Articles equipped with a contamination-resistant surface and methods for forming a contamination-resistant surface

Abstract

The present invention relates to an article having a contamination-preventing surface and a method for forming a contamination-preventing surface on the surface of an article.

Description

[Technical Field]

[0001] [Cross-reference with related applications] This application claims priority based on Korean Patent Application No. 10-2022-0061622 dated 19 May 2022, and all content disclosed in the said Korean Patent Application is incorporated herein as part of this specification.

[0002] The present invention relates to an article having a contamination-resistant surface and a method for forming a contamination-resistant surface on the surface of an article. [Background technology]

[0003] Anti-fouling coatings are used industrially to prevent the adhesion of foreign matter or the adsorption of contaminants onto specific surfaces.

[0004] Specifically, for example, surfaces such as display panels, camera lenses, infrared sensors, visible light sensors, camera sensors, radar, and lidar can become contaminated from time to time, even in typical usage environments, with human fingerprints, dust, and smudges originating from external sources.

[0005] If contamination occurs on the surface of such equipment, it can obstruct the user's field of vision or cause the equipment to malfunction. In particular, autonomous driving systems, which have recently attracted a lot of attention, use various sensors and radars, and if contamination occurs on the surface of such equipment, errors may occur in data interpretation due to the contaminants, which can seriously threaten the safety of autonomous driving users and people in the surrounding area.

[0006] Therefore, it is necessary to prevent contaminants from adhering to the surface of such equipment and to keep the equipment surface clean.

[0007] However, common glass and polymer resins used as surface substrates for such equipment tend to attract contaminants due to their properties, requiring periodic cleaning. This necessitates separate power supplies and equipment, and even with cleaning and drying, there is a risk of additional surface irregularities occurring.

[0008] Furthermore, in the case of superhydrophobic or superoleophobic coatings used to prevent the adhesion of contaminants, surface irregularities exist, and because the durability of these surface irregularities is not high, there is a problem in that the effect does not last long.

[0009] Therefore, research is needed on contamination-resistant surfaces that can prevent contaminants from adhering to the surface of equipment. [Overview of the project] [Problems that the invention aims to solve]

[0010] This specification provides articles having a contamination-resistant surface, and methods for forming a contamination-resistant surface on the surface of an article. [Means for solving the problem]

[0011] This specification provides an article having a contamination-resistant surface, comprising: a substrate; a first region present on a portion of the surface of the substrate on which a lubricating layer is formed; and a second region present on at least a portion of the region on the surface of the substrate other than the first region on which an anti-adhesion coating layer is formed.

[0012] According to one example of the invention, the surface energy of the second region may be greater than the surface energy of the first region.

[0013] Specifically, the lubricating layer has a surface energy of approximately 20 mJ / m 2 It is acceptable to be less than [a certain value].

[0014] Furthermore, the anti-adhesion coating layer has a surface energy of approximately 20 mJ / m². 2 That's fine too.

[0015] And the anti-adhesion coating layer may have a surface energy of about 40 mJ / m 2 or less.

[0016] According to another example of the invention, the second region can be formed to surround the first region.

[0017] And the first region can be formed in a convex or concave form.

[0018] According to an example of the invention, the thickness of the lubricating layer may be about 0.1 to 200 μm, or about 0.1 μm or more, or about 0.5 μm or more, or about 1 μm or more, or about 200 μm or less, or about 150 μm or less, or about 100 μm or less.

[0019] And the lubricating layer can include a hydrophobic inorganic cured layer, a fluorine-silane cured layer formed on the hydrophobic inorganic cured layer, and a fluorine oil layer formed on the fluorine-silane cured layer.

[0020] According to an example of the invention, the hydrophobic inorganic cured layer can include a cured product of alkyl-trialkoxysilane and tetraalkoxysilane.

[0021] And the thickness of the hydrophobic inorganic cured layer may be about 0.05 to 20 μm, or about 0.05 μm or more, or about 0.1 μm or more, and may be about 20 μm or less, or about 15 μm or less, or about 10 μm or less.

[0022] According to another example of the invention, the fluorine-silane cured layer can include a cured product of fluorinated polyether silane.

[0023] And the fluorine oil layer can include fluorinated polyether oil.

[0024] Furthermore, the total thickness of the fluorine-silane hardened layer and the fluorine oil layer may be approximately 0.1 to approximately 200 μm, or approximately 0.1 μm or more, or approximately 0.5 μm or more, or approximately 1 μm or more, or approximately 200 μm or less, or approximately 150 μm or less, or approximately 100 μm or less.

[0025] Furthermore, the anti-adhesion coating layer may contain a polydialkylsiloxane cured product and a silicone oil.

[0026] Furthermore, the silicone oil may have a viscosity of 1000 cSt or less.

[0027] On the other hand, this specification provides a method for forming a contamination-resistant surface, comprising the steps of: forming a first region including a hydrophobic inorganic hardened layer on a part of the surface of a substrate; forming a second region including an anti-adhesion coating layer on at least a part of the region of the substrate surface other than the first region; and forming a lubricating layer on the first region.

[0028] The terms used herein are for illustrative purposes only and are not intended to limit the invention.

[0029] A singular expression includes plural expressions unless the context clearly indicates otherwise.

[0030] In this specification, terms such as “includes,” “equip,” or “have” are used to describe the features, figures, stages, components, or combinations thereof that are implemented, and do not exclude one or more other features, figures, stages, components, combinations thereof, or add-ons.

[0031] Furthermore, in this specification, when it is referred to that each layer or element is formed "on top of" or "on top of" each layer or element, it means that each layer or element is formed directly on top of each layer or element, or that other layers or elements may be formed additionally between each layer, on the object, or on the substrate.

[0032] Because the present invention can be modified in various ways and take on many forms, specific embodiments are illustrated and described in detail below. However, this should not be understood as limiting the present invention to any particular disclosure, but rather as including all modifications, equivalents, or substitutions that fall within the spirit and technical scope of the present invention.

[0033] The present invention will be described in detail below.

