixture. Within this range, the thermoplastic resin composition may have good characteristics in terms of impact resistance, transparency, flowability, and the like.
In some embodiments, the aromatic vinyl monomer may be graft copolymerized with the rubber polymer, and may include, for example, styrene, alpha-methylstyrene, beta-methylstyrene, para-tert-butylstyrene, ethylstyrene, vinylxylenes, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like. These may be used alone or as a mixture thereof. The aromatic vinyl monomer may be present in an amount of about 10wt% to about 40wt%, for example, about 15wt% to about 35wt%, based on 100wt% of the monomer mixture. Within this range, the thermoplastic resin composition may have good characteristics in terms of impact resistance, transparency, heat resistance, flowability, and the like.
In some embodiments, the vinyl cyanide monomer is a monomer copolymerized with an aromatic vinyl monomer, and may include, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α -chloroacrylonitrile, and fumaronitrile, but is not limited thereto. These may be used alone or as a mixture thereof. For example, vinyl cyanide monomers can be acrylonitrile, methacrylonitrile, and the like. The vinyl cyanide monomer may be present in an amount of about 1wt% to about 30wt%, for example, about 5wt% to about 25wt%, based on 100wt% of the monomer mixture. Within this range, the thermoplastic resin composition may have good characteristics in terms of impact resistance, transparency, flowability, and the like.
In some embodiments, monomers for imparting processability and heat resistance may include, for example, (meth) acrylic acid, maleic anhydride, and N-substituted maleimide, and the like. The monomer for imparting processability and heat resistance may be present in an amount of about 15wt% or less, for example, about 0.1wt% to about 10wt%, based on 100wt% of the monomer mixture. Within this range, the monomer for imparting processability and heat resistance can impart processability and heat resistance to the thermoplastic resin composition without deteriorating other characteristics.
In some embodiments, the rubber modified vinyl graft copolymer may include, for example, methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer (g-MABS), and the like. Here, the g-MABS may include Polybutadiene (PBD) constituting a rubber polymer (core) and a methyl methacrylate-acrylonitrile-styrene copolymer shell grafted to the core, wherein the shell may include: an inner shell comprising acrylonitrile-styrene resin and an outer shell comprising poly (methyl methacrylate), but is not limited thereto.
In some embodiments, the rubber modified vinyl graft copolymer may be present in an amount of about 5wt% to about 50wt%, for example, about 10wt% to about 45wt%, based on 100wt% of the rubber modified aromatic vinyl copolymer resin. Within this range, the thermoplastic resin composition may exhibit good characteristics in terms of transparency, impact resistance, flowability, balance between them, and the like.
(A2) Aromatic vinyl copolymer resin
The aromatic vinyl copolymer resin according to an embodiment of the present invention is used to improve impact resistance, transparency, and the like of a thermoplastic resin composition, and may be a polymer of a monomer mixture including an alkyl (meth) acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer. For example, the aromatic vinyl copolymer resin may be obtained by polymerization of a monomer mixture by polymerization methods known to those skilled in the art. In addition, the monomer mixture may further include a monomer for imparting processability and heat resistance, as needed.
In some embodiments, the alkyl (meth) acrylate may be graft-copolymerized with the rubber polymer or may be graft-copolymerized with the aromatic vinyl monomer, and may include, for example, C (meth) acrylic acid 1 To C 10 Alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like, particularly methyl (meth) acrylate, and the like. The alkyl (meth) acrylate may be present in an amount of about 55wt% to about 85wt%, for example, about 60wt% to about 80wt%, based on 100wt% of the monomer mixture. Within this range, the thermoplastic resin composition may have good characteristics in terms of impact resistance, transparency, flowability, and the like.
In some embodiments, aromatic vinyl monomers may include, for example, styrene, alpha-methylstyrene, beta-methylstyrene, p-tert-butylstyrene, ethylstyrene, vinylxylenes, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like. These may be used alone or as a mixture thereof. The aromatic vinyl monomer may be present in an amount of about 10wt% to about 40wt%, for example, about 15wt% to about 35wt%, based on 100wt% of the monomer mixture. Within this range, the thermoplastic resin composition may have good characteristics in terms of impact resistance, transparency, flowability, and the like.
