KR20170021957A - Nanospray coating method of organic-metal ion complex, which is synthesized by gallate group containing compound and metal of the lanthanoid series salts or transition metal salts - Google Patents

Nanospray coating method of organic-metal ion complex, which is synthesized by gallate group containing compound and metal of the lanthanoid series salts or transition metal salts Download PDF

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KR20170021957A
KR20170021957A KR1020150116155A KR20150116155A KR20170021957A KR 20170021957 A KR20170021957 A KR 20170021957A KR 1020150116155 A KR1020150116155 A KR 1020150116155A KR 20150116155 A KR20150116155 A KR 20150116155A KR 20170021957 A KR20170021957 A KR 20170021957A
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coating
metal salt
gallate
group
transition metal
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KR101742683B1 (en
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최인성
박지훈
서혜린
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한국과학기술원
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C09D7/12—
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process

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Abstract

The present invention relates to a nano-spray coating method of a compound containing a gallate group and an organic-metal ion complex synthesized from a lanthanide metal salt or a transition metal salt. The nano spray coating method according to the present invention is a method of coating a compound containing a gallate group, And a lanthanide metal salt or a transition metal salt are introduced into an independent spray and sequentially sprayed onto the object to be coated, uniform coating can be rapidly performed without wasting the sample regardless of the size of the object to be coated, The organic-metal ion complex coating formed by the method has a hydroxyl group (-OH), which enables biological functionalization (attachment of proteins and enzymes) through hydrogen bonding, and also has antibacterial and antioxidant properties. , And the film is optically transparent in the ultraviolet (UV) region The coating material is not only protected from ultraviolet rays but also sensitive to a chelating agent such as EDTA or a hydrogen ion concentration index (pH), so that the coating can be freely decomposed at a desired time.

Description

The present invention relates to a nanospray coating method of an organic-metal ion complex synthesized from a compound containing a gallate group and a lanthanide metal salt or a transition metal salt. lanthanoid series salts or transition metal salts}

The present invention relates to a nano spray coating method of a compound containing a gallate group and an organic-metal ion complex synthesized from a lanthanide metal salt or a transition metal salt.

It is generally known that a polyphenol material including a gallate group present in nature forms a coordination bond with a metal ion obtained from a lanthanide metal salt or a transition metal salt to form an oil-inorganic composite nanofilm (Patent Document 1).

Polyphenol-metal ion composite nanofilms are formed on various surfaces (glass, silicon, metal surface, plastic, etc.) without pretreatment. They are used as chelating agents such as ethylenediaminetetraacetic acid (EDTA) It has the advantage that the coating can be freely decomposed at a desired time.

However, the coating method disclosed in Patent Document 1 is a solution-based process in which a sample is prepared and an aqueous solution of two coating materials is mixed and coated in a reaction vessel in which a sample is present, so that it is dispersed in a solution such as microparticles or nanoparticles In the case of a bulk sample or a substrate to be coated, there is a possibility that the sample may be damaged in the process of mixing the aqueous solution of the two coating materials at the time of coating, There is a problem that homogeneity is lowered when mixing, and the coating can not be uniformly performed. In addition, there is also a disadvantage in that the amount of the solution consumed in the process is large because the prepared coating material aqueous solution should be prepared to be locked to the bulk sample volume beyond the bulk sample volume and discarded immediately after coating. Furthermore, when coating low-density materials which do not settle in an aqueous solution, it is difficult to achieve limited surface contact with the aqueous coating material solution. Due to these drawbacks, the solution-based coating process has difficulties in practical application due to the difficulty and unevenness of the large-area coating.

In order to overcome the above problems and limitations, the inventors of the present invention have found that a compound containing a gallate group and a lanthanide metal salt or a transition metal salt disclosed in Patent Document 1 are introduced into an independent spray, Thereby forming an organic-metal ion complex as a coating material.

Layer-by-layer (LBL) method is one of the best known spray coating techniques. However, since the spray coating of the LBL method is a method of alternately coating a polymer solution having different electric charges, There is a problem that an uneven film can be formed.