[0034] According to one aspect of the present invention, an article is provided having a contamination-resistant surface, comprising: a substrate; a first region present on a portion of the surface of the substrate on which a lubricating layer is formed; and a second region present on at least a portion of the region on the surface of the substrate other than the first region on which an anti-adhesion coating layer is formed.

[0035] The inventors of the present invention discovered that when contaminants adhere to the surface of an article which includes both a first region on the substrate surface where a lubricating layer is formed and a second region where an anti-adhesion coating layer is formed, the contaminants move from the first region to the second region, and then detach from the surface of the anti-adhesion coating layer in the second region, preventing the contaminants from adhering to the surface of the article. This discovery led to the completion of the present invention.

[0036] First, in an article having a contamination-resistant surface according to one aspect of the present invention, the base material can mean the base material that constitutes the surface of the article itself, or it can mean a base material that is separately applied to the surface of a general article in order to realize the contamination-resistant surface.

[0037] Furthermore, the substrate surface may have a first region on which a lubricating layer is formed and a second region on which an anti-adhesion coating layer is formed, and the first region and the second region may be separated on the substrate surface in such a way that they do not overlap with each other.

[0038] Figure 1 shows an article equipped with a contamination-preventive surface according to an example of the present invention, and schematically illustrates a cross-section of the contamination-preventive surface.

[0039] Referring to Figure 1 above, an article equipped with a contamination-preventive surface according to an example of the present invention can be seen, in which the contamination-preventive surface comprises a base material 100; a first region 200 present on a part of the base material surface where a lubricating layer is formed; and a second region 300 present on at least a part of the area of ​​the base material surface other than the first region where an anti-adhesion coating layer is formed.

[0040] According to one example of the invention, the surface energy of the second region may be greater than the surface energy of the first region.

[0041] That is, in the case of the first region, the surface energy of the region where the lubricating layer is formed can be relatively small, and in the case of the second region, the surface energy of the region where the anti-adhesion coating is formed can be relatively large.

[0042] Conversely, in an example of the present invention, the region having a relatively small surface energy value among the mutually distinct first and second regions of the surface of an article can be referred to as the first region where a lubricating layer is formed, and the region having a relatively large surface energy value among the mutually distinct first and second regions of the surface of an article according to an example of the present invention can be referred to as the second region where an anti-adhesion coating layer is formed.

[0043] When contamination occurs on the aforementioned contamination-preventing surface, the adhering contaminants are pushed out by the surface energy difference from the region with a relatively small surface energy value, i.e., the first region where the lubricating layer is formed, to the region with a relatively small surface energy value, i.e., the second region where the anti-adhesion coating layer is formed.

[0044] Specifically, when contamination occurs on a contamination-preventing surface, the difference in surface energy between the first and second regions creates a difference between the first interfacial tension generated at the surface interface between the contaminant and the first region, and the second interfacial tension generated at the surface interface between the contaminant and the second region.

[0045] In other words, because the first interfacial tension value is greater than the second interfacial tension value, the portion of the contaminant that is over the first region tends to converge relatively towards the center of the contaminant, and the portion of the contaminant that is over the second region tends to spread relatively outwards, causing the center of the contaminant to gradually shift towards the second region.

[0046] The contaminants pushed into the second region are then detached and removed from the surface of the article by the anti-adhesion coating layer.

[0047] A contamination-resistant surface can be realized using this principle, and articles equipped with such a contamination-resistant surface can effectively prevent their surface from being contaminated by external sources of contamination.

[0048] In other words, the aforementioned effect occurs when the contaminant is in full contact with the interface between the lubricating layer and the anti-adhesion coating layer, due to the difference in surface tension acting at the interface between the lubricating layer and the contaminant, and at the interface between the anti-adhesion coating layer and the contaminant.

[0049] When a lubricating layer or an anti-adhesion coating layer is used alone, the aforementioned effects are difficult to obtain because spontaneous movement of contaminants due to surface tension differences does not occur on the layer.

[0050] Figure 2 is a schematic diagram illustrating the effects achieved by one embodiment of the present invention.

[0051] Referring to Figure 2, it can be seen that contaminants adhering to the surface move towards the anti-adhesion coating layer at the interface between the lubricating layer and the anti-adhesion coating layer due to the difference in surface energy, and then detach.

[0052] Figure 3 is a schematic diagram showing an example in which a contamination prevention effect is achieved with an article according to one embodiment of the present invention.

[0053] Referring to FIG. 3, when an article according to an embodiment of the present invention is a sensor recognized by a camera or the like, it can be confirmed that contaminants attached to the sensor move to the anti-adhesion coating layer side due to the difference in surface energy at the interface between the lubricating layer and the anti-adhesion coating layer. In this case, the possibility of sensor malfunction due to contamination adhesion can be reduced.

[0054] For example, the lubricating layer may be a layer capable of realizing the SLIPS (Slippery Liquid-Infused Porous Surfaces) effect. Here, the surface of the SLIPS layer does not necessarily have to be formed porous.

[0055] For example, the surface energy values of the lubricating layer and the anti-adhesion coating layer may all be about 50 mJ / / m 2 or less. That is, it is preferable that both the lubricating layer and the anti-adhesion coating layer have low surface energy values. More specifically, both the lubricating layer and the anti-adhesion coating layer may be hydrophobic layers. At the same time, the surface energy of the lubricating layer can have a relatively smaller value than the surface energy of the anti-adhesion coating layer, and conversely, the surface energy of the anti-adhesion coating layer can have a relatively larger value than the surface energy of the lubricating layer.

[0056] Specifically, for example, the surface energy of the lubricating layer is about 20 mJ / m 2 or less, or about 18 mJ / m 2 or less, or about 15 mJ / m 2 or less, or about 12 mJ / m 2 or less.

[0057] When the surface energy of the lubricating layer deviates from the above range, the above-described effect of contaminants moving from the lubricating layer to the anti-adhesion coating layer may not be shown.

[0058] And the anti-adhesion coating layer has a surface energy of about 20 mJ / m 2Above, or approximately 20 mJ / m³ 2 The above, or approximately 25 mJ / m³ 2 It may be greater than or equal to approximately 40 mJ / m 2 Below, 35mJ / m 2 The following, or approximately 30 mJ / m³ 2 The following is also acceptable.