In some embodiments, the vinyl cyanide monomer may be copolymerized with an aromatic vinyl monomer, and may include, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α -chloroacrylonitrile, fumaronitrile, and the like. These may be used alone or as a mixture thereof. The vinyl cyanide compound may be present in an amount of about 1wt% to about 30wt%, for example, about 5wt% to about 25wt%, based on 100wt% of the monomer mixture. Within this range, the thermoplastic resin composition may exhibit good characteristics in terms of impact resistance, transparency, flowability, and the like.
In some embodiments, the monomer for imparting processability and heat resistance may include, for example, (meth) acrylic acid, maleic anhydride, N-substituted maleimide, and the like, but is not limited thereto. The monomer for imparting processability and heat resistance may be present in an amount of about 15wt% or less, for example, about 0.1wt% to about 10wt%, based on 100wt% of the monomer mixture. Within this range, the monomer for imparting processability and heat resistance can impart processability and heat resistance to the thermoplastic resin composition without deteriorating other characteristics.
In some embodiments, the aromatic vinyl copolymer resin may have a weight average molecular weight of about 50,000g/mol to about 200,000g/mol, for example, about 100,000g/mol to about 180,000g/mol, as measured by GPC (gel permeation chromatography). Within this range, the thermoplastic resin composition may have good characteristics in terms of impact resistance, processability (flowability), and the like.
In some embodiments, the aromatic vinyl copolymer resin may be present in an amount of about 50wt% to about 95wt%, for example, about 55wt% to about 90wt%, based on 100wt% of the base resin. Within this range, the thermoplastic resin composition may exhibit good characteristics in terms of transparency, impact resistance, flowability, balance between them, and the like.
In some embodiments, the rubber-modified aromatic vinyl copolymer resin (base resin) may include, for example, methyl methacrylate-acrylonitrile-butadiene-styrene copolymer resin (MABS resin), which is a mixture of methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer (g-MABS) and methyl methacrylate-styrene-acrylonitrile copolymer resin (MSAN), but is not limited thereto. Here, the MABS resin may have a structure in which g-MABS is dispersed in MSAN.
(B) Polyether-ester-amide block copolymers
The polyether-ester-amide block copolymer according to an embodiment of the present invention is used together with a silver compound and zinc oxide in a rubber-modified aromatic vinyl copolymer resin to maintain transparency of a thermoplastic resin composition while improving antibacterial properties, antistatic properties, etc. of the thermoplastic resin composition, and may include a polyether-ester-amide block copolymer used as an antistatic agent, for example, a block copolymer including a reaction mixture of: aminocarboxylic acids, lactams or diamine-dicarboxylic acid salts having 6 or more carbon atoms; polyalkylene glycols; and dicarboxylic acids having 4 to 20 carbon atoms.
In some embodiments, the aminocarboxylic acid, lactam or diamine-dicarboxylic acid salt having 6 or more carbon atoms may include aminocarboxylic acids such as ω -aminocaproic acid, ω -aminoheptanoic acid, ω -aminocaprylic acid, ω -aminononanoic acid, ω -aminocaprylic acid, 1-aminoundecanoic acid, and 1, 2-aminododecanoic acid, and the like; lactams such as caprolactam, enantholactam, octalactam, dodecalactam and the like; and salts of diamines and dicarboxylic acids, such as salts of hexamethylenediamine-adipic acid and salts of hexamethylenediamine-isophthalic acid, and the like. For example, salts of 1, 2-aminododecanoic acid, caprolactam, and hexamethylenediamine-adipic acid, and the like can be used.
In some embodiments, the polyalkylene glycol may include polyethylene glycol, poly (1, 2-diol and 1, 3-propanediol), polytetramethylene glycol, polyhexamethylene glycol, block or random copolymers of ethylene glycol and propylene glycol, and copolymers of ethylene glycol and tetrahydrofuran, and the like. For example, polyethylene glycol, and a copolymer of ethylene glycol and propylene glycol, etc. can be used.
