KR20160119288A - Antibacterial Hydrophobic Nano-coating Agent for Vacuum Deposition and Method of Coating Using thereof - Google Patents

Abstract

The present invention relates to a functional coating agent having antimicrobial activity and water-repellency / oil-repellency at the same time, a method for preparing the same, and a coating method using the same. Specifically, the present invention relates to a method for preparing a coating agent which provides antimicrobial activity to a water-repellent / oil-repellent nano-coating in order for smart devices, etc., such as touch-type displays, to be hygienically used, and a coating method using vacuum deposition equipment.

Description

Technical Field [0001] The present invention relates to a nanoporous coating composition having an antibacterial activity and a coating method using the nanoporous coating composition.

The present invention relates to a functional coating agent that simultaneously implements antibacterial and water repellency and oil repellency, a method for producing the functional coating agent, and a coating method using the same. In order to hygienic use of a smart device such as a touch-type display, And a coating method using a vacuum deposition apparatus.

Conventionally, as the usage rate of smart devices such as Smart phone, Tablet PC, Smart watch, etc. is rapidly increased, the seriousness of hygiene problem is emerging and interest in antibacterial is increasing. However, there is an urgent need to develop a technology that can impart antimicrobial function to the touch screen window, which is a part frequently touched by users, because the anti-fingerprint coating currently applied has no antibacterial function.

The smartphone window (touch screen) that is being launched now has a thin film (tens of nanometers) anti-fingerprint coating (or anti-fouling coating). The anti-fingerprint coating uses a fluorine-based compound to impart water-repellent / water-repellent properties to the surface, which reduces the contact area between the fingerprint and external contaminants and the coated surface by lowering the surface energy, It has a polishing characteristic.

In order to form such a thin film, a coating method called " vacuum deposition " is usually used. In the case of coating (surface modification) using vacuum deposition, a coating material is coated with a high temperature heat source in a very short time, Nano-sized thin film coatings that are very excellent, have a small amount of chemical loss, and do not interfere with optical properties.

Although antimicrobial coatings using inorganic (Ti-based) agents are widely known in the market, most of them are using the wet type, so there are no producers of antimicrobial drugs among the producers of functional coatings for domestic / foreign certification. Inorganic coatings using vacuum deposition have a high ignition temperature and are limited to the coating base material (coating material is temperature-sensitive - tempered glass, plastic, etc.), and the surface of the material itself is discolored due to the inorganic or metal coating There arises a problem that the optical properties are impaired.

Korean Patent Application No. 10-2002-0066286 (Applicant: WIDE ENTECH Co., Ltd., a vacuum deposition system using nanotechnology using antibacterial action) The present invention relates to a technique for developing and utilizing a vacuum deposition system employing nanotechnology that has an antibacterial action. In this case, an attempt was made to achieve antibacterial action by using grass herb (oak, elm, plum, etc.) There is a problem that sustainability is difficult to maintain, and functionalities such as water repellency and slip properties are not realized.

US Patent Application No. US 2011-0025933 (Applicant: VIZIO INC., TELEVISION WITH ANTIMICROBIAL COATING) discloses a technique for coating the outer surface of a television with a coating agent containing an antibacterial agent to inhibit growth of microorganisms, Water repellency and slipperformability are not realized.

Japanese Patent Application No. 2007-322624 (Applicant: ZNO LAB, an antibacterial material and method for producing the same) is used for vacuum deposition on a glass substrate, plastic or the like usable on the surface of a touch panel or a mobile phone, Sputtering or the like to form a zinc oxide thin film, and a method for producing the zinc oxide thin film. However, the zinc oxide thin film also has a problem in that the functionalities such as water repellency / oil repellency and slip property are not realized, There is a problem that the optical characteristics are deteriorated.

DISCLOSURE Technical Problem In order to solve the above problems, the present invention provides a coating composition capable of simultaneously achieving water-repellent / oil-repellent and antimicrobial properties while satisfying both durability and optical characteristics while applying a vacuum evaporation method which is a touch- It has a soft touch feeling when using electronic appliances and household appliances, and can easily remove contamination of fingerprints and the like and at the same time, it can be used safely from contamination against bacteria.

In order to achieve the above object, the first aspect of the present invention provides a dry-type antimicrobial coating agent for vacuum deposition, which comprises a polycondensation reaction product of a fluorinated polymer and a functional or non-functional silane compound, and an antibacterial substance.

According to one embodiment of the first aspect of the present invention, the fluoropolymer and the functional or non-functional silane compound are polycondensed in the presence of the antimicrobial substance.