[0059] If the surface energy of the anti-adhesion coating layer deviates from the aforementioned range, the aforementioned effect of transferring contaminants from the lubricating layer to the anti-adhesion coating layer may not be observed, and a problem may arise in which contaminants do not detach from the anti-adhesion coating layer.

[0060] Surface energy can be measured by dropping droplets of water and diiodomethane onto the surface, measuring the contact angle using a contact angle meter, and then inputting the measured value into a model equation.

[0061] Specifically, the Fowkes equation or the van Oss-Chaudhury-Good equation can generally be used for surface energy calculations.

[0062] According to another example of the invention, the second region can be formed in a manner that surrounds the first region.

[0063] Figure 4 is a schematic image showing an article equipped with a contamination-preventive surface according to an example of the present invention, with the contamination-preventive surface viewed from above.

[0064] Referring to Figure 4, it can be confirmed that the second region 300 surrounds the first region 200.

[0065] In the case of Figure 4, the first region is shown as a circle and the second region as a square. This is for convenience to illustrate one configuration in which the second region surrounds the first region, and the shapes of the first and second regions are not necessarily limited to circles or specific polygons.

[0066] Furthermore, the contamination prevention surface may comprise one first region and one second region, as shown in the drawing, or it may comprise multiple first regions and second regions, and the number of first regions and second regions does not necessarily have to be the same.

[0067] Figure 5 is a schematic image showing an article equipped with a contamination-resistant surface according to another example of the present invention, with the contamination-resistant surface viewed from above.

[0068] According to one example of the invention, the average area of ​​the first region is approximately 5 cm². 2 The following is preferable:

[0069] Furthermore, it is preferable that the area ratio of the first region, i.e., the region where the lubricating layer is formed, to the total area of ​​the first region and the area of ​​the second region is approximately 20% to approximately 80%.

[0070] If the area of ​​the first region is excessively large, or the proportion of the first region is excessively high, that is, if the area ratio of the first region where the lubricating layer is formed is excessively large, a problem may arise in which contaminants adhering to the surface do not move from the first region to the second region, but remain in the middle of the first region. Furthermore, if the area of ​​the first region is excessively small, or the proportion of the first region is excessively low, that is, if the area ratio of the first region where the lubricating layer is formed is excessively small, a problem may arise in which transparency and visibility cannot be ensured.

[0071] Furthermore, the first region can be formed in a convex or concave shape. By forming the first region in a convex or concave shape, the aforementioned effect of contaminants adhering to the surface moving from the first region to the second region can be further promoted.

[0072] Figures 6 and 7 show an article equipped with a contamination-preventive surface according to an example of the present invention, and schematically illustrate the cross-section of the contamination-preventive surface.

[0073] Referring to Figures 6 and 7, an article equipped with a contamination-preventive surface according to an example of the present invention can be seen, comprising a base material 100; a first region 200 formed in a concave or convex shape; and a second region 300.

[0074] In the drawings, the first region, which is formed in a concave or convex shape, is shown in the form of an arc. However, the present invention is not necessarily limited to this, and the cross-section of the first region may be formed in a concave or convex shape in the form of various curves or polygons.

[0075] According to one example of the invention, the thickness of the lubricating layer may be about 0.1 to 200 μm, or about 0.1 μm or more, or about 0.5 μm or more, or about 1 μm or more, or about 200 μm or less, or about 150 μm or less, or about 100 μm or less.

[0076] If the thickness is too thin, problems may occur with reduced durability and lubrication effect, and if the thickness is too thick, problems may occur with cracking or excessive flow of lubricant from the lubrication layer.

[0077] The lubricating layer may include a hydrophobic inorganic hardened layer, a fluorine-silane hardened layer formed on the hydrophobic inorganic hardened layer, and a fluorine oil layer formed on the fluorine-silane hardened layer.

[0078] Here, the fluorine-silane hardened layer and the fluorine oil layer may have a boundary between them, clearly separating each layer, or, depending on the properties of the constituent materials, the boundary between the layers may not be clear, and they may not be separated into layers.

[0079] The hydrophobic inorganic hardened layer can be formed by the hardening of a coating liquid (hereinafter referred to as the first coating liquid) used to form it.

[0080] According to one example of the invention, the hydrophobic inorganic cured layer may contain cured alkyl-trialkoxysilane and tetraalkoxysilane, and the first coating solution may contain alkyl-trialkoxysilane and tetraalkoxysilane.

[0081] According to one embodiment of the invention, the alkyl-trialkoxysilane may be a compound represented by the following chemical formula 1.

[0082] [Chemical formula 1] R11-Si (R12) (R13) (R14)

[0083] In the above chemical formula 1, R11 is an alkyl group having 1 to 5 carbon atoms, and R12 to R14 are each independently alkoxy groups having 1 to 5 carbon atoms.

[0084] More specifically, R11 may be methyl, ethyl, propyl, butyl, or pentyl, and may be linear or branched.

[0085] R12 to R14 may each be independently methoxy, ethoxy, propoxy, butoxy, or pentoxy, and may be linear or branched.

[0086] Specifically, for example, the alkyl-trialkoxysilane may be one or more selected from the group consisting of methyl-trimethoxysilane, methyl-triethoxysilane, methyl-tripropoxysilane, methyl-tributoxysilane, methyl-tripentoxysilane, ethyl-trimethoxysilane, ethyl-triethoxysilane, ethyl-tripropoxysilane, ethyl-tributoxysilane, ethyl-tripentoxysilane, propyl-trimethoxysilane, propyl-triethoxysilane, propyl-tripropoxysilane, propyl-tributoxysilane, propyl-tripentoxysilane, butyl-trimethoxysilane, butyl-triethoxysilane, butyl-tripropoxysilane, butyl-tributoxysilane, butyl-tripentoxysilane, pentyl-trimethoxysilane, pentyl-triethoxysilane, pentyl-tripropoxysilane, and pentyl-tributoxysilane and pentyl-tripentoxysilane.

