CN107580636B - Antibacterial primer coating agent for vacuum deposition and multilayer coating method using same - Google Patents
Antibacterial primer coating agent for vacuum deposition and multilayer coating method using same Download PDFInfo
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- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
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- C03C2217/70—Properties of coatings
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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Abstract
The present invention relates to an antibacterial primer coating agent for vacuum deposition and a multi-layer coating method using the same, and more particularly, to an antibacterial primer coating agent for vacuum deposition capable of imparting antibacterial power to a primer coating layer coated between a base material and a functional coating layer in a nano thickness to improve adhesion, and a multi-layer coating method capable of forming a water/oil repellent functional coating layer on the antibacterial primer coating layer formed using the same to exhibit antibacterial power without hindering the water/oil repellency and durability of the water/oil repellent coating.
Description
Technical Field
The present invention relates to an antibacterial primer coating agent for vacuum deposition and a multi-layer coating method using the same, and more particularly, to an antibacterial primer coating agent for vacuum deposition capable of imparting antibacterial power to a primer coating layer coated between a base material and a functional coating layer in a nano thickness to improve adhesion, and a multi-layer coating method capable of forming a water/oil repellent functional coating layer on the antibacterial primer coating layer formed using the same to exhibit antibacterial power without hindering the water/oil repellency and durability of the water/oil repellent coating.
Background
In the related art, as the usage rate of Smart devices of touch type displays (Smart phones), tablet pcs (tablets), Smart watches (Smart watches), etc.) is sharply increased, the severity of sanitary problems is on the rise, and thus the concern about antibacterial is increasing. However, the currently used anti-fingerprint coating layer does not have an antibacterial function, so that it is urgently required to develop a technology capable of imparting an antibacterial function to a portion frequently touched by a user, i.e., a touch screen window.
At present, a smart phone window (touch screen) on the market is provided with a fingerprint-proof coating (or an anti-pollution coating) of a film (tens of nanometers). The anti-fingerprint coating layer imparts water/oil repellency to a surface using a fluorine-based compound, which can reduce surface energy, thereby reducing a contact area of fingerprints and external contaminants with the coated surface, thereby having characteristics of minimizing adhesion of contaminants and easily wiping off even if adhered.
In order to form such a thin film, coating (surface modification) by vacuum deposition is mostly performed by applying a high-temperature heat source to an object (coating agent) in a very short time using a coating method called "vacuum deposition", and thus it is possible to realize a nano-sized thin film coating that is very excellent in quality of a coating film, has a small amount of medicine loss, and does not hinder optical characteristics.
As is well known, many antibacterial coatings using inorganic substances (Ti series) are on the market, but most of them use a wet method, and there is no manufacturing company that manufactures antibacterial medicines among companies that manufacture functional coating agents for vacuum deposition at home and abroad. In the case of coating with inorganic substances deposited in vacuum, since the ignition temperature is high, the applicable base material is limited (coating material is temperature sensitive — tempered glass, plastic, etc.), and the surface of the material itself is discolored due to coating with inorganic substances or metals, thereby causing a problem of hindering optical characteristics.
Korean application No. 10-2002-0066286 (applicant: WIDE & TECH, vacuum deposition system using nanotechnology for antibacterial action) relates to a technology for developing and using a vacuum deposition system to which nanotechnology for antibacterial action is applied, in which antibacterial action is to be achieved by using trees and plant materials (kalopanax septemfasciata, elm, plum, etc.), but there are problems that antibacterial function is insufficient and endurance is difficult to maintain, and there is a problem that functionality such as water/oil repellency and slipperiness is not achieved.
U.S. publication No. US2011-0025933 (applicant: vivio WITH antibacterial COATING) discloses a technique for inhibiting the growth of microorganisms by COATING and covering the external surface of a TELEVISION WITH a COATING agent containing an antibacterial agent, but this technique also has a problem that functionality such as water/oil repellency and slipperiness is not achieved.