In some embodiments, dicarboxylic acids having 4 to 20 carbon atoms may include terephthalic acid, 1, 4-cyclohexanecarboxylic acid, sebacic acid, adipic acid, and laurecarboxylic acid, and the like.
In some embodiments, the bond between an aminocarboxylic acid, a lactam, or a diamine-dicarboxylate having 6 or more carbon atoms and a polyalkylene glycol may be an ester bond; the bond between an aminocarboxylic acid, a lactam or a diamine-dicarboxylic acid salt having 6 or more carbon atoms and a dicarboxylic acid having 4 to 20 carbon atoms may be an amide bond; and the bond between the polyalkylene glycol and the dicarboxylic acid having 4 to 20 carbon atoms may be an ester bond.
In some embodiments, the polyether-ester-amide block copolymers may be prepared by methods well known in the art, for example, by the methods disclosed in JP patent publication No. S56-045419 or JP unexamined patent publication No. S55-133424.
In some embodiments, the polyether-ester-amide block copolymer may include about 10wt% to about 95wt% polyether-ester blocks. Within this range, the thermoplastic resin composition may have good antistatic properties, heat resistance, and the like.
In some embodiments, the polyether-ester-amide block copolymer may have a refractive index of about 1.49 to about 1.52, for example, about 1.50 to about 1.51, when measured on a 2.5mm thick sample using a refractometer (manufacturer: ATAGO, model: abbe refractometer DR-A1) at 25 ℃. The difference between the refractive indices of the polyether-ester-amide block copolymer and the rubber modified aromatic vinyl copolymer resin is about 0.01 or less, for example, about 0.005 or less, especially about 0.001 to about 0.002. Within this range, the thermoplastic resin composition (molded article) may exhibit appropriate transparency.
In some embodiments, the polyether-ester-amide block copolymer may be present in an amount of about 4 parts by weight to about 23 parts by weight, for example, about 5 parts by weight to about 20 parts by weight, relative to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. With respect to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, if the content of the polyether-ester-amide block copolymer is less than about 4 parts by weight, the thermoplastic resin composition may suffer from deterioration of antibacterial properties, antistatic properties, impact resistance, and the like, and if the content of the polyether-ester-amide block copolymer exceeds about 23 parts by weight, the thermoplastic resin composition (molded article) may suffer from deterioration of transparency, heat resistance, and the like.
(C) Silver (Ag) compounds
The silver compound according to one embodiment of the present invention can improve antibacterial properties, transparency, etc. of the thermoplastic resin composition along with the polyether-ester-amide block copolymer and zinc oxide even when added in a small amount. The silver compound may be selected from any silver-containing compound without limitation. For example, the silver compound may include metallic silver, silver oxide, silver halide, a carrier containing silver ions, and combinations thereof. In particular, carriers containing silver ions can be used as silver compounds. The carrier may include zeolite, silica gel, calcium phosphate, zirconium phosphate, sodium zirconium hydrogen phosphate, and the like. The support preferably has a porous structure. Since the support having a porous structure may contain therein the silver component, the support may increase the content of the silver component while improving the durability (retention) of the silver component. Specifically, the silver compound may be silver sodium zirconium hydrogen phosphate.
In some embodiments, the silver compound may have an average particle size (D50) of about 1.5 μm or less, for example, about 0.1 μm to about 1 μm, as measured by a particle size analyzer (laser diffraction particle size analyzer LS I3 320,Beckman Coulter Co, ltd.).
In some embodiments, the silver compound may be present in an amount of about 0.03 parts by weight to about 1 part by weight, for example, about 0.05 parts by weight to about 0.7 parts by weight, relative to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. With respect to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, if the content of the silver compound is less than about 0.03 parts by weight, the thermoplastic resin composition may suffer from deterioration of antibacterial property and the like, and if the content of the silver compound exceeds about 1 part by weight, the thermoplastic resin composition may suffer from deterioration of transparency, impact resistance and the like.