[0087] The alkyl-trialkoxysilanes described above are components that constitute the main network of the inorganic coating film through a sol-gel reaction within the composition. In this case, the alkyl group increases the flexibility of the network structure, which can alleviate the stress generated during the reaction between silanols or between silanols and the substrate surface. If only alkylsilanes are used, the number of silanols participating in the reaction is small, which is disadvantageous in lowering the surface energy during subsequent fluorine coating. If only alkoxysilanes are used, the aforementioned stress-relieving effect cannot be obtained.

[0088] According to one embodiment of the invention, the tetraalkoxysilane may be a compound represented by the following chemical formula 2.

[0089] [Chemical formula 2] Si(R21)(R22)(R23)(R24)

[0090] In the above chemical formula 2, R21 to R24 are each independently alkoxy groups having 1 to 5 carbon atoms.

[0091] More specifically, each of the above-mentioned R21 to R24 may independently be methoxy, ethoxy, propoxy, butoxy, or pentoxy, and may be linear or branched.

[0092] Specifically, for example, the tetraalkoxysilane may be one or more selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetrapentoxysilane.

[0093] The tetraalkoxysilanes described above can increase the number of silanol groups in the composition that can participate in the aforementioned reactions between silanols or between silanols and the substrate surface, which helps to increase the degree of reactivity with fluorine-silane and realize a surface with low surface energy.

[0094] When tetraalkoxysilanes are used in excess, excessive reactions occur between silanols, which can induce strong shrinkage in the overall network, leading to problems such as cracking or delamination of the bonds.

[0095] Therefore, by mixing alkyl-trialkoxysilane and tetraalkoxysilane in appropriate proportions, it is possible to prevent the problem of crack formation in the overall coating layer network and to ensure that the surface has an appropriate amount of silanol reactive groups.

[0096] Furthermore, an organic acid may be used in the first coating solution.

[0097] According to one embodiment of the invention, the organic acid may be a carboxyl acid having 1 to 5 carbon atoms.

[0098] Specifically, for example, the organic acid may be one or more selected from the group consisting of formic acid, acetic acid, and propionic acid.

[0099] The organic acids described above can be used as catalysts to promote the hydrolysis of silane groups within the composition and can play a role in determining the overall network structure. Under acidic conditions with a low pH, the hydrolysis rate is dominant over the condensation rate, resulting in a linear structure formed by the silane bonds. Conversely, under basic conditions, the condensation rate is even faster, resulting in the formation of a particulate structure. Inorganic acids such as hydrochloric acid can also be used, but organic acids are more useful in adjusting the gel time.

[0100] Furthermore, the first coating solution may contain approximately 1 to 50 parts by weight of tetraalkoxysilane per 100 parts by weight of alkyl-trialkoxysilane.

[0101] If too little tetraalkoxysilane is used, the number of silanol groups that subsequently react with fluorine-silane will be too small, making it difficult to lower the surface energy to an appropriate level. Conversely, if too much is used, the excessive silanol group reaction will increase the stress acting on the overall coating network, which can lead to problems such as cracks in the coating layer or a decrease in the adhesion of the coating layer.

[0102] Furthermore, the first coating solution may contain about 1 to about 10 parts by weight of an organic acid per 100 parts by weight of alkyl-trialkoxysilane.

[0103] If the amount of organic acids is excessively low, the hydrolysis rate decreases, making it difficult to obtain a satisfactory linear network structure, which can lead to a decrease in the physical properties of the coating film. Conversely, if the amount is excessively high, the gel time decreases, making it difficult to regulate the reaction, and an excess of organic acids that do not participate in the network may be present, resulting in a decrease in the mechanical properties of the coating layer.

[0104] The pH of the first coating solution may be approximately 7 or less, or approximately 5 or less, or approximately 3 or less, and may be approximately 1 or more, or approximately 2 or more.

[0105] pH can affect the hydrolysis rate and the condensation reaction rate. The difference in the rates of these two reactions determines the structure of the coating film and affects the storage stability of the manufactured coating solution.

[0106] From this perspective, a stable inorganic coating can be obtained under acidic conditions with a pH within the aforementioned range.

[0107] The first coating solution may further contain an organic solvent in addition to the components described above. Specifically, such organic solvents may include, for example, alcohols or ethers, and the amount of organic solvent can be appropriately selected considering coating properties and drying after application.

[0108] Furthermore, the thickness of the hydrophobic inorganic hardened layer may be approximately 0.05 to 20 μm, or approximately 0.05 μm or more, or approximately 0.1 μm or more, and may be approximately 20 μm or less, or approximately 15 μm or less, or approximately 10 μm or less. If the thickness of the hydrophobic inorganic hardened layer is excessively thin, physical properties such as coating hardness may decrease, and if the thickness of the hydrophobic inorganic hardened layer is excessively thick, problems such as cracks occurring in the coating layer or peeling of the coating layer may occur.

[0109] The fluorine-silane hardened layer can be formed by the hardening of a coating solution (hereinafter referred to as the second coating solution) used to form it.

[0110] According to another example of the invention, the fluorine-silane cured layer may include a cured product of fluorinated polyethersilane.

[0111] According to one embodiment of the invention, the fluorinated polyethersilane may be a compound containing residues (moieties) represented by the following chemical formulas 3-1 to 3-4.

[0112] [Chemical formula 3-1] CF3- [Chemical formula 3-2] -CF2-CF2-O- [Chemical formula 3-3] -CF2-CF2-CF2-O- [Chemical formula 3-4] -Si(R31)(R32)(R33)

[0113] In the above chemical formulas 3-4, R31 to R33 are each independently alkoxy groups having 1 to 5 carbon atoms.

[0114] The aforementioned fluorinated polyethersilane is a compound having a fluorinated carbon at one end, an alkoxysilane group at the other end, and an intermediate fluorinated ethoxy or fluorinated propoxy group. It can directly form covalent bonds with the first coating layer to form a hard coating layer, and the large amount of fluorine chains can drastically lower the surface energy of the coating layer.

[0115] In the second coating solution, the fluorinated polyethersilane can be used together with an alkoxyfluoride alkyl solvent.

[0116] The alkyl alkoxyfluoride solvent used here may be an ether compound represented by the following chemical formula 4.

