Rapid coating agent for preventing attachment of biomaterial, and preparation method and coating method thereof

Abstract

The present invention relates to: a coating agent for preventing the attachment of a biomaterial; and a preparation method and a coating method thereof. According to the present invention, provided is a coating laminate comprising: a first coating layer; and a second coating layer formed on one surface of the first coating layer. The first coating layer is a medium layer disposed between the surface of a substrate and the second coating layer and functions to maintain the second coating layer on the surface of the substrate, and the medium layer contains: a polyalkylsiloxane compound having a polar functional group at the terminal; and an amine compound having a polar functional group including silicon. The second coating layer contains a lubricating component. The coating laminate can prevent the attachment of a biomaterial. In addition, according to the present invention, provided is a composition for forming a medium layer, the composition comprising: a polyalkylsiloxane compound having a polar functional group at the terminal; an amine compound having a polar functional group including silicon; and a solvent. The composition for forming a medium layer comprises 0.3-0.5 parts by weight of the amine compound having a polar functional group including silicon, per 1 part by weight of the polyalkylsiloxane compound having a polar functional group at the terminal. The composition for forming a medium layer makes it possible to form a medium layer which is disposed between the surface of a substrate and a lubricating layer and functions to satisfactorily maintain the lubricating layer on the surface of the substrate.

Description

Rapid coating agent for preventing adhesion of biological materials, its preparation and coating method

[0001] The present invention relates to a coating agent for preventing adhesion of biological materials, and to a method for producing and coating the same. Specifically, the present invention relates to a coating agent that can be formed without complex processes and imparts biological material adhesion prevention properties to the surface of a substrate, and to a method for producing and coating the same.

[0002] Anti-fouling coatings and water-repellent coatings have been reported as surface-resistant coatings. However, these coatings have limitations: they only prevent adhesion to either aqueous or oily liquids, and their anti-adhesion performance is limited to complex substances such as biological substances, or liquids with high viscosity and low surface tension.

[0003] Considering these points, recent proposals have proposed forming a lubricating layer containing a lubricating component on the surface of a substrate. However, forming a lubricating layer directly on the surface of a substrate is difficult, requiring various pre- and post-treatment steps, resulting in a complex coating process.

[0004] The present invention has been made with the above in mind. The purpose of the present invention is to provide a coating laminate that can prevent the adhesion of biological materials and can be quickly formed on the surface of a substrate without going through a complex process.

[0005] In addition, another object of the present invention is to provide a composition for forming a mediator layer that can form a mediator layer that can maintain a lubricating layer on the surface of the substrate by interposing between the surface of the substrate and the lubricating layer.

[0006] In addition, another object of the present invention is to provide a coating method capable of quickly forming a coating laminate capable of preventing adhesion of a biological material on the surface of a substrate.

[0007] The present inventors conducted extensive research aimed at advantageously solving the above-mentioned problem. As a result, they discovered that forming an intermediary layer between the surface of a substrate and a lubricating layer, which enables interaction between both the surface of the substrate and the lubricating layer, can effectively maintain the lubricating layer on the surface of the substrate, and can prevent the adhesion of biological materials by a coating laminate comprising the intermediary layer and the lubricating layer, thereby completing the present invention.

[0008] That is, according to the present invention,

[0009] A coating laminate comprising a first coating layer and a second coating layer formed on one surface of the first coating layer,

[0010] The first coating layer is an intermediary layer interposed between the surface of the substrate and the second coating layer, and functions to maintain the second coating layer on the surface of the substrate.

[0011] The above-mentioned intermediary layer comprises a polyalkylsiloxane compound having a polar functional group at the terminal and an amine compound having a polar functional group containing silicon,

[0012] The second coating layer is provided with a coating laminate containing a lubricating component.

[0013] In addition, according to the present invention,

[0014] A composition for forming a mediator layer comprising a polyalkylsiloxane compound having a polar functional group at a terminal, an amine compound having a polar functional group including silicon, and a solvent, wherein the composition for forming a mediator layer comprises 0.3 parts by weight or more and 0.5 parts by weight or less of the amine compound having a polar functional group including silicon per 1 part by weight of the polyalkylsiloxane compound having a polar functional group at a terminal.

[0015] In addition, according to the present invention, a coating method comprising the following steps is provided.

[0016] A step of contacting a substrate with a composition for forming a mediating layer and then drying it to form a first coating layer, which is a mediating layer, on at least one surface of the substrate;

[0017] A step of contacting a substrate having a first coating layer formed on at least one surface with a composition for forming a second coating layer containing a lubricating component, thereby forming a second coating layer on the other side of the surface in contact with the substrate of the first coating layer.

[0018] According to the present invention, a coating laminate is provided that can be well maintained on the surface of a substrate and prevents adhesion of a biological material.

[0019] In addition, according to the present invention, a composition for forming a medium layer is provided, which can form a medium layer that functions to maintain a lubricating layer well on the surface of the substrate by interposing between the surface of the substrate and the lubricating layer.

[0020] In addition, according to the present invention, a coating method is provided that can quickly form a coating laminate capable of preventing adhesion of a biological material on the surface of a substrate without going through a complicated process.

[0021] Figure 1 is a drawing schematically showing a structure in which a coating laminate according to the present invention is formed on the surface of a substrate and a coating method thereof.

