Anti-fouling coating solution and method of manufacturing same

Abstract

One aspect of the present disclosure may provide a polyurethane-based coating material and a coating solution comprising same, wherein the polyurethane-based coating material ensures mechanical rigidity on the basis of a polyurethane material and simultaneously induces super-hydrorepellent properties, thereby achieving antifouling and antibacterial properties. The anti-fouling coating solution according to an embodiment of the present invention may include fluorine-containing polyurethane polymer (FPU), fluorine-containing urethane monomer (FU), and polytetrafluoroethylene (PTFE).

Description

Antifouling coating solution and method for producing the same

[0001] The present invention relates to a polyurethane-based superhydrophobic material containing a fluorine group, a coating solution containing the same, and a method for producing the same, and more particularly, to an anti-fouling, antibacterial, or self-cleaning coating solution having superhydrophobic properties.

[0002] Superhydrophobic materials with a water contact angle of 150 degrees or more are attracting great attention because they can exhibit various functions such as self-cleaning, anti-icing, oil-water separation, and anti-fouling.

[0003] One aspect of the present disclosure is to provide a polyurethane-based coating material and a coating solution including the same, which can secure mechanical strength based on a polyurethane material and simultaneously induce superhydrophobic properties to implement antifouling and antibacterial properties.

[0004] The problems to be solved by the present invention are not limited to the problems mentioned above, and other technical problems not mentioned can be clearly understood by a person having ordinary skill in the technical field to which the present invention belongs from the description below.

[0005] The antifouling coating solution according to the invention is:

[0006] Containing a polyurethane polymer (FPU) containing fluorine, a urethane monomer (FU) containing fluorine, and polytetrafluoroethylene (PTFE),

[0007] The above fluorine-containing polyurethane polymer (FPU) is

[0008] volatile solvent;

[0009] Ca H2F 2a-1 Fluorinated alcohol expressed as OH (where a represents a natural number less than or equal to 10) and having a hydroxyl group attached to the terminal;

[0010] C b H4F 2b-4 Fluorodiol expressed as (OH)2 (where b represents a natural number less than or equal to 20) and having hydroxyl groups bonded to both terminals;

[0011] An alcohol containing two or more hydroxyl groups; and

[0012] Comprising an isocyanate crosslinking agent containing two or more isocyanate groups,

[0013] The ratio of the molecular weight of the fluorinated diol to the polyurethane polymer (FPU) containing the fluorine is 0.7 or more and 0.9 or less,

[0014] The ratio of the sum of the number of hydroxyl groups contained in the above fluorinated alcohol, the above fluorinated diol and the above alcohol and the number of isocyanate groups contained in the above isocyanate crosslinking agent is 1:1,

[0015] The above urethane single molecule (FU) containing fluorine is

[0016] C c H2F 2c-1 Fluorinated alcohol expressed as OH (where c means a natural number less than or equal to 10) and having a hydroxyl group attached to the terminal; and

[0017] An isocyanate crosslinking agent containing two or more isocyanate groups;

[0018] Includes.

[0019] In addition, a method for producing an antifouling coating solution according to the invention comprises the steps of producing a polyurethane polymer (FPU) containing fluorine;

[0020] A step of manufacturing a urethane single molecule (FU) containing fluorine; and

[0021] It includes a step of adding the fluorine-containing urethane monomer (FU) and polytetrafluoroethylene (PTFE) satisfying a weight ratio of 3:1 to the fluorine-containing polyurethane polymer (FPU) and stirring.

[0022] The step of manufacturing the polyurethane polymer (FPU) containing the above fluorine is as follows:

[0023] Volatile solvent, C a H2F 2a-1 Fluorinated alcohol, C, expressed as OH (where a represents a natural number less than or equal to 10) and having a hydroxyl group attached to the terminal b H4F 2b-4 A step of preparing a first solution by stirring a fluorinated diol expressed as (OH)2 (where b represents a natural number less than or equal to 20) and having hydroxyl groups bonded to both terminals, an alcohol containing two or more hydroxyl groups, an isocyanate crosslinking agent containing two or more isocyanate groups, and a catalyst;

[0024] A step of preparing a second solution by adding a volatile solvent and an isocyanate crosslinker containing two or more isocyanate groups;

[0025] A step of preparing a third solution by adding the second solution to the first solution and stirring at a temperature of 0°C or higher and 80°C or lower for 2 hours or longer and 4 hours or shorter;

[0026] Volatile solvents and C a H2F 2a-1 A step of preparing a fourth solution by stirring fluorinated alcohol expressed as OH (where a means a natural number less than or equal to 10) and having a hydroxyl group bonded to the terminal; and

[0027] A step of adding the fourth solution to the third solution and stirring at a temperature of 50°C or higher and 80°C or lower for 20 hours or longer and 46 hours or shorter,

[0028] The step of manufacturing the urethane single molecule (FU) containing the above fluorine is as follows:

[0029] Isocyanate crosslinking agent containing two or more isocyanate groups and C c H2F 2c-1 It includes a step of adding fluorinated alcohol expressed as OH (where c means a natural number less than or equal to 10) and having a hydroxyl group bonded to the terminal, stirring for 30 minutes to 2 hours, and pulverizing the formed particles.

[0030] According to the idea of ​​the present disclosure, a polyurethane-based coating material and a coating solution including the same can be provided that can secure mechanical strength through a polyurethane-based material while simultaneously inducing superhydrophobic properties to implement antifouling and antibacterial properties.

[0031] Figure 1 is a drawing showing the FT-IR of FPU.

[0032] Figure 2 is a diagram showing the FT-IR of FU.

[0033] Figure 3 is a diagram illustrating the optimization of the water contact angle according to the HFO composition.

[0034] Figure 4a is a diagram illustrating the optimization of the water contact angle according to the weight of the particle.

[0035] Figure 4b is a drawing showing the contact surface with water after coating the coating solution of the present invention on the surface of the device.

[0036] Figure 5 is a drawing illustrating a contact and friction test.

[0037] Figure 6a is an SEM image showing the presence and composition of particles containing fluorine groups.

[0038] Figure 6b shows the FPU 1PTFE-3FU This is a diagram showing a comparison of the contact angle when dried at room temperature or at a high temperature of 70 degrees.

[0039] Figure 7a is a diagram showing the change in contact angle according to the number of tape peelings.

[0040] Figure 7b is an SEM photograph of the surface of the coated material after 10 tape peelings.

[0041] Figure 8 is a diagram showing the results of 20 methlyene blue antifouling tests.

[0042] Figure 9 is a drawing showing the results of self-cleaning using SiC of the dust series.

[0043] Figure 10a is a SEM photograph of each of the superhydrophobic material and the bare substrate after uniform coating.