[0117] CF3-(CF2) n -O-(CH2) m -CH3

[0118] In the above chemical formula, n and m may each be an integer from 1 to 5, independently of each other.

[0119] The aforementioned ether compound has an oxygen atom at its center, with an alkyl group that is not substituted with fluorine linked to one side, and an alkyl group on the other side in which all hydrogen atoms are substituted with fluorine linked to the other side.

[0120] Such ether compounds exhibit excellent compatibility with the aforementioned fluorinated polyethersilane compounds, allowing for uniform dispersion of the fluorinated polyethersilane compounds in the second coating solution.

[0121] The fluorine oil layer can be formed by applying a coating liquid (third coating liquid) for its formation.

[0122] According to one embodiment of the invention, the fluorine oil layer may contain fluorinated polyether oil.

[0123] Furthermore, the fluorinated polyether oil may be a compound containing the group represented by the following chemical formulas 4-1 to 4-3.

[0124] [Chemical formula 4-1] CF3- [Chemical formula 4-2] -CF2-CF2-O- [Chemical formula 4-3] -CF2-CF2-CF2-O-.

[0125] The polyether oil described above is a type of perfluoropolyether containing CF3 at both ends and perfluoroalkylene oxide repeating units internally. This chemical structure allows for excellent bonding with the fluorine-silane hardened layer while also providing a lubricating effect, thereby achieving contamination prevention performance.

[0126] When the third coating liquid is applied to a metal surface on which a fluorine-silane hardened layer has been formed, the coating thickness may be approximately 0.1 to approximately 100 μm.

[0127] If the thickness is excessively thin, the lubricating effect may decrease, and if the thickness is excessively thick, problems may arise where the lubricant flows off the surface.

[0128] Furthermore, the total thickness of the fluorine-silane hardened layer and the fluorine oil layer may be approximately 0.1 to approximately 200 μm, or approximately 0.1 μm or more, or approximately 0.5 μm or more, or approximately 1 μm or more, or approximately 200 μm or less, or approximately 150 μm or less, or approximately 100 μm or less.

[0129] If the curing thickness of the fluorine-silane hardened layer is excessively thin, the coating may not be sufficient, resulting in a low fluorine content on the surface and an inability to maintain a properly low surface energy. Conversely, if the curing thickness of the fluorine-silane hardened layer is excessively thick, the polymer silane may clump together, leading to problems such as uneven formation of the coating layer and reduced economic efficiency.

[0130] Furthermore, the anti-adhesion coating layer may contain a polydialkylsiloxane cured product and a silicone oil.

[0131] In this case, the silicone oil can be encapsulated within the polydialkylsiloxane crosslinked polymer, providing excellent anti-adhesion performance while maintaining the durability of the coating layer. The coating surface remains solid, non-slip, and the silicone components do not leach off the surface.

[0132] The anti-adhesion coating layer can be formed by a two-component coating solution comprising a first solution containing a polydialkylsiloxane having ethylenically unsaturated groups at both ends, an organic solvent, and a silicone oil; and a second solution containing a crosslinking agent.

[0133] The polydialkylsiloxane may be a compound represented by the following chemical formula 5.

[0134] [ka]

[0135] In the above chemical formula 5, n is the number of repeats in the siloxane repeating unit, and is an integer between 10 and 1,000. R1 and R8 are independently hydrogen or an alkyl group having 1 to 5 carbon atoms. R2 to R7 are each independent alkyl groups with 1 to 5 carbon atoms.

[0136] The aforementioned n may be approximately 10 or more, or approximately 30 or more, or approximately 50 or more, and may be 1000 or less, or approximately 500 or less, or approximately 300 or less, or approximately 100 or less.

[0137] As described above, polydialkylsiloxane monomers, which have ethylenically unsaturated groups at both ends, are monomers with a long chain and can be polymerized with other monomer components.

[0138] When a coating layer is formed using such polydialkylsiloxane monomers and a crosslinking agent and polymerization is carried out, crosslinking bonds are formed between the polydialkylsiloxane monomers and the crosslinking agent, and a network structure of dialkylsiloxane unit chains can be formed.

[0139] In particular, the polydialkylsiloxane monomer described above has almost the same chemical properties as the silicone oil used to achieve anti-adhesion performance, and has excellent compatibility with the silicone oil, which allows the silicone oil to be well captured in the network structure of the polydialkylsiloxane.

[0140] In other words, by forming a coating layer using a coating composition according to one aspect of the present invention, the silicone oil component is trapped between the polydialkylsiloxane monomer and the crosslinking agent, thereby achieving an anti-adhesion effect while preventing the silicone oil from leaching outside the crosslinking network.

[0141] Furthermore, the polydialkylsiloxane monomers described above exhibit extremely strong bond strength after crosslinking polymerization, significantly improving the durability of the coating layer during its formation.

[0142] Furthermore, the number of siloxane repeating units in the polydialkylsiloxane monomer determines the length of the polydialkylsiloxane chain, and ultimately, after crosslinking polymerization, it is related to the size of the empty spaces in the crosslinked network structure, and the size of these empty spaces is directly related to whether or not the silicone oil dissolves outside the crosslinked polymerization network.

[0143] From this perspective, the n may be approximately 10 or more, or approximately 30 or more, or approximately 50 or more, or 1000 or less, or approximately 500 or less, or approximately 300 or less, or approximately 100 or less. However, the present invention is not necessarily limited thereto, and the n value is further related to the molecular size of the silicone oil used together.

[0144] In this case, the weight ratio of the polydialkylsiloxane component to the silicone oil is preferably about 1:5 to about 5:1, or about 1:5 to about 3.5:1, or 1:3.5 to 2.5:1.

[0145] If the silicone oil content exceeds the aforementioned range, the mechanical properties of the anti-adhesion coating formed by the composition may deteriorate, and problems such as slow curing for coating layer formation may occur. Conversely, if the silicone oil content is excessively low, problems such as reduced anti-adhesion performance may occur.

[0146] The organic solvent may include one or more selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, 2-butanol, xylene, and toluene.