[0022] Figure 2 is a flowchart showing one embodiment of a coating method according to the present invention.

[0023] Figure 3 is a photograph showing the results of a blood stain adhesion prevention test according to Experimental Example 1.

[0024] Figure 4 is a graph showing the contact angle measurement results for each substrate before and after forming the coating laminate of the present invention according to Experimental Example 2.

[0025] Figure 5 is a graph showing the results of contact angle and slip angle measurements of liquids with different surface tensions on a substrate formed with a coating laminate of the present invention according to Experimental Example 3.

[0026] Fig. 6 (a) is a graph showing the results of transmittance measurements according to Experimental Example 4, and is a graph showing the results of transmittance measurements for an uncoated substrate, a substrate formed with only a first coating layer, and a substrate formed with both a first coating layer and a second coating layer. Fig. 6 (b) is a photograph showing the results of observing a substrate formed with a coating laminate according to the present invention against the sky.

[0027] Fig. 7 (a) is a graph showing the measurement results of the coating thickness according to Experimental Example 5, and Fig. 7 (b) is a graph showing the measurement results of the surface topology aspect according to Experimental Example 5.

[0028] Figure 8 is a photograph showing the results of a physical durability test according to Experimental Example 6.

[0029] Figure 9 is a photograph showing the results of measuring the marine organism adhesion prevention performance according to Experimental Example 7.

[0030] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described below, and may be implemented by making any modifications without departing from the scope of the claims and equivalents thereof.

[0031] [Coating laminate]

[0032] The coating laminate according to the present invention comprises a first coating layer and a second coating layer formed on one surface of the first coating layer. As illustrated in Fig. 1, the coating laminate of the present invention can be formed on the surface of a substrate. When the coating laminate of the present invention is formed on the surface of a substrate, the first coating layer is interposed between the surface of the substrate and the second coating layer. One surface of the first coating layer interacts with the surface of the substrate, and the other surface interacts with the second coating layer. As a result, the first coating layer functions as an intermediary layer that serves to properly maintain the second coating layer on the surface of the substrate.

[0033] Meanwhile, in this specification, “interaction” is used as an expression encompassing the following.

[0034] a) In any one layer containing two or more components, various intermolecular forces acting between any component and any other component.

[0035] b) Various intermolecular forces acting between any component present in one layer and the surface of another layer or between components present in another layer.

[0036] In one embodiment of the present invention, the first coating layer, which functions as an intermediary layer, includes a polyalkylsiloxane compound having a polar functional group at a terminal and an amine compound having a polar functional group containing silicon. In this way, since the first coating layer includes a polyalkylsiloxane compound having a polar functional group at a terminal and an amine compound having a polar functional group containing silicon, the first coating layer interacts with both the surface of the substrate and the second coating layer, thereby allowing the second coating layer to be satisfactorily maintained on the surface of the substrate.

[0037] The mechanism by which the second coating layer can be well maintained on the surface of the substrate by the first coating layer including a polyalkylsiloxane compound having a polar functional group at the terminal and an amine compound having a polar functional group containing silicon is presumed to be as follows. The amine compound having a polar functional group containing polar silicon is bonded to the surface of the substrate through polar interaction. In addition, the polar functional group present at the terminal of the polyalkylsiloxane compound and the polar functional group or amine group of the amine compound having a polar functional group containing silicon are bonded through polar interaction. As a result, the first coating layer is formed on the surface of the substrate. In addition, the polyalkylsiloxane portion of the polyalkylsiloxane compound having a polar functional group at the terminal is located on the surface of the first coating layer that comes into contact with the second coating layer, thereby making the surface hydrophobic. Accordingly, the second coating layer can be well maintained on the first coating layer due to chemical affinity (hydrophobic interaction, surface tension similarity) with the second coating layer containing a hydrophobic lubricating component. As a result, the second coating layer can be well maintained on the surface of the substrate for a long period of time.

[0038] Here, a polyalkylsiloxane compound having a polar functional group at the terminal can be represented by the following formula.

[0039] [Chemical Formula 1]

[0040]

[0041] At least one of A1 and A2 is a polar functional group, and can independently be a hydroxyl group (-OH), a carboxylic acid group (-COOH), or an amine group (-NH2). When only one of A1 and A2 is a polar functional group, the other can be an alkyl group such as a methyl group (-CH3) or an ethyl group (-C2H5). In order to improve the interaction with the surface of the substrate and to better maintain the first coating layer on the surface of the substrate, it is preferable that both A1 and A2 are polar functional groups, and it is more preferable that both A1 and A2 are hydroxyl groups.

[0042] R1 to R6 are each independently an alkyl group such as a methyl group (-CH3) or an ethyl group (-C2H5). From the viewpoint of facilitating the interaction with the hydrophobic lubricating component included in the second coating layer and maintaining the first coating layer and the second coating layer on the surface of the substrate, and from the viewpoint of ease of acquisition, it is preferable that all of R1 to R6 are the same, and it is more preferable that all of them are methyl groups (-CH3).

[0043] n represents the number of repetitions of the repeating units constituting the polyalkylsiloxane compound, and is not particularly limited as long as the effects of the present invention are not impaired.