[0044] Figure 10b is a diagram showing the number of bacteria per area for each substrate in a superhydrophobic material and a bare substrate.

[0045] Preferred embodiments of the present invention are described below. However, the embodiments of the present invention may be modified in various ways, and the technical concept of the present invention is not limited to the embodiments described below. Furthermore, the embodiments of the present invention are provided to more fully explain the present invention to those of ordinary skill in the art.

[0046] The terminology used in this application is solely for the purpose of describing specific examples. Therefore, for example, singular expressions include plural expressions unless the context clearly dictates otherwise. Additionally, it should be noted that terms such as "comprise" or "have" used in this application are used to clearly indicate the presence of features, steps, functions, components, or combinations thereof described in the specification, and are not used to preliminarily exclude the presence of other features, steps, functions, components, or combinations thereof.

[0047] Meanwhile, unless otherwise defined, all terms used herein should be considered to have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Therefore, unless explicitly defined herein, specific terms should not be interpreted in an overly idealistic or formal sense. For example, singular expressions herein include plural expressions unless the context clearly indicates otherwise.

[0048] In addition, the terms "about", "substantially", etc. in this specification are used in the sense of or close to the numerical value when manufacturing and material tolerances inherent to the meanings mentioned are presented, and are used to prevent unscrupulous infringers from unfairly using the disclosure contents in which exact or absolute numerical values ​​are mentioned to aid in the understanding of the present invention.

[0049] The antifouling coating solution is described in detail with reference to the attached drawings below.

[0050] Previously, superhydrophobic properties were obtained by forming inorganic texture-based protrusions through various processes such as inorganic-based chemical vapor deposition or self-assembly, inspired by the micro-nano-scale protrusions on the surface of lotus leaves.

[0051] However, inorganic-based micro-nano scale protrusions have a fatal drawback in that their structures are easily destroyed, which leads to deterioration of their superhydrophobic properties, limiting their application as practical coating materials.

[0052] Meanwhile, polyurethane can be synthesized through a condensation polymerization reaction of diisocyanate and diol.

[0053] In particular, polyurethane can be widely used in various fields due to its excellent wear resistance and durability, and in particular, various characteristics can be imparted depending on the internal functional groups of the diisocyanate and diol used.

[0054] The present invention relates to a coating material and a coating solution that secure superhydrophobic properties and have mechanical strength at the same time through a polymerization reaction using a monomer containing a fluorine group during the polymerization of polyurethane and mixing it with a new organic molecule.

[0055] An embodiment of an antifouling coating solution is described in detail with reference to the drawings below.

[0056] An antifouling coating solution according to one disclosed embodiment comprises a fluorine-containing polyurethane polymer (FPU), a fluorine-containing urethane monomer (FU), and polytetrafluoroethylene (PTFE), wherein the fluorine-containing polyurethane polymer (FPU) comprises a volatile solvent; C a H2F 2a-1 Fluorinated alcohol expressed as OH (where a represents a natural number less than or equal to 10) and having a hydroxyl group attached to the terminal; C b H4F 2b-4 A fluorinated diol expressed as (OH)2 (wherein b represents a natural number of 20 or less) and having hydroxyl groups bonded to both terminals; an alcohol containing two or more hydroxyl groups; and an isocyanate crosslinking agent containing two or more isocyanate groups, wherein the ratio of the molecular weight of the fluorinated diol to the polyurethane polymer (FPU) containing fluorine is 0.7 or more and 0.9 or less, and the ratio of the sum of the numbers of hydroxyl groups contained in the fluorinated alcohol, the fluorinated diol, and the alcohol to the number of isocyanate groups contained in the isocyanate crosslinking agent is 1:1, and the urethane monomer (FU) containing fluorine is, Cc H2F 2c-1 It may include a fluorinated alcohol expressed as OH (where c means a natural number less than or equal to 10) and having a hydroxyl group bonded to the terminal; and an isocyanate crosslinking agent including two or more isocyanate groups.

[0057] The polyurethane polymer (FPU) containing the above fluorine can undergo polymerization through a urethane bonding reaction between the hydroxyl group at the molecular terminal represented by the following chemical formulae 1, 2, and 3 and the isocyanate group present in the isocyanate crosslinking agent. As an example, when polymerization is performed using hexamethylene diisocyanate (HDI) as the isocyanate crosslinking agent,

[0058] A prepolymer represented by the following chemical formula 4 can be manufactured through a process similar to the following reaction scheme 1, and then the polymerization reaction is terminated by introducing the following chemical formula 1 (1, 2,2,3,3,4,4,4-heptafluoro-1-butanol (1,2,2,3,3,4,4,4-Heptafluoro-1-butanol (HF))), thereby obtaining the molecular structure of a polyurethane polymer (FPU) containing fluorine, such as the following chemical formula 5.

[0059]

[0060] [Chemical Formula 4, Prepolymer]

[0061] (Here, n represents a natural number.)

[0062]

[0063] [Chemical Formula 5, Fluorine-containing polyurethane polymer (FPU)]

[0064] (Here, n represents a natural number.)

[0065]

[0066] [Reaction Formula 1]

[0067] (Here, n represents a natural number.)

[0068] As another example, when polymerization is performed using isocyanate as the isocyanate crosslinking agent, a prepolymer can be manufactured through a process as in the following reaction formula 2, and then the polymerization reaction can be terminated by introducing the following chemical formula 1 (1, 2,2,3,3,4,4,4-heptafluoro-1-butanol (1,2,2,3,3,4,4,4-Heptafluoro-1-butanol (HF))), thereby obtaining the molecular structure of a polyurethane polymer (FPU) containing fluorine.

[0069]

[0070] [Reaction Formula 2]

[0071] (Here, n represents a natural number.)

[0072] According to one embodiment of the disclosed antifouling coating solution, the volatile solvent may include acetone. Acetone has the advantage of not requiring heat during the coating process due to its high volatility, and is also a suitable solvent for the polymerization of polyurethane. In particular, it is important for the antifouling coating solution of the present invention to exhibit water-repellent properties through the formation of thorn-like morphology as shown in FIG. 7b. Acetone, due to its high volatility, can form the thorn-like morphology in the antifouling coating solution, making it suitable for securing the water-repellent properties required by the present invention.

[0073] According to one embodiment of the disclosed antifouling coating solution, a of the fluorinated alcohol contained in the polyurethane polymer (FPU) containing fluorine may be 4, b of the fluorinated diol may be 10, and c of the fluorinated alcohol contained in the urethane monomer (FU) containing fluorine may be 4. When a of the fluorinated alcohol contained in the polyurethane polymer (FPU) containing fluorine is 4, the solution has a structure as shown in the following chemical formula 1.