[0147] Since the aforementioned solvents are used to uniformly disperse the silicone oil, the present invention is not necessarily limited to these, and any solvent with high solubility in the silicone oil can be appropriately selected and used from among ketones, alcohols, acetates, and aromatic compounds.

[0148] According to one embodiment of the invention, the silicone oil may have a viscosity of 500 cSt or less, or 1 cSt or more and less than 500 cSt, with a lower limit of approximately 1 cSt or more, or approximately 5 cSt or more, or approximately 7 cSt or more, and an upper limit of approximately 500 cSt or less, or approximately 400 cSt or less, or approximately 300 cSt or less, or approximately 150 cSt or less.

[0149] If the viscosity of the silicone oil is excessively low, the amount of oil required to achieve the anti-adhesion effect will increase, which can lead to a decrease in adhesion to the substrate and the possibility of the coating peeling off. If the viscosity of the silicone oil is excessively high, the oil may dissolve onto the surface during coating, potentially causing oil contamination.

[0150] Furthermore, it is preferable to use a silicone oil with a weight-average molecular weight of approximately 1,000 to approximately 10,000, or approximately 1,000 to approximately 5,000.

[0151] If the molecular weight of the silicone oil is excessively low, the oil content will increase to achieve the anti-adhesion effect, similar to when the viscosity of the silicone oil is low. This can lead to problems such as reduced adhesion to the substrate and peeling of the coating during hot water resistance evaluation. Conversely, if the molecular weight of the silicone oil is excessively high, similar to when the viscosity of the silicone oil is excessively high, the oil may dissolve onto the surface during coating, causing oil contamination.

[0152] According to one embodiment of the invention, the first liquid preferably further comprises a volatile branched siloxane compound.

[0153] Such volatile branched siloxanes can improve the dispersibility of silicone oils, polydialkylsiloxanes with ethylenically unsaturated groups, and other similar compounds, thereby improving coating properties during coating layer formation. After application, they can be volatilized and removed within the coating layer.

[0154] Examples of such compounds include tetra(trialkylsiloxy)silane compounds, where the alkyl group may be a linear or branched alkyl group having 1 to 4 carbon atoms.

[0155] More specifically, examples of the volatile branched siloxane compounds include tetra(trimethylsiloxy)silane, tetra(triethylsiloxy)silane, tetra(tripropylsiloxy)silane, tetra(triisopropylsiloxy)silane, tetra(tributylsiloxy)silane, and tetra(triisobutylsiloxy)silane.

[0156] Furthermore, the crosslinking agent may include a siloxane compound containing three or more ethylenically unsaturated groups.

[0157] Specifically, the crosslinking agent may be a cyclic siloxane in which siloxane repeating units are linked together as shown below.

[0158] [ka]

[0159] In the above chemical formula, n may be between 3 and 10, or between 3 and 7. R1 and R2 are each independently an alkyl group having 1 to 5 carbon atoms, or an alkene having 2 to 5 carbon atoms containing an ethylenically unsaturated group, and at least one of R1 and R2 is an alkene having 2 to 5 carbon atoms containing an ethylenically unsaturated group.

[0160] In a coating composition according to one embodiment of the present invention, a polydialkylsiloxane having ethylenically unsaturated groups at both ends can be polymerized around the crosslinking agent to form a network-like crosslinked network.

[0161] According to another embodiment of the invention, the first liquid and the second liquid may each independently further contain silica surface-modified with ethylenically unsaturated groups.

[0162] Specifically, silica compounds surface-modified with ethylenically unsaturated groups may be in a form in which ethylenically unsaturated groups such as vinyl groups, or alkylated vinyl groups having 1 to 5 carbon atoms, or dialkylated vinyl groups having 1 to 5 carbon atoms, are linked to the terminals of the silanol groups on the surface of the silica group.

[0163] As described above, silica compounds surface-modified with ethylenically unsaturated groups can, during the polymerization process, have their ethylenically unsaturated groups linked with the aforementioned crosslinking agent and / or polydialkylsiloxane compounds having ethylenically unsaturated groups at both ends, and can also play a role in forming a network-like crosslinking network, which can particularly improve the mechanical properties and dimensional stability of the coating layer formed by polymerization.

[0164] On the other hand, this specification provides a method for forming a contamination-resistant surface, comprising the steps of: forming a first region including a hydrophobic inorganic hardened layer on a part of the surface of a substrate; forming a second region including an anti-adhesion coating layer on at least a part of the region of the substrate surface other than the first region; and forming a lubricating layer on the first region.

[0165] The coating liquid required to form each layer can be substituted with the one described above.

[0166] When applying the coating liquid, the application method is not particularly limited. Methods commonly used in the art to which this invention belongs can be selected, such as applying it directly with a brush or other tool, spraying it after appropriately adjusting its viscosity, or coating it using a bar.

[0167] After application, drying can be performed at room temperature for approximately 10 minutes to 1 hour. These drying conditions can be varied depending on the type and amount of solvent used.

[0168] After drying, curing can be performed at a temperature of approximately 100 to 150°C for approximately 30 minutes to 2 hours. [Effects of the Invention]

[0169] According to one example of the present invention, it is possible to effectively prevent contaminants from adhering to the surface of an article. [Brief explanation of the drawing]

[0170] [Figure 1] This is an image schematically showing a cross-section of an article equipped with a contamination-preventive surface according to an example of the present invention. [Figure 2] This diagram schematically illustrates the effects achieved by one embodiment of the present invention. [Figure 3] This is a schematic diagram illustrating an example in which a contamination prevention effect is achieved with an article according to one embodiment of the present invention. [Figure 4] This is a schematic image showing an article equipped with a contamination-preventive surface according to an example of the present invention, as observed from above. [Figure 5] This is a schematic image showing an article equipped with a contamination-preventive surface according to another example of the present invention, with the contamination-preventive surface viewed from above. [Figure 6] This is an image schematically showing a cross-section of an article equipped with a contamination-preventive surface according to an example of the present invention. [Figure 7] This is an image schematically showing a cross-section of an article equipped with a contamination-preventive surface according to an example of the present invention. [Figure 8] This diagram briefly illustrates the process for manufacturing an article with a contamination-resistant surface according to one embodiment of the present invention. [Figure 9] This is a photograph showing the evaluation of the contamination prevention performance of a contamination prevention article according to one embodiment of the present invention. [Modes for carrying out the invention]

[0171] The operation and effects of the invention will be described in more detail below through specific embodiments of the invention. However, these embodiments are presented merely as examples of the invention and do not determine the scope of the invention's rights. [Examples]

[0172] The lubricating layer was configured in the form of a hydrophobic inorganic hardened layer, a fluorine-silane hardened layer formed on the hydrophobic inorganic hardened layer, and a fluorine oil layer formed on the fluorine-silane hardened layer.