[0044] The amine compound having a polar functional group including silicon includes a polar functional group other than an amine group. The polar functional group including silicon may be an alkoxysilyl group or a halogenosilyl group. Here, the alkoxysilyl group may be a trimethoxysilyl group (-Si(OCH3)3) or a triethoxysilyl group (-Si(OC2H5)3), and the halogenosilyl group may be a trichlorosilyl group (-SiCl3) or a tribromosilyl group (-SiBr3). In addition, the amine compound having a polar functional group including silicon may have one or two amino groups, and when it has two amino groups, it may have a primary amino group (-NH2) and a secondary amino group (-NHR).

[0045] Specifically, the amine compound having an alkoxysilyl group as a polar functional group containing silicon may be N-[3-(trimethoxysilyl)propyl]ethylenediamine, N-[3-(triethoxysilyl)propyl]ethylenediamine, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, etc. In addition, the amine compound having a halogenosilyl group as a polar functional group containing silicon may be N-[(trichlorosilyl)propyl]ethylenediamine, N-[(tribromosilyl)propyl]ethylenediamine, 3-aminopropyltrichlorosilane, 3-aminopropyltribromosilane, etc.

[0046] Here, the amine compound having a polar functional group including silicon preferably has two amino groups, more preferably a primary amino group and a secondary amino group, and is more preferably N-[3-(trimethoxysilyl)propyl]ethylenediamine, N-[3-(triethoxysilyl)propyl]ethylenediamine, N-[(trichlorosilyl)propyl]ethylenediamine, or N-[(tribromosilyl)propyl]ethylenediamine, and is even more preferably N-[3-(trimethoxysilyl)propyl]ethylenediamine or N-[(trichlorosilyl)propyl]ethylenediamine. Thereby, the polar interaction with the surface of the substrate and the polar interaction with the polar functional group of the polyalkylsiloxane compound having a polar functional group at the terminal are improved, so that the first coating layer can be well maintained on the surface of the substrate.

[0047] The ratio of the content of the polyalkylsiloxane compound having a polar functional group at the terminal and the amine compound having a polar functional group containing silicon included in the first coating layer is preferably 0.3 parts by weight or more and 0.5 parts by weight or less of the amine compound having a polar functional group containing silicon per 1 part by weight of the polyalkylsiloxane compound having a polar functional group at the terminal, more preferably 0.35 parts by weight or more and 0.45 parts by weight or less, and still more preferably 0.38 parts by weight or more and 0.42 parts by weight or less. When the content ratio of the polyalkylsiloxane compound having a polar functional group at the terminal and the amine compound having a polar functional group containing silicon, which are included in the first coating layer, is within the above range, the polar interaction between the amine compound having a polar functional group containing polar silicon and the surface of the substrate, and the polar interaction between the amine compound having a polar functional group containing silicon and the polar functional group of the polyalkylsiloxane compound, can be improved, thereby allowing the first coating layer to be better maintained on the surface of the substrate. In addition, when the content ratio is within the above range, the amount of the polyalkylsiloxane portion having hydrophobicity is appropriately adjusted, thereby improving the hydrophobic interaction with the lubricating component of the second coating layer, thereby allowing the second coating layer to be better maintained on the first coating layer.

[0048] The second coating layer is formed on one surface of the first coating layer and may include a lubricating component with antifouling / waterproofing properties. The second coating layer is a lubricating oil layer that acts as a lubricant and can wet the surface of the coating laminate. Accordingly, the biological material can be prevented from adhering to the substrate and can slide along the surface of the substrate.

[0049] The second coating layer may include, as a lubricating component, at least one selected from the group consisting of perfluoropolyalkylether (PFPAE), polyalkylsiloxane, perfluoroperhydrophenanthrene, and perfluorodecalin. Among these, perfluoropolyalkylether and polyalkylsiloxane are preferable as the lubricating component included in the second coating layer. This can improve the hydrophobic interaction between the second coating layer and the first coating layer.

[0050] As described above, the coating laminate according to the present invention can be well maintained on the surface of a substrate by having a first coating layer that functions as an intermediary layer. Furthermore, the coating laminate according to the present invention can prevent the adhesion of biological materials for a long period of time by having a second coating layer formed on one surface of the first coating layer.

[0051] Here, the substrate on which the coating laminate according to the present invention can be formed is not particularly limited, and may be formed of one or more of glass, polycarbonate (PC), polyethylene (PE), polypropylene (PP), polytetrafluoroethylene (PTFE), polyvinylchloride (PVC), thermoplastic polyurethane, aluminum (Al), stainless steel, and titanium (Ti).

[0052] Meanwhile, Fig. 1 illustrates that the substrate on which the coating laminate according to the present invention is formed is plate-shaped. However, there is no particular limitation on the shape of the substrate on which the coating laminate according to the present invention can be formed, and as long as the shape is such that the coating method of the present invention described below can be applied, the coating laminate according to the present invention can be formed even on a substrate of a complex shape.

[0053] A preferred embodiment of the coating laminate according to the present invention is that the first coating layer, which is an intermediate layer, includes a polydimethylsiloxane compound having a hydroxyl group (-OH) at both ends and N-[3-(trimethoxysilyl)propyl]ethylenediamine, and the second coating layer includes polydimethylsiloxane as a lubricating component.