However, since the coating method according to the present invention does not require a pretreatment step for coating, it is possible to drastically reduce the pretreatment time required for the coating, and unlike the conventional coating method, Can be adjusted. Unlike the LBL method in which layers of +/- charge are alternately applied and stacked by electrostatic attraction to form a film, the coating method according to the invention is characterized in that the compound containing the gallate group is a lanthanide metal ion or a transition metal Ions are coordinated while a film is formed and a negative charge is generated by a plurality of -OH groups present in the gallate group. That is, since the same charge material can be applied many times, there is an advantage over the spray coating method of the LBL method in the homogeneous drawing of the coating material, and the time and cost can be remarkably reduced by the short cleaning time and coating time can do. Furthermore, various organic and inorganic materials can be injected together and deposited on the nanofilm to be used as a transmitter.

In addition, compounds containing a gallate group (especially tannic acid), and lanthanide metal salts or transition metal salts (especially FeCl 3 ) used in the coating process according to the present invention can be used in the FDA approved Generally Recognized as Safe , GRAS), it has advantages that can be applied to life-friendly application fields such as food and fruit coating. In addition, the coating method according to the present invention is different from the spray coating method using a conventional paint in that the nanometer coating is performed with a compound containing a gallate group dissolved in water or a metal ion, Because it is used, organic solvent-sensitive materials can be easily coated and can be applied to life-related applications such as food coating and tableware coating. Furthermore, the inventors of the present invention found that a compound containing a gallate group contained in a coating formed by the coating method according to the present invention has a hydroxyl group (-OH) and thus can be biologically functionalized (with a protein or an enzyme) through hydrogen bonding In addition, since it has antimicrobial and antioxidative properties, it can be applied to medical application fields. It is confirmed that the film has optical absorption properties in the ultraviolet (UV) region, and thus the coated material can be protected from ultraviolet rays. Completed.

WO 2014/197940 A1

It is an object of the present invention to provide a process for the preparation of

Figure pat00001
, And a step (step 1) of spraying an aqueous solution of a compound containing a gallate group and a solution of a lanthanide metal salt or a transition metal salt on the substrate (step 1).

Another object of the present invention is a process for the preparation of

Figure pat00002
, And a step (step 1) of spraying a solution of a compound containing a gallate group represented by the formula (1) and a solution of a lanthanide metal salt or a transition metal salt on the substrate to introduce hydrophilicity into the surface of the substrate .

Yet another object of the present invention is a process for the preparation of

Figure pat00003
And a step (step 1) of spraying a solution of a compound containing a gallate group represented by the formula (1) and an aqueous solution of a lanthanide metal salt or a transition metal salt on the substrate, wherein the antioxidant is introduced into the surface of the substrate .

Another object of the present invention is a process for the preparation of

Figure pat00004
And a compound containing a gallate group and a complex of a lanthanide metal ion or a transition metal ion coated thereon.

Yet another object of the present invention is a process for the preparation of

Figure pat00005
And a compound containing a gallate group and a complex of a lanthanide metal ion or a transition metal ion are coated on the surface.

In order to achieve the above object,

Figure pat00006
And a step (step 1) of spraying an aqueous solution of a compound containing a gallate group and a solution of a lanthanide metal salt or a transition metal salt on the substrate (step 1).

The present invention also provides a pharmaceutical composition comprising one or more compounds of formula

Figure pat00007
, And a step (step 1) of spraying a solution of a compound containing a gallate group represented by the formula (1) and a solution of a lanthanide metal salt or a transition metal salt on the substrate to introduce hydrophilicity into the surface of the substrate to provide.

Further,

Figure pat00008
And a step (step 1) of spraying a solution of a compound containing a gallate group represented by the formula (1) and an aqueous solution of a lanthanide metal salt or a transition metal salt on the substrate, wherein the antioxidant is introduced into the surface of the substrate to provide.

The present invention also provides a pharmaceutical composition comprising one or more compounds of formula

Figure pat00009
And a compound containing a gallate group and a complex of a lanthanide metal ion or a transition metal ion coated thereon.

Further,

Figure pat00010
And a compound containing a gallate group and a complex of a lanthanide metal ion or a transition metal ion are coated on the surface.

