Coating material, method for producing coating material, building structure, moving object, industrial product, furniture and equipment

Abstract

To provide a coating material that can reduce the amount of the coating material applied to a surface of the base material to be coated, can be applied at low cost, and has a viscosity that can be adjusted by means that do not adversely affect the human body.SOLUTION: A coating material 10B is applied to a surface of a base material to be coated to form a coating film on the surface of the base material. The coating material 10B is mixed with microbubbles 14 and / or nanobubbles 15, and the microbubbles 14 and / or the nanobubbles 15 are dispersed and mixed in the coating material 10B at a predetermined concentration. The viscosity of the coating material 10B after the microbubbles 14 and / or the nanobubbles 15 are introduced is lower than that of the coating material before the microbubbles 14 and / or the nanobubbles 15 are introduced, and the viscosity of the coating material 10B after the microbubbles 14 and / or the nanobubbles 15 are introduced is 1 mPa s or more and 1000 mPa s or less.SELECTED DRAWING: Figure 5

Description

Technical Field

[0001] The present invention relates to a paint to be applied to the surface of a substrate to be coated and a method for manufacturing the paint, and also relates to buildings, moving bodies, industrial products, and furniture and equipment.

Background Art

[0002] A paint containing a fluoropolymer, a polydimethylsilicone having a first crosslinkable group and a kinematic viscosity of 30 to 150 mm 2 / s, an acrylic silicone having a second crosslinkable group, and a curing agent having a reactive group capable of reacting with the first crosslinkable group and the second crosslinkable group is disclosed (see Patent Document 1). By using this paint, an antifouling coating film excellent in hot water resistance can be formed.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] It is preferable that the paint reduces the coating amount on the surface of the substrate to be coated and can be coated at low cost. However, since the coating film can protect the surface of the substrate by coating it with a predetermined film thickness on the surface of the substrate to be coated, it is necessary to ensure a film thickness of a predetermined thickness in the coating film after the applied paint has hardened, and the coating amount of the paint cannot be unconditionally reduced. Further, when the specific surface area of the substrate to which the paint is applied is large and the paint is applied to the entire surface thereof, the weight of the substrate including the coating film in which the paint has hardened increases.

[0005] In addition, lacquer thinner, urethane thinner, epoxy thinner, acrylic thinner, and melamine thinner are used as organic solvents for adjusting the viscosity of paints. The harmful substances such as toluene, xylene, isopropyl alcohol, 1-butanol, and methanol contained in these various thinners volatilize, and physical symptoms such as numbness in the hands and feet, dizziness, chronic bronchitis, peripheral neuritis, optic nerve atrophy, liver damage, and brain damage may appear in the human body that has inhaled them. Therefore, other means capable of adjusting the viscosity of the paint without using a thinner are desired. In addition, for water-based paints, since water is used for viscosity adjustment, it affects the global water shortage.

[0006] An object of the present invention is to provide a paint that can reduce the coating amount on the surface of a substrate to be coated and can be coated at low cost. Another object of the present invention is to provide a paint capable of forming a coating film that can minimize the increase in the weight of the substrate. Another object of the present invention is to provide a paint that can adjust the viscosity by means that do not have an adverse effect on the human body and can easily adjust the viscosity even in an environment with a low temperature. Another object of the present invention is to provide a paint manufacturing method for a paint that can be coated at low cost and can minimize the increase in weight. Another object of the present invention is to provide a building, a moving body, an industrial product, furniture, and equipment coated with a paint capable of forming a coating film that can be coated at low cost and can minimize the increase in weight.

Means for Solving the Problems

[0007] A first premise of the present invention for solving the above problems is a paint that is applied to the surface of a substrate to be coated and forms a coating film on the surface of the substrate.

[0008] As a characteristic of the paint of the present invention in the first premise, microbubbles and / or nanobubbles are introduced into the paint, and the microbubbles and / or nanobubbles are dispersed and mixed inside the paint at a predetermined concentration.

[0009] As an example of the paint of the present invention, the average particle size D of microbubbles and / or nanobubbles 50 is 100 μm or less.

[0010] As another example of the paint of the present invention, the average particle size D of microbubbles and / or nanobubbles 50 is 0.5 μm or less.

[0011] As another example of the paint of the present invention, the number of microbubbles and / or nanobubbles contained in 1 ml of the paint is 10 5 pieces / ml or more and 10 12 pieces / ml or less.

[0012] As another example of the paint of the present invention, microbubbles and / or nanobubbles are undergoing Brownian motion inside the paint.

[0013] As another example of the paint of the present invention, the viscosity of the paint after introducing microbubbles and / or nanobubbles is lower than that of the paint before introducing microbubbles and / or nanobubbles.

[0014] As another example of the paint of the present invention, the viscosity of the paint after introducing microbubbles and / or nanobubbles is in the range of 1 to 1000 mPa·s.

[0015] As another example of the present invention, the gas forming the microbubbles and / or nanobubbles is any one of air, nitrogen, argon, helium, xenon, neon, krypton, radon, hydrogen, oxygen, ozone, methane, ethylene, propane, butane, acetylene, ethanol, fluorine, chlorine, bromine, iodine, ammonia, hydrogen sulfide, sulfur dioxide, carbon monoxide, carbon dioxide, or a mixed gas obtained by mixing two or more of them.

[0016] As another example of the paint of the present invention, the paint is any one of a fluororesin paint, a silicone resin paint, an acrylic resin paint, a urethane resin paint, and an aqueous paint.

[0017] The second premise of the present invention for solving the above problems is a paint manufacturing method for manufacturing the paint.

[0018] The characteristics of the paint manufacturing method of the present invention in the second premise are that the paint manufacturing method introduces microbubbles and / or nanobubbles into the paint by using any one of a pressure dissolution method, a micropore and porous method, an ejector method, a Venturi method, an ultrasonic method, a static mixer method, a cavitation method, a swirling liquid flow method, and a shearing method, or by combining these methods.

[0019] As another example of the present invention, the object to be coated with the paint is a building, the paint is applied to the surface of the building, and a paint film is formed on the surface of the building by the cured paint.

[0020] As another example of the present invention, the object to be coated with the paint is a moving body, the paint is applied to the surface of the moving body, and a paint film is formed on the surface of the moving body by the cured paint.

[0021] As another example of the present invention, the object to be coated with the paint is an industrial product, the paint is applied to the surface of the industrial product, and a paint film is formed on the surface of the industrial product by the cured paint.

[0022] As another example of the present invention, the object to be coated with the paint is furniture and equipment, the paint is applied to the surface of the furniture and equipment, and a paint film is formed on the surface of the furniture and equipment by the cured paint.

Advantages of the Invention

[0023] According to the paint of the present invention, microbubbles and / or nanobubbles are introduced into the paint, and the microbubbles and / or nanobubbles of the independent bubbles are dispersed and mixed (dispersed and dissolved) inside the paint at a predetermined concentration, so that the proportion of the paint itself per unit volume of the paint can be reduced by the microbubbles and nanobubbles, and the amount of paint applied when the paint is applied to the surface of the substrate to be coated is reduced, making it possible to reduce the amount of paint applied to the substrate. Compared to a paint that does not have microbubbles and / or nanobubbles dispersed therein, the reduced amount of paint applied can reduce the unit price of the paint per unit area of ​​the substrate surface, and the paint can be applied inexpensively.

[0024] Average particle size D of microbubbles and / or nanobubbles 50 The paint with an average particle size of 100 μm or less has an average particle size D 50 Since microbubbles and / or nanobubbles with an average particle size D of 100 μm or less are dispersed and mixed (dispersed and dissolved) in the paint at a specified concentration, the proportion of the paint itself per unit area in the paint can be reduced by the fine microbubbles and ultrafine nanobubbles, and the amount of paint applied when applying the paint to the surface of the substrate to be coated can be reliably reduced. 50 By including microbubbles or nanobubbles, the amount of paint applied to the substrate is reduced, so the unit cost of paint per unit area of ​​the substrate surface can be reduced, making it possible to apply the paint inexpensively.

[0025] Average particle size D of microbubbles and / or nanobubbles 50 The average particle size D is 0.5 μm or less. 50 Since microbubbles and / or nanobubbles with an average particle size D of 0.5 μm or less are dispersed and mixed (dispersed and dissolved) in the paint at a specified concentration, the proportion of the paint itself per unit area in the paint can be reduced by the fine microbubbles and ultrafine nanobubbles, and the amount of paint applied when applying the paint to the surface of the substrate to be coated can be reliably reduced. 50By containing microbubbles and / or nanobubbles, the coating amount on the substrate is reduced, so that the unit price of the paint per unit area of the surface of the substrate can be lowered, and the paint can be applied at a low cost.

[0026] The paint containing 10 5 or more and 10 12 or less microbubbles and / or nanobubbles per milliliter of the paint has microbubbles and / or nanobubbles in the range in 1 ml of the paint in which microbubbles and / or nanobubbles are dispersed and mixed. Therefore, a large amount of microbubbles of fine bubbles and nanobubbles of ultrafine bubbles are dispersed and mixed (dispersed and dissolved) in the paint at a predetermined concentration. The ratio of the paint itself per unit area in the paint can be reduced by the microbubbles which are fine bubbles and the nanobubbles which are ultrafine bubbles, and the coating amount of the paint itself when applying the paint to the surface of the substrate to be coated can be surely reduced. The paint containing microbubbles and / or nanobubbles in the range of 10 5 or more and 10 12 or less microbubbles and / or nanobubbles per milliliter reduces the coating amount on the substrate, so that the unit price of the paint per unit area of the surface of the substrate can be lowered, and the paint can be applied at a low cost.

[0027] In the paint in which microbubbles and / or nanobubbles are performing Brownian motion inside the paint, its adhesiveness is reduced by the nanobubbles performing Brownian motion inside the paint, and by dissolving the nanobubbles, the intermolecular bonds are broken and the intermolecular interaction is weakened, so that the viscosity of the paint can be reduced. The average particle diameter D of the microbubbles and nanobubbles 50By adjusting the content of microbubbles and nanobubbles in the paint, the viscosity of the paint can be adjusted, and the ease of applying the paint to the surface of the substrate can be improved. Since the amount of organic solvents such as thinner used for viscosity adjustment of the paint can be reduced or there is no need to use it, the viscosity can be adjusted without reducing or using substances that may have an adverse effect on the human body. By using microbubbles and / or nanobubbles for viscosity adjustment, the paint can be adjusted in viscosity without using a large amount of thinner or the like, especially in a low-temperature environment where the viscosity of the paint is high. By using a paint containing a large amount of microbubbles and / or nanobubbles that dissolve in a low-temperature environment, it is possible to provide a paint that significantly reduces or does not require the use of substances that may have an adverse effect on the human body.

[0028] For a paint whose viscosity after introducing microbubbles and / or nanobubbles is lower than that before introducing microbubbles and / or nanobubbles, the viscosity of the paint can be reduced by microbubbles and nanobubbles dispersed and mixed (dispersed and dissolved) in the paint. Therefore, the viscosity of the paint after introducing microbubbles and / or nanobubbles can be made lower than that before introduction, and the ease of applying the paint after introducing microbubbles and / or nanobubbles to the surface of the substrate can be improved. By introducing microbubbles and / or nanobubbles into the paint, its viscosity can be reduced, and high-viscosity or medium-viscosity paint can be made into low-viscosity paint without reducing or using substances that may have an adverse effect on the human body. By using microbubbles and / or nanobubbles for viscosity adjustment, especially in a low-temperature environment where the viscosity of the paint is high, in a situation where more thinner or the like is used to adjust the viscosity, by using a paint containing a large amount of microbubbles and / or nanobubbles that dissolve in a low-temperature environment, it is possible to provide a paint that significantly reduces or does not require the use of substances that may have an adverse effect on the human body.

[0029] Paints with a viscosity in the range of 1 to 1000 mPa·s after introducing microbubbles and / or nanobubbles can have their viscosity reduced by the microbubbles and nanobubbles dispersed (dispersed and dissolved) in the paint, and the viscosity of the paint containing microbubbles and / or nanobubbles can be made low-viscosity within the said range, ensuring an improvement in the ease of applying the paint to the surface of the substrate. By introducing microbubbles and / or nanobubbles into the paint, its viscosity can be reduced, and high-viscosity or medium-viscosity paints can be made into low-viscosity paints without reducing or using substances that may have an adverse effect on the human body.