According to another embodiment of the first aspect of the present invention, the antibacterial substance is introduced into the resultant polycondensation reaction product of the fluoropolymer and the functional or non-functional silane compound, dispersed and mixed with each other.

According to a second aspect of the present invention there is provided a process for preparing a mixture comprising: a) preparing a mixture comprising a fluoropolymer, a functional organic silane compound and an antimicrobial material; And b) subjecting the mixture to a polycondensation reaction. A method for producing a dry vacuum-coated antimicrobial coating is provided.

According to a third aspect of the present invention, there is provided a process for preparing a fluorinated polymer comprising the steps of: i) preparing a mixture comprising a fluorinated polymer and a functional or non-functional silane compound; ii) subjecting the mixture to a polycondensation reaction; And iii) adding an antimicrobial substance to the resultant product of the polycondensation reaction and dispersing and mixing the resultant product.

According to a fourth aspect of the present invention, there is provided a method of manufacturing a substrate, comprising: 1) providing a substrate to be coated; And 2) vacuum depositing the dry antimicrobial coating agent of the present invention on the surface of the substrate.

According to a fifth aspect of the present invention, there is provided a coated article characterized by having on its surface a vacuum-deposited coating layer of the dry-type antimicrobial coating agent of the present invention.

The dry-type antimicrobial coating agent of the present invention exhibits excellent water repellency and oil repellency with a surface water contact angle of 115 ° or more and is excellent in anti-fingerprint (AF), durability and optical characteristics (transmittance) Function. Especially, it exhibits excellent abrasion resistance (in the eraser abrasion test, the degree of change of contact angle after testing after initial contact angle is within 15 °), exhibits excellent antibacterial effect with initial antibacterial power of 99.9%, and also applicable to various materials such as glass, plastic and metal And can be suitably used for surface coating applications such as smart devices having a touch-type display such as a mobile phone and a tablet PC, household appliances and other electronic products or parts thereof.

FIG. 1 schematically shows cross sections of a substrate coated with the antimicrobial coating agent of the present invention, wherein the left side shows an antimicrobial AF coating layer formed directly on a substrate, and the right side shows an inorganic substance or oxide Layer.
2 is a photograph showing antibacterial test results for each of (a) uncoated sample, (b) AF coated sample containing no antibacterial agent, and (c) antibacterial AF coated sample coated with the antibacterial coating agent of the present invention.

Hereinafter, the present invention will be described in more detail.

The first aspect of the present invention provides a dry vacuum-coated antimicrobial coating agent comprising a polycondensation reaction product of a fluorinated polymer and a functional or non-halogenated silane compound, and an antibacterial substance.

According to one embodiment of the first aspect of the present invention, the fluoropolymer and the functional or non-functional silane compound are polycondensed in the presence of the antimicrobial substance.

According to another embodiment of the first aspect of the present invention, the antibacterial substance is introduced into the resultant polycondensation reaction product of the fluoropolymer and the functional or non-functional silane compound, dispersed and mixed with each other.

The fluorine-based polymer usable in the present invention may be a perfluorinated polymer. Specifically, the fluoropolymer may be selected from the group consisting of perfluoropolyether, vinylidene fluoride polymer, tetrafluoroethylene polymer, hexafluoropropylene polymer, chlorotrifluoroethylene polymer, A combination thereof, and preferably a perfluoropolyether.

The functional or non-functional group silane compound usable in the present invention may contain at least one functional group (for example, an amino group, a vinyl group, an epoxy group, an alkoxy group, a halogen group, a mercaptan group, a sulfide group, etc.) for performing a polycondensation reaction with the fluorine- Or an imidazolyl group. Specifically, the functional or non-functional silane compound is selected from the group consisting of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, amino-methoxysilane, phenylaminopropyltrimethoxysilane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, gamma -aminopropyltriethoxysilane, gamma -aminopropyltriethoxysilane, gamma -aminopropyltrimethoxysilane, gamma -aminopropyltrimethoxysilane, gamma -aminopropyltrimethoxysilane, gamma -aminopropyltriethoxysilane, gamma- Vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri (methoxyethoxy) silane, di-, tri- or tetraalkoxysilane, vinylmethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, But are not limited to, vinyl epoxy silane, vinyltriethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, gamma -glycidoxypropyltriethoxysilane, Ethoxy silane, chlorotrimethane Silane, trichloroethylsilane, trichloromethylsilane, trichlorophenylsilane, trichlorovinylsilane, mercaptopropyltriethoxysilane, trifluoropropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, bis (Triethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) disulfide, (methacryloxy) propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, and combinations thereof, Preferably aminopropyltriethoxysilane or a combination comprising it.

