Water-repellent coating composition and article including the same

Abstract

A curable water-repellent coating composition for forming a cured film and an article formed by said coating composition are provided. said coating composition comprises an acrylate-based monomer; a urethane-based oligomer; a polysilazane polymer; and a photoinitiator.

Description

Technology Field

[0001] The present invention relates to a water-repellent coating composition and an article comprising the same. More specifically, it relates to a curable water-repellent coating composition for forming a cured film and an article formed by said coating composition. Background Technology

[0002] Glass is widely used as an exterior material for buildings and automobiles. Buildings and vehicles are routinely exposed to moisture; for instance, rainwater contains various inorganic salts and microorganisms that can cause stains or mold after water droplets dry. Furthermore, water stains affect light transmittance and reflectivity.

[0003] For this reason, various water-repellent coating compositions are being developed to form water-repellent films. Water-repellent films require not only excellent water repellency but also durability, such as chemical stability and scratch resistance. Prior art literature

[0004] KR 10-2087153 B1 (Patent Document 2) KR 10-2765456 B1 The problem to be solved

[0005] Generally, a solid surface is referred to as having water repellency if its contact angle with water exceeds 90°. One of the major problems with conventional water-repellent films is that water repellency deteriorates over time.

[0006] Meanwhile, in some cases, a water-repellent film or an article containing it may be required to block ultraviolet (UV) rays. However, UV blocking ability and water repellency may be inversely proportional.

[0007] The problem that the present invention aims to solve is to provide a water-repellent coating agent or a water-repellent coating composition capable of forming a water-repellent film having excellent water repellency, chemical stability, and durability. In particular, it aims to provide a water-repellent coating composition in which the water repellency can be substantially maintained even as time passes. Furthermore, it aims to provide a water-repellent coating composition capable of forming a water-repellent film having a predetermined UV blocking ability, suppressed discoloration, and high transparency.

[0008] Another problem that the present invention aims to solve is to provide a method for forming a film using the above-mentioned water-repellent coating composition.

[0009] Another problem that the present invention aims to solve is to provide a water-repellent film manufactured using the above water-repellent coating composition.

[0010] Another problem that the present invention aims to solve is to provide an article comprising the above-mentioned water-repellent film.

[0011] The problems of the present invention are not limited to the technical problems mentioned above, and other unmentioned technical problems will be clearly understood by those skilled in the art from the description below. means of solving the problem

[0012] A water-repellent coating composition according to one embodiment of the present invention for solving the above problem comprises an acrylate-based monomer; a urethane-based oligomer; a polysilazane polymer; and a photoinitiator.

[0013] With respect to the sum of the monomer, oligomer, and polysilazane content, the content of the polysilazane may be 25 wt% to 35 wt%.

[0014] The above monomer may be a monomer having two acrylate groups.

[0015] The above urethane-based oligomer is represented by the following chemical formula 1 and may have a molecular weight of 400 g / mol to 1,000 g / mol.

[0016] <Chemical Formula 1>

[0017]

[0018] In the above chemical formula 1, m1, m2, m3, and m4 are each independently natural numbers from 2 to 10, and R1 and R2 may each independently be hydrogen, a linear or branched alkyl group having 1 to 3 carbon atoms, an acrylic group, or a methacrylic group.

[0019] The above polysilazane polymer comprises repeating units represented by the following chemical formula 2 and may have a molecular weight of 2,000 g / mol to 4,000 g / mol.

[0020] <Chemical Formula 2>

[0021]

[0022] In the above chemical formula 2, R3 and R4 may each independently be hydrogen, an alkyl group having 1 to 2 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.

[0023] The content of the above polysilazane may be greater than the content of the monomer and less than the content of the oligomer.

[0024] In some embodiments, the coating solution composition may further include a UV absorber.

[0025] The above UV absorber can be represented by the following chemical formula 3.

[0026] <Chemical Formula 3>

[0027]

[0028] In the above chemical formula 3, R5 is an alkyl group having 10 to 15 carbon atoms, and R6 and R7 may each independently be an alkyl group having 1 to 3 carbon atoms.

[0029] The content of the UV absorber relative to the above polysilazane content may be 20 wt% to 28 wt%.