(D) Zinc oxide
The zinc oxide according to the present invention is used together with the polyether-ester-amide block copolymer and the silver compound to improve antibacterial properties, transparency, antistatic properties, and the like of the thermoplastic resin composition even when added in a small amount, and is composed of primary particles (single particles) and secondary particles formed by aggregation of the primary particles, wherein the primary particles may have an average particle diameter (D50) of about 1nm to about 50nm, for example, about 1nm to about 30nm, and the secondary particles may have an average particle diameter (D50) of about 0.1 μm to about 10 μm, for example, about 0.5 μm to about 5 μm, when measured using a particle size analyzer (laser diffraction particle size analyzer LS I3 320,Beckman Coulter Co, ltd.). The thermoplastic resin composition may suffer from deterioration of antibacterial property and the like if the average particle diameter of the primary zinc oxide particles is less than about 1nm, and may suffer from deterioration of transparency and the like if the average particle diameter of the primary zinc oxide particles exceeds about 50 nm. In addition, if the average particle diameter of the secondary zinc oxide particles is less than about 0.1 μm, the thermoplastic resin composition may suffer from deterioration of antibacterial properties and the like, and if the average particle diameter of the secondary zinc oxide particles exceeds about 10 μm, the thermoplastic resin composition may suffer from deterioration of transparency, mechanical properties and the like.
In some embodiments, zinc oxide may be present in an amount of about 0.05 parts by weight to about 4 parts by weight, for example, about 0.1 parts by weight to about 3 parts by weight, relative to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. With respect to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, if the content of zinc oxide is less than about 0.05 parts by weight, the thermoplastic resin composition may suffer from deterioration of antibacterial properties and the like, and if the content of zinc oxide exceeds about 4 parts by weight, the thermoplastic resin composition may suffer from deterioration of transparency, impact resistance and the like.
In some embodiments, the weight ratio of the polyether-ester-amide block copolymer to the sum of the silver compound and zinc oxide (polyether-ester-amide block copolymer: silver compound + zinc oxide) may be in the range of about 1:0.01 to about 1:0.5, for example, about 1:0.01 to about 1:0.25. Within this range, the thermoplastic resin composition may exhibit better characteristics in terms of antibacterial property, transparency, antistatic property, and the like.
In some embodiments, the weight ratio of silver compound to zinc oxide (silver compound: zinc oxide) may be in the range of about 1:0.5 to about 1:60, for example, about 1:0.6 to about 1:30. Within this range, the thermoplastic resin composition may exhibit better characteristics in terms of antibacterial property, transparency, and the like.
The thermoplastic resin composition according to an embodiment of the present invention may further include additives used in typical thermoplastic resin compositions. Examples of the additive may include, but are not limited to, flame retardants, fillers, antioxidants, anti-drip agents, lubricants, mold release agents, nucleating agents, stabilizers, pigments, dyes, mixtures thereof, and the like. The additive may be present in an amount of about 0.001 parts by weight to about 40 parts by weight, for example, about 0.1 parts by weight to about 10 parts by weight, relative to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin.
The thermoplastic resin composition according to an embodiment of the present invention may be prepared in the form of pellets by: the foregoing components are mixed and then melt extruded in a typical twin screw extruder at a temperature of from about 200 ℃ to about 280 ℃, for example, from about 220 ℃ to about 250 ℃.
In some embodiments, the thermoplastic resin composition has an antibacterial effect on various bacteria such as staphylococcus aureus, escherichia coli, bacillus subtilis, pseudomonas aeruginosa, salmonella, pneumonia, and MRSA (methicillin resistant staphylococcus aureus), and after inoculating 5cm×5cm samples with staphylococcus aureus and escherichia coli, respectively, according to JIS Z2801, and culturing for 24 hours at 35 ℃ and 90% rh, the thermoplastic resin composition has an antibacterial activity on each of staphylococcus aureus and escherichia coli when calculated according to formula 1, for example, about 2 to about 7, for example, about 3 to about 6.5.
[ formula 1]
Antibacterial activity = log (M1/M2)
Wherein M1 represents the number of bacteria when measured on a blank sample after culturing for 24 hours, and M2 represents the number of bacteria when measured on each of samples of the thermoplastic resin composition after culturing for 24 hours.