The nano spray coating method according to the present invention is a method in which a compound containing a gallate group and a lanthanide metal salt or a transition metal salt are introduced into an independent spray and sequentially sprayed onto an object to be coated, The coating of organic compound-metal ion complex formed by the coating method has a hydroxyl group (-OH), so that it can be biologically functionalized (attached with proteins and enzymes) through hydrogen bonding, And has anti-microbial and antioxidative properties. In addition, the film can be applied to medical applications. Since the film has an optical absorption property in the ultraviolet (UV) region, it can protect the coated material from ultraviolet rays, Sensitive to a chelating agent or a hydrogen ion concentration index (pH) To the effect that can degrade the coating freely.

1 is an image showing an example of a coating method according to the present invention.
2 is an image showing a scanning electron microscope photograph of a gold (Au) substrate before and after coating according to the coating method according to the present invention.
FIG. 3 is an image showing the result of FT-IR analysis for analyzing a coating material coated on the surface of a gold (Au) substrate.
4 is an image showing the result of measuring the contact angle after coating various kinds of substrates.
FIG. 5 is an image showing a change in the contact angle observed with the naked eye when vinegar spray is applied to a drop tomato coated with a coating method according to the present invention.
FIG. 6 is an image showing the result of an experiment to confirm whether the coating formed by the coating method according to the present invention is easily biologically functionalized.
FIG. 7 is an image showing the result of an experiment to evaluate the anti-fogging effect of the coating formed by the coating method according to the present invention.
8 is an image obtained by coating a quartz cell with a tannic acid-iron ion film (five times coating) and observing it through a UV-Vis absorption spectrum.
9 is an image showing a quartz cell before and after the coating.
FIG. 10 is an image obtained by performing the coating of the present invention five times on an apple and observing changes with time to evaluate the antibacterial effect of the coating formed by the coating method according to the present invention.

Hereinafter, the present invention will be described in detail.

The present invention relates to a process for the preparation of

Figure pat00011
And a step (step 1) of spraying an aqueous solution of a compound containing a gallate group and a solution of a lanthanide metal salt or a transition metal salt on the substrate (step 1).

Hereinafter, the nano spray coating method according to the present invention will be described step by step.

In the nano spray coating method according to the present invention,

Figure pat00012
(Gallate group), and an aqueous solution of a lanthanide metal salt or a transition metal salt onto the substrate.

At this time, the lanthanide metal ion of the lanthanide metal salt or the transition metal ion of the transition metal salt may be represented by the formula

Figure pat00013
To form a complex with the gallate group.

The compound containing the gallate group can be used without particular limitation as long as it is a compound containing a gallate group. More specifically, it is possible to use tannic acid (TA), gallic acid, Theaflavin-3-gallate, Epigallocatechin gallate, epicatechin gallate, and the like can be used, and most preferably, tannic acid (TA) Can be used.

Furthermore, cerium (Ce), europium (Eu), gadolinium (Gd), and terbium (Tb) can be used as the metal of the lanthanide metal salt.

The metal of the transition metal salt may be at least one selected from the group consisting of Al, vanadium, manganese, iron, zinc, zirconium, , Rhodium (Rh), or the like can be used.

Further, the anion that can form a salt with the metal of the lanthanide metal salt or the metal of the transition metal salt is not particularly limited, and examples thereof include Cl - , NO 3 2- , SO 4 2- , CH 3 CO 2 - , PO 4 3 - can be used.

When performing the nano spray coating, the spray may be performed using a spray using compressed air (air flow rate: 0.5 to 15.0 L / min). More specifically, one or more compounds of formula

Figure pat00014
, And an aqueous solution of a lanthanide metal salt or a transition metal salt into a first spray and a second spray, respectively, and spraying the first spray and the second spray at the same time It can be sprayed sequentially.

The present invention also provides a pharmaceutical composition comprising one or more compounds of formula

Figure pat00015
, And a step (step 1) of spraying a solution of a compound containing a gallate group represented by the formula (1) and a solution of a lanthanide metal salt or a transition metal salt on the substrate to introduce hydrophilicity into the surface of the substrate to provide.

At this time, the hydrophilicity is generated by the hydroxyl group (-OH) present in the gallate group. When the hydrophilic property is introduced into the surface of the substrate due to the hydroxyl group, the functionalization (protein and enzyme attachment) is possible through hydrogen bonding, and the effect of preventing frost is also generated.