[0074]

[0075] [Chemical Formula 1, 2,2,3,3,4,4,4-Heptafluoro-1-butanol (HF)]

[0076] In addition, when b of the above fluorinated diol is 10, it has a structure as shown in the following chemical formula 2.

[0077]

[0078] [Chemical Formula 2, 1H,1H,10H,10H-Hexadecafluoro-1,10-decanediol (HFO)]

[0079] In addition, when c of the fluorinated alcohol contained in the urethane single molecule (FU) containing the fluorine is 4, it has a structure as shown in the following chemical formula 3.

[0080]

[0081] [Chemical Formula 3, Poly(tetrahydrofuran) (PTHF)]

[0082] Here, n is a natural number greater than or equal to 1 and less than or equal to 5000. The molecular weight of Poly(tetrahydrofuran) (PTHF) corresponding to the above chemical formula 3 may be about 2000 (Mn), but is not limited thereto.

[0083] The antifouling coating solution according to the disclosed embodiment may be one or more selected from the group consisting of the following compounds, wherein the alcohol containing two or more hydroxyl groups is a natural number (wherein n, m and a, y represent natural numbers).

[0084] Poly(tetrahydrofuran) (PTHF)

[0085]

[0086] polycaprolactone diol,

[0087]

[0088] poly(hydroxybutyrate) diol,

[0089]

[0090] poly(lactide-co-caprolactone) diol,

[0091]

[0092] poly(ethylene glycol) diol,

[0093]

[0094] poly(ethylene terephthalate) diol,

[0095]

[0096] Fatty acid-based linear diol,

[0097]

[0098] polylactide diol,

[0099]

[0100] poly(butylene glycol) diol,

[0101]

[0102] poly(propylene oxide) diol,

[0103]

[0104] poly(tetramethylene oxide) diol,

[0105]

[0106] poly(ethylene adipate) diol,

[0107]

[0108] Castor oil-based diol,

[0109]

[0110] polyglycolide diol,

[0111]

[0112] poly(lactide-b-glycolide) diol,

[0113]

[0114] poly(hexamethylene carbonate) diol,

[0115]

[0116] polycarbonate diol,

[0117]

[0118] poly(butylene adipate) diol and

[0119]

[0120] Soybean oil-based diol

[0121]

[0122] The alcohols containing two or more hydroxyl groups have the same structure as above, but are not necessarily limited thereto, and if they are polyfunctional alcohols containing two or more hydroxyl groups, they can be used without any special restrictions.

[0123] According to one embodiment of the disclosed antifouling coating solution, the isocyanate crosslinking agent is selected from the group consisting of hexamethylene diisocyanate (HIDI), diphenylmethane 4,4'-diisocyanate, 1,3-phenylene diisocyanate, isophorone diisocyanate, polyhexamethylene diisocyanate, triphenylmethan-4,4',4''-triisocyanate, 1,3,5-triisocyanato-2-methylbenzene, and It may be at least one selected from the group consisting of 1,3,5-triisocyanato-2,4,6-trimethylbenzene. However, the isocyanate crosslinking agent containing two or more isocyanate groups is not necessarily limited thereto, and any isocyanate crosslinking agent containing two or more isocyanate groups may be used without special restrictions.

[0124] According to one embodiment of the disclosed antifouling coating solution, the fluorine-containing polyurethane polymer (FPU) and the fluorine-containing urethane monomer (FU) may further include one or more catalysts selected from dibutyltin dilaurate (DBTDL), dimethylaminopyridine (DMAP), triethylamine (TEA), diazabicyclo[2,2,2]octane, and 1,4-diazabicyclo[2,2,2]octane. However, the catalyst is not necessarily limited thereto, and any catalyst capable of catalyzing a reaction between an isocyanate group and a hydroxyl group may be used without particular limitation.

[0125] The antifouling coating solution according to one disclosed embodiment may have a ratio of the molecular weight of the fluorinated diol to the polyurethane polymer (FPU) containing fluorine of 0.8.

[0126] According to one disclosed embodiment, the antifouling coating solution may have a water contact angle of 143 degrees or more and 150 degrees or less for the polyurethane polymer (FPU) containing fluorine. It can be confirmed that when the ratio of the molecular weight of HFO, which is a chain extender containing a large amount of fluorine groups, to the polyurethane polymer (FPU) containing fluorine during synthesis of the polyurethane polymer (FPU) containing fluorine is 0.8, the water contact angle has a maximum value of about 143 degrees.

[0127] This is because as the ratio of the molecular weight of HFO increases, the density of fluorine groups within the polymer chain increases, resulting in more fluorine groups oriented toward the air layer during coating. However, when the ratio of the molecular weight of the fluorinated diol to the fluorine-containing polyurethane polymer (FPU) exceeds 0.8, the adhesion to the substrate is poor, resulting in peeling after coating, and the water contact angle thereafter tends to decrease.

[0128] According to one disclosed embodiment, the antifouling coating solution may have a weight ratio of the fluorine-containing urethane monomer (FU) and the polytetrafluoroethylene (PTFE) of 3:1. When the ratio of PTFE and FU is 1:3 in the fluorine-containing polyurethane polymer (FPU) optimized for the molecular weight ratio of HFO to 0.8, it can be confirmed through Fig. 4a, which illustrates the optimization of the water contact angle according to the weight of the particles, that the solution has an improved water contact angle compared to the case where the ratio of PTFE and FU is 3:1.

[0129] According to one embodiment of the disclosed antifouling coating solution, the weight ratio of the fluorine-containing urethane monomer (FU) to the fluorine-containing polyurethane polymer (FPU) and the polytetrafluoroethylene (PTFE) may be 40 wt% or more and 80 wt% or less.

[0130] According to one disclosed embodiment, the antifouling coating solution may have a water contact angle of 150 degrees or more and 160 degrees or less. As a result of measuring the water contact angle by increasing the weight ratio of PTFE and FU while satisfying 1:3 in a fluorine-containing polyurethane polymer (FPU) in which the molecular weight ratio of HFO is optimized to 0.8, it can be seen that when the weight sum of the fluorine-containing urethane monomer (FU) and the polytetrafluoroethylene (PTFE) to the fluorine-containing polyurethane polymer (FPU) is 40 wt% or more and 80 wt% or less, the FPU exhibits a superhydrophobic property of 150 degrees.

[0131] In particular, when the weight sum ratio of the fluorine-containing urethane monomer (FU) and the polytetrafluoroethylene (PTFE) to the fluorine-containing polyurethane polymer (FPU) is 60 wt%, the contact angle is the highest at about 158 ​​degrees, and as shown in Fig. 4b, which shows the contact surface with water after coating the coating solution of the present invention on the surface of a device, it can be confirmed that the contact area between the part where the antifouling coating solution is applied and water is minimized. In addition, the water-repellent property that repels water not only during contact with water but also during the process of friction with a water droplet can be confirmed through Fig. 5. This means that not only one part shows super-hydrophobic properties, but the entire coated area secures super-hydrophobic properties.