[0030] For paints where the gas forming the microbubbles and / or nanobubbles is any one of air, nitrogen, argon, helium, xenon, neon, krypton, radon, hydrogen, oxygen, ozone, methane, ethylene, propane, butane, acetylene, ethanol, fluorine, chlorine, bromine, iodine, ammonia, hydrogen sulfide, sulfur dioxide, carbon monoxide, carbon dioxide, or a mixed gas of two or more of them, a large amount of microbubbles and nanobubbles of ultrafine bubbles made from the exemplified gases or their mixed gas are dispersed (dispersed and dissolved) inside the paint. By this, the proportion of the paint itself per unit area of the paint can be reduced by the microbubbles of fine bubbles and the nanobubbles of ultrafine bubbles. When the paint is applied to the surface of the substrate to be coated, the coating amount of the paint itself decreases, and the coating amount of the paint on the substrate can be reduced. Also, as the coating amount decreases, the unit price of the paint per unit area of the substrate surface decreases, and the substrate surface can be coated inexpensively with the paint. The paint can have its viscosity reduced by the microbubbles and nanobubbles of the exemplified gases or their mixed gas, and the ease of applying the paint to the surface of the substrate can be improved. The viscosity of the paint varies depending on the type of gas forming the microbubbles and nanobubbles, and fine adjustment of the paint viscosity is possible by selecting the gas to be used.

[0031] When the paint is any one of fluororesin paints, silicone resin paints, acrylic resin paints, urethane resin paints, and water-based paints, the proportion of the paint itself per unit volume of these paints can be reduced by microbubbles and / or nanobubbles. When these paints are applied to the surface of a substrate to be coated, the coating amount of the paint itself decreases, and the coating amount of the paint on the substrate can be reduced. Compared with the case where microbubbles and / or nanobubbles are not dispersed and mixed in these paints, the coating amount of the paint decreases, so that the unit price of these paints per unit area of the substrate surface can be lowered, and these paints can be applied at low cost. Even if a substrate formed with a fluororesin coating film made from a fluororesin paint, a silicone resin coating film made from a silicone resin paint, an acrylic resin coating film made from an acrylic resin paint, a urethane resin coating film made from a urethane resin paint, or an aqueous paint coating film made from an aqueous paint receives various damages, the substrate can be protected from various damages by these coating films made from these paints, and deterioration of the substrate due to these damages can be prevented. When the paint is an aqueous paint, since the amount of water used for viscosity adjustment is reduced or water is not required for viscosity adjustment, it becomes a useful paint in areas with water shortage or environments where water cannot be used.

[0032] A paint manufacturing method for introducing microbubbles and / or nanobubbles into a paint by using any one of a pressure dissolution method, a micropore and porous method, an ejector method, a Venturi method, an ultrasonic method, a static mixer method, a cavitation method, a swirling flow method, and a shear method or by combining these methods can surely introduce microbubbles and / or nanobubbles into the interior of the paint by these methods, can produce a paint capable of reducing the coating amount on a substrate, and can produce a paint capable of being applied at low cost. The paint manufacturing method can produce a paint whose viscosity can be made low viscosity and can produce a paint capable of improving the ease of application to the surface of a substrate.

[0033] When the object to be coated with a paint introduced with microbubbles and / or nanobubbles is a building, the paint is applied to the surface of the building, and a paint film is formed by the paint cured on the surface of the building. The building can reduce the application amount of the paint itself when applying a paint in which independent bubble microbubbles and / or nanobubbles are dispersed and mixed (dispersed and dissolved) at a predetermined concentration to the surface of the building. By reducing the application amount, the unit price of the paint per unit area of the building surface can be lowered, the paint can be applied to the building surface at a low cost, and the construction cost of the building can be reduced. Since the viscosity of the paint becomes low viscosity when microbubbles and / or nanobubbles are dispersed and mixed (dispersed and dissolved) in the paint applied to the surface of the building, the paint can be easily applied to the surface of the building, and the painting operation time of the paint on the surface of the building can be shortened. Since the mass of the paint per unit volume decreases compared to the case where nanobubbles are not dispersed and mixed (dispersed and dissolved) in the paint, the increase in the weight of the building including the paint film formed from the paint when the paint is applied to the surface of the building can be minimized.

[0034] When the object to be coated with a paint introduced with microbubbles and / or nanobubbles is a moving body, the paint is applied to the surface of the moving body, and a paint film is formed by the paint cured on the surface of the moving body. The moving body can reduce the application amount of the paint itself when applying a paint in which independent bubble microbubbles and / or nanobubbles are dispersed and mixed (dispersed and dissolved) at a predetermined concentration to the surface of the moving body. By reducing the application amount, the unit price of the paint per unit area of the moving body surface can be lowered, the paint can be applied to the moving body surface at a low cost, and the manufacturing cost of the moving body can be reduced. Since the viscosity of the paint becomes low viscosity when microbubbles and / or nanobubbles are dispersed and mixed (dispersed and dissolved) in the paint applied to the surface of the moving body, the paint can be easily applied to the surface of the moving body, and the painting operation time of the paint on the surface of the moving body can be shortened. Since the mass of the paint per unit volume decreases compared to the case where nanobubbles are not dispersed and mixed (dispersed and dissolved) in the paint, the increase in the weight of the moving body including the paint film formed from the paint when the paint is applied to the surface of the moving body can be minimized.

[0035] When the object to be coated, onto which a paint introduced with microbubbles and / or nanobubbles is applied, is an industrial product, the paint is applied to the surface of the industrial product, and a coating film is formed by the paint cured on the surface of the industrial product, the coating amount of the paint itself decreases when a paint in which microbubbles and / or nanobubbles of independent bubbles are dispersed and mixed (dispersed and dissolved) at a predetermined concentration is applied to the surface of the industrial product. By reducing the coating amount, the unit price of the paint per unit area of the surface of the industrial product can be lowered, the paint can be inexpensively applied to the surface of the industrial product, and the manufacturing cost of the industrial product can be reduced. Since the viscosity of the paint becomes low viscosity when microbubbles and / or nanobubbles are dispersed and mixed (dispersed and dissolved) in the paint applied to the surface of the industrial product, the paint can be easily applied to the surface of the industrial product, and the coating operation time of the paint on the surface of the industrial product can be shortened. Since the mass of the paint per unit volume decreases in the industrial product as compared with the case where nanobubbles are not dispersed and mixed (dispersed and dissolved) in the paint, an increase in the weight of the industrial product including the coating film formed from the paint can be minimized when the paint is applied to the surface of the industrial product.

[0036] The object to be coated with a paint into which microbubbles and / or nanobubbles are introduced is furniture and equipment. The paint is applied to the surface of the furniture and equipment, and a coating film is formed on the surface of the furniture and equipment by the cured paint. The furniture and equipment can reduce the coating amount of the paint itself when the paint in which microbubbles and / or nanobubbles of independent bubbles are dispersed and mixed (dispersed and dissolved) at a predetermined concentration is applied to the surface of the furniture and equipment. By reducing the coating amount, the unit price of the paint per unit area of the surface of the furniture and equipment can be lowered, and the paint can be applied to the surface of the furniture and equipment at a low cost, and the manufacturing cost of the furniture and equipment can be reduced. Since the viscosity of the paint becomes low when microbubbles and / or nanobubbles are dispersed and mixed (dispersed and dissolved) in the paint applied to the surface of the furniture and equipment, the paint can be easily applied to the surface of the furniture and equipment, and the coating operation time of the paint on the surface of the furniture and equipment can be shortened. Since the mass of the paint per unit volume of the furniture and equipment is reduced compared to the case where nanobubbles are not dispersed and mixed (dispersed and dissolved) in the paint, the increase in the weight of the furniture and equipment including the coating film formed from the paint when the paint is applied to the surface of the furniture and equipment can be minimized.

Brief Description of the Drawings

[0037]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Embodiments for Carrying Out the Invention

[0038] Referring to the accompanying drawings, the details of the paint and the paint manufacturing method according to the present invention will be described as follows. FIG. 1 is a configuration diagram showing an example of a gas introduction device 16 for mixing microbubbles 14 and / or nanobubbles 15 into the paint 10A. FIG. 2 is a configuration diagram showing an example of a static fluid mixing device 21 among the gas introduction devices 16. FIG. 3 is an image diagram showing an example of the structure of a fluororesin coating film. FIG. 4 is an image diagram showing an example of the structure of a silicone resin coating film. FIG. 5 is a diagram illustrating an image of microbubbles 14 and nanobubbles 15 dispersed and mixed (dispersed and dissolved) inside the paint 10. FIG. 6 is a diagram illustrating an image of microbubbles 14 and nanobubbles 15 dispersed and mixed (dispersed and dissolved) inside the coating film 13 formed by curing the paint 10. FIG. 7 is a diagram for explaining the drying process of an emulsion-based paint 10B. FIG. 8 is a diagram for explaining the drying process of a solvent-based paint 10B. In FIGS. 5 and 6, the microbubbles 14 and nanobubbles 14 are illustrated as visible images, but in reality, it is difficult to visually observe the microbubbles 14, and it is impossible to visually observe the nanobubbles 15.

[0039] The paint 10B mixed with microbubbles 14 and / or nanobubbles 15 is applied to the surface 12 (outer surface, inner surface) of a substrate 11 (such as a building, a moving body, an industrial product, furniture and equipment, etc.) to be coated. The cured paint 10B forms a coating film 13 that covers the surface 12 of the substrate 11. As the paint 10A before mixing microbubbles 14 and / or nanobubbles 15, any one of a fluororesin paint, a silicone resin paint (silicone resin), an acrylic resin paint, a urethane resin paint, and an aqueous paint is used. Inside the paint 10B (fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, aqueous paint) (in the paint), there is an average particle size D described later50 is 100 μm or less, preferably, the average particle size D 50 is 0.5 μm or less, more preferably, the average particle size D 50 is 0.2 μm or less, and the microbubbles 14 of independent fine bubbles or the nanobubbles 15 of independent ultrafine bubbles are dispersed and mixed (dispersed and dissolved) at a predetermined concentration, or the average particle size D 50 is 100 μm or less, preferably, the average particle size D 50 is 0.5 μm or less, more preferably, the average particle size D 50 is 0.2 μm or less, and the microbubbles 14 of independent fine bubbles and the nanobubbles 15 of independent ultrafine bubbles are dispersed and mixed (dispersed and dissolved) at a predetermined concentration. The nanobubbles 15 have a particle size D 50 in the range of 1 to 800 nm.

[0040] After the fluororesin paint is applied to the surface 12 of the base material 11, it cures to form a fluororesin coating film 13 having a predetermined thickness. After the silicone resin paint is applied to the surface 12 of the base material 11, it cures to form a silicone resin coating film 13 having a predetermined thickness. After the acrylic resin paint is applied to the surface 12 of the base material 11, it cures to form an acrylic resin coating film 13 having a predetermined thickness. After the urethane resin paint is applied to the surface 12 of the base material 11, it cures to form a urethane resin coating film 13 having a predetermined thickness. After the water-based paint is applied to the surface 12 of the base material 11, it cures to form a water-based paint coating film 13 having a predetermined thickness.

[0041] Fluororesin paint is a paint mainly composed of fluororesin. As the fluororesin that is the main component of the fluororesin paint, a solution in which any one or a blend of two or more of PTFE (polytetrafluoroethylene), PFA (perfluoroalkoxyalkane), FEP (perfluoroethylene propene copolymer), and ETFE (ethylene-tetrafluoroethylene copolymer) is used. Incidentally, as the fluororesin, a high-temperature modified type that increases the adhesion to the surface 12 of the base material 11 and improves the wear resistance without lowering its heat resistance can also be used, and a low-temperature modified type that can be processed at low temperatures while taking advantage of the low friction and non-stick properties of the fluororesin can also be used.

[0042] The molecular structure of PTFE (polytetrafluoroethylene) is represented by the following general formula (1).

[0043]

Chemical formula

[0044] The molecular structure of PFA (perfluoroalkoxyalkane) is represented by the following general formula (2).

[0045]

Chemical formula

[0046] The molecular structure of FEP (perfluoroethylene propylene copolymer) is represented by the following general formula (3).

[0047]

Chemical formula

[0048] The molecular structure of ETFE (ethylene - tetrafluoroethylene copolymer) is represented by the following general formula (4).

[0049]

Chemical formula

[0050] Silicone resin paint is a paint mainly composed of silicone resin. The molecular structure of the silicone resin (silicone resin), which is the main component of the silicone resin paint, is represented by the following general formula (5).