Further,

Figure pat00016
And a step (step 1) of spraying a solution of a compound containing a gallate group represented by the formula (1) and an aqueous solution of a lanthanide metal salt or a transition metal salt on the substrate, wherein the antioxidant is introduced into the surface of the substrate to provide.

In this case, the antimicrobial activity is generated by a compound containing a gallate group. When the antimicrobial property is introduced into the surface of the substrate by the above-described method, it can be applied to a medical application field.

The present invention also provides a pharmaceutical composition comprising one or more compounds of formula

Figure pat00017
And a compound containing a gallate group and a complex of a lanthanide metal ion or a transition metal ion coated thereon.

At this time, the anti-fogging property is characterized in that the surface is hydrophilized due to the hydroxyl group (-OH) of the gallate group, so that the fogging does not occur.

Further,

Figure pat00018
A compound including a gallate group and a complex of a lanthanide metal ion or a transition metal ion is coated on the surface to provide an antibiotic fruit.

In this case, the antimicrobial activity is generated by a compound containing a gallate group.

The nano spray coating method according to the present invention and the thus-produced substrate coated with a nano-shell are stably protected from external environmental stimuli such as light irradiation, silver nanoparticles, heat, etc., There is an effect of decomposing. Specifically, a substrate-independent coating (TA-Fe III ) using coordination complexes of tannic acid (TA) and Fe III ions Shell) is highly biocompatible and progresses rapidly within a few seconds (see FIG. 1).

1 is an image showing a coating method according to the present invention performed in Experimental Example 1 to be described later.

As a result, it was found that coating thickness was increased in proportion to the number of repetitions of coating in the coating method according to the present invention (Experimental Example 1 (See Table 1).

As a result of conducting an experiment to confirm whether the gold (Au) substrate can be easily coated according to the coating method according to the present invention, the coating method according to the present invention can facilitate coating uniformly when gold (Au) (See Fig. 2 of Experimental Example 2).

Furthermore, analysis of the coating material coated on the surface of the gold (Au) substrate revealed that the gold substrate coated with the tin acid-iron ion nanofilm spray was similar to the IR result of tannic acid See Figure 3 of Example 2).

Further, as a result of conducting an experiment to measure the contact angle before and after the coating, it was found that when coating was carried out according to the coating method according to the present invention, a large number of hydroxyl groups (-OH) existing in a compound containing a gallate group resulted in high hydrophilicity The contact angle with water was significantly lowered. From this, it can be seen that the coating formed by the coating method according to the present invention will facilitate biological functionalization (attachment of proteins and enzymes) through hydrogen bonding (see FIG. 4 of Experimental Example 3)

Further, as a result of conducting experiments to evaluate the decomposability of the coating formed by the coating method according to the present invention, the coating formed by the coating method according to the present invention is easily decomposed by HCl or vinegar, (See FIG. 5 of Experimental Example 4 and Experimental Example 5).

In addition, in order to confirm whether the coating formed by the coating method according to the present invention is easily biologically functionalized, it was found that in the case of the sample not coated with the tannic acid-iron ion nanofilm, the functionalization of BSA with the fluorescent dye was not induced . On the other hand, in the case of the coating method using the coating method according to the present invention, the fluorescence was observed due to the functionalization of the fluorescent dye-coated BSA in the case of the sample coated with the tannic acid-iron ion nanofilm. From this, it can be seen that the compound containing a gallate group contained in the coating formed by the coating method according to the present invention has a hydroxyl group (-OH), thereby facilitating the biological functionalization (attachment of proteins and enzymes) through hydrogen bonding (See FIG. 6 of Experimental Example 6).

Further, in order to evaluate the anti-fogging effect of the coating formed by the coating method according to the present invention, a coating was formed only on the right lens of the spectacles, As a result, it was found that the lens coated with the coating method according to the present invention effectively prevented the fogging even in an environment rich in water vapor (see FIG. 7 of Experimental Example 7).

In order to evaluate the ultraviolet shielding effect of the coating formed by the coating method according to the present invention, the ultraviolet absorption test was performed using a Quartz cell (Hellma Analytics, manufactured by Synthetic Quartz, Light path: 10 mm, Type No. 100.600- QG) showed that the tannic acid-iron ion film absorbs light in the UV region of less than 400 nm in the UV-Vis spectrum. The peak near the maximum absorption wavelength of 300 nm is known as the UV-B region, the ultraviolet ray which is not absorbed by ozone, and it is known to be a region that damages the human body. In addition, the peak near the maximum absorption wavelength of 210 nm is mostly absorbed in the ozone as the UV-C region, but if the ultraviolet ray which is not absorbed is exposed to the human body, It is possible to protect the coating material from ultraviolet rays (see FIGS. 8 and 9 of Experimental Example 8).