[0132] However, when the weight sum of the fluorine-containing urethane monomer (FU) and the polytetrafluoroethylene (PTFE) to the fluorine-containing polyurethane polymer (FPU) is less than 40 wt%, the water contact angle does not approach 150 degrees, failing to secure superhydrophobic properties, and when it exceeds 80 wt%, the viscosity increases, making it unsuitable for use as a coating solution. Therefore, it is preferable that the weight sum of the fluorine-containing urethane monomer (FU) and the polytetrafluoroethylene (PTFE) to the fluorine-containing polyurethane polymer (FPU) be 40 wt% or more and 80 wt% or less. More preferably, the weight ratio of the fluorine-containing urethane monomer (FU) to the polytetrafluoroethylene (PTFE) polymer (FPU) containing fluorine may be 60 wt%.

[0133] Above, the antifouling coating solution has been explained.

[0134] Below, the coating method of the antifouling coating solution is described.

[0135] A coating method of an antifouling coating solution according to one disclosed embodiment may include a step of coating the antifouling coating solution on a product and drying the product at a temperature of 10°C or higher and 50°C or lower for 1 hour or longer and 48 hours or shorter. Here, the product may be a substrate of any object requiring antifouling, water-repellent, or antibacterial properties. Preferably, the product may be an aluminum substrate, but is not necessarily limited thereto.

[0136] Below, the method for manufacturing an antifouling coating solution is described in detail.

[0137] A method for manufacturing an antifouling coating solution according to one embodiment of the present disclosure comprises the steps of manufacturing a polyurethane polymer (FPU) containing fluorine; manufacturing a urethane monomer (FU) containing fluorine; and adding the urethane monomer (FU) containing fluorine and polytetrafluoroethylene (PTFE) satisfying a weight ratio of 3:1 to the polyurethane polymer (FPU) containing fluorine and stirring the mixture, wherein the step of manufacturing the polyurethane polymer (FPU) containing fluorine comprises: mixing a volatile solvent, C a H2F 2a-1 Fluorinated alcohol, C, expressed as OH (where a represents a natural number less than or equal to 10) and having a hydroxyl group attached to the terminal b H4F 2b-4A step of preparing a first solution by stirring a fluorinated diol expressed as (OH)2 (wherein b represents a natural number of 20 or less) and having hydroxyl groups bonded to both terminals, an alcohol containing two or more hydroxyl groups, an isocyanate crosslinking agent containing two or more isocyanate groups, and a catalyst; a step of preparing a second solution by adding a volatile solvent and an isocyanate crosslinking agent containing two or more isocyanate groups; a step of preparing a third solution by adding the second solution to the first solution and stirring at a temperature of 0°C or more and 80°C or less for 2 hours or more and 4 hours or less; a volatile solvent and C a H2F 2a-1 A step of preparing a fourth solution by stirring fluorinated alcohol expressed as OH (where a represents a natural number of 10 or less) and having a hydroxyl group bonded to the terminal; and a step of adding the fourth solution to the third solution and stirring at a temperature of 50° C. or more and 80° C. or less for 20 hours or more and 46 hours or less, wherein the step of preparing a urethane single molecule (FU) containing fluorine comprises an isocyanate crosslinking agent containing two or more isocyanate groups and C c H2F 2c-1 It may include a step of adding fluorinated alcohol expressed as OH (where c represents a natural number less than or equal to 10) and having a hydroxyl group bonded to the terminal, stirring for 30 minutes to 2 hours, and pulverizing the formed particles. Here, in the step of adding the fourth solution to the third solution and stirring, if the temperature is greater than or equal to 50°C and less than or equal to 80°C and the time is outside the range of 20 hours to 46 hours, the degree of curing, mechanical properties, and water-repellent characteristics of the coating may decrease, and therefore, the step of adding the fourth solution to the third solution and stirring is preferably performed at a temperature of greater than or equal to 50°C and less than or equal to 80°C and the time is greater than or equal to 20 hours and less than or equal to 46 hours.

[0138] In addition, since the above-mentioned fluorinated alcohol, the above-mentioned fluorinated diol, the above-mentioned isocyanate crosslinking agent and the catalyst have good solubility when stirred with a volatile solvent such as acetone, stirring can be performed using hands, a vial or vortexing, but is not necessarily limited to these methods.

[0139] When manufacturing the urethane monomer (FU) containing the above fluorine, the mixture is stirred for 30 minutes to 2 hours until it becomes a white solid, and then a grinding tool such as a bowl is used to finely grind it into particles. This is a process of mixing two liquid monomers to manufacture a solid monomer in the case of the process of manufacturing the urethane monomer (FU) containing the above fluorine. When the two transparent liquids are mixed and the reaction is complete, the solidified white solid remains in the same volume as the liquid in the reactor, which means the work of artificially grinding it in a mortar or the like to add it to the fluorine-containing polyurethane polymer (FPU) in an appropriate composition ratio.

[0140] Above, the method for manufacturing an antifouling coating solution has been described.

[0141] Below, the manufacturing examples and experimental examples of the antifouling coating solution are described in detail.

[0142] <Experiment preparation>

[0143] 2,2,3,3,4,4,4-Hpetafluoro-1-butanol (HF, >98%), 1H,1H,10H,10H-Hexadecafluoro-1,10-decanediol (HFO, >97.0%), Hexamethylene diisocyanate (HDI, >98%), Dibutyltin dilaurate (DBTDL, >95%) were purchased from TCI, Acetone (>99.7%) from Samchun Chemical, Poly(tetrahydrofuran) (PTHF, >97.0%) from Sigma-Aldrich, and PTFE (99.9%, 260 nm) from Nanografi, and were used as received.

[0144] {Manufacturing Example 1}

[0145] Manufacturing of fluorine-containing polyurethane polymers (FPU):

[0146] In vial 1, add acetone (1 mL), PTHF (0.05 mmol), HFO (0.25 mmol), and HF (5.7 mmol) and mix well. In a round flask, add a magnetic stir bar and acetone (9 mL), HDI (3.3 mmol), and DBTDL (3 mol%) in that order, and slowly add the solution in vial 1 while stirring. Seal the flask and maintain it at 70°C and stir for 4 hours. Then, add acetone (5 mL) and HF (0.3 mmol) to vial 2, mix well, and slowly add to the flask and stir for 20 more hours to complete the reaction and recover it as a solution.