[0173] The following coating liquid was prepared for forming a hydrophobic inorganic hardened layer (hereinafter referred to as the 1-1 coating liquid).

[0174] Five parts by weight of methyl-trimethoxysilane was used as the alkyl-trialkoxysilane component, one part by weight of tetraethoxysilane was used as the tetraalkoxysilane component, and four parts by weight of a 6 wt% acetic acid solution diluted in water was used as the organic acid component. These were then mixed together. (pH approximately 2.3)

[0175] The first coating solution was prepared by diluting 100 parts by weight of the coating solution with approximately 50 parts by weight of isopropyl alcohol as a solvent.

[0176] The following coating solutions were prepared for forming the fluorine-silane hardened layer (hereinafter referred to as the first and second coating solutions).

[0177] As the fluorinated polyethersilane component, we used Optool-DSX, a perfluoropolyethersilane from Daikin, dissolved at a concentration of 1 wt% in Novec-7200 from 3M, which was used as the solvent.

[0178] The following coating solutions were prepared for forming the fluorine oil layer (hereinafter referred to as the 1st to 3rd coating solutions).

[0179] As the fluorinated polyether oil component, DEMNUM-S65, a perfluoropolyether from Daikin, was dissolved at a concentration of 1 wt% in Novec-7200 from 3M as the solvent. (Surface energy after drying: 18 mN / m²) 2 ;manufacturer's TDS data standards)

[0180] For the coating liquid (hereinafter referred to as the second coating liquid) for forming the anti-adhesion coating layer, a polydialkylsiloxane having ethylenically unsaturated groups at both ends and Dow's Sylgard (R) 184 silicone elastomer kit, 2 parts by weight of base resin and 0.2 parts by weight of crosslinking agent were used. As the silicone oil, 3.3 parts by weight of Gelest's polydimethylsiloxane-based silicone oil, with a viscosity value of 10 cSt measured at 25°C (Kinematic viscosity, surface energy 21 mN / m, based on manufacturer's TDS data), was prepared and mixed with 3 parts by weight of methyl ethyl ketone as the solvent.

[0181] Example 1 The process shown in Figure 8 was used to manufacture articles with a contamination-resistant surface.

[0182] Figure 8 is a simplified diagram illustrating the process for manufacturing an article with a contamination-resistant surface according to one embodiment of the present invention.

[0183] A glass slide measuring 1 mm in thickness and 1 cm in both length and width was prepared as a substrate (hereinafter referred to as the first substrate) 110 for forming a lubricating layer. The 1-1 coating liquid was applied to the surface of the first substrate using a brush, dried at room temperature for about 30 minutes, and then cured at a temperature of about 130°C for about 1 hour to form a hydrophobic inorganic cured layer 210 with a thickness of about 5 μm.

[0184] The 1-2 coating liquids were then applied again using a brush, dried at room temperature for about 30 minutes, and then cured at a temperature of about 130°C for about 1 hour to form a fluorine-silane cured layer 220 with a thickness of about 50 nm.

[0185] Separately, a glass slide measuring 1 mm thick and 3 cm in both width and length was prepared as a substrate (hereinafter referred to as the second substrate) 120 for forming an anti-adhesion coating layer, and the second coating liquid was applied to the surface of the second substrate using a roller. (Dry thickness approximately 1 mm)

[0186] Before the second coating liquid applied to the surface of the second substrate was completely cured, the first substrate was positioned so that the second coating liquid surrounded the first substrate on which the fluorine-silane cured layer had been formed. The article was then cured at room temperature for approximately 6 hours to produce a specimen on which an anti-adhesion coating layer 300 with a dry thickness of approximately 1 mm was formed. (Surface energy of the anti-adhesion coating layer: 23 mJ / m 2 )

[0187] The 1-3 coating liquids were applied to a thickness of approximately 10 μm using a brush onto the fluorine-silane cured layer 220 of the first substrate, which was surrounded by the anti-adhesion coating layer of the second substrate, to form a fluorine oil layer 230.

[0188] Example 2 The procedure was the same as in Example 1, except that a convex lens with a diameter of 2 cm was used as the first substrate, a concave lens with a diameter of 3.5 cm was used as the second substrate, and the lubricating layer was formed in a convex shape.

[0189] Example 3 The following preparations were made for the fluorine oil layer formation coating liquid (coating liquids 1-3).

[0190] As the fluorinated polyether oil component, DEMNUM-S200, a perfluoropolyether from Daikin, was dissolved at a concentration of 1 wt% in Novec-7200 from 3M, which was used as the solvent. (Surface energy after curing: 19 mN / m²)2 ;manufacturer's TDS data standards)

[0191] Otherwise, the procedure was the same as in Example 1.

[0192] Example 4 Instead of using coating liquids 1-1 and 1-3 to form a lubricating layer, a Teflon sheet (manufacturer: ALPHAFLON, product name: AG018AD.AS, thickness: 0.18 mm, surface energy: 19 mN / m²) used for antistatic purposes is applied to the substrate. 2 The procedure was carried out in the same manner as in Example 1, except that it was used with ().

[0193] Comparative Example 1 The lubricating layer was formed only in the center of the substrate surface. (Anti-adhesion coating layer was absent.)

[0194] A glass slide measuring 1 mm thick and 3 cm in both length and width was prepared as a substrate for forming the lubricating layer. The 1-1 coating liquid was applied to the surface of the first substrate using a brush, dried at room temperature for about 30 minutes, and then cured at a temperature of about 130°C for about 1 hour to form a hydrophobic inorganic cured layer with a thickness of about 5 μm.