Further, in order to evaluate the antibacterial effect of the coating formed by the coating method according to the present invention, the coating according to the present invention was applied to apples five times, and the change with time was observed. As a result, The uncoated apples bruised and retreated as shown in the picture, but the coated apples were hard and remained in their original condition. From this, it can be seen that the tannic acid-iron ion nanofilm formed by the coating method according to the present invention is excellent in antibacterial effect (see FIG. 10 of Experimental Example 9).

Hereinafter, the present invention will be described in detail with reference to Examples and Experimental Examples.

However, the following examples and experimental examples are illustrative of the present invention, and the present invention is not limited thereto.

< Experimental Example  1> Fruit Coating

The following experiment was carried out in order to confirm whether an easy coating of fruit was possible according to the coating method according to the present invention.

Tannic acid aqueous solution (170.01 mg / 10 ml DI, 10 mM) and FeCl 3 (27.02 mg / 10 ml DI, 10 mM) was placed in a spray vessel using compressed air, and the same time (1 second) was applied at the same speed (flow rate 10.5 L / min) subsequently (tannic acid → FeCl 3) was sprayed on the surface (FIG. 1) for.

The sequential spray was repeatedly sprayed six times in total and the thickness of the coated layer was measured through an ellipsometer (Gaertner L116s ellipsometer, Gaertner Scientific Corportion) every time the spray was repeated. The results are shown in Table 1 below.

Number of repetitions of coating Thickness (nm) One 2.59 2 13.44 3 22.35 4 33.69 5 41.86 6 50.18

As shown in Table 1, the coating thickness was found to increase in proportion to the number of coating repetitions of the coating method according to the present invention.

< Experimental Example  2> Analysis of coating materials by coating of gold (Au) substrate and FT-IR (Fourier Transform Infrared Spectroscopy)

The following experiment was conducted to confirm whether the gold (Au) substrate can be easily coated according to the coating method according to the present invention.

First, a 10 mM tannic acid solution was applied to a gold substrate for 1 second, a 10 mM iron chloride solution was applied for 1 second, washed with distilled water, and then blown with argon gas. The above procedure was repeated 5 times to form a 5-layer coating, which was coated with Pt and then SEM images were taken. The results are shown in Fig.

2 is an image showing a scanning electron microscope photograph of a gold (Au) substrate before and after coating according to the coating method according to the present invention.

As shown in FIG. 2, when coating gold (Au) with the coating method according to the present invention, uniform coating was easy.

In addition, the coating material coated on the surface of the gold (Au) substrate was analyzed by FT-IR for analysis. The results are shown in FIG.

FIG. 3 is an image showing the result of FT-IR analysis for analyzing a coating material coated on the surface of a gold (Au) substrate.

As shown in FIG. 3, the gold substrate coated with tannic acid-iron ion nanofilm spray was similar to the IR result of tannic acid. More specifically, when comparing the spectra, it can be seen that the main peaks overlap in the main region of IR corresponding to 1000-1750 cm -1 , indicating that tannic acid was applied by spray coating (red arrow Peaks are overlapping peaks). The IR spectrum of the spray-coated tannic acid-iron ion film was obtained through a Nexus FT-IR spectrophotometer (Thermo Nicolet) and the IR spectrum of the tannic acid was obtained through an ALPHA FT-IR spectrometer (Bruker Corporation) equipped with a ZnSe ATR crystal .

< Experimental Example  3> Coating of various substrates and Contact angle  evaluation

Coating of various types of substrates including a gold (Au) substrate was performed in the same manner as in Experimental Example 2, and contact angles before and after coating were measured. The results are shown in Fig.

4 is an image showing the result of measuring the contact angle after coating various kinds of substrates.