[0051] [Chemical formula] Silicone resin paint has excellent durability, water resistance, chemical resistance, and flexibility, and forms a coating film 13 (three-dimensional glass skeleton film) with high adhesion to the surface 12 of the base material 11. The silicone resin coating film 13 made from the silicone resin paint is composed of siloxane bonds (Si-O, silicon-oxygen), and contains some silicates (SiO4 / 2) or silsesquioxanes (R-SiO3 / 2). R is various alkyl groups or allyl groups, and typical functional groups are methyl groups or phenyl groups. Compared with organic resins composed of carbon-carbon bonds (C-C), it shows stronger resistance to decomposition by heat and radiation. The resistance of the silicone resin coating film lies in the strength of the oxygen-hydrogen bond (the silicon-oxygen bond is 108 kcal / mol while the carbon-carbon bond is 82.6 kcal / mol), the property of transmitting visible light and ultraviolet light, and its originally partially oxidized structure.

[0052] By adding organic functional groups, the siloxane polymer becomes more linear, and physical properties (such as flexibility) and performance derived from the organic functional groups are imparted. The introduction of phenyl groups into the siloxane skeleton has the effects of enhancing the compatibility with organic resins, enhancing toughness, and maintaining thermal stability at medium temperature (250 °C). On the one hand, the methyl group imparts properties such as improved curability, resistance to thermal shock, and reduced weight loss under humidity limits. The silicone polymer coating solution (silicone resin) is produced by hydrolyzing chlorosilane or alkoxysilane, and in the process, highly reactive silanol groups (Si-OH) are formed. RSiCl3 + 3H2O → RSi(OH)3 + 3HCl, RSi(OR’)3 + 3H2O → RSi(OH)3 + 3R’OH, In the initial condensation reaction during the reaction, an oligomer structure of siloxane is formed. 2RSi(OH)3 → RSi(OH)2-O-SiR(OH)2 + H2O. As the condensation reaction further proceeds, a three-dimensional cross-linked structure of siloxane is formed. By incorporating heat and a catalyst during the condensation reaction, the molecular weight increases and the physical properties are improved. On the other hand, the viscosity of the polymer increases, and dilution and dissolution in a solvent are required. Similarly, in cases where application properties are required, by reacting the hydroxyl groups of an organic resin (for example, polyester) with silanol groups and alkoxy groups, a composite resin of silicon-organic resin can be formed, and it is possible to improve the performance according to the degree of siloxane modification. The cold blend of the resin intermediate and the organic resin can be carried out with a small amount of solvent used. However, in order to proceed with the reaction and ensure curing, a higher and longer heat curing process is required. In addition to the selection of the optimal silicone resin, other components included in the formulation play an important role in the performance of the coating.

[0053] When prototyping a silicon resin paint, first clarify the required properties for the target application and determine the available resin binders. The heat, chemicals, ultraviolet light that the silicon resin paint is exposed to during curing, as well as the required physical properties, also affect the selection of the resin binder. Silicon resin paints (silicone resins) contribute to improving the heat resistance, chemical resistance, and durability against ultraviolet light of the silicon resin coating film. However, other performances and physical properties can also be imparted by the combination of silicon and specific organic binders (coating film hardness: phenols and melamine resins, room temperature drying property: acrylic resins, corrosion resistance: epoxy resins, toughness: alkyd resins). Note that the amount of silicon compounded in the coating formulation is determined according to the performance requirement level for that application.

[0054] Silicon resin paints contain formulation components such as catalysts, curing conditions, solvents, and thinners. Silanol-functional resins thermally cure without adding a catalyst. However, the addition of metal driers (for example, zinc, iron, cobalt octoate) accelerates the curability. The normal catalyst addition amount is 0.1 to 0.2% by metal amount based on the resin solid content. Silicon resin paints formulated with silanol-functional silicon resins require heat curing to exhibit optimal coating film performance, but their curability varies depending on the silicon content and the curing conditions of other main components. The curing method for 100% silicon resin systems is 30 minutes at 232°C (450°F) or 60 minutes at 204°C (400°F). Silicon resin paints (silicone resins) can use aromatic hydrocarbons (for example, toluene, xylene), ketones, esters, acetates, and chlorine-based solvents as solvents. The stability of the silicon resin is improved by adding a small amount (less than 5%) of glycol ethers and alcohols (for example, butanol).

[0055] Acrylic resin paint is a paint with acrylic resin as the main component. Acrylic resin paint forms an acrylic resin coating film 13 having excellent weather resistance, gloss, transparency, water resistance, adhesion, and corrosion protection. As the acrylic resin, water-based acrylic resin or solvent-based acrylic resin can be used. As the water-based acrylic resin, acrylic emulsion, acrylic-styrene emulsion, hydroxyl group-containing acrylic emulsion, room temperature drying type water-soluble acrylic resin, baking type acrylic dispersion, hydroxyl group-containing acrylic dispersion, etc. can be used. As the solvent-based acrylic resin, isocyanate curable acrylic resin, room temperature / forced drying type acrylic resin, acrylic resin for melamine baking, moisture curable silicon-acrylic resin, etc. can be used. As the organic solvent, dibutyl ether, turpentine oil, benzene, toluene, etc. are used.

[0056] Urethane resin paint is composed of a polyol having a plurality of hydroxyl groups and a polyisocyanate as the main agent. Incidentally, the urethane resin paint may be an acrylic urethane paint having an acrylic polyol as the main agent. Also, the urethane resin paint may contain acrylic polyol and cellulose acetate butyrate. Urethane resin paint forms a urethane resin coating film 13 having excellent coating film performance, finish, weather resistance, adhesion, flexibility, and chemical resistance. Urethane resin paint can be diluted with an organic solvent. As the organic solvent, alcohol-based, carboxylic acid ester-based, ketone-based, amide-based, aliphatic-based, and aromatic hydrocarbon-based solvents, etc. are used.

[0057] As the polyol, 1,6-hexanediol, cyclohexyl dimethanol, neopentyl glycol, butylethylpropanediol, trimethylolethane, trimethylolpropane, polycaprolactone triol, ditrimerolpropane, pentaerythritol, polycaprolactone tetraol, dipentaerythritol, sorbitol, mannitol, etc. are used. Also, a mixture of at least two or more of them is used.

[0058] For the polyisocyanate, an isocyanate compound having two or more functional groups is used. As the bifunctional isocyanate compound, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 4,4-dicyclohexyldiisocyanate, etc. are used. As the isocyanate compound having three or more functional groups, those synthesized from a diisocyanate compound as a starting material, such as a biuret body, a trimethylolpropane adduct body, an isocyanurate body, an allophanate body, etc. are used. In order to increase the crosslinking density of the urethane resin coating film made from the urethane resin paint and improve the weather resistance and stain resistance of the coating film, it is preferable that the polyisocyanate is an isocyanate compound having three or more functional groups.

[0059] As the isocyanate compound having three or more functional groups, a biuret body of hexamethylene diisocyanate, an adduct body of hexamethylene diisocyanate, an isocyanurate body of hexamethylene diisocyanate, a blocked isocyanate body, a trimethylolpropane adduct body of 1,3-bis(isocyanatomethyl)cyclohexane, an isocyanurate body of 1,3-bis(isocyanatomethyl)cyclohexane, a trimethylolpropane adduct body of isophorone diisocyanate, an allophanate body of hexamethylene diisocyanate, etc. are used. Also, a mixture of at least two or more of those isocyanate compounds is used. In addition, for the water-based paint, any of an emulsion type, an emulsion type with aggregate, and a water-soluble resin type is used.

[0060] Fluororesin paints, silicone resin paints, acrylic resin paints, urethane resin paints, and water-based paints contain various additives and pigments as required. Additives include matting agents that reduce the gloss of the coating film, surfactants that prevent a decrease in surface tension, sag inhibitors that prevent the paint from running off, color separation inhibitors that prevent color unevenness caused by pigment mixing, preservatives and fungicides that prevent corrosion of the coating film, plasticizers that improve the flexibility and adhesion of the paint, skin formation inhibitors that prevent the formation of a skin on the surface during paint storage, and leveling agents that ensure the fluidity of the coating film. Additives also include curing agents that cure the coating film and improve weather resistance, water resistance, chemical resistance, heat resistance, etc. Curing agents include blocked isocyanates such as hexamethylene isocyanate trimer or its emulsified dispersion, melamine resins such as methylated melamine, methylolated melamine, butyrolated melamine, and urea resins such as methylated urea and butylated urea. Pigments include inorganic coloring pigments, organic coloring pigments, and extender pigments. Fluororesin paints, silicone resin paints, acrylic resin paints, and urethane resin paints include both water-based and oil-based types, as well as both one-component and two-component types. Additionally, as other additives, there may be film-forming aids, thickeners, light stabilizers, design agents, surface modifiers, and in some cases, a water-based medium is added. The water-based medium is used to dilute the water-based dispersion. As thickeners, urethane-based thickeners, polyacrylic-based thickeners, polyamide-based thickeners, cellulose-based thickeners, and thickeners of clay minerals such as bentonite are used. The fluororesin coating film 13 made from fluororesin paint, the silicone resin coating film 13 made from silicone resin paint, the acrylic resin coating film 13 made from acrylic resin paint, the urethane resin coating film 13 made from urethane resin paint, and the coating film 13 made from water-based paint have a water contact angle of 60° or less. As a method for measuring the water contact angle, a water droplet with a diameter of 1 to 2 mm is dropped onto the coating film 13, and the water droplet after 30 seconds is photographed with a video camera for image analysis. The water contact angle is defined as twice the angle between the line connecting the apex and the end point of the water droplet and the coating film 13.

[0061] As the means for introducing (mixing) microbubbles 14 and nanobubbles 15 into the paint, any one of a pressure dissolution method, a micropore and porous method, an ejector method, a Venturi method, an ultrasonic method, a static mixer method, a cavitation method, a swirling liquid flow method, and a shearing method is used. Incidentally, it is also possible to introduce microbubbles 14 and nanobubbles 15 into the paint by combining these methods.

[0062] In the pressure dissolution method, a pump capable of pressure driving (pressure gauges are installed on the suction side and the discharge side of the pump) is used to circulate the paint in the storage (any one of a fluororesin paint, a silicone resin paint, an acrylic resin paint, a urethane resin paint, and an aqueous paint). At this time, a gas (one or more of air, nitrogen, argon, helium, xenon, neon, krypton, radon, hydrogen, oxygen, ozone, methane, ethylene, propane, butane, acetylene, ethanol, fluorine, chlorine, bromine, iodine, ammonia, hydrogen sulfide, sulfur dioxide, carbon monoxide, and carbon dioxide) is taken in from the suction pipeline of the pump. As a method for taking in the gas, a negative pressure is generated by attaching a valve and narrowing the flow path to self-aspirate the gas. The gas-liquid mixed phase flow with the paint into which the gas has been taken in is stirred by the pump and pressurized and dissolved in the dissolution tank by the discharge pipe. The excess gas that has not been dissolved is released to the outside air.

[0063] The micropore and porous method involves placing a porous body or a porous film obtained by sintering or weakly bonding glass, metal, ceramic, etc. in a state with open micropores, or a porous body or porous film formed by stretching a thin glass tube, etc. in a paint (any one of fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, aqueous paint), pressurizing a gas (one or more of air, nitrogen, argon, helium, xenon, neon, krypton, radon, hydrogen, oxygen, ozone, methane, ethylene, propane, butane, acetylene, ethanol, fluorine, chlorine, bromine, iodine, ammonia, hydrogen sulfide, sulfur dioxide, carbon monoxide, carbon dioxide) into the interior of the porous body or porous film, ejecting the gas as bubbles from the micropore outlets, and further generating fine bubbles of microbubbles 14 and ultrafine bubbles of nanobubbles 15 by applying a liquid flow and mixing the microbubbles 14 and nanobubbles 15 into the paint. In the micropore and porous method, the bubble size can be adjusted by regulating the liquid flow rate and the supply pressure of the gas.

[0064] The ejector method is formed by a nozzle, a negative pressure chamber, a mixing chamber, and an energy conversion unit. A gas (one or more of air, nitrogen, argon, helium, xenon, neon, krypton, radon, hydrogen, oxygen, ozone, methane, ethylene, propane, butane, acetylene, ethanol, fluorine, chlorine, bromine, iodine, ammonia, hydrogen sulfide, sulfur dioxide, carbon monoxide, carbon dioxide) is attracted to the negative pressure chamber where the maximum negative pressure is generated by a high-speed liquid jet from the nozzle. When the pressure is reduced below the saturated vapor pressure at that time, cavitation also occurs and it is led to the mixing chamber while being gas-liquid mixed. Here, the pressure is recovered while being turbulently mixed by a large shearing action, and the gas is micro-bubbled and induced to the energy conversion unit as a gas-liquid mixed-phase flow. In the energy conversion unit, the micro-bubbles contract, expand, collapse, and are crushed (there may be a shock wave accompanying the cavitation collapse), generating micro-bubbles of micro-bubbles 14 and ultra-fine bubbles of nano-bubbles 15, and mixing the micro-bubbles 14 and nano-bubbles 15 into a paint (any of fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, water-based paint). In the ejector method, in order to effectively generate micro-bubbles, the nozzle diameter and the diameter of the mixing chamber are accurately axially centered, and the ratio of the nozzle diameter to the diameter of the mixing chamber, the structure of the nozzle and the negative pressure chamber, and the structural balance of the energy conversion unit are important, and the micro-bubble characteristics differ depending on those structures.