The antimicrobial substance usable in the present invention may be selected from a natural material or an extract thereof, an antimicrobial polymer compound and a combination thereof.

Examples of the natural materials or extracts thereof include crabs, shrimp shells or their extracts (for example chitosan), green tea or its extracts (for example catechin), orchards or extracts thereof (for example, Paeonol, Paeoniflorin, Grapefruit or its extracts (e.g. naringin), citral, licorice or its extracts (e.g. flavonoids), white flour Or extracts such as bamboo or its extracts (eg polyphenols), sprouts or extracts thereof (eg glyceolins), gold or extracts thereof (eg tyrosinase), wasabi or extracts thereof For example, isothiocyanate), mustard or its extract, hinokitol And combinations thereof. The extracts may be prepared by a known extraction method.

Examples of the antimicrobial polymer include at least one polymer compound selected from aromatic or heterocyclic polymers, acrylic or methacrylic polymers, cationic conjugated polyelectrolytes, polysiloxane polymers, natural polymer mimetic polymers, and phenol or benzoic acid derivative polymers, Or a group having at least one functional group selected from an ammonium salt group, a phosphonium salt, a sulfonium salt or other onium salt base, a phenylamide group and a diquaternide group attached to a branched polymer chain.

According to a preferred embodiment of the present invention, an antimicrobial coating material prepared by using the above-mentioned natural material or its extract or an antimicrobial polymer compound which is harmless to the human body and has stability and continuity is coated on a glass surface, And an excellent antimicrobial effect can be obtained.

According to a more preferred embodiment of the present invention, chitosan, 1- (2-hydroxy-4-methoxyphenyl) ethanone, or a combination thereof may be used as the antibacterial substance.

In the antimicrobial coating agent of the present invention, the content of the polycondensation reaction product of the fluorine-containing polymer and the functional or non-functional silane compound is preferably 50 to 99.9% by weight, more preferably 80 to 95% by weight, Is more preferable.

In the antimicrobial coating agent of the present invention, the content of the antimicrobial agent is preferably 0.1 to 50% by weight, more preferably 5 to 20% by weight, based on 100% by weight of the total weight of the coating agent.

According to a second aspect of the present invention there is provided a process for preparing a mixture comprising: a) preparing a mixture comprising a fluoropolymer, a functional organic silane compound and an antimicrobial material; And b) subjecting the mixture to a polycondensation reaction. A method for producing a dry vacuum-coated antimicrobial coating is provided.

According to a third aspect of the present invention, there is provided a process for preparing a fluorinated polymer comprising the steps of: i) preparing a mixture comprising a fluorinated polymer and a functional or non-functional silane compound; ii) subjecting the mixture to a polycondensation reaction; And iii) adding an antimicrobial substance to the resultant product of the polycondensation reaction and dispersing and mixing the resultant product.

There are no particular restrictions on the method and equipment used for preparing the mixture, and conventional reaction vessels or mixing equipment can be used. The conditions of the polycondensation reaction in the polycondensation reaction step are not particularly limited. For example, the polycondensation reaction may be carried out in a refluxing reaction at 100 to 200 ° C under an inert gas (for example, argon, nitrogen). Further, in order to facilitate the polycondensation radical reaction, the reaction mixture may be irradiated with ultrasound and / or UV during the reaction.

The result of the polycondensation reaction may optionally undergo a stabilization step. There are no particular restrictions on the stabilization condition, and for example, the result of the polycondensation reaction can be stabilized by keeping it at room temperature for 24 hours.

According to a fourth aspect of the present invention, there is provided a method of manufacturing a substrate, comprising: 1) providing a substrate to be coated; And 2) vacuum depositing the dry antimicrobial coating agent of the present invention on the surface of the substrate.

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, plastic and metal can be coated by the method of the present invention.

The dry antimicrobial coating may be deposited directly onto the substrate surface in a vacuum, alternatively may be vacuum deposited onto the layer mineral or oxide (e.g., SiO ₂₎ previously formed on the substrate surface.

The vacuum deposition method is not particularly limited, and can be performed using a conventional vacuum deposition method and equipment. According to one embodiment of the present invention, a vacuum deposition coating can be performed using a 2050 Ø vacuum evaporation apparatus (thermal evaporation, thermal sputter, etc.) in a PVD (Physical Vapor Deposition) method. The advantage of vacuum deposition is that a variety of materials can be easily applied to the coating, and there is little loss of coating material, and a clean, uniform thin film can be formed. In addition, the overall structure of the device is relatively simple, and the thermal and electrical complexity is small when the thin film is formed. Therefore, it is suitable for studying the physical properties of the film at the time of forming the thin film.