Japanese patent application 2007 & 322624 (applicant: ZNO LAB, Antibacterial material and method for producing the same) discloses an Antibacterial material and method for producing the same, which is characterized in that a zinc oxide thin film is formed on a glass substrate, plastic, or the like that can be used on the surface of a touch panel or mobile phone by a method such as vacuum deposition, sputtering, or the like, but this technique also has a problem that functionality such as water/oil repellency and slipperiness is not achieved, and a problem that optical characteristics are reduced by a metal thin film.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide an antibacterial primer coating agent for vacuum deposition and a multi-layer coating method, thereby having soft touch feeling when used in intelligent electronic equipment and household appliances, and being capable of easily removing contamination such as fingerprints, and being used with ease without worrying about contamination by bacteria, wherein the antibacterial primer coating agent for vacuum deposition can impart antibacterial power to a primer coating layer coated between a base material and a functional coating layer in a nano thickness to improve adhesion, and a vacuum deposition method can be used as a coating method of a touch-type display in which a water/oil repellent functional coating layer is formed on the antibacterial primer coating layer formed using the antibacterial primer coating agent for vacuum deposition, thereby being capable of exhibiting antibacterial power without hindering the water and oil repellency and durability of the water/oil repellent coating.
Technical scheme
The first aspect of the present invention provides a dry antibacterial primer coating agent for vacuum deposition, which comprises a silicon (silicone) -based polymer, a polycondensation reaction product of a functional organic or inorganic silane compound, and an antibacterial substance.
According to one specific example of the first aspect of the present invention, the silicon-based polymer and the functional organic or inorganic silane compound are subjected to polycondensation in the presence of the antibacterial substance.
According to another embodiment of the first aspect of the present invention, the antibacterial substance is put and dispersed in the polycondensation reaction product of the silicon-based polymer and the functional organic or inorganic silane compound to be mixed with each other.
According to a second aspect of the present invention, there is provided a method for preparing a dry antibacterial primer coating agent for vacuum deposition, comprising the steps of: a) preparing a mixture comprising a silicon-based polymer, a functional organic or inorganic silane compound, and an antibacterial substance; and b) subjecting the mixture to a polycondensation reaction.
According to a third aspect of the present invention, there is provided a method for preparing a dry antibacterial primer coating agent for vacuum deposition, comprising the steps of: i) preparing a mixture comprising a silicon-based polymer and a functional organic or inorganic silane compound; ii) subjecting the mixture to a polycondensation reaction; and iii) adding and dispersing an antibacterial substance into the product of the polycondensation reaction, and mixing.
According to a fourth aspect of the present invention, there is provided a method of multilayer coating of a substrate comprising the steps of: 1) providing a substrate to be coated; 2) vacuum depositing the dry antibacterial primer coating agent of the present invention on the surface of the base material to form an antibacterial primer coating layer; and 3) vacuum-depositing a dry water/oil repellent coating agent for vacuum deposition comprising a polycondensation reaction product of a fluorine-based polymer and a functional organic or inorganic silane compound on the antibacterial primer coating layer, thereby forming a water/oil repellent functional coating layer.
According to a fifth aspect of the present invention, there is provided a coated article characterized by having a multi-layer coating layer on a surface, the multi-layer coating layer comprising a vacuum-deposited coating layer of the dry antibacterial primer coating agent of the present invention, and a water/oil repellent functional coating layer vacuum-deposited thereon.
Effects of the invention
The vacuum deposition multilayer coating formed in the present invention has a surface water contact angle of 115 ° or more, exhibits excellent water and oil repellency, is excellent in anti-fingerprint properties (AF), durability and optical characteristics (transmittance), and exhibits excellent antibacterial function, and is also applicable to various materials such as glass, plastic and metal, and particularly can greatly improve the substrate adhesion function of an alkoxysilane terminal group of an AF coating layer that is difficult to adhere to the surface of plastic, and thus is particularly applicable to surfaces of smart devices having a touch-sensitive display such as a mobile phone and a tablet computer, home appliances, and other electronic products or parts thereof.
Drawings
FIG. 1 schematically shows a cross-section of a substrate having a vacuum deposited multilayer coating formed in the present invention on a surface.