[0065] The Venturi method involves flowing paint (any one of fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, water-based paint) and gas (one or more of air, nitrogen, argon, helium, xenon, neon, krypton, radon, hydrogen, oxygen, ozone, methane, ethylene, propane, butane, acetylene, ethanol, fluorine, chlorine, bromine, iodine, ammonia, hydrogen sulfide, sulfur dioxide, carbon monoxide, carbon dioxide) simultaneously into a Venturi tube that has a constriction portion called a throat in the middle of the fluid flow path. The shock wave generated by the sudden change in liquid flow velocity crushes the bubbles to generate fine bubbles of microbubbles 14 and ultrafine bubbles of nanobubbles 15, and the microbubbles 14 and nanobubbles 15 are mixed into the paint. In the Venturi method, the bubbles dissolved in the paint fluid accelerate in velocity at the constriction portion (minimum constriction portion), and the pressure rapidly decreases (cavitation occurs when the pressure is below the saturated vapor pressure of the paint), so the bubbles expand temporarily, but they collapse (crush) due to the rapid pressure increase in the downstream expansion portion, and the bubbles are refined. In the Venturi tube method (gas-liquid two-phase flow), the velocity accelerates and the pressure decreases at the constriction portion (constriction portion) of the Venturi tube, so the bubbles expand, and they further become supersonic in the downstream expansion portion and expand due to further pressure reduction. However, in the downstream expansion portion, the pressure rapidly increases, and the contraction, crushing, and shock wave of the bubbles are formed, generating micro-nanobubbles 14 and nanobubbles 15. In the Venturi method, in order to exhibit the bubble refinement performance, it is necessary to have the expansion of the bubbles accompanying a sufficient pressure decrease at the constriction portion of the Venturi tube and the rapid pressure recovery leading to the subsequent violent collapse, and for this purpose, the flow velocity at the inlet portion is required to be sufficiently fast. Also, it is required to exceed a predetermined flow velocity in order to cause refinement efficiently.

[0066] The ultrasonic method is formed by a hollow ultrasonic horn, an ultrasonic vibrator, a vibration circuit, and a gas supply means. The hollow ultrasonic horn has a structure in which a gas flow path is provided inside a stepped cylindrical shape, and ultrasonic vibration is amplified according to the area ratio between the large end face and the small end face. Also, a gas (one or more of air, nitrogen, argon, helium, xenon, neon, krypton, radon, hydrogen, oxygen, ozone, methane, ethylene, propane, butane, acetylene, ethanol, fluorine, chlorine, bromine, iodine, ammonia, hydrogen sulfide, sulfur dioxide, carbon monoxide, carbon dioxide) passes through the inside of the hollow ultrasonic horn from a gas inlet provided on the side surface and is discharged into a paint (any of fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, water-based paint) from the gas discharge port of the ultrasonic vibration surface. In the gas supply means, the supply amount and supply pressure of the gas from the gas cylinder are adjusted using a regulator, a valve, and a flow meter. In the ultrasonic method, the tip of the hollow ultrasonic horn is inserted into the paint, and while supplying gas, the hollow ultrasonic horn is ultrasonically vibrated, so that the gas-liquid interface formed at the tip of the hollow ultrasonic horn is refined by the disturbance caused by the ultrasonic waves, and microbubbles 14 and nanobubbles 15 are mixed into the paint.

[0067] The static mixer method passes a gas-liquid mixed fluid (or a fluid in which gas is pressurized and dissolved at a high concentration) through a special structure nozzle having a guide vane or a screw that generates a strong swirling flow inside and a mushroom-shaped protrusion row (current cutter) on the inner wall to generate a high-speed rotating fluid. The high-speed rotating fluid collides with protrusions (current cutters) protruding from the inner wall of the pipeline, generating cavitation and shock waves due to a strong shearing action and a large negative pressure. In the center of the high-speed rotating fluid, a recirculation region of the negative pressure region is formed, which is subdivided by cavitation and shock waves behind the protrusions, and the turbulent mixing of the gas-liquid two-phase flow is promoted by the recirculation flow, generating fine bubbles of microbubbles 14 and ultrafine bubbles of nanobubbles 15, and microbubbles 14 and nanobubbles 15 are mixed into the paint.

[0068] The cavitation method is a method of sending a gas-liquid mixture into a pump and generating bubbles by utilizing cavitation. Microbubbles and nanobubbles generated by cavitation are mixed into a paint (any one of a fluororesin paint, a silicone resin paint, an acrylic resin paint, a urethane resin paint, and an aqueous paint). In the cavitation method, when the flow path is rapidly expanded or hit against an obstacle, the boundary layer peels off behind it and a negative pressure region is formed. When the negative pressure exceeds a certain limit value, voids (voids) are generated by overcoming the intermolecular force of the fluid, and fine bubbles of microbubbles 14 and ultrafine bubbles of nanobubbles 15 are generated from the voids.

[0069] The swirling liquid flow method generates a large negative pressure at the center of a cylindrical container by swirling the high-speed water flow of a paint (any one of a fluororesin paint, a silicone resin paint, an acrylic resin paint, a urethane resin paint, and an aqueous paint) at the speed of light in the tangential direction of the cylindrical container, sucks in a gas (one or more of air, nitrogen, argon, helium, xenon, neon, krypton, radon, hydrogen, oxygen, ozone, methane, ethylene, propane, butane, acetylene, ethanol, fluorine, chlorine, bromine, iodine, ammonia, hydrogen sulfide, sulfur dioxide, carbon monoxide, and carbon dioxide), causes a turbulent flow by the shearing action of the entrained flow, atomizes the gas to generate fine bubbles of microbubbles 14 and ultrafine bubbles of nanobubbles 15, and mixes the microbubbles 14 and nanobubbles 15 into the paint. Due to its structure, the swirling liquid flow method generates further fine bubbles accompanied by crushing and shock waves.

[0070] The shearing method (mechanical shearing method) involves rotating a rotating blade installed inside a cylindrical casing to suck in a gas (one or more of air, nitrogen, argon, helium, xenon, neon, krypton, radon, hydrogen, oxygen, ozone, methane, ethylene, propane, butane, acetylene, ethanol, fluorine, chlorine, bromine, iodine, ammonia, hydrogen sulfide, sulfur dioxide, carbon monoxide, carbon dioxide), mixing it with a paint (any of fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, water-based paint), and while the rotating blade rotates, the shearing action of the rotating blade causes the bubbles to be agitated and refined to generate fine bubbles of microbubbles 14 and ultrafine bubbles of nanobubbles 15, and the paint mixed with the microbubbles 14 and nanobubbles 15 is discharged in the direction of the mixing outlet. As an example, the rotor rotates to suck in the paint and discharge it through the stator, sucks in the gas by Bernoulli's law, causes turbulence by the action of two types of blades, a fixed blade and a rotating blade, to shear the bubbles, and refine the bubbles. As another example, a turbo mixer using a vortex turbo pump automatically sucks in and decompresses the gas, instantly dissolves it in the paint, and performs pressurization and mixing simultaneously and continuously.

[0071] A specific example of a gas introduction device 16 for introducing (mixing) microbubbles 14 and nanobubbles 15 into the paint 10A by the static mixer method will be described below. As shown in FIG. 1, the gas introduction device 16 is formed from a paint storage tank 17 having a predetermined volume, a gas supply tank 18, a water supply pump 19 and a gas supply pump 20, a static fluid mixing device 21 (static mixer), a coating liquid storage tank 22 having a predetermined volume and storing the paint 10B in which microbubbles 14 and nanobubbles 15 are dispersed and mixed, a cooling device (not shown), and a controller (not shown). Electric power is supplied to the gas introduction device 16 from a power source (not shown). The paint storage tank 17 stores any of the aforementioned fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, water-based paint (the paint 10A before microbubbles 14 and nanobubbles 15 are dispersed and mixed (dispersed and dissolved)).

[0072] A level meter (not shown) is installed in the paint storage tank 17. The level meter is connected to the controller via a signal line, measures the level (water storage volume) of the paint 10A (fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, water-based paint) stored in the paint storage tank 17, and transmits the measured level to the controller. The paint storage tank 17 is connected to the water supply pump 19 via a water supply pipe 23 (water supply pipe). Although not shown in the figure, a flow meter, a check valve, and a water supply solenoid valve are installed in the water supply pipe 23. The flow meter is connected to the controller via a signal line, measures the flow rate of the paint 10A flowing through the water supply pipe 23, and transmits the measured flow rate to the controller. The control part of the water supply solenoid valve is connected to the controller via a signal line, and its start / stop (opening / closing) is controlled by the controller.

[0073] The gas supply tank 18 stores a gas to be dispersed and mixed into the paint 10A at a predetermined pressure. As the gas to be dispersed and mixed into the paint 10A, any one of air, nitrogen, argon, helium, xenon, neon, krypton, radon, hydrogen, oxygen, ozone, methane, ethylene, propane, butane, acetylene, ethanol, fluorine, chlorine, bromine, iodine, ammonia, hydrogen sulfide, sulfur dioxide, carbon monoxide, carbon dioxide, or a mixed gas obtained by mixing two or more of them is used. The gas supply tank 18 is connected to the mixing pipe 25 (mixing pipe) via a gas supply pipe 24 (gas supply pipe). Although not shown in the figure, a pressure gauge, a check valve, and a gas supply solenoid valve are installed in the gas supply pipe 24. The pressure gauge is connected to the controller via a signal line, measures the gas pressure of the gas stored in the gas supply tank 18, and transmits the measured gas pressure to the controller. The control part of the gas supply solenoid valve is connected to the controller via a signal line, and its start / stop (opening / closing) is controlled by the controller. A gas supply pump 20 is installed in the gas supply pipe 24. The control part of the gas supply pump 20 is connected to the controller via a signal line. The start / stop and output of the gas supply pump 20 are controlled by the controller.

[0074] The water supply pump 19 is installed in the water supply pipeline 23, and its control unit is connected to the controller via a signal line. The start / stop and output of the water supply pump 19 are controlled by the controller. The water supply pump 19 is connected to the static fluid mixing device 21 via the mixing pipeline 25. The static fluid mixing device 21 is connected to a paint storage tank 22 with a predetermined volume via a supply pipeline 26. A level meter (not shown) is installed in the paint storage tank 22. The level meter is connected to the controller via a signal line, measures the level (water storage volume) of the paint 10B in which the microbubbles 14 and nanobubbles 15 are dispersed and mixed, and transmits the measured level to the controller.

[0075] As shown in FIG. 2, the static fluid mixing device 21 (static mixer) is formed by a cylindrical unit 27 having an inlet and an outlet, and a plurality of honeycomb structure elements 28 (stirring vanes) arranged inside the cylindrical unit 27. These honeycomb structure elements 28 are arranged in a state of being connected in series inside the cylindrical unit 27. The static fluid mixing device 21 passes the paint 10A and gas through the inside of the honeycomb structure element 28 by the centrifugal force generated by high-speed rotation, thereby miniaturizing the gas to the micro level and ultrafine to the nano level to generate microbubbles 14 and nanobubbles 15, and uniformly mixing (dissolving) the generated microbubbles 14 and nanobubbles 15 into the paint 10A, and producing the paint 10B in which the microbubbles 14 and nanobubbles 15 are uniformly dispersed and mixed (dispersed and dissolved).

[0076] In addition, in the static fluid mixing device 21, the miniaturization (micro level) and ultrafine (nano level) of the gas proceed as the paint 10A and the gas pass through the inside of the honeycomb structure element 28 many times, and the mixing (dissolving) of the miniaturized gas and the ultrafine gas into the paint 10A proceeds. The cooling device cools the cylindrical unit 27 of the static fluid mixing device 21 to a set temperature by circulating a refrigerant (for example, hydrofluorocarbon). The control unit of the cooling device is connected to the controller via a signal line. The start / stop and output of the cooling device are controlled by the controller.