As shown in FIG. 4, when the coating is performed by the coating method according to the present invention, since the hydrophilic property is increased due to a large number of hydroxyl groups (-OH) present in the compound containing a gallate group, Respectively. From this, it can be seen that the coating formed by the coating method according to the present invention will facilitate biological functionalization (attachment of proteins, enzymes) through hydrogen bonding.

< Experimental Example  4> of the coating Degradability  Rating 1

In order to evaluate the decomposability of the coating formed by the coating method according to the present invention, the following experiment was conducted.

First, an aqueous solution of tannic acid (170.01 mg / 10 ml DI, 10 mM) and FeCl 3 (27.02 mg / 10 ml DI, 10 mM) was placed in a spray vessel using compressed air, and the same time (1 second) was applied at the same speed (flow rate 10.5 L / min) while were injected repeatedly in sequence (tannic acid → FeCl 3) 3 times over the surface. At this time, the coating thickness was analyzed by an ellipsometer (Gaertner L116s ellipsometer, Gaertner Scientific Corportion), and the coating thickness was found to be 25.24 nm.

Thereafter, the coated drop tomato was immersed in 0.1 M HCl for 2 hours and 30 minutes to induce decomposition of the coating, and then the coated thickness was analyzed by an ellipsometer. As a result, the coated thickness was found to be 7.44 nm . It was also confirmed that the drop tomato remained intact even after inducing the decomposition of the coating.

From this, it can be seen that the coating formed by the coating method according to the present invention is easily decomposed by HCl, so that the coating can be freely decomposed at desired times.

< Experimental Example  5> of the coating Degradability  Rating 2

The same procedure as in Experimental Example 4 was carried out except that the surface-coated tomatoes were coated with HCl instead of carrying the vinegar sprayed with the coating method according to the present invention, and the results are shown in FIG.

FIG. 5 is an image showing a change in the contact angle observed with the naked eye when vinegar spray is applied to a drop tomato coated with a coating method according to the present invention.

As shown in FIG. 5, when the vinegar spray is applied to the drop tomato coated with the coating method according to the present invention, the coating angle is easily decomposed, so that the contact angle is increased similarly to before coating.

< Experimental Example  6> Evaluation of biological functionalization

Experiments were conducted to confirm that the coating formed by the coating method according to the present invention is easy to biological functionalization.

First, an aqueous solution of tannic acid (170.01 mg / 10 ml DI, 10 mM) and FeCl 3 (27.02 mg / 10 ml DI, 10 mM) was placed in a spray vessel using compressed air, and the same time (flow rate: 10.5 L / min) was applied at a distance of about 10 cm from the PDMS (Polydimethylsiloxane) (Tannic acid - &gt; FeCl3) surface for 3 seconds.

Then, BSA (Bovine Serum Albumin) with a fluorescent dye (Alexa 647) was spin coated on the PDMS pattern, and microcontact printing (μcp) was performed on the substrate to evaluate whether protein immobilization was induced (circle diameter: 100 μm). The results are shown in Fig.

FIG. 6 is an image showing the result of an experiment to confirm whether the coating formed by the coating method according to the present invention is easily biologically functionalized.

As shown in Fig. 6, in the case of the sample not coated with the tannic acid-iron ion nanofilm, functionalization of BSA with a fluorescent dye was not induced. On the other hand, in the case of the coating method using the coating method according to the present invention, the fluorescence was observed due to the functionalization of the fluorescent dye-coated BSA in the case of the sample coated with the tannic acid-iron ion nanofilm.

From this, it can be seen that the compound containing a gallate group contained in the coating formed by the coating method according to the present invention has a hydroxyl group (-OH), thereby facilitating the biological functionalization (attachment of proteins and enzymes) through hydrogen bonding .

< Experimental Example  7> Anti-fogging evaluation

In order to evaluate the anti-fogging effect of the coating formed by the coating method according to the present invention, a coating was formed only on the right lens of the spectacles, The swelling phenomenon was observed. The results are shown in Fig.

FIG. 7 is an image showing the result of an experiment to evaluate the anti-fogging effect of the coating formed by the coating method according to the present invention.

As shown in FIG. 7, the lens coated with the coating method according to the present invention was found to effectively prevent fogging even in an environment rich in water vapor.