Fig. 2 is a photograph showing the results of the antibacterial test of (a) Tempered Glass (TG), (b) Polycarbonate (PC), and (c) polymethyl methacrylate (PMMA), respectively, having a vacuum deposition multi-layer coating formed on the surface thereof in the present invention.
Detailed Description
The present invention will be described in more detail below.
A first aspect of the present invention provides a dry antibacterial primer coating agent for vacuum deposition, comprising a silicon-based polymer, a polycondensation reaction product of a functional organic or inorganic silane compound, and an antibacterial substance.
According to one specific example of the first aspect of the present invention, the silicon-based polymer and the functional organic or inorganic silane compound are subjected to polycondensation in the presence of the antibacterial substance.
According to another embodiment of the first aspect of the present invention, the antibacterial substance is put and dispersed in the polycondensation reaction product of the silicon-based polymer and the functional organic or inorganic silane compound to be mixed with each other.
Specific examples of the silicon-based polymer usable in the present invention include modified silicon polymers having one or more functional groups selected from amino groups, epoxy groups, carboxyl groups, carbinol groups, methacryloyl groups, mercapto groups, and phenyl groups, or combinations thereof, and preferred examples include polymers of aminoalkylsilanes.
The functional organic or inorganic silane compound usable in the present invention may be an organic or inorganic silane compound having one or more functional groups (for example, amino group, vinyl group, epoxy group, alkoxy group, halogen group, mercapto group, thioether group, etc.) which undergo a polycondensation reaction with the silicon-based polymer. Specifically, the functional organic or inorganic silane compound may be selected from aminopropyltriethoxysilane, aminopropyltrimethoxysilane, amino-methoxysilane, phenylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyldimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxy) silane, dialkoxysilane, trialkoxysilane or tetraalkoxysilane, vinylmethoxysilane, vinyltrimethoxysilane, a mixture thereof, and a method for producing the same, Vinylepoxysilane, vinyltriphenoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, trimethylchlorosilane, ethyltrichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, mercaptopropyltriethoxysilane, trifluoropropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, bis (3-triethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) disulfide, (methacryloyloxy) propyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, di (tert-butyl) ethyltrimethoxysilane, dimethylglycidoxypropyltrimethoxysilane, dimethylglycid, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane and combinations thereof, preferably aminopropyltriethoxysilane or combinations comprising the same.
The antibacterial substance usable in the present invention may be selected from natural materials or extracts thereof, antibacterial high molecular compounds, metal-containing antibacterial compounds, and combinations thereof.
Examples of the natural material or the extract thereof include, for example, skin or extract thereof selected from crab, shrimp (e.g., chitosan), green tea or extract thereof (e.g., catechin), moutan bark or extract thereof (e.g., Paeonol (Paeonol), Paeoniflorin (Paeoniflorin), paeonoloside (Paeonolide), sitosterol (sitosterol), Gallic acid (Gallic acid), Methyl gallate (Methyl gallate), Tannic acid (Tannic acid), Quercetin (Quercetin), etc.), grapefruit or extract thereof (e.g., naringin), citral (tracil), licorice or extract thereof (e.g., flavonoid (flavanoids)), japanese cypress or extract thereof (e.g., phytoncide (phytoncide)), bamboo or extract thereof (e.g., polyphenol), sprouted bean or extract thereof (e.g., soybean antitoxin (soybean antitoxin)), or extract thereof (tyrosinase), tyrosinase (e.g., tyrosinase), etc.) Wasabi (wasabi) or an extract thereof (e.g., Isothiocyanate), mustard (mustard) or an extract thereof, hinokitiol (hinokitiol), and combinations thereof. The extract can be prepared by a known extraction method.
Examples of the antibacterial polymer compound include at least one polymer compound selected from aromatic or heterocyclic polymers, acrylic or methacrylic polymers, cationic conjugated polymer electrolytes, polysiloxane polymers, natural polymer mimetic polymers, and phenol or benzoic acid derivative polymers, and include compounds having at least one functional group selected from ammonium salt groups, phosphonium salt groups, sulfonium salt groups, or other onium salt groups, benzamide groups, and biguanide groups attached to a linear or branched polymer chain thereof.