[0077] The controller is a physical computer having a central processing unit (CPU or MPU) and a memory (main memory and cache memory), and operates under an independent operating system (OS), and implements a large-capacity storage area. Input devices such as keyboards and mice, and output devices such as displays and printers are connected to the controller via an interface. Based on the control by the operating system (OS), the central processing unit of the controller starts a nanobubble-mixed application stored in the memory, and performs a mixing operation of dispersing and mixing (dispersing and dissolving) microbubbles 14 and nanobubbles 15 into the paint 10A according to the application.

[0078] When the switch of the gas introduction device 16 is turned ON, a mixing operation of mixing microbubbles 14 and nanobubbles 15 into the paint 10A (fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, aqueous paint) stored in the paint storage tank 17 is started. Incidentally, a predetermined amount of the paint 10A is filled in the paint storage tank 17, and a gas (air, nitrogen, argon, helium, xenon, neon, krypton, radon, hydrogen, oxygen, ozone, methane, ethylene, propane, butane, acetylene, ethanol, fluorine, chlorine, bromine, iodine, ammonia, hydrogen sulfide, sulfur dioxide, carbon monoxide, carbon dioxide, any one of them or a mixed gas of two or more of them) is stored in the gas supply tank 18 at a predetermined pressure. When the switch of the gas introduction device 16 is turned ON, the controller transmits a water supply signal to the control unit of the water supply pump 19, transmits a gas supply signal to the control unit of the gas supply pump 20, and transmits a cooling signal to the control unit of the cooling device. Further, the controller transmits an open signal to the control unit of the water supply solenoid valve, transmits an open signal to the control unit of the gas supply solenoid valve, and transmits a measurement signal to the level meter, flow meter, and barometer.

[0079] Upon receiving a water supply signal, the control unit of the water supply pump 19 starts the water supply pump 19 at a predetermined output (set output). Upon receiving an air supply signal, the control unit of the air supply pump 20 starts the air supply pump 20 at a predetermined output (set output). Upon receiving a cooling signal, the control unit of the cooling device starts the cooling device at a predetermined output (set output). Upon receiving an open signal, the control unit of the water supply solenoid valve opens the water supply solenoid valve, and upon receiving an open signal, the control unit of the air supply solenoid valve opens the air supply solenoid valve. Upon receiving a measurement signal, the level gauge starts measuring the level of the paint 10A stored in the paint storage tank 17, and upon receiving a measurement signal, the flow meter starts measuring the flow rate of the paint 10A flowing through the water supply pipeline 23. Upon receiving a measurement signal, the barometer starts measuring the air pressure of the gas flowing through the air supply pipeline 24.

[0080] The paint 10A stored in the paint storage tank 17 is forcibly supplied from the paint storage tank 17 to the static fluid mixer 21 by the start of the water supply pump 19 (paint water supply process). The paint 10A flows from the water supply pipeline 23 through the water supply pump 19 into the mixing pipeline 25 and then into the static fluid mixer 21 through the mixing pipeline 25. The gas contained in the gas supply tank 18 is forcibly supplied from the gas supply tank 18 to the static fluid mixer 21 by the start of the air supply pump 20 (gas supply process). The gas flows from the air supply pipeline 24 through the air supply pump 20 into the mixing pipeline 25, is mixed with the paint 10A in the mixing pipeline 25, and then flows into the static fluid mixer 21 together with the paint 10A. In the mixing pipeline 25, the paint 10A supplied by the water supply pump 19 and the gas supplied by the air supply pump 20 are mixed to produce a gas-mixed paint (mixing process). The gas-mixed paint flows into the static fluid mixer 21.

[0081] The controller that receives the measured level measured by the level meter of the paint storage tank 17 outputs (displays) a water injection message on the display when the measured level drops to the water injection level. The water injection message enables the amount of paint 10A injected into the paint storage tank 17 to be known. The controller that receives the measured flow rate measured by the flow meter adjusts the output of the water supply pump 19 so that the measured flow rate becomes the target flow rate. The controller that receives the measured air pressure measured by the barometer adjusts the output of the air supply pump 20 so that the measured air pressure becomes the target air pressure.

[0082] The cooling device continuously cools the cylindrical unit 27 of the static fluid mixer 21 using a refrigerant during the operation of the gas introduction device 16 (cooling step). The temperature of the cylindrical unit 27 is maintained at a set temperature (for example, 10 to 20 °C) by the cooling device. In the static fluid mixer 21, the paint 10A with gas mixed therein flows in from its inlet, and the mixed paint 10A becomes a continuous-phase fluid and a dispersed-phase fluid by a plurality of honeycomb structure elements 28 (stirring vanes), and the continuous-phase and dispersed-phase fluids of the mixed paint 10A flow while meandering through the honeycomb structure elements 28. The fluid (gas) as the dispersed phase is refined by the shear force received at that time, and a refined mixed fluid is generated.

[0083] Next, after the flow of the generated refined mixed fluid is rectified, the rectified refined mixed fluid flows while meandering through the honeycomb structure elements 28 arranged on the downstream side, and the refined mixed fluid (gas) as the dispersed phase is further refined by the shear force received at that time. Finally, the gas mixed in the paint 10A is refined to the micro level or the nano level, and microbubbles 14 and / or nanobubbles 15 of independent fine bubbles with an average particle size D 50 of 100 μm or less, preferably an average particle size D 50 of 0.5 μm or less, more preferably an average particle size D 50 of 0.2 μm or less are dispersed and mixed (dispersed and dissolved) in the paint 10B, and an average particle size D 50A paint 10B is produced in which independent ultrafine bubbles (nanobubbles) 15 in the range of 1 to 800 nm, preferably 1 to 300 nm, are dispersed and mixed (dispersed and dissolved) at a predetermined concentration (nanobubble-containing paint production step).

[0084] In addition, when the microbubbles 14 and nanobubbles 15 are introduced (mixed) into the paint 10A, the temperature of the paint 10B in the cylindrical unit 27 in which the microbubbles 14 and / or nanobubbles 15 are dispersed and mixed due to the friction between the paint 10A and the microbubbles 14 and nanobubbles 15 rises. However, by cooling the cylindrical unit 27 with a cooling device, the paint 10B in the cylindrical unit 27 is maintained at a temperature of 10 to 20°C. The paint 10B in which the microbubbles 14 and / or nanobubbles 15 are dispersed and mixed (dispersed and dissolved) is stored in the paint storage tank 22 through the supply pipe 26. The controller that receives the measured level measured by the level meter of the paint storage tank 22 outputs (displays) the measured level on the display. The amount of stored water of the paint 10B in which the microbubbles 14 and / or nanobubbles 15 are dispersed and mixed can be known from the measured level output on the display.

[0085] The paint production method can surely introduce the microbubbles 14 and / or nanobubbles 15 into the paint 10A by those methods (pressure dissolution method, micropore and porous method, ejector method, venturi method, ultrasonic method, static mixer method, cavitation method, swirling liquid flow method, shearing method), and can produce a paint 10B capable of reducing the coating amount on the surface 12 of the base material 11, and can produce a paint 10B that can be coated at low cost. The paint production method can produce a paint 10B whose viscosity can be made low viscosity, and can produce a paint 10B that can improve the ease of coating on the surface 12 of the base material 11.

[0086] The paint 10B in which a large amount of microbubbles 14 and / or nanobubbles 15 are dispersed and mixed (dispersed and dissolved) inside by those bubble introduction methods and the gas introduction device 16 of FIGS. 1 and 2 has hydrogen ions H + concentration and hydroxide ions OH- The property regarding acid-base with substantially equal concentration is substantially neutral or alkaline. The microbubbles 14 and nanobubbles 15 dispersed and mixed inside the paint 10B are mixed into the paint 10B in the state of spheres having a high internal bubble pressure and are negatively charged.

[0087] For the paint 10B in which the microbubbles 14 and / or nanobubbles 15 are dispersed and mixed (dispersed and dissolved), the ratio of the paint 10B itself per unit volume of the paint 10B (the paint 10B in which the microbubbles 14 and nanobubbles 15 are dispersed and mixed (dispersed and dissolved)) can be reduced by the microbubbles 14 and the nanobubbles 15. When the paint 10B (the paint 10B in which the microbubbles 14 and nanobubbles 15 are dispersed and mixed (dispersed and dissolved)) is applied to the surface 12 of the base material 11 to be coated, the coating amount of the paint 10B itself decreases, and the coating amount of the paint 10B on the base material 11 can be reduced. Also, compared with the case where the microbubbles 14 and nanobubbles 15 are not dispersed and mixed in the paint 10B, the unit price of the paint 10B per unit area of the surface 12 of the base material 11 decreases due to the reduction of the coating amount, and the paint 10B can be applied (used) at low cost. Since the mass per unit volume of the paint 10B decreases compared with the case where the microbubbles 14 or nanobubbles 15 are not dispersed and mixed (dispersed and dissolved) therein, when it is applied to the surface 12 of the base material 11 to be coated with it, the increase in the weight of the base material 11 including the coating film 13 formed from the paint 10B can be minimized.

[0088] The paint 10B with microbubbles 14 dispersed and mixed therein has a viscosity in the range of 1 to 1000 mPa·s, preferably in the range of 1 to 100 mPa·s. By dispersing and mixing microbubbles 14 into the paint 10A before the microbubbles 14 are dispersed and mixed, the viscosity of the paint 10A before the microbubbles 14 are dispersed and mixed can be reduced to 1 / 3 to 1 / 2. For example, by dispersing and mixing microbubbles 14 into a high-viscosity paint 10A with a viscosity of 180 mPa·s, its viscosity can be reduced to 60 to 90 mPa·s, and by dispersing and mixing microbubbles 14 into a medium-viscosity paint 10A with a viscosity of 60 mPa·s, its viscosity can be reduced to 20 to 30 mPa·s. The paint 10B can reduce its viscosity by introducing (mixing) microbubbles 14 therein, and can turn the high-viscosity or medium-viscosity paint 10A into a low-viscosity paint 10B without reducing or using substances that may have an adverse effect on the human body.

[0089] The paint 10B has an average particle size D of the microbubbles 14 50 and the content of the microbubbles 14 in the paint 10B can be adjusted to adjust the viscosity of the paint 10B and improve the ease of application of the paint 10B to the surface 12 of the substrate 11. By using microbubbles 14 to adjust the viscosity of the paint 10B, especially in a low-temperature environment where the viscosity of the paint 10B is high, in a scenario where more thinner or the like is used to adjust the viscosity, by using the paint 10B containing microbubbles 14 that dissolve in a large amount in a low-temperature environment, it is possible to provide a paint 10B that greatly reduces or does not require the use of substances that may have an adverse effect on the human body. The viscosity of the paint 10B varies depending on the types of the gases forming the microbubbles 14, and fine adjustment of the viscosity of the paint is possible by selecting the gas to be used. When the paint 10B is an aqueous paint, since the amount of water used for viscosity adjustment can be reduced or water is not required for viscosity adjustment, it becomes a useful paint 10B in areas with water shortage or environments where water cannot be used.

[0090] The microbubbles 14 inside the paint 10B have an average particle size D50 is 100 μm or less. The number of microbubbles 14 per 1 ml of the paint 10B in which the microbubbles 14 are dispersed and mixed is 10 5 pieces / ml or more and 10 12 pieces / ml or less (in the range of 10 5 to 10 12 pieces / ml).

[0091] Since the number of microbubbles 14 per 1 ml of the paint 10B in which the microbubbles 14 are dispersed and mixed is within the above range, the microbubbles 14 of the fine bubbles are dispersed and mixed (dispersed and dissolved) in a large amount at a predetermined concentration inside the paint 10B. The ratio of the paint 10B itself per unit area in the paint 10B can be reduced by the microbubbles 14 which are fine bubbles, and when applying the paint 10B to the surface 12 of the base material 11 to be coated, the coating amount of the paint 10B itself can be surely reduced. Since the paint 10B contains microbubbles 14 in the range of 10 5 to 10 12 pieces / ml, the coating amount on the base material 11 decreases. Therefore, the unit price of the paint 10B per unit area of the surface 12 of the base material 11 can be lowered, and the paint 10B can be applied at low cost.