[0054] As described above, the coating laminate according to the present invention can be maintained well on the surface of a substrate. Furthermore, the coating laminate according to the present invention can impart a performance that prevents the adhesion of biological materials to the surface of the substrate, thereby enabling the substrate to be used in environments prone to the adhesion of biological materials, and is particularly suitable for use as a medical device.

[0055] [Composition for forming a medium layer]

[0056] The composition for forming a mediator layer according to the present invention is used to form a first coating layer, which is a mediator layer, on the surface of a substrate.

[0057] The composition for forming a mediator layer according to the present invention comprises a polyalkylsiloxane compound having a polar functional group at a terminal, an amine compound having a polar functional group containing silicon, and a solvent. Here, the polyalkylsiloxane compound having a polar functional group at a terminal and the amine compound having a polar functional group containing silicon are the same as the polyalkylsiloxane compound having a polar functional group at a terminal and the amine compound having a polar functional group containing silicon described in the above-mentioned [Coating Laminate] section, and the ratio of their contents is also the same.

[0058] As a solvent included in the composition for forming a mediating layer, a mixed solvent containing a non-polar solvent and a polar solvent is preferable.

[0059] The composition for forming an intermediate layer comprises a non-polar solvent in an amount of 2.0 to 3.0 parts by weight, preferably 2.1 to 2.8 parts by weight, and more preferably 2.3 to 2.5 parts by weight, per 1 part by weight of a polyalkylsiloxane compound having a polar functional group at a terminal. In addition, the composition for forming an intermediate layer comprises a polar solvent in an amount of 0.2 to 1.0 parts by weight, and more preferably 0.3 to 0.8 parts by weight, and more preferably 0.4 to 0.6 parts by weight, per 1 part by weight of an amine compound having a polar functional group containing silicon. By setting the content of the nonpolar solvent and the polar solvent included in the composition for forming the intermediate layer within the above range, the polyalkylsiloxane compound having a polar functional group at the terminal and the amine compound having a polar functional group containing silicon can be suitably dissolved in the solvent, and the polyalkylsiloxane compound having a polar functional group at the terminal and the amine compound having a polar functional group containing silicon can be uniformly distributed. As a result, the interaction between the first coating layer, which is the intermediate layer, and the surface of the substrate and the interaction between the first coating layer and the second coating layer can be made uniform, so that the coating laminate including the first coating layer and the second coating layer can be better maintained on the surface of the substrate.

[0060] The nonpolar solvent included in the composition for forming the intermediate layer is not particularly limited, and for example, an aliphatic hydrocarbon having 5 to 10 carbon atoms or an alicyclic hydrocarbon having 5 to 10 carbon atoms is preferable. Examples of the aliphatic hydrocarbon having 5 to 10 carbon atoms include pentane, hexane, heptane, octane, nonane, and decane. Examples of the alicyclic hydrocarbon having 5 to 10 carbon atoms include cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, and cyclodecane. Among these, as a non-polar solvent included in the composition for forming a mediating layer, an aliphatic hydrocarbon having 5 to 10 carbon atoms is preferable, and heptane is more preferable.

[0061] The polar solvent included in the composition for forming the intermediate layer is not particularly limited, and for example, an alcohol having 2 to 5 carbon atoms or a ketone having 3 to 5 carbon atoms is preferable. Examples of the alcohol having 2 to 5 carbon atoms include ethanol (Ethanol), n-propyl alcohol (n-propanol), isopropanol (iso-Propyl alcohol; IPA), n-butanol (n-Butanol), n-pentanol (n-Pentyl alcohol; n-Pentanol), etc. Examples of the ketone having 3 to 5 carbon atoms include acetone, 2-butanone (Ethyl methyl ketone; 2-butanone), 2-pentanone (Methyl propyl ketone; 2-pentanone), etc. Among these, alcohol is preferred as the polar solvent included in the composition for forming the intermediate layer, and isopropanol (IPA) is more preferred.

[0062] [Coating method]

[0063] The coating laminate according to the present invention can be manufactured according to a coating method comprising the following steps.

[0064] A step of contacting a substrate with the above-described composition for forming a mediating layer and then drying it to form a first coating layer, which is a mediating layer, on at least one surface of the substrate;

[0065] A step of contacting a substrate having a first coating layer formed on at least one surface with a composition for forming a second coating layer containing a lubricating component, thereby forming a second coating layer on the other side of the surface in contact with the substrate of the first coating layer.

[0066] Here, the composition for forming the second coating layer includes a lubricating component, and the lubricating component is the same as the lubricating component described in the above-mentioned [coating laminate] item. A commercially available product can be used as the composition for forming the second coating layer. For example, Chemours (registered trademark) Krytox 101, Krytox 103, Krytox 105 containing perfluoropolyalkyl ether (PFPAE), Silicone oil (product name, manufactured by sigma-aldrich, viscosity 10 cSt to 500 cSt) containing polyalkylsiloxane, Vitreon, FluoroMed APF-215HP containing perfluoroperhydrophenanthrene, Flutec PP6 containing perfluorodecalin, etc. can be used as the composition for forming the second coating layer.

[0067] The method of contacting a substrate with a composition for forming a medium layer and the method of contacting a substrate having a first coating layer formed on at least one surface with a composition for forming a second coating layer are not particularly limited, and are preferably performed through dip coating or spray coating, and more preferably through dip coating. Thereby, the first coating layer and the second coating layer can be uniformly and easily formed on the surface of the substrate.