Examples of the metal-containing antibacterial compound include organic compounds or complexes containing metal ions such as silver, copper, and zinc, and specifically include metal-chitin/chitosan, metal-carbonate, metal-sulfate, metal-nitrate, metal-acetate, metal-zeolite, and metal-phosphate compounds or complexes. Examples of the organic substance having an excellent chelate-forming ability with respect to metal ions include chitin/chitosan. Such metal-containing antibacterial compounds can be prepared from a variety of organic compounds.
According to a preferred embodiment of the present invention, an antibacterial coating agent prepared by using the natural material or the extract thereof, or the antibacterial polymer compound, which is harmless to the human body and has stability and durability, as an antibacterial substance, is coated on the surface of glass, thereby obtaining an excellent antibacterial effect with an initial antibacterial power of 99.9%.
According to a more preferred embodiment of the present invention, chitosan (chitosans), paeonol (1- (2-hydroxy-4-methoxyphenyl) ethanone)) or a combination thereof may be used as the antibacterial substance.
In the antibacterial primer coating agent of the present invention, the content of the polycondensation reaction product of the silicon-based polymer and the functional organic or inorganic silane compound is preferably 80 to 99% by weight, more preferably 85 to 95% by weight, based on 100% by weight of the total dry weight of the coating agent.
In the antibacterial primer coating agent of the present invention, the content of the antibacterial substance is preferably 1 to 20% by weight, more preferably 5 to 15% by weight, based on 100% by weight of the total dry weight of the coating agent.
According to a second aspect of the present invention, there is provided a method for preparing a dry antibacterial primer coating agent for vacuum deposition, comprising the steps of: a) preparing a mixture comprising a silicon-based polymer, a functional organic or inorganic silane compound, and an antibacterial substance; and b) subjecting the mixture to a polycondensation reaction.
According to a third aspect of the present invention, there is provided a method for preparing a dry antibacterial primer coating agent for vacuum deposition, comprising the steps of: i) preparing a mixture comprising a silicon-based polymer and a functional organic or inorganic silane compound; ii) subjecting the mixture to a polycondensation reaction; and iii) adding and dispersing an antibacterial substance into the polycondensation reaction product, and mixing.
The method and apparatus used in the preparation of the mixture are not particularly limited, and a conventional reaction vessel or mixing apparatus may be used. In addition, the conditions of the polycondensation reaction in the polycondensation reaction step are not particularly limited, and for example, the polycondensation reaction may be performed by a reflux reaction at a temperature of 100 to 200 ℃ under an inert gas (e.g., argon, nitrogen). In addition, in order to make the condensation radical reaction more easily proceed, ultrasonic waves and/or ultraviolet rays (UV) may be irradiated to the reaction mixture during the reaction.
The product of the polycondensation reaction may optionally be subjected to a stabilization step. The stabilization conditions are not particularly limited, and for example, the polycondensation reaction product may be left to stand at ordinary temperature for 24 hours to be stabilized.
According to a fourth aspect of the present invention, there is provided a method of multilayer coating of a substrate comprising the steps of: 1) providing a substrate to be coated; 2) vacuum depositing the dry antibacterial primer coating agent of the present invention on the surface of the base material to form an antibacterial primer coating layer; and 3) vacuum-depositing a dry water/oil repellent coating agent for vacuum deposition comprising a polycondensation reaction product of a fluorine-based polymer and a functional organic or inorganic silane compound on the antibacterial primer coating layer, thereby forming a water/oil repellent functional coating layer.
In the antibacterial primer coating layer, an antibacterial substance is arranged at the base of the coating layer, thereby exerting antibacterial power during the maintenance of the life of the coating layer. Further, the water/oil repellent functional coating layer can exert stain resistance, water/oil repellency, surface lubricity, fingerprint resistance and the like.
The substrate to be coated is not particularly limited as long as it can be coated by a vacuum deposition method, and substrates of various materials such as Glass (e.g., Tempered Glass (TG), etc.), plastic (e.g., acrylic resin, Polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene (ABS) resin, etc.), and metal (e.g., stainless steel (SUS), etc.) can be coated by the method of the present invention.