< Experimental Example  8> Evaluation of ultraviolet shielding effect

In order to evaluate the ultraviolet shielding effect of the coating formed by the coating method according to the present invention, the ultraviolet absorption test was carried out in a quartz cell (Hellma Analytics, manufactured by Synthetic Quartz, Light path: 10 mm, Type No. 100.600-QG) Were used to conduct experiments.

First, the quartz cell was coated five times with tannic acid and iron on spray coating, and UV-Vis spectra were obtained using ultraviolet spectrophotometer (UV-Vis Spectrometer, SHIMADZU, UV-2550). The results are shown in Fig. 8 and Fig.

8 is an image obtained by coating a quartz cell with a tannic acid-iron ion film (five times coating) and observing it through a UV-Vis absorption spectrum.

9 is an image showing a quartz cell before and after the coating.

As shown in FIG. 8 and FIG. 9, in the UV-Vis spectrum, the tannic-iron ion film absorbs light in the UV region of less than 400 nm. The peak near the maximum absorption wavelength of 300 nm is known as the UV-B region, the ultraviolet ray which is not absorbed by ozone, and it is known to be a region that damages the human body. In addition, the peak near the maximum absorption wavelength of 210 nm is mostly absorbed in the ozone in the UV-C region, but if the ultraviolet ray which is not absorbed is exposed to the human body, It is possible to protect the coating material from ultraviolet rays.

< Experimental Example  9> Evaluation of antibacterial effect

In order to evaluate the antibacterial effect of the coating formed by the coating method according to the present invention, the coating according to the present invention was applied to apples five times and the change with time was observed. The results are shown in Fig.

FIG. 10 is an image obtained by performing the coating of the present invention five times on an apple and observing changes with time to evaluate the antibacterial effect of the coating formed by the coating method according to the present invention.

As shown in Fig. 10, after 7 days, the apples that were not coated were bruised and retreated as shown in the photograph, but the coated apples were hard and maintained the same as the initial state. From this, it can be seen that the tannic acid-iron ion nanofilm formed by the coating method according to the present invention is excellent in antibacterial effect.

Claims (8)

One or more compounds of formula
Figure pat00019
And a step (step 1) of spraying an aqueous solution of a compound containing a gallate group and a solution of a lanthanide metal salt or a transition metal salt onto the substrate.
The method according to claim 1,
The lanthanide metal ion of the lanthanide metal salt or the transition metal ion of the transition metal salt is represented by the formula
Figure pat00020
Is capable of forming a complex with a gallate group represented by the formula (I).
The method according to claim 1,
The gallate group-containing compound may be selected from the group consisting of tannic acid (TA), gallic acid, theaflavin-3-gallate, epigallocatechin gallate Wherein the coating composition is at least one selected from the group consisting of epigallocatechin gallate and epicatechin gallate.
The method according to claim 1,
The metal of the lanthanide metal salt is at least one selected from the group consisting of cerium (Ce), europium (Eu), gadolinium (Gd) and terbium (Tb); And
The transition metal salt may be at least one selected from the group consisting of aluminum (Al), vanadium (V), manganese (Mn), iron (Fe), zinc (Zn), zirconium (Zr), molybdenum (Mo), ruthenium (Rh). &Lt; / RTI &gt;
One or more compounds of formula
Figure pat00021
And a step (step 1) of spraying a solution of a compound containing a gallate group represented by the formula (1) and a solution of a lanthanide metal salt or a transition metal salt on the substrate to introduce hydrophilicity into the surface of the substrate As a result,
Wherein the hydrophilicity is generated by a hydroxyl group (-OH) present in the gallate group.
One or more compounds of formula
Figure pat00022
, And a step (step 1) of spraying an aqueous solution of a compound containing a gallate group represented by the formula (1) and a solution of a lanthanide metal salt or a transition metal salt on the substrate As a result,
Wherein said antimicrobial activity is generated by a compound comprising a gallate group.
One or more compounds of formula
Figure pat00023
And a compound containing a gallate group and a complex of a lanthanide metal ion or a transition metal ion,
Wherein the surface of the lens is hydrophilized by the hydroxyl group (-OH) of the gallate group so that the surface of the lens is not frozen.
One or more compounds of formula
Figure pat00024
And antibiotic fruits coated with a compound containing a gallate group and a complex of a lanthanide metal ion or a transition metal ion,
Wherein the antimicrobial activity is caused by a compound containing a gallate group.
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