[0068] It is preferable that the temperature of the composition for forming the intermediate layer and the composition for forming the second coating layer be 15°C or higher and 30°C or lower.

[0069] The viscosity of the composition for forming the intermediate layer is preferably 3 cSt or more and 60 cSt or less, and 4 cSt or more and 55 cSt or less. When the viscosity of the composition for forming the intermediate layer is within the above range, the first coating layer as the intermediate layer can be coated more uniformly on the surface of the substrate.

[0070] The viscosity of the composition for forming the second coating layer is preferably 80 cSt or more and 220 cSt or less, and 90 cSt or more and 210 cSt or less. When the viscosity of the composition for forming the second coating layer is within the above range, the second coating layer can be coated more uniformly on the surface of the first coating layer.

[0071] Meanwhile, the time for drying after bringing the substrate into contact with the composition for forming a medium layer is not particularly limited, and for example, it can be 3 seconds or more and 20 seconds or less, and preferably 4 seconds or more and 15 seconds or less.

[0072] As described above, according to the coating method according to the present invention, a first coating layer as an intermediary layer and a second coating layer as a lubricating layer can be quickly formed on the surface of a substrate without going through complicated pretreatment and posttreatment processes.

[0073] Example

[0074] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples, and may be implemented by making any modifications without departing from the scope of the claims and their equivalents.

[0075] If specific experimental methods and conditions are not mentioned below, the experiment can be conducted using conventional experimental methods and conditions.

[0076] [Manufacturing Example] - Manufacturing of a Composition for Forming a Medium Layer

[0077] A composition for forming a mediator layer (referred to as 'Link Solution A1') was prepared by mixing 25 wt% of polydimethylsiloxane having a hydroxyl group (-OH) at both terminals as a polyalkylsiloxane compound having a polar functional group at the terminal, 10 wt% of N-[3-(trimethoxysilyl)propyl]ethylenediamine as an amine compound having a polar functional group containing silicon, 60 wt% of heptane as a nonpolar solvent, and 5 wt% of isopropanol (IPA) as a polar solvent.

[0078] [Experimental Example 1] - Blood stain adhesion prevention performance test

[0079] (Example 1)

[0080] <Formation of the first coating layer>

[0081] As illustrated in Fig. 2, a glass plate as a substrate was immersed in the composition for forming an intermediate layer (solution A1) manufactured in the above-described [Manufacturing Example], then taken out and dried for 5 to 10 seconds, thereby forming a first coating layer as an intermediate layer on the surface of the glass plate. At this time, the temperature of the composition for forming an intermediate layer was room temperature (approximately 20°C), and the viscosity of the composition for forming an intermediate layer was 5 to 50 cSt.

[0082] <Formation of the second coating layer>

[0083] A composition containing polydimethylsiloxane (referred to as 'Link Solution A2') was prepared as a composition for forming a second coating layer.

[0084] As illustrated in Fig. 2, a glass plate having a first coating layer formed on the surface was immersed in a second coating layer forming composition (solution A2) and then taken out. At this time, the temperature of the second coating layer forming composition was room temperature (about 20°C), and the viscosity of the second coating layer forming composition was 100 cSt to 200 cSt. Then, the glass plate was tilted to remove the second coating layer forming composition that was excessively adhered to the surface, thereby forming a coating laminate sequentially including a first coating layer as an intermediary layer and a second coating layer as a lubricating layer on the surface of the glass plate.

[0085] Blood stain adhesion prevention performance test

[0086] A glass plate having a coating laminate formed on its surface was installed at an angle on a horizontal plane. Blood was then dropped onto the surface of the inclined glass plate using a dropper, and the condition of the glass plate surface was observed over time. The results are shown in Fig. 3. In Fig. 3, "coated glass" refers to a glass plate having a coating laminate formed on its surface according to Example 1.

[0087] (Comparative Example 1)

[0088] A blood stain adhesion prevention performance test was performed in the same manner as in Example 1, except that the glass plate was used as is without forming the first coating layer as an intermediary layer and the second coating layer as a lubricating layer on the surface of the glass plate, i.e., without forming the coating laminate according to the present invention. The results are shown in Fig. 3. In Fig. 3, "normal glass" is a glass plate on which the coating laminate according to Comparative Example 1 is not formed.

[0089] As can be seen from Fig. 3, when the coating laminate according to the present invention is formed on the surface of a glass plate, blood stains slide down the slope without adhering, thus preventing the attachment of biological substances (Example 1). In contrast, when the coating laminate according to the present invention is not formed on the surface of a glass plate, blood stains are found to adhere (Comparative Example 1).

[0090] [Experimental Example 2] - Contact Angle Measurement According to the Type of Substrate

[0091] (Examples 2 to 11)

[0092] <Formation of coating laminate>

[0093] A first coating layer as an intermediary layer and a second coating layer as a lubricating layer were formed in the same manner as in Example 1, except that polycarbonate (PC) board (Example 2), polyethylene (PE) board (Example 3), polypropylene (PP) board (Example 4), polytetrafluoroethylene (PTFE) board (Example 5), polyvinylchloride (PVC) board (Example 6), thermoplastic polyurethane (TPU) board (Example 7), aluminum (Al) board (Example 8), stainless steel (STS 304) board (Example 9), stainless steel (STS 316L) board (Example 10), and titanium (Ti) board (Example 11) were used as the substrates, respectively.