The water/oil repellent coating agent for forming the water/oil repellent functional coating layer comprises a polycondensation reaction product of a fluorine-based polymer and a functional organic or inorganic silane compound.
The fluorine-based polymer that can be used in the water/oil repellent coating agent may be a perfluoropolymer. Specifically, the fluorine-based polymer may be selected from perfluoropolyether (perfluoropolyether), Vinylidene fluoride (Vinylidene fluoride) polymer, tetrafluoroethylene (tetrafluoroethylene) polymer, hexafluoropropylene (hexafluoropropylene) polymer, chlorotrifluoroethylene (chlorotrifluoroethylene) polymer, and a combination thereof, and preferably may be perfluoropolyether.
The functional organic or inorganic silane compound usable in the water/oil repellent coating agent may be the compound usable in the antibacterial primer coating agent described above, without limitation.
The method of the vacuum deposition is not particularly limited, and may be performed using a conventional vacuum deposition method and apparatus. According to an embodiment of the present invention, PVD (Physical vapor deposition) can be used in combination
Vacuum deposition coating is performed with equipment (Electron beam evaporation), Thermal evaporation, Thermal sputtering, etc.) for vacuum deposition. The advantage of vacuum deposition is that it can be easily carried outWhen a plurality of substances are used for coating, the loss amount of the coating medicine is almost eliminated, and a clean and uniform film can be formed. Further, the entire device has a relatively simple structure, and the complexity in thermal and electrical properties is small when a thin film is formed, so that it is suitable for the study of the physical properties of a film when a thin film is formed.
According to a fifth aspect of the present invention, there is provided a coated article characterized by having a multi-layer coating layer on a surface, the multi-layer coating layer comprising a vacuum-deposited coating layer of the dry antibacterial primer coating agent of the present invention, and a water/oil repellent functional coating layer vacuum-deposited thereon.
The article can be a smart device with a touch display such as a mobile phone and a tablet computer made of various materials such as glass, plastic and metal, a household appliance, a vending machine, a public interactive information device, an external electronic product capable of being manually touched, or a component thereof, and preferably can be a smart device with a touch display or a component thereof.
The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples.
[ examples ]
Example 1
20g of (3-glycidoxypropyl) trimethoxysilane and 30g of a silicon oligomer having an epoxy group were charged into a reaction vessel, stirred at 150 ℃ for 1 hour under an inert argon atmosphere, and then 10g of paeonol (paeonol, extracted from moutan cortex Radicis) was added thereto as an antibacterial substance. 50g of aminopropyltriethoxysilane (aminopropyltriethoxysilane) as a functional organic or inorganic silane compound was charged therein and subjected to a polycondensation reaction under an inert argon atmosphere at a temperature of about 150 ℃, and then the reaction product was stabilized at normal temperature for 24 hours, thereby preparing a dry antibacterial primer coating agent.
In addition, 50g of aminopropyltriethoxysilane as a functional organic or inorganic silane compound was charged into 50g of perfluoropolyether (perfluoropolyether) as a fluorine-based polymer, and a polycondensation reaction was performed under an inert argon atmosphere at a temperature of about 150 ℃, and then the reaction product was stabilized at normal temperature for 24 hours, thereby preparing a dry water/oil repellent coating agent (AF coating agent).
Using the prepared dry antibacterial primer coating agent and dry waterproof/oilproof coating agent, and
the Tempered Glass (TG) was multi-coated by E/B (Electron-beam) evaporation in a vacuum deposition apparatus. For smooth coating, the tempered glass was wet-cleaned with 5 wt% alkaline detergent (detergent for tempered glass) in a 10-tank (bath) scrubber before coating. The vacuum deposition conditions were initial etching: 180 seconds, temperature: 80 ℃.
For the coated samples, the following physical property evaluations were performed.
(1) Contact angle measuring method
After coating, the contact angle of the coated side was measured using a contact angle measuring device. When the contact angle was measured, the size of one water drop was set to 3 μ l, and in order to confirm the uniformity of coating, the contact angle was averaged after measuring five points in each sample coated.