[0147] Manufacturing of urethane single molecules (FU) containing fluorine:

[0148] Add HDI (6.24 mmol) and DBTDL (3 mol%) sequentially to vial 3, then add HF (12.48 mmol) while stirring, and stir for 1 hour until a white solid forms. After the reaction is complete, grind into fine particles using a bowl.

[0149] Preparation and coating of superhydrophobic coating solution:

[0150] Add FU:PTFE = 3:1 weight ratio to the synthesized FPU solution (wherein FU+PTFE is 60 wt% of the total solution) and mix well. Then, perform ultrasonic treatment for about 30 minutes to ensure uniform dispersion. Afterwards, apply it on an Al substrate and dry it sufficiently at room temperature for 24 hours.

[0151] {Manufacturing Example 2}

[0152] Manufacturing of fluorine-containing polyurethane polymers (FPU):

[0153] In vial 1, add polylactide diol (0.05 mmol), 2,2,3,3,4,4-Hexafluoro-1,5-pentandiol (0.25 mmol), and 2,2,3,3,4,4,5,5-Octafluoro-1-pentanol (5.7 mmol) to acetone (1 mL) and mix well. In a round flask, add a magnetic stir bar and acetone (9 mL), HDI (3.3 mmol), and DBTDL (3 mol%) in that order, and slowly add the solution in vial 1 while stirring. Seal the flask and maintain it at 70℃ and stir for 4 hours. Then, add acetone (5 mL) and HF (0.3 mmol) to vial 2, mix well, and slowly add to the flask and stir for 20 more hours to complete the reaction and recover it in a solution state.

[0154] Manufacturing of urethane single molecules (FU) containing fluorine:

[0155] Add HDI (6.24 mmol) and DBTDL (3 mol%) sequentially to vial 3, then add 2,2,3,3,4,4,5,5-Octafluoro-1-pentanol (12.48 mmol) while stirring, and stir for 1 hour until a white solid forms. After the reaction is complete, grind into fine particles using a bowl.

[0156] Preparation and coating of superhydrophobic coating solution:

[0157] Add FU:PTFE = 3:1 weight ratio to the synthesized FPU solution (wherein FU+PTFE is 60 wt% of the total solution) and mix well. Then, perform ultrasonic treatment for about 30 minutes to ensure uniform dispersion. Afterwards, apply it on an Al substrate and dry it sufficiently at room temperature for 24 hours.

[0158] {Experimental Example 1}: Synthesis confirmation of FPU through FT-IR

[0159] In the case of Fig. 1, which shows the FT-IR of FPU, it was confirmed that the synthesis of FPU proceeded normally through the disappearance of the residual NCO peak in FPU and Pre-FPU.

[0160] In addition, in the case of Fig. 2 showing the FT-IR of FU, it was confirmed that the synthesis of FU proceeded normally through the disappearance of the NCO peak in FU.

[0161] {Experimental Example 2}: Water contact angle test

[0162] During the synthesis of FPU, the contact angle was optimized according to the composition of HFO, a chain extender containing a large amount of fluorine groups. In the case of the sample, the overall water contact angle tended to increase as the molar ratio of HFO increased, but it was confirmed through Fig. 3 that the maximum water contact angle of approximately 143 degrees was observed at the point where the molar ratio of HFO satisfied 0.8. In addition, it was confirmed that as the molar ratio of HFO increased, the density of fluorine groups within the polymer chain increased, so that more fluorine groups were oriented in the air layer during coating, thereby improving the water contact angle. However, when the molar ratio of HFO exceeded 0.8, the adhesion with the substrate decreased, and it was confirmed that peeling occurred after coating.

[0163] In addition, the water contact angle was measured by increasing the wt% of FPU while maintaining the ratio of PTFE and FU at 1:3 in the secured optimal FPU composition. As a result, when 60 wt% was used, it was confirmed that the superhydrophobic property of approximately 158 degrees was exhibited through Fig. 4a, which illustrates the water contact angle optimization according to the weight of the particles. At this time, it was confirmed that the contact area between water and the coating surface was minimized, as shown in Fig. 4b, which illustrates the contact surface with water after coating the coating solution of the present invention on the surface of the device.

[0164] In addition, through water contact and friction tests, it was confirmed through Fig. 5 that the superhydrophobic properties were maintained over the entire coating area rather than just one point on the surface.

[0165] {Experimental Example 3}: Microstructure analysis using SEM

[0166] FPU 1PTFE-3FU In order to analyze the cause of the superhydrophobic property, the microstructure was analyzed using SEM, and as a result, it was confirmed through Fig. 6a that when the ratio of PTFE:FU = 1:3 in FPU, a surface morphology oriented toward the air like a coral reef was shown. This is because in the case of fluorine groups, due to their low surface energy, they tend to be oriented toward the air interface after coating, and in the case of acetone, the solvent used in the present invention, while PTFE, which is a commercial particle, does not dissolve, urethane single molecules (FU) containing fluorine dissolve, and when dissolved in acetone and applied to the coating, the morphology occurs because it affects the speed of acetone vaporizing after removing the applied solid content. In addition, when PTFE and fluorine-containing urethane monomer (FU) were mixed in a ratio of 1:3 with the fluorine-containing polyurethane polymer (FPU) developed under the condition of 60 wt% of FPU, the vaporization rate of acetone at room temperature in the composition was optimized to most suitably orient the fluorine groups contained in the composition toward the air interface, which was confirmed through the SEM image of Fig. 6a to be oriented in the shape of a coral reef.

[0167] To disprove this, FPU 3PTFE-1FU When drying at a high temperature of 70 degrees Celsius instead of room temperature, it was confirmed through the second row and third column of Fig. 6a that a coral reef-like surface morphology did not occur. In addition, FPU 3PTFE-1FU When drying was performed at a high temperature of 70 degrees instead of room temperature, it was confirmed through Fig. 6b that the contact angle decreased from 157 degrees to 143 degrees.

[0168] {Experimental Example 4}: Mechanical robustness verification

[0169] ASTM D3359-17 standard does not have a standard for the adhesive strength of the tape, but 634 Nm -1 to 700Nm -1 (steel value) is recommended, but 3M VHB test (2,600 Nm) -1 ) was used, it was confirmed through Fig. 7a that the water contact angle was maintained at 150 degrees or more for up to 10 times. In addition, the VHB test (2,600 Nm) between 3M -1 ) was used, it was confirmed through Figure 7b that the coral reef-like surface morphology on the surface of the coating material was maintained up to 10 times, and that there was no significant effect on the superhydrophobic properties.