Here, the "blank sample" refers to a control sample for comparison with a test sample (sample of the thermoplastic resin composition). Specifically, a blank sample was prepared by: the empty petri dishes were inoculated with bacteria suitable for checking whether the bacteria grew normally, followed by incubation for 24 hours under the same conditions as the test samples. The antibacterial properties of the test samples were evaluated based on a comparison of the number of cultured bacteria between the blank samples and the test samples. Here, the "number of cultured bacteria" may be determined by the following procedure: wherein each sample is inoculated with bacteria, followed by incubation for 24 hours, and then the inoculated solution of bacteria is recovered and diluted, followed by bacterial growth into colonies on a petri dish. When the colony is too large to count, the number of cultured bacteria can be determined by: colonies are divided into a plurality of sectors, the colony size of one sector is measured, and the measured value is converted into the total colony.
In some embodiments, the thermoplastic resin composition may have a haze of about 1% to about 13%, for example, about 1% to 10%, and a light transmittance of about 82% to about 95%, for example, about 85% to 92%, when measured on a 1mm thick sample according to ASTM D1003.
In some embodiments, the thermoplastic resin composition may have a thickness of about 1X 10 when measured on a 3.2mm thick injection molded sample according to ASTM D257 8 Up to about 5X 10 12 Omega/sq, e.g. about 1X 10 8 Up to about 1X 10 11 Surface resistance of Ω/sq.
In some embodiments, the thermoplastic resin composition may have a notched Izod impact strength of about 5kgf cm/cm to about 20kgf cm/cm, e.g., about 6kgf cm/cm to about 150kgf cm/cm, when measured on a 1/8' thick sample according to ASTM D256.
The molded article according to the present invention is formed from the above thermoplastic resin composition. The antimicrobial thermoplastic resin composition may be prepared in the form of pellets. The pellets produced can be made into various molded articles (molded articles) by various molding methods such as injection molding, extrusion, vacuum molding, casting, and the like. These molding methods are well known to those skilled in the art.
In some embodiments, the molded article has good characteristics in terms of antibacterial properties, transparency, antistatic properties, impact resistance, balance between them, and the like, and thus is used as an antibacterial film or the like that can frequently contact the body.
In some embodiments, the antimicrobial film may have a thickness of about 0.1mm to about 3mm, for example, about 0.2mm to about 2 mm. Within this range, the antibacterial film may exhibit good characteristics in terms of transparency, antibacterial characteristics, antistatic characteristics, mechanical characteristics, and the like.
MODE OF THE INVENTION
Next, the present invention will be described in more detail with reference to some embodiments. It is to be understood that these examples are provided for illustration only and are in no way to be construed as limiting the invention.
Examples
Details of the components used in the examples and comparative examples are as follows:
(A) Rubber modified aromatic vinyl copolymer resin
A rubber-modified aromatic vinyl copolymer resin (A) is used, which comprises 30% by weight of (A1) a rubber-modified vinyl graft copolymer and 70% by weight of (A2) an aromatic vinyl copolymer resin.
(A1) Rubber modified vinyl graft copolymer
A core-shell graft copolymer (g-MABS) was used, which was obtained by graft copolymerizing 45% by weight of styrene, acrylonitrile and methyl methacrylate (styrene/acrylonitrile/methyl methacrylate: 20% by weight/10% by weight/70% by weight) to 55% by weight of butadiene rubber particles having an average (Zaverage) particle diameter of 0.28. Mu.m.
(A2) Aromatic vinyl copolymer resin
A resin (weight average molecular weight: 160,000 g/mol) obtained by polymerizing 70% by weight of methyl methacrylate, 20% by weight of styrene and 10% by weight of acrylonitrile was used.
(B) Block copolymers
(B1) Polyamide-6-polyethylene oxide block copolymer (PA 6-b-PEO, manufacturer: sanyo chemical Co., ltd., product name: PELECTRON AS, refractive index: 1.51) was used.
(B2) Polypropylene-polyethylene oxide block copolymer (PP-b-PEO, manufacturer: sanyo Chemical Co., ltd., product name: PELECTRON PVL, refractive index: 1.50) was used.