[0030] With respect to the sum of the contents of the monomer, oligomer, polysilazane, and UV absorber, the content of the UV absorber may be 5.0 wt% to 7.5 wt%.

[0031] A water-repellent film according to one embodiment of the present invention for solving any other problem mentioned above has a polymer structure of an acrylate-based monomer, a urethane-based oligomer, and a polysilazane.

[0032] An article according to one embodiment of the present invention for solving any other problem above comprises a base; and a film disposed on the base, wherein the film may be according to the present invention.

[0033] The above base may be transparent.

[0034] Specific details of other embodiments are included in the detailed description. Effects of the invention

[0035] According to embodiments of the present invention, a water-repellent film that maintains excellent water repellency over time and an article containing the same can be provided. Additionally, a water-repellent film with excellent UV blocking ability and an article containing the same can be provided.

[0036] The water-repellent coating according to the present invention is expected to be applicable to metal surfaces of automobiles, front and rear windows, side windows, glass covers of solar panels, glass covers of display devices, etc.

[0037] The effects according to the embodiments of the present invention are not limited to those exemplified above, and a wider variety of effects are included in this specification. Brief explanation of the drawing

[0038] FIG. 1 is a flowchart illustrating a method for manufacturing an article including a water-repellent film according to one embodiment of the present invention. Figures 2 and 3 are cross-sectional schematic diagrams to explain the method of Figure 1. Figure 4 is an image showing the light transmittance measurement results according to Example 1. Figure 5 is an image showing the light transmittance measurement results according to Example 2. Figure 6 is an image showing a dust adhesion experiment. Specific details for implementing the invention

[0039] The advantages and features of the present invention and the methods for achieving them will become clear by referring to the embodiments described below in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below but can be implemented in various different forms. The embodiments are provided merely to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention, and the present invention is defined only by the scope of the claims.

[0040] Furthermore, the scope of patent claims is not a matter describing the technical content that constitutes the substance of the invention, but rather a matter indicating what scope is claimed as a right based on the technical configuration disclosed in the detailed description of the invention. Therefore, it is somewhat inevitable that the scope of patent claims is composed of abstract higher-level concepts that include the technology disclosed in the detailed description of the invention, and if a person skilled in the art can understand the technical configuration, combination, and functional effects belonging to the scope of patent claims through the entire specification, then the scope of patent claims should be considered to be supported by the detailed description of the invention.

[0041] That is, various modifications may be made to the embodiments presented in the present invention. The embodiments described below are not intended to limit the forms of practice and should be understood to include all modifications, equivalents, and substitutions thereof.

[0042] If any term described in this specification is to be used with a specific meaning, such meaning may be defined and used, and it should be interpreted accordingly. Unless otherwise defined, all terms used in this specification (including technical and scientific terms) may be used in a meaning that is commonly understood by those skilled in the art to which the present invention pertains. Furthermore, terms defined in commonly used dictionaries are not to be interpreted ideally or excessively unless explicitly and specifically defined otherwise.

[0043] In this specification, "and / or" includes each of the mentioned items and all combinations of one or more. Also, the singular form includes the plural form unless specifically stated otherwise in the text. As used in this specification, "comprises" and / or "comprising" do not exclude the presence or addition of one or more other components in addition to the mentioned components. A numerical range indicated by "to" indicates a numerical range that includes the values ​​listed before and after it as a lower and upper limit, respectively. "Approximately" or "about" means a value or numerical range within 20% of the value or numerical range listed after it.

[0044] The size, thickness, width, length, etc., of the components depicted in the drawings may be exaggerated or reduced for convenience and clarity of explanation, so the present invention is not limited to the depicted form.

[0045] In this specification, "*" indicates a bonding site where adjacent atoms form a covalent bond. In this specification, "C A-B "" means having a number of carbon atoms greater than A and less than or equal to B. For example, C 1-5 An alkyl group refers to an alkyl group having any one of 1 to 5 carbon atoms.

[0046] As used herein, the term "alkyl group" refers to a monovalent atomic group excluding one hydrogen atom in straight-chain or branched-chain aliphatic saturated hydrocarbons, and "*-C n H 2n+1 It can be expressed as "(where n is a natural number)".