[0092] The particle size of the microbubbles 14 dispersed and mixed inside the paint 10B was measured by visualization method, light scattering method, laser diffraction / scattering method, and interference image method. The content rate and total number of the microbubbles 14 dispersed and mixed inside the paint 10B were measured by electrical sensing zone method and image analysis method. The visualization method uses an imaging device such as a digital microscope or a CCD camera to photograph the microbubbles 14, and performs black-and-white binarization by image processing to measure the particle size (bubble diameter). The light scattering method uses a laser particle size distribution analyzer, irradiates a beam-shaped laser light into the paint containing the microbubbles 14, detects the scattered light with a photomultiplier tube, and measures the particle size (bubble diameter) from Mie's scattering theory. The laser diffraction / scattering method irradiates laser light, and in the case of microbubbles, the diffracted / scattered light is instantaneously scattered forward, backward, and laterally, and the particle size (bubble diameter) is measured by correlating the scattered light pattern with the bubble diameter. In the interference image method, when laser light is irradiated onto spherical bubbles, a scattering pattern is obtained, but interference fringes are observed on a plane out of focus. The particle size (bubble diameter) is determined from the number of interference fringes by a CCD camera.

[0093] For the paint 10B in which the microbubbles 14 are dispersed and mixed, the rising speed of the microbubbles 14 inside the paint 10B at room temperature is in the range of 0.00005 mm / min or more and 0.0005 mm / min or less (0.0005 - 0.00005 mm / min). Since the volume of the microbubbles 14 is small, the rising speed inside the paint 10B is extremely slow. When the rising speed of the microbubbles 14 inside the paint 10B exceeds 0.0005 mm / min, it is difficult to keep the microbubbles 14 in the paint 10B for a long time, and the microbubbles 14 may volatilize from the paint 10B within the target residence time. Since the rising speed of the microbubbles 14 inside the paint 10B at room temperature is within the above range, the microbubbles 14 are difficult to volatilize from the paint 10B, and the microbubbles 14 can be retained in the paint 10B for a long time, and the coating amount of the paint 10B itself can be surely reduced when the paint 10B is applied to the substrate 11 to be coated.

[0094] The nanobubbles 15 dispersed and mixed (dispersed and dissolved) inside the paint 10B are performing Brownian motion inside the paint 10B at the room temperature of the storage location where the paint 10B is stored. The paint 10B in which the nanobubbles 15 are dispersed and mixed has a viscosity in the range of 1 to 1000 mPa·s, preferably in the range of 1 to 100 mPa·s. By dispersing and mixing the nanobubbles 15 into the paint 10A before the nanobubbles 15 are dispersed and mixed, the viscosity of the paint 10A before the nanobubbles 15 are dispersed and mixed can be reduced to 1 / 4 to 1 / 2. For example, by dispersing and mixing the nanobubbles 15 into the high-viscosity paint 10A with a viscosity of 180 mPa·s, the viscosity can be reduced to 45 to 90 mPa·s, and by dispersing and mixing the nanobubbles 15 into the medium-viscosity paint 10A with a viscosity of 60 mPa·s, the viscosity can be reduced to 15 to 30 mPa·s. The paint 10B can have its viscosity reduced by introducing (mixing) the nanobubbles 15 into it, and it is possible to turn the high-viscosity or medium-viscosity paint 10A into the low-viscosity paint 10B without reducing or using substances that may have an adverse effect on the human body.

[0095] The adhesiveness of the paint 10B is reduced by the nanobubbles 15 performing Brownian motion inside the paint 10B, and since the nanobubbles 15 dissolve to break the intermolecular bonds and weaken the intermolecular interactions, the viscosity of the paint 10B can be decreased, and the average particle size D of the nanobubbles 15 50By adjusting the content of the nanobubbles 15 in the paint 10B, the viscosity of the paint 10B can be adjusted, and the ease of applying the paint 10B to the surface 12 of the base material 11 can be improved. By using nanobubbles 15 to adjust the viscosity of the paint 10B, especially in a low-temperature environment where the viscosity of the paint 10B is high, in a situation where more thinner or the like is used to adjust the viscosity, by using the paint 10B containing a large amount of nanobubbles 15 that dissolve in a large amount in a low-temperature environment, it is possible to significantly reduce or eliminate the need to use substances that may have an adverse effect on the human body. The viscosity of the paint 10B varies depending on the type of gas forming the nanobubbles 15, and fine adjustment of the viscosity of the paint is possible by selecting the gas to be used. When the paint 10B is an aqueous paint, since its viscosity is adjusted by using nanobubbles 15, the amount of water used for viscosity adjustment can be reduced or there is no need to use water for viscosity adjustment, so it becomes a useful paint 10B in areas with water shortages or environments where water cannot be used.

[0096] The nanobubbles 15 inside the paint 10B have an average particle size D 50 of 0.5 μm or less, preferably 1 nm or more and 800 nm or less, more preferably 1 nm or more and 300 nm or less. The number of nanobubbles 15 per 1 ml of the paint 10B in which the nanobubbles 15 are dispersed and mixed is 10 5 particles / ml or more and 10 12 particles / ml or less (in the range of 10 5 to 10 12 ml).

[0097] Since the content rate of the nanobubbles 15 in the paint 10B in which the nanobubbles 15 are dispersed and mixed is within the above range, the ultrafine bubbles of the nanobubbles 15 are dispersed and mixed (dispersed and dissolved) in a large amount at a predetermined concentration inside the paint 10B, and the ratio of the paint 10B itself per unit area in the paint 10B can be reduced by the nanobubbles 15 which are ultrafine bubbles, and when applying the paint 10B to the surface 12 of the base material 11 to be coated, the coating amount of the paint 10B itself can be surely reduced. The paint 10B is 10 5 to 10 12Since the coating amount on the substrate 11 is reduced by including the nanobubbles 15 in the range of [unit not specified] / ml, the unit price of the paint 10B per unit area of the surface 12 of the substrate 11 can be reduced, and the paint 10B can be applied at a low cost.

[0098] The particle size, content rate, and total number of the nanobubbles 15 dispersed and mixed inside the paint 10B were measured by the nanoparticle tracking analysis method (NTA). In the nanoparticle tracking analysis method, the particle size (particle size distribution), content rate, and total number (particle number concentration) of the nanobubbles 15 in the paint 10B, as well as their aggregation state, can be measured with high resolution. In the nanoparticle tracking analysis method, the paint 10B in which the nanobubbles 15 are dispersed and mixed is accommodated in a sample chamber, and the sample chamber is irradiated with laser light. The nanoparticle tracking analysis method detects the scattered light at 90° of each nanobubble 15 irradiated with the laser light using a highly sensitive CMOS camera. The Brownian motion of the detected particles is observed as the movement of bright spots on the camera image and tracked. By tracking this movement, the diffusion count is obtained, and the particle size of the nanobubbles 15 is determined by the Stokes-Einstein equation. The particle distribution (concentration) is obtained by finding the number of nanobubble 15 particles per milliliter from the total count of all particles within the camera field of view with a known volume, determining the content rate of the nanobubbles 15 in the paint 10B, and calculating the total number of nanobubble 15 particles per milliliter of the paint 10B. When ultrafine particles of nanosize are mixed in the paint 10B, it becomes possible to count the total number of the nanobubbles 15 by comparing with the results of the paint 10A. In the nanoparticle tracking analysis method, the zeta potential of the particles is determined by measuring the electrophoretic mobility when a constant voltage is applied to the cell. Incidentally, the volume of the nanobubbles 15 dispersed and mixed inside the paint 10B can also be measured by the laser diffraction / scattering method, and the number of the nanobubbles 15 dispersed and mixed inside the paint 10B can also be measured by the electrical sensing zone method or the image analysis method.

[0099] The paint 10B mixed with the nano-bubbles 15 has a rising rate of the nano-bubbles 15 inside the paint 10B at room temperature in the range of 0.000005 mm / min or more and 0.00005 mm / min or less (0.00005 - 0.000005 mm / min). Since the volume of the nano-bubbles 15 is extremely small, the rising rate inside the paint 10B is extremely slow. When the rising rate of the nano-bubbles 15 inside the paint 10B exceeds 0.00005 mm / min, it is difficult to keep the nano-bubbles 15 in the paint 10B for a long time, and the nano-bubbles 15 may volatilize from the paint 10B within the target residence time. Since the rising rate of the nano-bubbles 15 inside the paint 10B at room temperature is in the above range, the nano-bubbles 15 are difficult to volatilize from the paint 10B, and the nano-bubbles 15 can be retained in the paint 10B for a long time, and the coating amount of the paint 10B itself when the paint 10B is applied to the base material 11 to be coated can be surely reduced.

[0100] The rising rate of the nano-bubbles 15 with an extremely slow rising rate inside the paint 10B in the paint 10B depends on the liquid physical properties of the paint 10B. In water, the diameter is about 1 μm and the Reynolds number Re becomes approximately 1, forming spherical bubbles. The rising rate U of a spherical bubble with diameter d follows Stokes' formula: U = pgd 2 / 18μ. Here, p is the liquid density, g is the gravitational acceleration, and μ is the liquid viscosity.

[0101] The nanobubbles 15 mixed (dissolved) inside the coating 10B have a high internal bubble pressure (bubble internal pressure) (self-pressurizing effect). The internal bubble pressure becomes ΔP higher than the pressure around the bubble according to Young-Laplace's equation: ΔP = 4σ / d due to the influence of the surface tension σ. Regarding the relationship between the diameter d of the bubbles in the coating 10B and the internal bubble pressure, the smaller the bubbles, the higher the pressure inside the bubbles (3.87 "atm" at 1 μm, 29.7 "atm" at 100 nm, surface tension of water σ: 72.8 mN / m (20 °C), and the pressure around the bubbles is 1 "atm"). Therefore, when the bubbles shrink, the partial pressure of the gas dissolved component, that is, the driving force for dissolution, increases, and by making the gas nano-sized, the gas becomes more likely to dissolve in the coating 10B, and a large amount of nanobubbles 15 dissolve in the coating 10B.

[0102] The nanobubbles 15 mixed (dissolved) inside the coating 10B have a large gas-liquid interface area. The gas-liquid interface area per unit volume A / V is represented by the formula: A / V = 6 / d. As the bubble diameter d decreases, A / V increases, which greatly contributes to the amount of gas mixed (dissolved) in the coating 10B. The amount of nanobubbles 15 mixed (dissolved) is extremely large. The mass transfer rate N "mol / s" of the bubbles into the coating 10B is given by the formula: N = K G A(p - p*). Here, K G is the overall mass transfer coefficient based on the gas phase "mol / m 2 sPa", A is the surface area of the bubbles [m 2 , p is the partial pressure of the dissolved component in the bubbles "Pa", and p* is the gas phase partial pressure in equilibrium with the dissolved component in the liquid phase "Pa".

[0103] When the nanobubbles 15 dissolve (mix) inside the coating 10B, according to the double-film theory consisting of a gas boundary film and a liquid boundary film across the gas-liquid interface, the overall mass transfer resistance 1 / K L or 1 / K G H is the sum of the liquid phase resistance 1 / k L and the gas phase resistance 1 / k G H, and like Ohm's law of electrical resistance, the formula: 1 / K L = 1 / K G H = 1 / k L + 1 / k Gbecomes H. Here, K L is the overall mass transfer coefficient based on the liquid phase, and H is the Henry's constant (p = H C ), Equation: 1 / K L = 1 / K G H = 1 / k L + 1 / k G H in the gas-side mass transfer resistance 1 / K G If H can be neglected, the overall mass transfer coefficient K L based on the liquid phase and the liquid-side mass transfer coefficient K L become approximately equal.

[0104] When the Reynolds number Re < 1 for spherical bubbles and the rising velocity is expressed by the Stokes' equation: U = pgd 2 / 18μ, the liquid-side mass transfer coefficient k L is expressed by the equation: k L = D L / d[l + (1 + dU / D L ) 1 / 3 . Here, D L is the diffusion coefficient of the gas in the liquid phase, d is the bubble diameter, and U is the rising velocity of the bubble. For example, from the equation: k L = D L + dl + [(1 + dU / D L ) 1 / 3 , the relationship between the bubble diameter and the oxygen-water system liquid-side mass transfer coefficient k L is obtained. When the bubble diameter d is 100 μm, k L is 1.817·10 -4 "m / s", when the bubble diameter d is 10 μm, k L is 5.37·10 -4 "m / s", and when the bubble diameter d is 1 μm, k L is 5.20·10 -3 "m / s". Incidentally, the diffusion coefficient D L of oxygen inside the paint 10 is 2.60·10 -9 "m 2 / s" was used.

[0105] Using the value of k L for the bubble diameter d and the bubble internal pressure "atm" for the bubble diameter d, the equation: N = K GThe mass transfer rate N was determined by A(p - p*) and, as a result of rearrangement, when the bubble diameter d was 10 μm, the rising velocity U was 3.26·10 -3 "m / min", the pressure difference ΔP was 2.91·10 4 , the bubble number ratio was 1.0·10 6 , the area ratio was 100, the mass transfer rate ratio was 6.15·10 4 "mol / s" and 1.0·10 8 "mol / mm", and when the bubble diameter d was 100 nm, the rising velocity U was 3.15·10 -7 "m / min", the pressure difference ΔP was 2.91·10 6 , the bubble number ratio was 1.0·10 12 , the area ratio was 1.0·10 4 , the mass transfer rate ratio was 5.95·10 10 "mol / s" and 1.0·10 18 "mol / mm".