[0170] {Experimental Example 5}: Antifouling and self-cleaning test

[0171] FPU 1PTFE-3FU Based on the superhydrophobic properties of the coating solution, an antifouling test was conducted using methylene blue as a contaminant. As a result, unlike the bare substrate where methylene blue remained on the substrate for more than 20 times after being immersed in methylene blue for more than 20 times, the substrate coated with the coating solution of the present invention showed relatively excellent antifouling properties as shown in Fig. 8, as the contaminants flowed off and no contaminants remained even after being immersed in methylene blue for about 20 times.

[0172] In addition, in the results of a self-cleaning test conducted using SiC of the dust series, it was confirmed through Figure 9 that SiC remained even when the bare substrate was tilted when immersed in SiC, and further, SiC remained even when the substrate was immersed in water.

[0173] On the other hand, when the antifouling coating of the present invention was applied, it was confirmed through Fig. 9 that SiC was removed simply by tilting the substrate when immersing it in SiC, and when the antifouling coating substrate was immersed in water, SiC was completely removed, showing relatively excellent self-cleaning ability.

[0174] {Experimental Example 6}: Biological antifouling test

[0175] (a) Staphylococcus aureus or Streptococcus mutans was cultured in tryptic soy broth and brain heart infusion broth, respectively, at 37°C for 24 hours, and then the strains were spread on agar plates. The spread plates were further cultured at 37°C for 24 hours, and a strain isolated from a single colony among the colonies formed was cultured again in a new medium at 37°C for 24 hours.

[0176] The resulting bacterial culture suspension was diluted to exhibit an absorbance at a wavelength of 600 nm of 0.4 and then applied to a superhydrophobic material and a bare substrate. After incubation at 37°C for 24 hours, the superhydrophobic material and bare substrate with the bacteria applied were washed once with phosphate buffered saline and then incubated in phosphate buffered saline containing 2.5 vol% glutaraldehyde at 25°C for 12 hours to fix the applied bacteria.

[0177] Afterwards, the substrate was washed once with phosphate-buffered saline and once with deionized water, and then dehydrated by immersion in a 50-95 vol% ethanol aqueous solution. Afterwards, the substrate was dried in a vacuum oven at 25°C for 18 hours, mounted on a SEM stub, and SEM specimens were produced through Pt sputtering and observed using an SEM. The antibacterial performance was compared by counting the number of attached bacteria per unit area.

[0178] As a result of conducting the antifouling test using the bacteria as above, in the case of bare (Al substrate), the unit area (10) on the surface 3While approximately 22.8 S. aureus and 28.4 S. mutans were fixed per mm, FPU 1PTFE-3FU In the case of the unit area on the surface (10 3 It was confirmed through Figures 10a and 10b that bacterial contamination was significantly low, with approximately 0.1 S. aureus per mm and 0 S. mutans not detected.

[0179] An antifouling coating solution according to one embodiment comprises a fluorine-containing polyurethane polymer (FPU), a fluorine-containing urethane monomer (FU), and polytetrafluoroethylene (PTFE), wherein the fluorine-containing polyurethane polymer (FPU) comprises a volatile solvent; C a H2F 2a-1 Fluorinated alcohol expressed as OH (where a represents a natural number less than or equal to 10) and having a hydroxyl group attached to the terminal; C b H4F 2b-4 A fluorinated diol expressed as (OH)2 (wherein b represents a natural number of 20 or less) and having hydroxyl groups bonded to both terminals; an alcohol containing two or more hydroxyl groups; and an isocyanate crosslinking agent containing two or more isocyanate groups, wherein the ratio of the molecular weight of the fluorinated diol to the polyurethane polymer (FPU) containing fluorine is 0.7 or more and 0.9 or less, and the ratio of the sum of the numbers of hydroxyl groups contained in the fluorinated alcohol, the fluorinated diol, and the alcohol to the number of isocyanate groups contained in the isocyanate crosslinking agent is 1:1, and the urethane monomer (FU) containing fluorine is, C c H2F 2c-1It may include a fluorinated alcohol expressed as OH (where c represents a natural number less than or equal to 10) and having a hydroxyl group bonded to the terminal; and an isocyanate crosslinking agent including two or more isocyanate groups. Through this, a polyurethane-based coating material and a coating solution including the same can be provided that can secure mechanical strength based on a polyurethane material and at the same time induce superhydrophobic properties, thereby implementing antifouling and antibacterial properties.

[0180] The above antifouling coating solution may include acetone as the volatile solvent.

[0181] The antifouling coating solution may have a value of a of the fluorinated alcohol contained in the fluorine-containing polyurethane polymer (FPU) as 4, b of the fluorinated diol as 10, and c of the fluorinated alcohol contained in the fluorine-containing urethane monomer (FU) as 4.

[0182] The antifouling coating solution is a solution in which the alcohol containing two or more hydroxyl groups is selected from the group consisting of poly(tetrahydrofuran) (PTHF), polycaprolactone diol, poly(hydroxybutyrate) diol, poly(lactide-co-caprolactone) diol, poly(ethylene glycol) diol, poly(ethylene terephthalate) diol, fatty acid-based linear diol, polylactide diol, poly(butylene glycol) diol, poly(propylene oxide) diol, and poly(tetramethylene oxide) diol. oxide) diol), poly(ethylene adipate) diol, castor oil-based diol, polyglycolide diol, poly(lactide-b-glycolide) diol, poly(hexamethylene carbonate) diol, polycarbonate diol, poly(butylene adipate) diol, and soybean oil-based diol.

[0183] The above antifouling coating solution is a solution in which the isocyanate crosslinking agent is selected from the group consisting of hexamethylene diisocyanate (HIDI), diphenylmethane 4,4'-diisocyanate, 1,3-phenylene diisocyanate, isophorone diisocyanate, polyhexamethylene diisocyanate, triphenylmethan-4,4',4''-triisocyanate, 1,3,5-triisocyanato-2-methylbenzene, and It may be at least one selected from the group consisting of 1,3,5-triisocyanato-2,4,6-trimethylbenzene.

[0184] The above antifouling coating solution may further include one or more catalysts selected from the group consisting of the fluorine-containing polyurethane polymer (FPU) and the fluorine-containing urethane monomer (FU), dibutyltin dilaurate (DBTDL), dimethylaminopyridine (DMAP), triethylamine (TEA), diazabiclo[2,2,2]octane, and 1,4-diazabicyclo[2,2,2]octane.

[0185] The above antifouling coating solution may have a water contact angle of 140 degrees or more and 150 degrees or less for the polyurethane polymer (FPU) containing the fluorine.

[0186] The above antifouling coating solution may have a ratio of the molecular weight of the fluorinated diol to the polyurethane polymer (FPU) containing fluorine of 0.8.