[0094] <Contact angle measurement>

[0095] Blood drops were dropped onto the surfaces of each of the substrates in Examples 2 to 11 on which the coating laminates according to the present invention were formed, and then the contact angles were measured. Here, the contact angles were measured at room temperature using a free interface droplet analysis device (SmartDrop, manufactured by Femtobiomed). The results are shown in Fig. 4. The graph "after treatment" in Fig. 4 represents the contact angle measurement results for the substrates on which the coating laminates according to Examples 2 to 11 were formed.

[0096] (Comparative examples 2 to 11)

[0097] The contact angles were measured using the same substrates as in Examples 2 to 11, using the same method, except that the first coating layer as an intermediary layer and the second coating layer as a lubricating layer were not formed on the surface of each substrate, i.e., each substrate was used as is without forming the coating laminate according to the present invention. The results are shown in Fig. 4. In Fig. 4, the graph “before treatment” is the contact angle measurement result for the substrates on the surface of which the coating laminate was not formed according to Comparative Examples 2 to 11.

[0098] As is clear from FIG. 4, the coating laminate according to the present invention can be formed on the surfaces of various substrates, and the contact angle of a blood droplet on all substrates on which the coating laminate according to the present invention is formed is close to 120°, indicating that adhesion of blood droplets can be prevented (Examples 2 to 11). In contrast, the contact angle of a blood droplet on each substrate itself, on which the coating laminate according to the present invention is not formed, is significantly lower than that of Examples 2 to 11 on which the coating laminate according to the present invention is formed, indicating that adhesion of blood droplets cannot be prevented (Comparative Examples 2 to 11). Accordingly, it can be seen that adhesion of biological materials can be prevented by forming the coating laminate according to the present invention on the surfaces of various substrates on which adhesion of biological materials could not be prevented originally.

[0099] [Experimental Example 3] - Measurement of contact angle and slip angle for various liquids with different surface tensions

[0100] (Examples 12 to 16)

[0101] <Preparation of a glass plate having a coating laminate>

[0102] In the same manner as in <Formation of the first coating layer> and <Formation of the second coating layer> of Example 1, a coating laminate including a first coating layer as an intermediary layer and a second coating layer as a lubricating layer was formed on the surface of a glass plate in that order.

[0103] <Measurement of contact angle and slip angle>

[0104] Liquid droplets having different surface tensions were dropped onto the surface of a glass plate on which a coating laminate according to the present invention was formed, and then the contact angle was measured. Here, the contact angle was measured at room temperature using a free interface droplet analysis device (SmartDrop, manufactured by Femtobiomed). As the liquid droplets having different surface tensions, ethanol (EtOH, Example 12), ethylene glycol (EG, Example 13), blood (Blood, Example 14), glycine (Glycine, Example 15), and deionized water (DIW, Example 16) were used. The measurement results of the contact angle and the sliding angle are shown in Fig. 5. In Fig. 5, the graph of "CA" represents the measurement results of the contact angle (Contact Angle), and the graph of "SA" represents the measurement results of the sliding angle (Slide Angle).

[0105] As can be clearly seen from Fig. 5, the glass plate having a coating laminate according to the present invention formed on its surface exhibits high contact angles and low sliding angles for various liquids with different surface tensions. Therefore, it can be seen that by forming a coating laminate according to the present invention on its surface, adhesion of various liquids with different surface tensions can be prevented.

[0106] [Experimental Example 4] - Transmittance Measurement

[0107] (Preparation of a glass plate having a first coating layer and a coating laminate)

[0108] In the same manner as in <Formation of the first coating layer> of Example 1, a first coating layer as an intermediary layer was formed on the surface of the glass plate.

[0109] In addition, in the same manner as in <Formation of the first coating layer> and <Formation of the second coating layer> of Example 1, a coating laminate including a first coating layer as an intermediary layer and a second coating layer as a lubricating layer was formed on the surface of a glass plate in that order.

[0110] (Transmittance measurement)

[0111] A UV-Vis spectrophotometer was used to measure the transmittance at a wavelength of 200 nm to 1200 nm for a glass plate before forming a coating laminate on the surface, a glass plate having a first coating layer formed on the surface, and a glass plate having a coating laminate (including a first coating layer and a second coating layer) formed on the surface. The results are shown in Fig. 6 (a). In Fig. 6 (a), “bare” represents a glass plate before forming a coating laminate on the surface, “A1” represents a glass plate having a first coating layer formed on the surface, and “A2” represents a glass plate having a coating laminate (including a first coating layer and a second coating layer) formed on the surface.

[0112] In addition, the results of observing a glass plate with a first coating layer and a second coating layer formed on the surface while holding it up to the sky are shown in Fig. 6 (b).

[0113] As is clear from Figures 6 (a) and (b), the coating laminate according to the present invention does not affect the inherent transmittance of the substrate. Therefore, the coating laminate according to the present invention can be used to prevent the adhesion of biological materials, even in products where light transmission is essential.