[0106] When a spherical bubble with a diameter of 1 mm is divided into bubbles with a diameter of 10 μm, the number increases to 10 6 pieces, and when the surface area of the 1 - mm - diameter bubble is taken as 1, the surface area becomes 100 times. When a spherical bubble with a diameter of 1 mm is divided into bubbles with a diameter of 100 nm, the number increases to 10 12 pieces, and when the surface area of the 1 - mm - diameter bubble is taken as 1, the surface area becomes 10 4 times. Therefore, when the mass transfer rate (dissolution rate) per unit time of a 1 - mm - diameter bubble is taken as 1, for 10 - μm - diameter bubbles, the mass transfer rate (dissolution rate) becomes 6·10 4 times, and when the mass transfer rate (dissolution rate) per unit time of a 1 - mm - diameter bubble is taken as 1, for 100 - nm - diameter bubbles, the mass transfer rate (dissolution rate) becomes 6·10 10 times. Thus, in calculation, when the bubble becomes nano - sized, due to the increase in surface area and internal partial pressure of the bubble and the decrease in rising velocity, the mass transfer rate (dissolution rate) for Paint 10B increases rapidly.

[0107] Using an electrophoresis experiment device, the surface potential of the nanobubbles 15 was measured. The nanobubbles 15 generated in the container were introduced into an electrophoresis cell (thickness 1 mm, height 23.0 mm, width 75.0 mm). By switching the electric field direction of the electrodes every 1 s, the negatively charged nanobubbles 15 perform a zigzag motion. The bubble diameter was determined using the Stokes equation by measuring the rising speed, and the zeta potential of the bubbles was determined using Smoluchowski's equation: ζ = μu / ε from the horizontal velocity. Here, ζ is the zeta potential "V", μ is the viscosity of the paint 10B "kg / ms", u is the mobility of the bubbles "m 2 / sV", and ε is the dielectric constant of the paint 10B "s 2 C 2 / kgm 3 ".

[0108] The nanobubbles 15 are negatively charged at -30 to -40 "mV" regardless of their bubble diameter (the microbubbles 14 are also similar). The cluster structure of the paint 10B is formed from the molecules of the paint 10B and the ionized + and - ions. The + and - ions are likely to be accommodated in the structure, but particularly the - ions are likely to accumulate at the interface, so it is negatively charged. Since the nanobubbles 15 are negatively charged, the nanobubbles 15 in the paint 10B repel each other, as do the microbubbles 15, and the nanobubbles 14 and microbubbles 15. The possibility of these nanobubbles 15 and microbubbles 15, and the nanobubbles 14 and microbubbles 15 combining (coalescing) due to electrostatic repulsion is low.

[0109] Paint 10B has negatively charged nanobubbles 15 (microbubbles 15) mixed (dissolved) therein. Due to this, the nanobubbles 14 and microbubbles 15 dispersed and mixed within Paint 10B, and the nanobubbles 14 and microbubbles 15 repel each other, and the nanobubbles 14 and microbubbles 15, and the nanobubbles 14 and microbubbles 15 do not combine (unite). It is possible to prevent the formation of large bubbles of nanobubbles 14 and microbubbles 15 due to the combination of nanobubbles 14 and microbubbles 15, and it is possible to maintain the dispersed and mixed state of microbubbles 15, which are fine bubbles, and the dispersed and mixed state of nanobubbles 15, which are ultrafine bubbles, in Paint 10B. Since microbubbles 14 and nanobubbles 15, and nanobubbles 14 and microbubbles 15 do not combine (unite) in Paint 10B, and the microbubbles 14 of fine bubbles and / or the nanobubbles 15 of ultrafine bubbles are dispersed and mixed (dispersed and dissolved) in Paint 10B, the nanobubbles 15 and microbubbles 14 are difficult to volatilize from Paint 10B, and the nanobubbles 15 and microbubbles 14 can be retained in Paint 10B for a long time.

[0110] Paint 10B is not in a state where the nanobubbles 15 are combined in a columnar shape, but is dispersed and mixed (dispersed and dissolved) in Paint 10B in a spherical state having a high internal bubble pressure at a predetermined concentration, and the average particle size D 50 is 0.5 μm or less, preferably 1 nm or more and 800 nm or less, more preferably 1 nm or more and 300 nm or less of nanobubbles 15 are dispersed and mixed in Paint 10B at a predetermined concentration (high concentration), and the number of nanobubbles 15 per 1 ml of Paint 10B is 10 5 pieces / ml or more and 10 12 pieces / ml or less. Therefore, the proportion of Paint 10B itself per unit volume in Paint 10B (Paint 10B in which nanobubbles 15 are mixed (dissolved)) can be reduced by the nanobubbles 15, which are ultrafine bubbles, and when applying Paint 10B (Paint 10B in which nanobubbles 15 are mixed (dissolved)) to the surface 12 of the base material 11 to be coated, the coating amount of Paint 10B itself can be surely reduced.

[0111] Paint 10B has a large amount of microbubbles 14 dispersed and mixed (dispersed and dissolved) at a predetermined concentration inside the paint 10B in the state of spheres having a high internal bubble pressure, and an average particle size D 50 Microbubbles 14 with a size of 100 μm or less are dispersed and mixed in a large amount at a predetermined concentration (high concentration) inside the paint 10B, and the number of microbubbles 14 per 1 ml of the paint 10B is 10 5 pieces / ml or more and 10 12 pieces / ml or less. Therefore, the ratio of the paint 10B itself per unit volume in the paint 10B (the paint 10B in which the microbubbles 14 are mixed (dissolved)) can be reduced by the microbubbles 14 which are fine bubbles, and when applying the paint 10B (the paint 10B in which the microbubbles 15 are mixed (dissolved)) to the surface 12 of the base material 11 to be coated, the coating amount of the paint 10B itself can be surely reduced.

[0112] The forces acting on the nanobubbles 15 inside the paint 10B are buoyancy and drag. The buoyancy is proportional to the volume of the nanobubbles 15 (proportional to the cube of the radius of the nanobubbles 14). The drag is proportional to the cross-sectional area of the nanobubbles 15 (proportional to the square of the radius of the nanobubbles 15) and proportional to the square of the rising speed of the nanobubbles 15. Specifically, when the radius of the nanobubbles 15 is r, the density of the paint 10B is ρ, the gravitational acceleration is g, the viscosity of the paint 10B is η, and the moving speed of the nanobubbles 15 is u, the buoyancy acting on the nanobubbles 15 (the density of the nanobubbles 15 is ignored) is, according to Archimedes' principle, Equation (1): F = 4πr 3 ρg / 3.

[0113] Also, the drag acting on the nanobubbles 15 is expressed by Equation (2): F = 6πηru according to Stokes' theorem. From Equation (1) and Equation (2), the moving speed u of the nanobubbles 15 inside the paint 10B is expressed by Equation (3): u = (2 / 9)r 2 ρg / η. The rising speed of the nanobubbles 15 in the paint 10B is obtained from Equation (3). As is clear from Equation (3), the larger the radius r (particle size) of the nanobubbles 15, the higher the moving speed u of the nanobubbles 15 in the paint 10B.

[0114] When the radius r of the nanobubble 15 under 1 atm is a, the radius r and the water depth h are expressed by Equation (4): r = a × {101325 / (ρgh + 101325)}. 1 / 3 As is clear from Equations (3) and (4), as the water depth of the paint 10B becomes shallower, the particle size of the nanobubble 15 becomes larger and the rising speed becomes higher.

[0115] As a hypothesis, nanobubbles 15 with a diameter of less than 1.0 μm have a reduced solubility due to the salting-out phenomenon and will stably exist inside the paint 10B for a long time. Due to the salting-out phenomenon, if the nanobubbles 15 continue to stably exist for a long time, there will be no paint 10B containing nanobubbles 15 with a pH close to 7. However, there are cases where stable nanobubbles 15 exist even in neutral liquids.

[0116] In addition, when the nanobubbles 15 and the larger microbubbles 14 coexist in the paint 10B, the life of the nanobubbles 15 may be shortened due to the floating of the nanobubbles 15 under the influence of the latter's larger microbubbles 14 or the influence of cavitation damage caused by the external pressure.

[0117] An example of the base material 11 (object) to be coated with the paint 10B in which the microbubbles 14 and / or the nanobubbles 15 are dispersed and mixed is a building. The paint 10B in which the microbubbles 14 and / or the nanobubbles 15 are dispersed and mixed is applied to the surface (front and back surfaces) of the building, and a coating film 13 in which the microbubbles 14 and / or the nanobubbles 15 are dispersed and mixed is formed on the surface (front and back surfaces) of the building by the cured paint 10B.

[0118] Buildings include structures such as buildings and certain fixtures attached thereto, and artifacts other than buildings. Buildings include fixtures for viewing, offices, stores, theaters, warehouses, and other similar facilities provided in underground or elevated fixtures, building equipment, civil engineering structures such as bridges and sluice gates, and construction materials (mortar, concrete, ALC, siding boards, extruded cement boards, gypsum boards, slates, wooden parts, PC boards, etc.). Artifacts include chimneys, towers, elevated water tanks, and other similar ones, viaducts, elevated roads, elevated railways, and other similar ones, manufacturing facilities, storage facilities, supply facilities such as water supply and electricity, treatment facilities for garbage, and other similar ones, sports facilities such as baseball fields and tennis courts, amusement facilities such as amusement parks, and other similar ones.

[0119] For a building coated with paint 10B into which microbubbles 14 and / or nanobubbles 15 are introduced (mixed in), when the paint 10B in which the independent microbubbles 14 and / or nanobubbles 15 are dispersed and mixed (dispersed and dissolved) at a predetermined concentration is applied to the surface of the building, the application amount of the paint 10B itself decreases. By reducing the application amount, the unit price of the paint 10B per unit area of the building surface can be lowered, and the paint 10B can be applied to the building surface at a low cost, and the construction cost of the building can be reduced. Since the viscosity of the paint 10B becomes low viscosity when microbubbles 14 and / or nanobubbles 15 are dispersed and mixed (dispersed and dissolved) in the paint 10B applied to the surface of the building, the paint 10B can be easily applied to the building surface, and the application work time of the paint 10B to the building surface can be shortened. Since the mass of the paint 10B per unit volume decreases compared to the case where microbubbles 14 or nanobubbles 15 are not dispersed and mixed (dispersed and dissolved) in the paint 10B, when the paint 10B is applied to the building surface, the increase in the weight of the building including the paint film 13 formed from the paint 10B can be minimized.

[0120] Another example of the substrate 11 (object) to which the paint 10B mixed with microbubbles 14 and / or nanobubbles 15 is applied is a moving body. The paint 10B mixed with microbubbles 14 and / or nanobubbles 15 is applied to the surface (front and back surfaces) of the moving body, and a coating film 13 in which microbubbles 14 and / or nanobubbles 15 are dispersed and mixed is formed on the surface (front and back surfaces) of the moving body by the cured paint 10B.

[0121] Moving bodies include automobiles, motorcycles, motorized bicycles, bicycles, trains, flying objects, and ships. Automobiles include all types of automobiles such as ordinary automobiles, compact cars, light automobiles, large special automobiles, and small special automobiles, all body types (SUVs, light automobiles, minivans, one-boxes, sedans, station wagons, etc.), all engine and power sources (gasoline vehicles, diesel vehicles, hybrid vehicles, EVs, fuel cell vehicles), and all drive systems (2WD, 4WD). Note that automobiles include all those to be developed in the future. The paint 10B is applied to the exterior (surface), interior (surface), parts (surface), etc. of automobiles.

[0122] Motorcycles include ordinary motorbikes and large motorbikes. Motorcycles include all those to be developed in the future. Bicycles include city bikes, folding bikes, electric assist bikes, minivelos, mountain bikes, road bikes, cross bikes, pista bikes, cyclocross, BMX, kick bikes, and bicycles with training wheels. Bicycles include all those to be developed in the future. The paint 10B is applied to the exterior (surface) and parts (surface), etc. of motorcycles and bicycles.