[0047] As used herein, the term "alkenyl group" refers to a monovalent atomic group excluding one hydrogen atom in an aliphatic unsaturated hydrocarbon having a double bond, and "*-C n H 2n-1 It can be expressed as "(where n is a natural number)." For example, a vinyl group is an alkenyl group with 2 carbon atoms.

[0048] The term “acrylate group” as used in this specification is an ester derivative of acrylic acid and can be expressed as “*-C=C-COOR”.

[0049] The term “methacrylate group” used in this specification is an ester derivative of acrylic acid and can be expressed as “*-C(CH3)=C-COOR”.

[0050] The term “urethane group” as used in this specification may be expressed as “*-NH-COO-*”.

[0051] As used herein, the term "polysilazane" refers collectively to materials having silazane units as repeating units. Here, a silazane unit refers to a repeating unit containing Si-N bonds.

[0052] Unless otherwise specified, "molecular weight" in this specification means "number average molecular weight (Mn)".

[0053] The present invention will be described in detail below.

[0054] [Coating agent composition]

[0055] The coating composition according to the present invention comprises an acrylate-based monomer, a urethane-based oligomer, a polysilazane polymer, and a photoinitiator, and may further comprise an ultraviolet (UV) absorber.

[0056] Acrylate monomers refer to compounds having acrylate groups as reactive groups. Acrylate monomers may have two acrylate groups and may include compounds with 10 to 14 carbon atoms. In exemplary examples, the acrylate monomer may include 1,6-hexanediol diacrylate or consist solely of 1,6-hexanediol diacrylate.

[0057] Urethane-based oligomers refer to oligomers that have at least a urethane group as a reactive element. Oligomers have a larger molecular weight than monomers and form complex chain structures, which can improve the mechanical strength of the film after curing, such as hardness, tensile strength, and flexibility.

[0058] In an exemplary embodiment, the urethane-based oligomer can be represented by the following chemical formula 1.

[0059] <Chemical Formula 1>

[0060]

[0061] The oligomer represented by the above chemical formula 1 may have a molecular weight of about 400 g / mol to 1,000 g / mol, 500 g / mol to 900 g / mol, 600 g / mol to 800 g / mol, or 600 g / mol to 750 g / mol. In chemical formula 1, m1, m2, m3, and m4 may each independently be any natural number from 2 to 10. Also, R1 and R2 may each independently be hydrogen, a linear or branched alkyl group having 1 to 3 carbon atoms, an acrylic group, or a methacrylic group.

[0062] Polysilazane can be added to impart water repellency to the film. Polysilazane may have one or more functional groups. Organic polysilazanes with a linear structure may be used. For example, the polysilazane may include repeating units represented by the following chemical formula 2a.

[0063] <Chemical Formula 2a>

[0064]

[0065] In the above formula 2a, R3 and R4 may each independently be hydrogen, an alkyl group having 1 to 2 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms. Also, n may be a natural number. The lower limit of the molecular weight of the polysilazane polymer based on n may be about 2,000 g / mol or more, 2,200 g / mol or more, 2,400 g / mol or more, or 2,500 g / mol or more. Also, the upper limit of the molecular weight of the polysilazane polymer may be about 4,000 g / mol or less, 3,600 g / mol or less, 3,200 g / mol or less, 3,000 g / mol or less, or 2,800 g / mol or less. If the molecular weight of the polysilazane falls outside the above range, polymerization of the monomer and oligomer may be difficult, or the mechanical properties of the formed film may deteriorate.

[0066] More specifically, the polysilazane polymer according to the present embodiment may be a copolymer having repeating units represented by the following chemical formula 2b and repeating units represented by the chemical formula 2c.

[0067] <Chemical Formula 2b>

[0068]

[0069] <Chemical Formula 2c>

[0070]

[0071] In the above formulas 2b and 2c, n1 and n2 are each positive numbers. For example, the ratio of n1 to n2 may be in the range of about 15:85 to 25:75, or 18:82 to 22:78.