[0187] The above antifouling coating solution may have a water contact angle of the polyurethane polymer (FPU) containing the fluorine of 143 degrees or more and 150 degrees or less.

[0188] The above antifouling coating solution may have a weight ratio of the urethane monomer (FU) containing fluorine and the polytetrafluoroethylene (PTFE) of 3:1.

[0189] The above antifouling coating solution may have a weight ratio of the fluorine-containing urethane monomer (FU) to the fluorine-containing polyurethane polymer (FPU) and the polytetrafluoroethylene (PTFE) of 40 wt% or more and 80 wt% or less.

[0190] The above antifouling coating solution may have a water contact angle of 150 degrees or more and 160 degrees or less.

[0191] The above antifouling coating solution may have a weight ratio of the fluorine-containing urethane monomer (FU) to the fluorine-containing polyurethane polymer (FPU) and the polytetrafluoroethylene (PTFE) of 60 wt%.

[0192] The above antifouling coating solution may have a water contact angle of 157 degrees or more and 160 degrees or less.

[0193] A method for manufacturing an antifouling coating solution according to one embodiment comprises the steps of: manufacturing a polyurethane polymer (FPU) containing fluorine; manufacturing a urethane monomer (FU) containing fluorine; and adding the urethane monomer (FU) containing fluorine and polytetrafluoroethylene (PTFE) satisfying a weight ratio of 3:1 to the polyurethane polymer (FPU) containing fluorine and stirring, wherein the step of manufacturing the polyurethane polymer (FPU) containing fluorine comprises: mixing a volatile solvent, CaH2F 2a-1 Fluorinated alcohol, C, expressed as OH (where a represents a natural number less than or equal to 10) and having a hydroxyl group attached to the terminal b H4F 2b-4 A step of preparing a first solution by stirring a fluorinated diol expressed as (OH)2 (wherein b represents a natural number of 20 or less) and having hydroxyl groups bonded to both terminals, an alcohol containing two or more hydroxyl groups, an isocyanate crosslinking agent containing two or more isocyanate groups, and a catalyst; a step of preparing a second solution by adding a volatile solvent and an isocyanate crosslinking agent containing two or more isocyanate groups; a step of preparing a third solution by adding the second solution to the first solution and stirring at a temperature of 0°C or more and 80°C or less for 2 hours or more and 4 hours or less; a volatile solvent and C a H2F 2a-1 A step of preparing a fourth solution by stirring fluorinated alcohol expressed as OH (where a represents a natural number of 10 or less) and having a hydroxyl group bonded to the terminal; and a step of adding the fourth solution to the third solution and stirring at a temperature of 50° C. or more and 80° C. or less for 20 hours or more and 46 hours or less, wherein the step of preparing a urethane single molecule (FU) containing fluorine comprises an isocyanate crosslinking agent containing two or more isocyanate groups and C c H2F 2c-1It may include a step of adding fluorinated alcohol expressed as OH (where c means a natural number less than or equal to 10) and having a hydroxyl group bonded to the terminal, stirring for 30 minutes to 2 hours, and pulverizing the formed particles.

[0194] The method for manufacturing the above antifouling coating solution may include the volatile solvent including acetone.

[0195] The method for manufacturing the antifouling coating solution may be such that a of the fluorinated alcohol contained in the fluorine-containing polyurethane polymer (FPU) is 4, b of the fluorinated diol is 10, the ratio of the sum of the number of hydroxyl groups contained in the fluorinated alcohol, the fluorinated diol, and the alcohol contained in the fluorine-containing polyurethane polymer (FPU) to the number of isocyanate groups contained in the isocyanate crosslinking agent is 1:1, and c of the fluorinated alcohol contained in the fluorine-containing urethane monomer (FU) may be 4.

[0196] The method for manufacturing the above antifouling coating solution may be such that the ratio of the molecular weight of the fluorinated diol to the polyurethane polymer (FPU) containing fluorine is 0.8.

[0197] The method for manufacturing the above antifouling coating solution may be such that the weight ratio of the fluorine-containing urethane monomer (FU) to the fluorine-containing polyurethane polymer (FPU) and the polytetrafluoroethylene (PTFE) is 60 wt%.

[0198] The method for manufacturing the antifouling coating solution is characterized in that the alcohol containing two or more hydroxyl groups is selected from the group consisting of poly(tetrahydrofuran) (PTHF), polycaprolactone diol, poly(hydroxybutyrate) diol, poly(lactide-co-caprolactone) diol, poly(ethylene glycol) diol, poly(ethylene terephthalate) diol, fatty acid-based linear diol, polylactide diol, poly(butylene glycol) diol, poly(propylene oxide) diol, poly(tetramethylene oxide). At least one selected from the group consisting of poly(tetramethylene oxide) diol, poly(ethylene adipate) diol, castor oil-based diol, polyglycolide diol, poly(lactide-b-glycolide) diol, poly(hexamethylene carbonate) diol, polycarbonate diol, poly(butylene adipate) diol and soybean oil-based diol, and the isocyanate crosslinking agent is hexamethylene diisocyanate (HIDI), diphenylmethane 4,At least one selected from the group consisting of 4'-diisocyanate, 1,3-phenylene diisocyanate, isophorone diisocyanate, polyhexamethylene diisocyanate, triphenylmethan-4,4',4''-triisocyanate, 1,3,5-triisocyanato-2-methylbenzene and 1,3,5-triisocyanato-2,4,6-trimethylbenzene, and the polyurethane polymer (FPU) containing the fluorine and the The urethane monomer (FU) containing fluorine may further include one or more catalysts selected from dibutyltin dilaurate (DBTDL), dimethylaminopyridine (DMAP), triethylamine (TEA), diazabicyclo[2,2,2]octane, and 1,4-diazabicyclo[2,2,2]octane.

[0199] Above, the antifouling coating solution and the method for manufacturing the antifouling coating solution according to one embodiment have been described.

[0200] According to the idea of ​​the present disclosure, a polyurethane-based coating material and a coating solution including the same can be provided that can secure mechanical strength through a polyurethane-based material while simultaneously inducing superhydrophobic properties to implement antifouling and antibacterial properties.

[0201] The effects that can be obtained from the present disclosure are not limited to the effects mentioned above, and other effects that are not mentioned can be clearly understood by a person having ordinary skill in the art to which the present disclosure belongs from the description below.

[0202] Although the embodiments of the invention disclosed above have been illustrated and described, the disclosed invention is not limited to the specific embodiments described above, and various modifications may be implemented by a person having ordinary skill in the art to which the disclosed invention pertains without departing from the gist claimed in the claims.