[0114] [Experimental Example 5] - Measurement of coating thickness and surface topology

[0115] (Preparation of glass plate having coating laminate)

[0116] In the same manner as in <Formation of the first coating layer> and <Formation of the second coating layer> of Example 1, a coating laminate including a first coating layer as an intermediary layer and a second coating layer as a lubricating layer was formed on the surface of a glass plate in that order.

[0117] (Measurement of coating thickness and surface topology)

[0118] For a glass plate having a coating laminate according to the present invention formed on its surface, the thickness and surface topology of the coating laminate were measured using a film thickness measuring device (DEKTAK-XT manufactured by Bruker) and an atomic force microscope (AFM). The results are shown in Fig. 7 (a) and (b).

[0119] As shown in Fig. 7 (a), the thickness of the coating laminate according to the present invention, measured based on the height of the uncoated surface, on the glass plate formed with the coating laminate according to the present invention was 20 nm or more. Therefore, it can be seen that the coating laminate according to the present invention was well formed on the surface of the glass plate with a thickness sufficient to prevent the adhesion of biological materials. In addition, it can be seen from Fig. 7 (b) that the coating laminate according to the present invention has good surface roughness characteristics.

[0120] [Experimental Example 6] - Physical Durability Test

[0121] (Example 17)

[0122] <Preparation of a glass plate having a coating laminate on its surface>

[0123] In the same manner as in <Formation of the first coating layer> and <Formation of the second coating layer> of Example 1, a coating laminate including a first coating layer as an intermediary layer and a second coating layer as a lubricating layer was formed on the surface of a glass plate.

[0124] Physical Durability Test

[0125] The second coating layer side of a glass plate having a coating laminate formed on the surface was rubbed with a cotton swab and then installed at an angle on a horizontal stand. Then, a blood droplet was dropped onto the second coating layer side of the glass plate installed at an angle using a dropper, and the blood droplet was allowed to pass over the area rubbed with the cotton swab, and it was observed whether a blood stain was attached to the area rubbed with the cotton swab. The results are shown in Fig. 8. Meanwhile, for comparison, the results when a blood droplet was dropped onto a glass plate having a coating laminate formed on the surface without rubbing it with a cotton swab are also shown in Fig. 8.

[0126] (Comparative Example 12)

[0127] <Preparation of a glass plate having a first coating layer on the surface>

[0128] In the same manner as in <Formation of the first coating layer> of Example 1, a first coating layer, which is an intermediate layer, was formed on the surface of the glass plate.

[0129] Physical Durability Test

[0130] The first coating layer side of a glass plate having only a first coating layer formed on its surface was rubbed with a cotton swab and then installed at an angle on a horizontal stand. Then, a blood droplet was dropped onto the first coating layer side of the inclined glass plate using a dropper, and the blood droplet was allowed to pass over the area rubbed with the cotton swab, and it was observed whether a blood stain was attached to the area rubbed with the cotton swab. The results are shown in Fig. 8. Meanwhile, for comparison, the results when a blood droplet was dropped onto a glass plate having only a first coating layer formed on its surface without rubbing it with a cotton swab are also shown in Fig. 8.

[0131] As is clear from Fig. 8, both the glass plate having only the first coating layer formed on the surface and the glass plate having the coating laminate formed on the surface were able to prevent adhesion of blood stains before being rubbed with a cotton swab. However, since the first coating layer of the glass plate having only the first coating layer formed on the surface is damaged when the surface on the first coating layer side is rubbed with a cotton swab, pinning is observed when a blood droplet passes over the area rubbed with the cotton swab. In contrast, the glass plate having the coating laminate according to the present invention formed on the surface is not damaged even when the surface on the second coating layer side is rubbed with a cotton swab, and thus pinning is not observed even when a blood droplet passes over the area rubbed with the cotton swab. Therefore, it can be seen that the coating laminate according to the present invention has excellent physical durability.

[0132] [Experimental Example 7] - Anti-attachment test in a marine environment

[0133] (Example 18)

[0134] <Production of test specimens>

[0135] Except that an aluminum 5052 plate measuring 30 cm in width, 35 cm in length, and 2 mm in thickness was used as a substrate, a coating laminate including a first coating layer as an intermediate layer and a second coating layer was formed on the surface of the aluminum 5052 plate in the same manner as in <Formation of the first coating layer> and <Formation of the second coating layer> of Example 1.

[0136] <Marine Life Anti-Attachment Test>

[0137] The fabricated test specimens were immersed 3 m below sea level at the South Sea Research Institute of the Korea Institute of Ocean Science and Technology. After 43 days, they were raised above sea level and observed for the presence of marine organisms on the surface. The results are shown in Figure 9.

[0138] (Comparative Example 13)

[0139] A test for preventing adhesion of marine organisms was conducted in the same manner as in Example 18, except that the first coating layer and the second coating layer, which are intermediary layers on the surface, were not formed, i.e., the coating laminate according to the present invention was not formed and the aluminum 5052 plate was used as is. The results are shown in Fig. 9.

[0140] As is clear from Fig. 9, it can be seen that by forming a coating laminate according to the present invention on the surface, attachment of marine organisms can be prevented.

Claims

1. A coating laminate comprising a first coating layer and a second coating layer formed on one surface of the first coating layer, The first coating layer is an intermediary layer interposed between the surface of the substrate and the second coating layer, and functions to maintain the second coating layer on the surface of the substrate. The above-mentioned intermediary layer comprises a polyalkylsiloxane compound having a polar functional group at the terminal and an amine compound having a polar functional group containing silicon, The second coating layer is a coating laminate containing a lubricating component.