[0072] The coating composition may further include a solvent. The solvent is not particularly limited as long as it is advantageous for dissolving or dispersing the solid, but may be, for example, toluene.

[0073] With respect to the sum of the contents of the reactive materials, for example, the sum of the contents of the aforementioned monomer, oligomer, and polysilazane, the content of the oligomer may be about 60 wt% to 70 wt%, 62 wt% to 68 wt%, or 64 wt% to 68 wt%. In addition, the content (weight) of the polysilazane may be greater than the content of the monomer and less than the content of the oligomer.

[0074] For specific examples, the lower limit of the polysilazane content relative to the sum of the monomer, oligomer, and polysilazane content may be approximately 25 wt%, 26 wt%, or 27 wt%. If the polysilazane content is lower than the above range, sufficient water repellency may not be provided. Additionally, the upper limit of the polysilazane content relative to the above sum may be approximately 35 wt%, 32.5 wt%, or 30 wt%. If the polysilazane content is higher than the above range, water repellency may decrease, and / or water repellency may gradually decrease over time after film formation.

[0075] For more specific examples, the content of polysilazane relative to the total weight of the coating composition including a solvent, a photoinitiator, etc. may be about 8.0 wt% to 15 wt%, or about 9.0 wt% to 13 wt%, or about 9.5 wt% to 11 wt%.

[0076] The coating composition according to the present embodiment can form a film through photocuring. To this end, the coating composition may further include a photoinitiator. The photoinitiator may be appropriately selected to be capable of initiating a polymerization mechanism, such as radical polymerization of acrylates, methacrylates, urethanes, and / or silanes (Si-H). For example, the photoinitiator may include 1-hydroxycyclohexyl phenyl ketone or be composed of 1-hydroxycyclohexyl phenyl ketone. The content of the photoinitiator may be appropriately selected.

[0077] As described above, a film formed by a coating composition comprising an acrylate-based monomer, a urethane-based oligomer, and a polysilazane can have excellent water repellency. In particular, it can maintain excellent water repellency even over time.

[0078] In some embodiments, the coating composition may further include additives such as UV absorbers or UV blockers. UV absorbers (or additives) can impart UV absorption capabilities to the cured film. In particular, various experimental results by the inventors of the present invention confirmed that water repellency is reduced by UV absorbers, or that water repellency significantly decreases as UV absorption continues. However, if a specific type of UV absorber is used and mixed within a specific content range, such problems can be suppressed.

[0079] In an exemplary embodiment, the ultraviolet absorber can be represented by the following chemical formula 3a.

[0080] <Chemical Formula 3a>

[0081]

[0082] In the above formula 3a, R5 is an alkyl group having 10 to 15 carbon atoms, preferably an alkyl group having 12 or 13 carbon atoms, and R6 and R7 may each independently be an alkyl group having 1 to 3 carbon atoms, preferably a methyl group.

[0083] More specifically, the ultraviolet absorber of the coating composition according to the present embodiment can be represented by the following chemical formula 3b.

[0084] <Chemical Formula 3b>

[0085]

[0086] In the above chemical formula 3b, R5 is the same as in chemical formula 3a.

[0087] If the content of the UV absorber is too high, it may be difficult to form a film by photocuring, or the mechanical properties and / or water repellency of the film may be reduced. In this regard, the upper limit of the content of the UV absorber relative to the sum of the contents of the aforementioned monomer, oligomer, polysilazane, and UV absorber may be about 7.5 wt%, 7.0 wt%, or about 6.5 wt%. In terms of providing sufficient UV absorption capacity, the lower limit of the above ratio may be about 5.0 wt%, 5.5 wt%, or 6.0 wt%.

[0088] To provide a more specific content range for the UV absorber, the content of the UV absorber relative to the polysilazane content may be about 20 wt% to 28 wt%, or about 22 wt% to 26 wt%. Within the above range, excellent water repellency and UV absorption ability can be imparted. In addition, the transparency of the formed film, such as light transmittance for light in the visible light wavelength band, is high, and discoloration can be suppressed over time.

[0089] [Water-repellent coating and articles containing the same]

[0090] This is a flowchart illustrating a method for manufacturing an article including a water-repellent film according to one embodiment of the present invention. FIGS. 2 and FIGS. 3 are schematic cross-sectional diagrams for explaining the method of FIGS. 1.