(2) High temperature high humidity test
After leaving at 60 ℃ and 90% RH for 72 hours, the contact angle was measured. The method comprises the following steps: the contact angle after the test was within 15 ° of the initial contact angle of the coated sample, and the coated sample was judged to be PASS (PASS).
(3) Ultraviolet testing
The contact angle was measured after being left for 72 hours in a UV-B type ultraviolet apparatus. The method comprises the following steps: the contact angle after the test was within 15 ° of the initial contact angle of the coated sample, and the coated sample was judged to be PASS (PASS).
(4) Salt spray test
A 5 wt% concentration aqueous solution of sodium chloride (NaCl) was sprayed on the surface of the coated sample and left for 72 hours, and then the contact angle was measured. The method comprises the following steps: the contact angle after the test was within 15 ° of the initial contact angle of the coated sample, and the coated sample was judged to be PASS (PASS).
(5) Abrasion resistance test
Abrasion resistance tests were performed after coating in order to confirm durability. Abrasion tests were performed 1500 times using abrasion resistant rubber. The method comprises the following steps: as a result, the degree of change in contact angle after the test was within 15 ° from the initial contact angle of the coated sample, and the coated sample was judged to be PASS (PASS).
(6) Measurement of total light transmittance
The measurement was performed using a UV-Spectrophotometer (Spectrophotometer) apparatus.
(7) Measurement of Haze (Haze)
The measurement was performed using a spectrocolorimeter.
(8) Pencil hardness (pencil hardness) test
H to 9H pencils were prepared, and the test was performed by setting the load to 1kg and making 2 strokes on each coated surface.
(9) Antibacterial ability confirmation test
Escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 6538P) were used and tested in accordance with JIS Z2801. 400. mu.l of diluted bacterial liquid was inoculated on the surface of the coated sample and cultured in a constant temperature and humidity environment for 24 hours, and then desorbed and the antibacterial result was confirmed.
The physical property evaluation results of the multi-layer coated tempered glass sample prepared in example 1 are shown in the following table 1.
TABLE 1 (example 1: substrate-toughened glass)
Example 2
20g of (3-glycidoxypropyl) trimethoxysilane and 30g of a silicon oligomer having an epoxy group were charged into a reaction vessel and stirred at a temperature of 150 ℃ for 1 hour under an inert argon atmosphere, and then 50g of aminopropyltriethoxysilane (aminopropyltriethoxysilane) as a functional organic or inorganic silane compound was charged therein and a polycondensation reaction was performed under an inert argon atmosphere at a temperature of about 150 ℃. 10g of paeonol (extracted from moutan cortex) as an antibacterial substance is added into the reaction product, and uniformly dispersed and mixed, thereby preparing the dry antibacterial primer coating agent.
In addition, a dry water/oil repellent coating agent (AF coating agent) was prepared in the same manner as in example 1.
Using the prepared dry antibacterial primer coating agent and dry waterproof/oilproof coating agent, multi-layer coating of tempered glass and a polymethyl methacrylate (PMMA) substrate (PMMA is coated at a temperature of 60 ℃) was performed in the same manner as in example 1. For the prepared samples, the initial contact angle and the contact angle after abrasion resistance test were measured by the above-described methods, and the initial antibacterial power was tested. The test results are shown in the following Table 2-1.
In addition, contact angles after the ultraviolet ray test and after the salt spray test were measured for the coated samples of the PMMA substrate and the antibacterial power was tested, and the results thereof are shown in the following table 2-2.
TABLE 2-1 (example 2: substrate-toughened glass and PMMA)
TABLE 2-2 (example 2: substrate-PMMA)
Example 3
A Polycarbonate (PC) substrate was multilayer coated in the same manner as in example 2. For the prepared samples, the initial contact angle was measured by the above-described method, and the initial antibacterial power was tested. The test results are shown in table 3 below.