Claims

1. Contains a polyurethane polymer (FPU) containing fluorine, a urethane monomer (FU) containing fluorine, and polytetrafluoroethylene (PTFE). The polyurethane polymer (FPU) containing the above fluorine is volatile solvent; C a H 2 F 2a-1 Fluorinated alcohol expressed as OH (where a is a natural number less than or equal to 10) and having a hydroxyl group attached to the terminal; C b H 4 F 2b-4 (OH) 2 (where b represents a natural number less than or equal to 20) and a fluorinated diol having hydroxy groups bonded to both terminals; An alcohol containing two or more hydroxyl groups; and Comprising an isocyanate crosslinker containing two or more isocyanate groups, The ratio of the molecular weight of the fluorinated diol to the polyurethane polymer (FPU) containing the fluorine is 0.7 or more and 0.9 or less, The ratio of the sum of the number of hydroxyl groups contained in the above fluorinated alcohol, the above fluorinated diol and the above alcohol and the number of isocyanate groups contained in the above isocyanate crosslinking agent is 1:1, The above urethane single molecule (FU) containing fluorine is C c H 2 F 2c-1 Fluorinated alcohols expressed as OH (where c is a natural number less than or equal to 10) and having a hydroxyl group attached to the terminal; and An isocyanate crosslinker comprising two or more isocyanate groups; Including, Anti-fouling coating solution.

2. In claim 1, The above volatile solvent is an antifouling coating solution containing acetone.

3. In claim 1, The a of the fluorinated alcohol contained in the polyurethane polymer (FPU) containing the above fluorine is 4, The b of the above fluorinated diol is 10, An antifouling coating solution in which c of the fluorinated alcohol contained in the urethane monomer (FU) containing the above fluorine is 4.

4. In claim 1, The alcohol containing two or more hydroxy groups is poly(tetrahydrofuran) (PTHF), polycaprolactone diol, poly(hydroxybutyrate) diol, poly(lactide-co-caprolactone) diol, poly(ethylene glycol) diol, poly(ethylene terephthalate) diol, fatty acid-based linear diol, polylactide diol, poly(butylene glycol) diol, poly(propylene oxide) diol, poly(tetramethylene oxide) diol, An antifouling coating solution, wherein at least one is selected from the group consisting of poly(ethylene adipate) diol, castor oil-based diol, polyglycolide diol, poly(lactide-b-glycolide) diol, poly(hexamethylene carbonate) diol, polycarbonate diol, poly(buthylene adipate) diol, and soybean oil-based diol.

5. In claim 1, The above isocyanate crosslinking agent is hexamethylene diisocyanate (HIDI), diphenylmethane 4,4'-diisocyanate, 1,3-phenylene diisocyanate, isophorone diisocyanate, polyhexamethylene diisocyanate, triphenylmethan-4,4',4''-triisocyanate, 1,3,5-triisocyanato-2-methylbenzene, and An antifouling coating solution, wherein at least one is selected from the group consisting of 1,3,5-triisocyanato-2,4,6-trimethylbenzene.

6. In claim 1, An antifouling coating solution, wherein the polyurethane polymer (FPU) containing fluorine and the urethane monomer (FU) containing fluorine further contain at least one catalyst selected from dibutyltin dilaurate (DBTDL), dimethylaminopyridine (DMAP), triethylamine (TEA), diazabiclo[2,2,2]octane and 1,4-diazabicyclo[2,2,2]octane.

7. In claim 3, An antifouling coating solution having a water contact angle of 140 degrees or more and 150 degrees or less of a polyurethane polymer (FPU) containing the above fluorine.

8. In claim 3, An antifouling coating solution having a molecular weight ratio of the fluorinated diol to the polyurethane polymer (FPU) containing the fluorine of 0.

8.

9. In claim 8, An antifouling coating solution having a water contact angle of 143 degrees or more and 150 degrees or less of a polyurethane polymer (FPU) containing the above fluorine.

10. In claim 8, An antifouling coating solution having a weight ratio of the urethane monomer (FU) containing the above fluorine and the polytetrafluoroethylene (PTFE) of 3:

1.

11. In claim 10, An antifouling coating solution in which the weight ratio of the fluorine-containing polyurethane monomer (FU) to the polytetrafluoroethylene (PTFE) is 40 wt% or more and 80 wt% or less in relation to the fluorine-containing polyurethane polymer (FPU).

12. In claim 11, An antifouling coating solution having a water contact angle of 150 degrees or more and 160 degrees or less.

13. In claim 10, An antifouling coating solution in which the weight ratio of the fluorine-containing polyurethane monomer (FU) and the polytetrafluoroethylene (PTFE) to the fluorine-containing polyurethane polymer (FPU) is 60 wt%.

14. In claim 13, An antifouling coating solution having a water contact angle of 157 degrees or more and 160 degrees or less.

15. A step for producing a polyurethane polymer (FPU) containing fluorine; A step for producing a urethane single molecule (FU) containing fluorine; and It comprises a step of adding the fluorine-containing urethane monomer (FU) and polytetrafluoroethylene (PTFE) satisfying a weight ratio of 3:1 to the fluorine-containing polyurethane polymer (FPU) and stirring. The step of manufacturing the polyurethane polymer (FPU) containing the above fluorine is as follows: Volatile solvent, C a H 2 F 2a-1 Fluorinated alcohol, C, expressed as OH (where a is a natural number less than or equal to 10) and having a hydroxyl group attached to the terminal b H 4 F 2b-4 (OH) 2 A step of preparing a first solution by stirring a fluorinated diol expressed as (wherein b represents a natural number less than or equal to 20) and having hydroxy groups bonded to both terminals, an alcohol containing two or more hydroxy groups, an isocyanate crosslinking agent containing two or more isocyanate groups, and a catalyst; A step of preparing a second solution by adding a volatile solvent and an isocyanate cross-linking agent including two or more isocyanate groups; A step of preparing a third solution by adding the second solution to the first solution and stirring at a temperature of 0°C or higher and 80°C or lower for 2 hours or longer and 4 hours or shorter; Volatile solvents and C a H 2 F 2a-1 A step of preparing a fourth solution by stirring fluorinated alcohol expressed as OH (where a means a natural number less than or equal to 10) and having a hydroxyl group bonded to the terminal; and A step of adding the fourth solution to the third solution and stirring at a temperature of 50°C or higher and 80°C or lower for 20 hours or longer and 46 hours or shorter, The step of manufacturing the urethane single molecule (FU) containing the above fluorine is: Isocyanate crosslinking agent containing two or more isocyanate groups and C c H 2 F 2c-1 A step of adding fluorinated alcohol expressed as OH (where c means a natural number less than or equal to 10) and having a hydroxyl group bonded to the terminal and stirring for 30 minutes to 2 hours to form particles, comprising the step of pulverizing the formed particles. Method for preparing an antifouling coating solution.

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