[0091] Referring to FIGS. 1 to 3, a method for manufacturing an article including a water-repellent film according to the present embodiment may include the steps of applying a coating composition (200) onto a base (100) (S100) and photocuring the coating composition (200) to form a film (250) or a film layer (S200).

[0092] The base (100) refers to a surface to be coated on which a film (250) is to be formed, and may be metal, glass, plastic, etc. In some embodiments, when the coating composition (200) includes a UV absorber, etc., and is intended to transmit light, the base (100) may be a light-transmitting material such as glass or transparent plastic.

[0093] The coating method is not particularly limited, but spin coating, spray coating, dip coating, or slit coating may be used. The coating composition (200) is the same as described above, so a redundant description is omitted.

[0094] After applying a coating composition (200) onto a base (100), a cured film (250) can be formed by irradiating the coating layer with light, such as ultraviolet light. The formed film (250) may have a polymer network structure formed by polymerizing reactive materials of the aforementioned coating composition (200), such as acrylate-based monomers, urethane-based oligomers, and / or polysilazane. An article (10) comprising the film (250) according to the present embodiment may have excellent durability and water repellency on its upper surface. In particular, it may maintain water repellency properties even after a period of time. In addition, in some embodiments, the film (250) may have excellent blocking properties against light in the ultraviolet wavelength band, particularly light in the UV-C and UV-B wavelength bands.

[0095] The present invention will be described in more detail below with further reference to experimental examples of the present invention.

[0096] [Example 1: Polysilazane Content]

[0097] Coating compositions were prepared with various compositions as shown in Table 1 below, applied to a 3 cm × 3 cm glass surface, and then photocured. The coating thickness was set to 7.0 µm ± 10%. The light intensity for curing was 2.1 W / cm². 2 It was set to 20 seconds, and the curing time was set to 20 seconds.

[0098] Examples Initiator (g) Solvent (g) Monomer(g)(A) Oligomer(g)(B) Polysilazane(g)(C) (A)+(B)+(C) Example 1-1 0.30 6.65 0.20 3.00 0.00 3.20 Examples 1-2 0.30 6.65 0.20 3.00 0.50 3.70 Examples 1-3 0.30 6.65 0.20 3.00 1.00 4.20 Examples 1-4 0.30 6.65 0.20 3.00 1.25 4.45 Examples 1-5 0.30 6.65 0.20 3.00 1.50 4.70 Examples 1-6 0.30 6.65 0.20 3.00 1.75 4.95 Examples 1-7 0.30 6.65 0.20 3.00 2.00 5.20 Examples 1-8 0.30 6.65 0.20 3.00 2.50 5.70

[0099] 1-hydroxycyclohexylphenyl ketone was used as the initiator, and toluene was used as the solvent.

[0100] In addition, 1,6-hexanediol diacrylate was used as the monomer. Urethane acrylate methacrylate resin sold by Merck was used as the oligomer. The structure of the oligomer is represented by the aforementioned Chemical Formula 1, the viscosity of the oligomer is 2900 to 3100 cp (@25℃), and the molecular weight is 700 g / mol to 900 g / mol.

[0101] The polysilazane used was Durazane 1800® sold by Merck. The polysilazane contained repeating units represented by the aforementioned chemical formulas 2b and 2c, with an n1:n2 ratio of approximately 15:85 to 25:75. The molecular weight was approximately 2,500 g / mol to 3,200 g / mol.

[0102] Then, a water droplet was applied to the surface of the film to measure the water contact angle (WCA), and the results are shown in Table 2. Glass without a film was used as a comparative example.

[0103] Examples Contact angle (°) @t=0s @t=60s Comparative example 45 45 Example 1-1 89 54 Examples 1-2 116 80 Examples 1-3 116 92 Examples 1-4 124 124 Examples 1-5 118 118 Examples 1-6 120 120 Examples 1-7 117 117 Examples 1-8 107 106

[0104] Referring to Table 2 above, uniquely, the contact angle increased or decreased with increasing polysilazane content, and the highest contact angle was observed in Examples 1-4. In addition, the light transmittance of Comparative Example and Examples 1-1 to 1-8 was measured and is shown in Figure 4. The light transmittance was measured using a UV-VIS spectrophotometer. The average light transmittance of Comparative Example and Examples 1-1 to 1-8 was 91%, showing high light transmittance despite the formed film.