(C) Silver (Ag) compounds
Silver sodium zirconium hydrogen phosphate (manufacturer: toa Gosei co., ltd., product name: novaron AGZ 030) was used.
(D) Zinc oxide
(D1) Zinc oxide (manufacturer: SH Energy & Chemical, product name: ANYZON) comprising primary particles having an average particle diameter (D50) of 10nm and secondary particles having an average particle diameter (D50) of 1.7 μm was used.
(D2) Zinc oxide (manufacturer: PJ ChemTech, product name: KS-1) comprising uniform particles and having an average particle diameter (D50) of 1 μm was used.
Examples 1 to 7 and comparative examples 1 to 8
The aforementioned components were mixed in the amounts listed in tables 1 and 2, followed by extrusion at 230℃to prepare thermoplastic resin compositions in the form of pellets. Here, extrusion was carried out using a twin-screw extruder (L/D: 36, diameter: 45 mm). The prepared pellets were dried at 80℃for 2 hours or more, and then injection molded using a6 oz injection molding machine (molding temperature: 230 ℃ C., mold temperature: 60 ℃ C.) to prepare samples. The prepared samples were evaluated for the following properties. The results are shown in tables 1 and 2.
Characteristic evaluation
(1) Antibacterial activity: a5 cm. Times.5 cm sample was inoculated with Staphylococcus aureus and Escherichia coli, respectively, according to JIS Z2801, and cultured at 35℃and 90% RH for 24 hours, followed by calculation of antibacterial activity according to formula 1.
[ formula 1]
Antibacterial activity = log (M1/M2),
where M1 represents the number of bacteria when measured on a blank sample after 24 hours of incubation, and M2 represents the number of bacteria when measured on each sample after 24 hours of incubation.
(2) Haze and transmittance (unit:%): haze and light transmittance were measured on 1mm thick samples according to ASTM D1003 using a haze meter NDH 2000 (Nippon Denshoku co., ltd.).
(3) Surface resistance (unit: Ω/sq): the surface resistance was measured on an injection molded sample having dimensions of 10mm×10mm×3.2mm using a surface resistance meter (manufacturer: mitsubishi Chemical co., ltd., model: hiresta-UP (MCP-HT 450)) according to ASTM D257.
(4) Notched Izod impact Strength (unit: kgf. Cm/cm): notched Izod impact strength was measured on 1/8' thick samples according to ASTM D256.
TABLE 1
TABLE 2
From the results, it can be seen that the thermoplastic resin composition according to the present invention has good characteristics in terms of antibacterial property, transparency, antistatic property, impact resistance, and the like.
In contrast, it can be seen that the resin composition of comparative example 1 prepared using an insufficient amount of polyether-ester-amide block copolymer suffers from deterioration of antibacterial properties, antistatic properties, impact resistance, and the like; and the resin composition of comparative example 2 prepared using an excessive amount of polyether-ester-amide block copolymer suffers from deterioration in transparency and the like. In addition, it can be seen that the resin composition of comparative example 3 prepared using the polypropylene-polyethylene oxide block copolymer (B2) instead of the polyether-ester-amide block copolymer according to the present invention suffers from deterioration in impact resistance and the like, and exhibits poor transparency and the like as compared with the resin composition of examples. It can be seen that the resin composition of comparative example 4 prepared using an insufficient amount of the silver compound suffers from deterioration of antibacterial property and the like; the resin composition of comparative example 5 prepared using an excessive amount of silver compound suffers from deterioration in transparency and the like; the resin composition of comparative example 6 prepared using an insufficient amount of zinc oxide suffers from deterioration of antibacterial property and the like; and the resin composition of comparative example 7 prepared using an excessive amount of zinc oxide suffered from deterioration in transparency, impact resistance, and the like. Further, it can be seen that the resin composition of comparative example 8 prepared using zinc oxide (D2) instead of zinc oxide according to the present invention suffers from deterioration in antibacterial property, transparency, and the like.