According to a fifth aspect of the present invention, there is provided a coated article characterized by having on its surface a vacuum-deposited coating layer of the dry-type antimicrobial coating agent of the present invention.

The article may be a smart device having a touch display such as a cell phone or a tablet PC of various materials such as glass, plastic and metal, a household appliance, a vending machine, a public interactive information device, an external electronic product which can be hand- And preferably a smart device having a touch-type display or a component thereof.

In the coating layer formed by vacuum evaporation of the coating agent of the present invention, the antimicrobial substance is arranged at the base of the coating layer to exhibit stain resistance, water and oil repellency, surface lubricity, and glossiness while maintaining the coating life, and exhibit antibacterial activity.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by these examples.

[ Example ]

Example  One

15 g of chitosan as an antibacterial substance was added to 50 g of perfluoropolyether which is a fluoropolymer. 50 g of aminopropyltriethoxysilane, which is a functional or non-functional silane compound, was added and the resultant was subjected to a polycondensation reaction at a temperature of about 150 ° C. in an inert argon gas atmosphere. The reaction product was stabilized at room temperature for 24 hours, Coating agent was prepared.

Example  2

A dry antimicrobial coating agent was prepared in the same manner as in Example 1, except that 8 g of paeonol was further added as an antibacterial substance.

Example  3

50 g of aminopropyltriethoxysilane was added to 50 g of perfluoropolyether and the mixture was subjected to a polycondensation reaction at about 150 ° C in an inert argon gas atmosphere. Then, paeonol was added thereto as an antibacterial substance, And the mixture was uniformly dispersed and mixed to prepare a dry antimicrobial coating agent.

Test Example  1: Evaluation of Coating Property of Dry Antibacterial Coating Agent

The dry antimicrobial coatings prepared in Examples 1 to 3 were coated with tempered glass by E / B (Electron-beam) evaporation method in a 2050 진 vacuum evaporation equipment. To facilitate coating, tempered glass was wet cleaned with a 5 wt% alkaline detergent (a cleaning agent for tempered glass) in a 10-bath washer before coating. The conditions for the vacuum deposition were as follows: initial etching: 300 seconds; SiO ₂ thickness: 120 ANGSTROM: 80 DEG C.

For the coated specimens, properties were evaluated as follows.

(One) Contact angle  How to measure

After the coating, the contact angle of the coated surface was measured using a contact angle measuring apparatus. To measure the contact angle, the size of one droplet was adjusted to 3 μl, and the contact angle of 5 points per coated sample was measured to check the uniformity of the coating.

(2) Abrasion resistance test

The wear resistance test was carried out to confirm the durability after coating. The abrasion test of 1500 times was carried out using an abrasion eraser. As a result of the test, when the degree of change of the contact angle after the test was within 15 ° as compared with the initial contact angle of the coated sample, it was proceeded to be PASS.

(3) Test of antibacterial activity

In order to confirm the initial antimicrobial activity, Examples 1 and 2 were tested in accordance with JIS Z 2801 standard using E. coli (ATCC 8739), Staphylococcus aureus (ATCC 6538P), and P. aeruginosa (ATCC 15442) , And Example 3 was carried out in the same standard using E. coli (ATCC 8739) in a KOLAS accredited testing laboratory. 400 μl of the diluted bacterial solution was inoculated on the surface of the coated sample and incubated in a constant temperature and humidity environment for 24 hours, followed by desorption to confirm the antibacterial result.

The results of the above physical property evaluation are shown in Tables 1 to 3 below.

Test Example  2 : Uncoated  Comparison of antibacterial activity with coating samples not containing samples and antimicrobial agents

(a) an uncoated sample (i.e., tempered glass itself), (b) an AF coating sample without an antimicrobial agent (i.e., a tempered glass sample coated with a coating prepared in the same manner as in Example 1 without using an antimicrobial agent) (c) Contact angle was measured and an antibacterial activity test was carried out on an antibacterial AF (anti-fingerprint) coating sample (i.e., a tempered glass sample coated with the coating prepared in Example 1) as described above. The results are shown in Table 4 and FIG.