[0105] [Example 2: UV absorber content]

[0106] Coating compositions were prepared with various compositions as shown in Table 3 below, and applied to a glass surface and then photocured as in Example 1.

[0107] Examples Initiator (g) Solvent (g) Monomer(g)(A) Oligomer(g)(B) Polysilazane(g)(C) UV absorber (g)(D) (A)+(B)+(C)+(D) Example 2-1 0.30 6.65 0.20 3.00 1.25 0.00 4.45 Example 2-2 0.30 6.65 0.20 3.00 1.25 0.15 4.60 Examples 2-3 0.30 6.65 0.20 3.00 1.25 0.20 4.65 Examples 2-4 0.30 6.65 0.20 3.00 1.25 0.30 4.75 Examples 2-5 0.30 6.65 0.20 3.00 1.25 0.40 4.85 Examples 2-6 0.30 6.65 0.20 3.00 1.25 1.25 5.70 Examples 2-7 0.30 6.65 0.20 3.00 1.25 2.00 6.45 Examples 2-8 0.30 6.65 0.20 3.00 1.25 2.50 6.95 Examples 2-9 0.30 6.65 0.20 3.00 1.25 3.00 7.45

[0108] RIASORB UV-400® was used as the ultraviolet absorber. The ultraviolet absorber had the structure of chemical formula 3b and was in a mixed state in which R5 was a 12-carbon alkyl group and a 13-carbon alkyl group.

[0109] Although not shown in the table as experimental results, when an oligomer having only acrylate and / or methacrylate groups and having a molecular weight similar to that of the oligomer of the present invention was used without urethane groups, the film curing was insufficient, or the durability of the formed film was inferior. Specifically, when the other oligomer was used, curing occurred normally when it did not contain a UV absorber as in Example 1, but curing did not occur normally when a UV absorber was added as in Example 2.

[0110] Then, water droplets were applied to the surface of the film to measure the contact angle, and the results are shown in Table 4.

[0111] Examples Contact angle (°) @t=0s @t=120s Example 2-1 124 124 Example 2-2 97 96 Examples 2-3 96 96 Examples 2-4 96 96 Examples 2-5 92 91 Examples 2-6 85 85 Examples 2-7 80 73 Examples 2-8 81 71 Examples 2-9 80 72

[0112] Referring to Table 4, it can be observed that the contact angle tends to decrease with increasing UV absorber content. It can be seen that Examples 2-2 to 2-4 substantially maintain the contact angle despite the increase in UV absorber content. Furthermore, Example 2-5 showed a significantly reduced contact angle compared to Example 2-4. It can be observed that as the UV absorber content increases, the degree of decrease in the contact angle over time (i.e., after 120 seconds) becomes greater.

[0113] In addition, the light transmittance of Comparative Example, Examples 2-1 to 2-9 was measured and is shown in FIG. 5. Referring to FIG. 5, in the case of Example 2-1, which did not contain a UV absorber, light in the UV-B band and UV-A band was transmitted.

[0114] When comparing Examples 2-2 to 2-4, in the case of Example 2-4, the transmittance for light of about 350 nm or less was less than 1%, whereas in the case of Examples 2-2 and 2-3, the transmittance for light between about 300 nm and 350 nm was an average of 5% or more.

[0115] [Durability Life Test]

[0116] The durability test of the coated glass of the previously prepared Examples 2-4 to 2-6 was conducted. Specifically, the coated glass was stored for 1,000 hours at a temperature of 85±2℃ and a relative humidity of 85±5%. As a result of the experiment, in the case of Example 2-5, the coating showed slight yellowing. In the case of Example 2-6, cracks occurred along with discoloration, and problems of partial delamination occurred. In the case of Example 2-4, no noticeable changes occurred, and the contact angle was maintained at a level of 94° to 96° even after prolonged exposure under extreme conditions. The light transmittance in the ultraviolet wavelength band also maintained the performance before the experiment.