[0195] The 1-2 coating solutions were then applied again using a brush, dried at room temperature for about 30 minutes, and then cured at a temperature of about 130°C for about 1 hour to form a fluorine-silane cured layer with a thickness of about 50 nm.

[0196] The 1-3 coating solutions were applied to the fluorine-silane cured layer 220 using a brush to a thickness of approximately 10 μm to form a fluorine oil layer.

[0197] Comparative Example 2 The substrate surface was designed so that only an anti-adhesion coating layer was formed in the center.

[0198] A glass slide measuring 1 mm thick and 3 cm in both length and width was prepared as the base material.

[0199] A sample was prepared by applying the second coating liquid to the center of the substrate using a brush in an area measuring 1 cm in length and width, curing it at room temperature for approximately 6 hours, and forming a coating layer with a dry thickness of approximately 1 mm.

[0200] For reference, Comparative Examples 1 and 2 can be seen as examples in which a hydrophobic surface is formed on a slide glass that is otherwise hydrophilic.

[0201] Comparative Example 3 The procedure is the same as in Example 1, but the steps for forming the hydrophobic inorganic cured layer 210 and the fluorine-silane cured layer 220 are omitted. Instead, the 1-3 coating liquids are applied to the first substrate, surrounded by the anti-adhesion coating layer of the second substrate, using a brush to a thickness of approximately 10 μm, thereby forming only the fluorine oil layer 230.

[0202] Pollution prevention performance evaluation For evaluation purposes, we prepared saturated aqueous solution of potassium chloride (KCl), a hydrophilic substance, and instant adhesive (Loctite495), a hydrophobic substance, as contaminants.

[0203] 100 μl each of contaminants was dropped onto the lubrication layer interface of the above-mentioned examples and comparative examples. The spontaneous movement of the contaminants from the lubrication layer to the anti-adhesion coating layer and the ability of the contaminants to detach from the anti-adhesion coating layer were evaluated as O and X, respectively.

[0204] The evaluation results are summarized in the table below.

[0205] [Table 1]

[0206] In one embodiment of the present invention, it was confirmed that even if contaminants adhere to the contamination-preventing article, the contaminants move from the lubricating layer to the anti-adhesion coating layer at the interface between the lubricating layer and the anti-adhesion coating layer, and then detach from the anti-adhesion coating layer, demonstrating excellent contamination prevention performance.

[0207] However, whether only a lubricating layer is formed (Comparative Example 1), only an anti-adhesion coating layer is formed (Comparative Example 2), or a structure similar to the present invention is formed, if the lubricating layer is not satisfactorily formed, the spontaneous movement and detachment of contaminants are not satisfactorily realized, and the anti-contamination performance is insufficient.

[0208] Figure 9 is a photograph showing the evaluation of the contamination prevention performance of a contamination prevention article according to one embodiment of the present invention.

[0209] Referring to Figure 9, it can be confirmed that contaminants move from the lubricating layer to the anti-adhesion coating layer at the interface between the lubricating layer and the anti-adhesion coating layer, and then detach from the anti-adhesion coating layer.

Claims

1. Base material; A first region present on a part of the surface of the substrate, on which a lubricating layer is formed; and It includes a second region that is present in at least a portion of the region other than the first region on the surface of the substrate and on which an anti-adhesion coating layer is formed, The lubricating layer includes a hydrophobic inorganic hardened layer, a fluorine-silane hardened layer formed on the hydrophobic inorganic hardened layer, and a fluorine oil layer formed on the fluorine-silane hardened layer. The anti-adhesion coating layer comprises a polydialkylsiloxane cured product and a silicone oil. Articles equipped with a contamination-resistant surface.

2. An article having a contamination-preventing surface according to claim 1, wherein the surface energy of the second region is greater than the surface energy of the first region.

3. The lubricating layer has a surface energy of 20 mJ / m ２ An article having a contamination-resistant surface according to claim 1, wherein the surface is less than [amount missing].

4. The aforementioned anti-adhesion coating layer has a surface energy of 20 mJ / m². ２ The above describes the article having a contamination-resistant surface as described in claim 1.

5. The aforementioned anti-adhesion coating layer has a surface energy of 40 mJ / m². ２ The article having a contamination-resistant surface as described in claim 1, which is as follows:

6. An article having a contamination-preventing surface according to claim 1, wherein the second region is formed in such a manner that it surrounds the first region.

7. The article having a contamination-preventing surface according to claim 1, wherein the first region is formed in the shape of a convex or concave form.

8. An article having a contamination-preventing surface according to claim 1, wherein the thickness of the lubricating layer is 0.1 to 200 μm.

9. The article having a contamination-preventive surface according to claim 1, wherein the hydrophobic inorganic cured layer comprises cured products of alkyl-trialkoxysilane and tetraalkoxysilane.

10. An article having a contamination-preventing surface according to claim 1, wherein the thickness of the hydrophobic inorganic hardened layer is 0.05 to 20 μm.

11. The article having a contamination-preventive surface according to claim 1, wherein the fluorine-silane cured layer comprises a cured product of fluorinated polyethersilane.

12. The article having a contamination-preventive surface according to claim 1, wherein the fluorine oil layer contains fluorinated polyether oil.

13. An article having a contamination-preventive surface according to claim 1, wherein the total thickness of the fluorine-silane cured layer and the fluorine oil layer is 0.1 to 200 μm.

14. The article having a contamination-preventing surface according to claim 1, wherein the silicone oil has a viscosity of 1000 cSt or less.

15. A step of forming a first region containing a hydrophobic inorganic hardened layer on a part of the substrate surface; A step of forming a second region including an anti-adhesion coating layer in at least a portion of the region other than the first region on the surface of the substrate; and The step includes forming a lubricating layer in the first region, The lubricating layer includes a hydrophobic inorganic hardened layer, a fluorine-silane hardened layer formed on the hydrophobic inorganic hardened layer, and a fluorine oil layer formed on the fluorine-silane hardened layer. The anti-adhesion coating layer comprises a polydialkylsiloxane cured product and a silicone oil. A method for forming a contamination-resistant surface.

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