2. In paragraph 1, A coating laminate, wherein the above-mentioned intermediary layer comprises an amine compound having a polar functional group including silicon in an amount of 0.3 parts by weight or more and 0.5 parts by weight or less per 1 part by weight of a polyalkylsiloxane compound having a polar functional group at the terminal.

3. In paragraph 1, A coating laminate, wherein a polyalkylsiloxane compound having a polar functional group at the terminal has a polar functional group at both terminals, and the polar functional group is a hydroxyl group (-OH), a carboxylic acid group (-COOH), or an amine group (-NH2), and the alkyl group is a methyl group (-CH3) or an ethyl group (-C2H5).

4. In paragraph 1, A coating laminate, wherein the polar functional group of the amine compound having a polar functional group including the above silicon is an alkoxysilyl group or a halogenosilyl group.

5. In paragraph 1, A coating laminate, wherein the amine compound having a polar functional group including the silicon is at least one selected from the group consisting of N-[3-(trimethoxysilyl)propyl]ethylenediamine, N-[3-(triethoxysilyl)propyl]ethylenediamine, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-[(trichlorosilyl)propyl]ethylenediamine, N-[(tribromosilyl)propyl]ethylenediamine, 3-aminopropyltrichlorosilane, and 3-aminopropyltribromosilane.

6. In paragraph 1, A coating laminate, wherein the lubricating component is at least one selected from the group consisting of perfluoropolyalkylether (PFPAE), polyalkylsiloxane, perfluoroperhydrophenanthrene, and perfluorodecalin.

7. A composition for forming a mediator layer, comprising a polyalkylsiloxane compound having a polar functional group at a terminal, an amine compound having a polar functional group including silicon, and a solvent, wherein the composition for forming a mediator layer comprises 0.3 parts by weight or more and 0.5 parts by weight or less of the amine compound having a polar functional group including silicon per 1 part by weight of the polyalkylsiloxane compound having a polar functional group at a terminal.

8. In paragraph 7, The above solvent includes a non-polar solvent and a polar solvent, A composition for forming a mediator layer, comprising 2.0 parts by weight or more and 3.0 parts by weight or less of the nonpolar solvent per 1 part by weight of the polyalkylsiloxane compound having a polar functional group at the terminal, and 0.3 parts by weight or more and 1.0 parts by weight or less of the polar solvent per 1 part by weight of the amine compound having a polar functional group including silicon.

9. In paragraph 7, A composition for forming a mediator layer, wherein a polyalkylsiloxane compound having a polar functional group at the terminal has a polar functional group at both terminals, and the polar functional group is a hydroxyl group (-OH), a carboxylic acid group (-COOH), or an amine group (-NH2), and the alkyl group is a methyl group (-CH3) or an ethyl group (-C2H5).

10. In paragraph 7, A composition for forming a mediator layer, wherein the polar functional group of the amine compound having a polar functional group including the above silicon is an alkoxysilyl group or a halogenosilyl group.

11. In paragraph 7, A coating laminate, wherein the amine compound having a polar functional group including the silicon is at least one selected from the group consisting of N-[3-(trimethoxysilyl)propyl]ethylenediamine, N-[3-(triethoxysilyl)propyl]ethylenediamine, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-[(trichlorosilyl)propyl]ethylenediamine, N-[(tribromosilyl)propyl]ethylenediamine, 3-aminopropyltrichlorosilane, and 3-aminopropyltribromosilane.

12. In paragraph 8, The above nonpolar solvent is an aliphatic hydrocarbon having 5 to 10 carbon atoms or an alicyclic hydrocarbon having 5 to 10 carbon atoms, A composition for forming a mediator layer, wherein the polar solvent is an alcohol having 2 to 5 carbon atoms or a ketone having 3 to 5 carbon atoms.

13. A step of contacting the substrate with the composition for forming a mediator layer as described in paragraph 7 and then drying it to form a first coating layer as a mediator layer on at least one surface of the substrate; and A coating method comprising the step of contacting a substrate having a first coating layer formed on at least one surface with a composition for forming a second coating layer including a lubricating component, thereby forming a second coating layer on the other side of the surface that contacts the substrate with the first coating layer.

14. In paragraph 13, The temperature of the composition for forming the above intermediate layer and the composition for forming the second coating layer is 15°C or more and 30°C or less, The viscosity of the composition for forming the above intermediary layer is 3 cSt or more and 60 cSt or less, A coating method, wherein the viscosity of the composition for forming the second coating layer is 80 cSt or more and 220 cSt or less.

15. In paragraph 13, A coating method comprising: bringing the substrate into contact with the composition for forming the intermediate layer, and bringing the substrate on which the first coating layer is formed on at least one surface into contact with the composition for forming the second coating layer, through dip coating or spray coating.

16. In paragraph 13, A coating method, wherein the above-mentioned substrate is made of at least one selected from the group consisting of glass, polycarbonate (PC), polyethylene (PE), polypropylene (PP), polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), thermoplastic polyurethane (TPU), aluminum (Al), stainless steel, and titanium (Ti).

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