[0117] [Dust Adhesion Test]

[0118] A dust adhesion test was performed using bare glass, specifically the samples from Examples 2-4 that underwent a comparative example and a durability life test. A total of six samples (three from each of the two types) and 0.02 g of dust were placed into a chamber, and the dust was dispersed and evenly deposited on the surface of the samples by injecting air for 15 minutes. The dust-attached samples were then placed at a 30° angle from the horizontal plane, and water was sprayed using a spray gun from a position 20 cm away in the horizontal direction. The spray rate was 0.23 ml / s. The samples were then dried, and the resulting image is shown in Fig. 6.

[0119] Then, the light-transmitting area of ​​the dried samples was calculated. The light-transmitting area refers to the area excluding the region obscured by dust from the total size of the sample. As a result, the average light-transmitting area of ​​the three samples of Examples 2-4 was calculated to be approximately 2.7 times the average light-transmitting area of ​​the three comparative example samples. That is, an article having a water-repellent film according to the present invention achieved an increase in light-transmitting area of ​​approximately 170% compared to an article without such a film.

[0120] Although the present invention has been described above with reference to embodiments, this is merely illustrative and does not limit the invention. Those skilled in the art will understand that various modifications and applications not exemplified above are possible within the scope of the essential characteristics of the embodiments of the invention.

[0121] Accordingly, the scope of the present invention should be understood to include modifications, equivalents, or substitutions of the technical concept exemplified above. For example, each component specifically shown in the embodiments of the present invention may be implemented with modifications. Furthermore, differences related to such modifications and applications should be interpreted as being included within the scope of the present invention as defined in the appended claims. Explanation of the symbols

[0122] 10: Article containing a water-repellent film 100: Bass 250: Coating

Claims

Claim 1 A coating liquid composition comprising an acrylate-based monomer; a urethane-based oligomer; a polysilazane polymer; and a photoinitiator. Claim 2 A coating liquid composition according to claim 1, wherein the content of the polysilazane is 25 wt% to 35 wt% with respect to the sum of the content of the monomer, oligomer, and polysilazane. Claim 3 A coating solution composition according to claim 2, wherein the monomer is a monomer having two acrylate groups, the urethane-based oligomer is represented by the following chemical formula 1 and has a molecular weight of 400 g / mol to 1,000 g / mol, and the polysilazane polymer comprises repeating units represented by the following chemical formula 2 and has a molecular weight of 2,000 g / mol to 4,000 g / mol. <Chemical Formula 1> <Chemical Formula 2> (In the above Chemical Formula 1, m1, m2, m3, and m4 are each independently natural numbers from 2 to 10, and R1 and R2 are each independently hydrogen, a linear or branched alkyl group having 1 to 3 carbon atoms, an acrylic group, or a methacrylic group; and in the above Chemical Formula 2, R3 and R4 are each independently hydrogen, an alkyl group having 1 to 2 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms) Claim 4 In paragraph 3, the coating liquid composition in which the content of the polysilazane is greater than the content of the monomer and less than the content of the oligomer. Claim 5 A coating liquid composition according to claim 1, further comprising a UV absorber. Claim 6 In claim 5, the UV absorber is a coating liquid composition represented by the following chemical formula 3. <Chemical Formula 3> (In the above chemical formula 3, R5 is an alkyl group having 10 to 15 carbon atoms, and R6 and R7 are each independently an alkyl group having 1 to 3 carbon atoms) Claim 7 A coating liquid composition according to claim 6, wherein the content of the UV absorber relative to the polysilazane content is 20 wt% to 28 wt%. Claim 8 A coating liquid composition according to claim 7, wherein the content of the UV absorber is 5.0 wt% to 7.5 wt% with respect to the sum of the contents of the monomer, oligomer, polysilazane, and UV absorber. Claim 9 A film having a polymer structure of acrylate monomers, urethane oligomers, and polysilazanes. Claim 10 An article comprising a base; and a film of claim 9 disposed on the base. Claim 11 In item 10, the above base is an article made of a material having light-transmitting properties.

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