The invention has been described above with reference to example embodiments. It will be understood by those skilled in the art that various modifications, changes, variations and equivalent embodiments may be made without departing from the spirit and scope of the invention.

Claims (14)

1. A thermoplastic resin composition comprising:
about 100 parts by weight of a rubber modified aromatic vinyl copolymer resin;
about 4 parts by weight to about 23 parts by weight of a polyether-ester-amide block copolymer;
about 0.03 parts by weight to about 1 part by weight of a silver (Ag) compound; and
about 0.05 parts by weight to about 4 parts by weight of zinc oxide,
wherein the zinc oxide comprises primary particles having an average particle diameter (D50) of about 1nm to about 50nm and secondary particles having an average particle diameter (D50) of about 0.1 μm to about 10 μm.
2. The thermoplastic resin composition of claim 1, wherein the weight ratio of said polyether-ester-amide block copolymer to the sum of said silver compound and said zinc oxide (polyether-ester-amide block copolymer: silver compound + zinc oxide) is in the range of about 1:0.01 to about 1:0.5.
3. The thermoplastic resin composition of claim 1 or 2, wherein the weight ratio of the silver compound to the zinc oxide (silver compound: zinc oxide) is in the range of about 1:0.5 to about 1:60.
4. The thermoplastic resin composition of any of claims 1-3, wherein the rubber-modified aromatic vinyl copolymer resin comprises about 5 wt.% to about 50 wt.% of the rubber-modified vinyl graft copolymer and about 50 wt.% to about 95 wt.% of the aromatic vinyl copolymer resin.
5. The thermoplastic resin composition of claim 4, wherein said rubber-modified vinyl graft copolymer is obtained by graft polymerizing an alkyl (meth) acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer to a rubber polymer.
6. The thermoplastic resin composition according to claim 4, wherein the aromatic vinyl copolymer resin is obtained by polymerization of an alkyl (meth) acrylate, an aromatic vinyl monomer and a vinyl cyanide monomer.
7. The thermoplastic resin composition of any of claims 1-6, wherein the polyether-ester-amide block copolymer is a block copolymer comprising a reaction mixture of: aminocarboxylic acids, lactams or diamine-dicarboxylic acid salts having 6 or more carbon atoms; polyalkylene glycols; and dicarboxylic acids having 4 to 20 carbon atoms.
8. The thermoplastic resin composition of any of claims 1-7, wherein the silver compound comprises at least one of metallic silver, silver oxide, silver halide, and a carrier containing silver ions.
9. The thermoplastic resin composition according to any one of claims 1 to 8, wherein the thermoplastic resin composition has an antibacterial activity against each of staphylococcus aureus and escherichia coli of about 2 to about 7 when calculated according to formula 1 after inoculating 5cm x 5cm samples with staphylococcus aureus and escherichia coli, respectively, according to JIS Z2801, and culturing for 24 hours under conditions of 35 ℃ and 90% rh (relative humidity):
[ formula 1]
Antibacterial activity = log (M1/M2)
Wherein M1 represents the number of bacteria when measured on a blank sample after culturing for 24 hours, and M2 represents the number of bacteria when measured on each of the samples of the thermoplastic resin composition after culturing for 24 hours.
10. The thermoplastic resin composition of any of claims 1-9, wherein the thermoplastic resin composition has a haze of about 1% to about 13% and a light transmittance of about 82% to about 95% when measured according to ASTM D1003 on a 0.1mm thick sample.
11. The thermoplastic resin composition of any of claims 1-10, wherein the thermoplastic resin composition has a weight ratio of about 1 x 10 when measured according to ASTM D257 on a 3.2mm thick injection molded sample 8 Up to about 5X 10 12 Surface resistance of Ω/sq.
12. The thermoplastic resin composition of any of claims 1-11, wherein the thermoplastic resin composition has a notched izod impact strength of about 5 kgf-cm/cm to about 20 kgf-cm/cm when measured according to ASTM D256 on a 1/8 "thick sample.
13. A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 12.
14. The molded article of claim 13, wherein the molded article is an antimicrobial film having a thickness of about 0.1mm to about 3 mm.
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