Table 3 (example 3: substrate-PC)
| Evaluation item | Evaluation results |
| Contact angle (initial stage) | 119.3° |
| Antibacterial power (initial stage) | 99.9％ |
[ description of symbols ]
1: water/oil repellent functional coating (AF coating)
2: antibacterial primer coating
3: base material
4: antibacterial substance
Claims (9)
1. The dry antibacterial primer coating agent for vacuum deposition is characterized by comprising 85-95 wt% of a polycondensation reaction product of a silicon polymer and a functional organic or inorganic silane compound and 5-15 wt% of an antibacterial substance, wherein the antibacterial substance is paeonol, the silicon polymer and the functional organic or inorganic silane compound are subjected to polycondensation in the presence of the antibacterial substance, and the silicon polymer is a modified silicon polymer or a combination thereof with more than one functional group selected from amino, epoxy, carboxyl, carbinol, methacryl, mercapto and phenyl.
2. The dry antibacterial primer coating agent for vacuum deposition as claimed in claim 1, wherein the functional organic or inorganic silane compound is selected from aminopropyltriethoxysilane, aminopropyltrimethoxysilane, amino-methoxysilane, phenylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane, γ -aminopropyltrimethoxysilane, γ -aminopropyldimethoxysilane, γ -aminopropyltriethoxysilane, γ -aminopropyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxy) silane, dialkoxysilane, trialkoxysilane or tetraalkoxysilane, a silane compound having a structure of a structure represented by formula (I), a silane compound having a structure represented by formula (II), a silane compound having a structure represented by formula (III), a silane compound having a structure represented by formula (II), and a silane compound having a structure represented by formula (, Vinylmethoxysilane, vinyltrimethoxysilane, vinylepoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, trimethylchlorosilane, ethyltrichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, mercaptopropyltriethoxysilane, trifluoropropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, bis (3-triethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) disulfide, (methacryloyloxy) propyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, poly (ethylene-co-propylene) carbonate, poly (ethylene-, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, and combinations thereof.
3. The preparation method of the dry antibacterial primer coating agent for vacuum deposition is characterized by comprising the following steps: a) preparing a mixture containing 25 to 30 wt% of a silicon-based polymer, 60 to 65 wt% of a functional organic or inorganic silane compound, and 5 to 15 wt% of an antibacterial substance, based on 100 wt% of the total dry weight of the coating agent; and b) performing a polycondensation reaction on the mixture, wherein the antibacterial substance is paeonol, the polycondensation reaction is performed by a reflux reaction at a temperature of 100-200 ℃ in an inert gas, and the silicon polymer is a modified silicon polymer or a combination thereof, wherein the modified silicon polymer has one or more functional groups selected from amino groups, epoxy groups, carboxyl groups, carbinol groups, methacryl groups, mercapto groups and phenyl groups.
4. The method of preparing the dry antibacterial primer coating agent for vacuum deposition as claimed in claim 3, wherein the functional organic or inorganic silane compound is selected from aminopropyltriethoxysilane, aminopropyltrimethoxysilane, amino-methoxysilane, phenylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane, γ -aminopropyltrimethoxysilane, γ -aminopropyldimethoxysilane, γ -aminopropyltriethoxysilane, γ -aminopropyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxy) silane, dialkoxysilane, silane, Trialkoxysilane or tetraalkoxysilane, vinylmethoxysilane, vinyltrimethoxysilane, vinylepoxysilane, vinyltriphenoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, trimethylchlorosilane, ethyltrichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, mercaptopropyltriethoxysilane, trifluoropropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, bis (3-triethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) disulfide, (methacryloxy) propyltrimethoxysilane, vinyltrimethoxysilane, vinyl, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, and combinations thereof.
5. A method for multilayer coating of a substrate comprising the steps of: 1) providing a substrate to be coated; 2) vacuum depositing the dry antibacterial primer coating agent according to any one of claims 1 to 2 on the surface of the base material to form an antibacterial primer coating layer; and 3) vacuum-depositing a dry water/oil repellent coating agent for vacuum deposition comprising a polycondensation reaction product of a fluorine-based polymer and a functional organic or inorganic silane compound on the antibacterial primer coating layer, thereby forming a water/oil repellent functional coating layer.
6. Method for the multilayer coating of a substrate according to claim 5, characterized in that the substrate is a glass, plastic or metal material.