Claims (16)

Polycondensation reaction products of fluorinated polymers and functional or non-functionalized silane compounds; And an antimicrobial material. The method of claim 1, Wherein the fluoropolymer and the functional or non-functional silane compound are polycondensed in the presence of an antibacterial substance. The method of claim 1, Wherein the antimicrobial substance is added to and dispersed in the resultant polycondensation reaction product of the fluorine-based polymer and the functionalized or non-bonded silica-based compound, and they are mixed with each other. The method of claim 1, wherein the fluoropolymer is selected from perfluoropolyether, fluorinated vinylidene polymer, tetrafluoroethylene polymer, hexafluoropropylene polymer, chlorinated ethylene fluoride polymer, and combinations thereof. Antibacterial coatings. The method of claim 1, wherein the functional or non-functional silane compound is selected from the group consisting of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, amino-methoxysilane, phenylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3- Aminopropyltrimethoxysilane, N- (? -Aminoethyl) -? - aminopropylmethyldimethoxysilane,? -Aminopropyltrimethoxysilane,? -Aminopropyldimethoxysilane,? -Aminopropyltriethoxysilane , vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri (methoxyethoxy) silane, di-, tri- or tetraalkoxysilane, vinylmethoxysilane, vinyltrimethoxy Silane, vinyl epoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, y-glycidoxypropyltriethoxysilane, y-methacryloxypropyl Trimethoxysilane, chlorotrimethyl (Trimethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) silane, bis (trimethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) silane, trichloroethylsilane, trichlorophenylsilane, trichlorovinylsilane, mercaptopropyltriethoxysilane, (Triethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) disulfide, (methacryloxy) propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, and combinations thereof. Dry vacuum coating with antimicrobial agent. The dry antimicrobial coating composition according to claim 1, wherein the antimicrobial substance is selected from a natural material or an extract thereof, an antimicrobial polymer compound and a combination thereof. The dry antimicrobial coating composition according to claim 1, wherein the antibacterial substance is chitosan, phenol, or a combination thereof. a) preparing a mixture comprising a fluoropolymer, a functional organic silane compound and an antimicrobial material; And b) subjecting the mixture to a polycondensation reaction. i) preparing a mixture comprising a fluoropolymer and a functional or non-functional silane compound; ii) subjecting the mixture to a polycondensation reaction; And iii) adding an antimicrobial substance to the resultant product of the polycondensation reaction and dispersing and mixing the resultant product. 10. The method according to claim 8 or 9,
Wherein the fluoropolymer is selected from perfluoropolyether, fluorinated vinylidene polymer, tetrafluoroethylene polymer, hexafluoropropylene polymer, chlorinated ethylene fluoride polymer and combinations thereof;
The functionalized or non-functional compound may be selected from the group consisting of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, amino-methoxysilane, phenylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane , N- (? -Aminoethyl) -? - aminopropylmethyldimethoxysilane,? -Aminopropyltrimethoxysilane,? -Aminopropyldimethoxysilane,? -Aminopropyltriethoxysilane,? -Aminopropyldi Vinyltriethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, di-, tri- or tetraalkoxysilane, vinylmethoxysilane, vinyltrimethoxysilane, vinyl epoxysilane, Vinyltriethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Methacryloxypropyltrimethoxysilane, chloro Trimethylsilane, trichloro (Trimethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) amine, bis (trimethylsilyl) silane, trichloromethylsilane, trichlorophenylsilane, trichlorovinylsilane, mercaptopropyltriethoxysilane, Ethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) disulfide, (methacryloxy) propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, and combinations thereof;
Characterized in that the antimicrobial substance is selected from a natural material or an extract thereof, an antimicrobial polymer compound and a combination thereof.
A method for manufacturing a dry antimicrobial coating agent by vacuum evaporation. 10. The method of claim 8 or 9, wherein the polycondensation reaction is carried out in a reflux reaction at a temperature of 100 to 200 DEG C under an inert gas. 1) providing a substrate to be coated; And 2) vacuum-depositing the dry antimicrobial coating agent of any one of claims 1 to 7 on the surface of the substrate. 13. The method of claim 12, wherein the substrate is glass, plastic or metal. 13. The method of claim 12, wherein the dry antimicrobial coating is vacuum deposited directly onto the substrate surface, or vacuum deposited over a previously formed inorganic or oxide layer on the substrate surface. A coated article characterized by having on its surface a vacuum-deposited coating layer of the dry-type antimicrobial coating composition of any one of claims 1 to 7. 16. The coated article of claim 15, wherein the article is a smart device having a touch-sensitive display, a household appliance, a vending machine, a public interactive information device, a hand-held external electronic product, or a component thereof.

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