7. The method of multilayer coating of a substrate according to claim 5, wherein the fluorine-based polymer is selected from the group consisting of perfluoropolyethers, vinylidene fluoride polymers, tetrafluoroethylene polymers, hexafluoropropylene polymers, chlorotrifluoroethylene polymers, and combinations thereof.
8. A coated article characterized by having a multi-layer coating layer on a surface, the multi-layer coating layer comprising a vacuum-deposited coating layer of the dry antibacterial primer coating agent according to any one of claims 1 to 2, and a water/oil repellent functional coating layer vacuum-deposited thereon.
9. The coated article of claim 8, wherein the article is a smart device with a touch-sensitive display, a home appliance, a vending machine, a public interactive information device, a manually touchable external electronic product, or a component thereof.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020150053693A KR101690091B1 (en) | 2015-04-16 | 2015-04-16 | Antibacterial primer coating agent for vacuum deposition and method of multi-layered coating by using the same |
| KR10-2015-0053693 | 2015-04-16 | ||
| PCT/KR2016/003916 WO2016167587A1 (en) | 2015-04-16 | 2016-04-15 | Antibacterial primer coating agent for vacuum deposition and multi-coating method using same |
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| CN107580636A CN107580636A (en) | 2018-01-12 |
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| JP (1) | JP6595696B2 (en) |
| KR (1) | KR101690091B1 (en) |
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| CN108294857A (en) * | 2018-01-18 | 2018-07-20 | 青岛高新区尚达医药研究所 | A kind of antibacterial lubricant type sheath and preparation method thereof |
| CN108646927A (en) * | 2018-07-18 | 2018-10-12 | 杨程飞扬 | A kind of portable computer keyboard |
| KR102229354B1 (en) * | 2019-06-17 | 2021-03-17 | 계명대학교 산학협력단 | A primer manufacturing method for antifouling coating of plastic matreial based on vacuum deposition |
| CN117241670A (en) * | 2020-09-08 | 2023-12-15 | 汉高股份有限及两合公司 | Antimicrobial surfaces and related methods |
| CN112281120A (en) * | 2020-09-28 | 2021-01-29 | 东莞法克泰光电科技有限公司 | Coating process of waterproof antibacterial film layer |
| CN114381200A (en) * | 2020-10-21 | 2022-04-22 | 惠州市海兰新材料有限公司 | Composite antibacterial mildew-proof coating and use method thereof |
| CN115926409A (en) * | 2020-12-10 | 2023-04-07 | 好维股份有限公司 | Biological antibacterial master batch for degradable toothbrush and degradable antibacterial toothbrush handle |
| CN112741558B (en) * | 2020-12-30 | 2022-04-22 | 深圳市捷安纳米复合材料有限公司 | Antibacterial sweeper and manufacturing process of garbage storage bin of antibacterial sweeper |
| CN112770487B (en) * | 2020-12-31 | 2022-01-28 | 深圳市捷安纳米复合材料有限公司 | Flexible composite circuit board with virus killing function and manufacturing process thereof |
| JP2022120796A (en) * | 2021-02-05 | 2022-08-18 | 住友化学株式会社 | laminate |
| WO2022224892A1 (en) * | 2021-04-20 | 2022-10-27 | 富士フイルム株式会社 | Laminate |
| WO2022255158A1 (en) | 2021-05-31 | 2022-12-08 | 信越化学工業株式会社 | Water-repellent, oil-repellent member having anti-microbial, anti-mold, and anti-viral properties, method for producing water-repellent, oil-repellent member, and article |
| CN113698816B (en) * | 2021-08-12 | 2022-08-02 | 盘锦海兴科技股份有限公司 | Antibacterial coating and preparation method and application thereof |
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| KR20160123540A (en) | 2016-10-26 |
| WO2016167587A1 (en) | 2016-10-20 |
| DE112016001751T5 (en) | 2018-01-18 |
| JP2018521199A (en) | 2018-08-02 |
| CN107580636A (en) | 2018-01-12 |
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| KR101690091B1 (en) | 2016-12-27 |
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