[0123] The vehicles include bullet trains, superconducting maglev trains, special-type trains, general-type trains, limited express diesel multiple units, ordinary diesel multiple units, passenger cars, electric locomotives, and diesel locomotives. The vehicles include all those to be developed in the future. The paint 10B is applied to the exterior (surface), interior (surface), parts (surface), etc. of the vehicles. The flying objects include airplanes (single-engine passenger planes, reciprocating passenger planes, large propeller passenger planes, large jet passenger planes, civilian cargo planes, fighter / attack planes), drones, balloons, sounding rockets, artificial satellites, etc. The flying objects include all those to be developed in the future. The paint 10B is applied to the exterior (surface), interior (surface), parts (surface), etc. of the flying objects.

[0124] For a moving object coated with the paint 10B into which microbubbles 14 and / or nanobubbles 15 are introduced (mixed in), when the paint 10B with the microbubbles 14 and / or nanobubbles 15 of independent bubbles dispersed and mixed (dispersed and dissolved) at a predetermined concentration is applied to the surface of the moving object, the coating amount of the paint 10B itself decreases. By reducing the coating amount, the unit price of the paint 10B per unit area of the surface of the moving object can be lowered, and the paint 10B can be applied to the surface of the moving object at low cost, and the manufacturing cost of the moving object can be reduced. Since the viscosity of the paint 10B becomes low viscosity when the microbubbles 14 and / or nanobubbles 15 are dispersed and mixed (dispersed and dissolved) in the paint 10B applied to the surface of the moving object, the paint 10B can be easily applied to the surface of the moving object, and the coating operation time of the paint 10B on the surface of the moving object can be shortened. Since the mass of the paint 10B per unit volume of the moving object decreases as compared with the case where the microbubbles 14 or nanobubbles 15 are not dispersed and mixed (dispersed and dissolved) in the paint 10B, when the paint 10B is applied to the surface of the moving object, the increase in the weight of the moving object including the paint film 13 formed from the paint 10B can be minimized.

[0125] Another example of the substrate 11 (object) to which the paint 10B mixed with microbubbles 14 and / or nanobubbles 15 is applied is an industrial product. The paint 10B in which microbubbles 14 and / or nanobubbles 15 are dispersed and mixed is applied to the surface (front surface, back surface) of the industrial product, and a coating film 13 in which microbubbles 14 and / or nanobubbles 15 are dispersed and mixed is formed on the surface (front surface, back surface) of the industrial product by the cured paint 10B. An industrial product is an article manufactured by consuming raw materials in industries such as the metal industry, chemical industry, and machinery industry. Industrial products include factory machines and equipment, cutting tools, machine tools, pipelines, smartphones, TVs, displays, computers, cameras, electrical wiring, etc. Industrial products include all those to be developed in the future.

[0126] For an industrial product coated with the paint 10B into which microbubbles 14 and / or nanobubbles 15 are introduced (mixed), when the paint 10B in which the independent microbubbles 14 and / or nanobubbles 15 are dispersed and mixed (dispersed and dissolved) at a predetermined concentration is applied to the surface of the industrial product, the coating amount of the paint 10B itself decreases. By reducing the coating amount, the unit price of the paint 10B per unit area of the surface of the industrial product can be lowered, the paint 10B can be applied to the surface of the industrial product at low cost, and the manufacturing cost of the industrial product can be reduced. Since the viscosity of the paint 10B becomes low viscosity when microbubbles 14 and / or nanobubbles 15 are dispersed and mixed (dispersed and dissolved) in the paint 10B applied to the surface of the industrial product, the paint 10B can be easily applied to the surface of the industrial product, and the coating operation time of the paint 10B on the surface of the industrial product can be shortened. Since the mass of the paint 10B per unit volume of the industrial product decreases as compared with the case where microbubbles 14 or nanobubbles 15 are not dispersed and mixed (dispersed and dissolved) in the paint 10B, when the paint 10B is applied to the surface of the industrial product, the increase in the weight of the industrial product including the coating film 13 formed from the paint 10B can be minimized.

[0127] Another example of the substrate 11 (object) to which the paint 10B mixed with microbubbles 14 and / or nanobubbles 15 is applied is furniture and equipment. The paint 10B mixed with microbubbles 14 and / or nanobubbles 15 is applied to the surface (front and back) of the furniture and equipment, and a coating film 13 in which microbubbles 14 and / or nanobubbles 15 are dispersed and mixed is formed on the surface (front and back) of the furniture and equipment by the cured paint 10B.

[0128] Furniture and equipment include Japanese-style furniture, utensils, chests of drawers, dressing tables, Japanese desks, low tables, desks, kitchen cabinets, writing desks, bamboo furniture, rattan furniture, wicker furniture, plywood, chopping boards, ironing boards, Western-style furniture, tables, chairs, sofa sets, furniture for ships, furniture for schools, beds, cabinets for radios, televisions, and stereos, sewing tables, wardrobes, bookshelves, furniture for hospitals, medicine cabinets, metal furniture, metal cabinets, metal lockers, metal chairs, metal beds, metal tables, metal storage cabinets and wardrobes, etc. Furniture and equipment include all of those to be developed in the future.

[0129] Furniture and equipment coated with paint 10B into which microbubbles 14 and / or nanobubbles 15 are introduced (mixed in) can reduce the coating amount of the paint 10B itself when the paint 10B in which the independent microbubbles 14 and / or nanobubbles 15 are dispersed and mixed (dispersed and dissolved) at a predetermined concentration is applied to the surface of the furniture and equipment. By reducing the coating amount, the unit price of the paint 10B per unit area of the surface of the furniture and equipment can be lowered, and the paint 10B can be applied to the surface of the furniture and equipment at a low cost, and the manufacturing cost of the furniture and equipment can be reduced. Since the viscosity of the paint 10B becomes low viscosity when microbubbles 14 and / or nanobubbles 15 are dispersed and mixed (dispersed and dissolved) in the paint 10B applied to the surface of the furniture and equipment, the paint 10B can be easily applied to the surface of the furniture and equipment, and the coating operation time of the paint 10B on the surface of the furniture and equipment can be shortened. Since the mass of the paint 10B per unit volume of the furniture and equipment is reduced compared to the case where the microbubbles 14 or nanobubbles 15 are not dispersed and mixed (dispersed and dissolved) in the paint 10B, the increase in the weight of the furniture and equipment including the paint film 13 formed from the paint 10B when the paint 10B is applied to the surface of the furniture and equipment can be minimized.

[0130] Another example of the substrate 11 (object) to be coated with the paint 10B in which microbubbles 14 and / or nanobubbles 15 are dispersed and mixed includes metal molded products, plastic molded products, glass molded products, rubber molded products, leather molded products, wood molded products, paper molded products, woven fabric molded products, and non-woven fabric molded products. Examples of the materials for metal molded products include iron, aluminum, duralumin, stainless steel, copper, gold, silver, titanium, nickel, alloys, and the like. The shapes of the metal molded products made of these materials include plates, bars, and other various three-dimensional shapes. Examples of the materials for plastic molded products include known thermoplastic resins such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyamide (nylon), vinyl chloride resin, acrylic resin, silicone resin, fluororesin, polyimide resin, and polysulfone resin, and thermosetting resins such as epoxy resin, melamine resin, phenol resin, and unsaturated polyester resin. The shapes of the plastic molded products made of these materials include film-like, sheet-like, plate-like, and other various three-dimensional shapes.

[0131] As an example of the method for applying the fluororesin paint, first, the substrate 11 is degreased. As the degreasing treatment, the substrate 11 is heated in a furnace and subjected to dry burning to thermally decompose oils, fats, and dirt at a temperature higher than the firing temperature. Alternatively, solvent cleaning is performed to wash away dirt and oil from the substrate of a material or shape unsuitable for dry burning with a solvent.

[0132] Next, a base treatment (pretreatment) is performed. In the base treatment, the surface 12 (coating surface) of the substrate 11 is blasted with Morandum, grid abrasive grains, and air to remove rust, dirt, etc., and roughen it to about 3 to 6 microns (blasting). Alternatively, when blasting cannot be performed or according to the functions to be used, an etching or chemical film treatment base treatment is performed. After the base treatment, a primer is applied to the surface 12 (coating surface) of the substrate 11 to improve the adhesion between the substrate 11 and the fluororesin (primer coating). Next, the primer is baked using a furnace (firing).

[0133] After firing, a fluororesin paint is applied to the surface 12 (coating surface) of the base material 11 using a coating device such as a brush, roller, dipping, spraying, roll coater, die coater, applicator, spin coater, etc. After applying the fluororesin paint, the fluororesin paint is dried to form a coating film. The drying temperature of the fluororesin paint is about normal temperature to 300 °C. When heating and drying the fluororesin paint, it is fired in a firing furnace.

[0134] Silicone resin paint, acrylic resin paint, urethane resin paint, and water-based paint are applied by a coating method suitable for the shape of the base material 11 (various articles). For example, they are applied by a spray method, dipping method, brush painting method, roll coating method, gravure coating method, flexo method, inkjet method, etc. The drying temperature of the silicone resin paint is about normal temperature to 50 °C. The drying temperature of the acrylic resin paint is about normal temperature to 120 °C. The drying temperature of the urethane resin paint is about normal temperature to 100 °C. In the application of silicone resin paint, acrylic resin paint, and urethane resin paint, similar to the fluororesin paint, blasting may be performed with the abrasive grains of the grid and air to remove rust, dirt, etc., and a substrate treatment may be performed to roughen the surface to about 3 to 6 microns.

[0135] Fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, and water-based paint may be applied in multiple layers in addition to single-layer coating. There is no particular limitation on the coating amount of fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, and water-based paint, and the coating amount is determined according to the surface performance required for the base material 11 (various articles) to be coated. The coating film formed by drying fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, and water-based paint has a coating thickness in the range of 60 to 300 μm, preferably 90 to 270 μm. Incidentally, the measurement of the coating thickness of the coating film is performed using an electromagnetic film thickness gauge, an eddy current film thickness gauge, or an outside micrometer.

[0136] The microbubbles 14 and / or nanobubbles 15 incorporated (dissolved) inside the paint 10B applied to a predetermined film thickness (60 to 300 μm, preferably 90 to 270 μm) gradually increase in particle size from the bottom to the top of the paint 10B within the said range. Therefore, the microbubbles 14 and / or nanobubbles 15 located at the bottom of the paint 10B have the smallest particle size, the microbubbles 14 and / or nanobubbles 15 located at the top of the paint 10B have the largest particle size, and the microbubbles 14 and / or nanobubbles 15 located in the middle part of the paint 10B have a size intermediate between those of the microbubbles 14 and / or nanobubbles 15 located at the bottom and the top.

[0137] In the drying process after applying the emulsion-based (aqueous) paint 10B to the surface 12 (coating surface) of the substrate 11, as shown in Fig. 7, as the solvent (moisture) gradually evaporates, the polymer particles dissolved in the solvent (moisture) are deformed and the polymer particles fuse together. Thereafter, mutual diffusion of the polymer chains occurs, and when film formation is completed, a coating film 13 is formed on the surface 12 of the substrate 11. The coating film 13 formed from the emulsion-based paint 10 has a film thickness in the range of 20 to 110 μm, preferably 30 to 90 μm.

[0138] Inside the coating film 13 formed by drying and curing the emulsion-based paint 10B on the surface 12 of the substrate 11 (various articles), the average particle size D of the bubbles 50 is 100 μm or less for the microbubbles 14 and / or the average particle size D of the bubbles 50 is 0.5 μm or less, preferably 1 nm or more and 800 nm or less, more preferably 1 nm or more and 300 nm or less for the nanobubbles 15, and the nanobubbles 15 remain trapped without evaporating into the outside air, and the microbubbles 14 and / or nanobubbles 15 are dispersed and mixed (dispersedly dissolved) at a predetermined concentration. The microbubbles 14 and / or nanobubbles 15 dispersed and mixed inside the coating film 13 made from the emulsion-based paint 10B are mixed in a spherical state with a high internal bubble pressure, similar to the state in which they were dispersed and incorporated in the paint 10B.

[0139] A coating film 13 made from an emulsion-based paint 10B in which microbubbles 14 and / or nanobubbles 15 are dispersed and mixed, per 1 cm 3 The total number of microbubbles 14 per centimeter is 10 5 pieces / cm 3 or more and 10 12 pieces / cm 3 or less, and the total number of nanobubbles 15 per 1 cm of the coating film 13 is 10 3 or more and 10 5 pieces / cm 3 or less. 12 pieces / cm 3 It is in the following range.

[0140] In the drying process after applying the solvent-based paint 10B to the surface 12 (coating surface) of the substrate 11, as shown in FIG. 8, the solvent (solvent) gradually volatilizes, the polymer chains dissolved in the solvent (solvent) gradually contract, and mutual diffusion of the polymer chains occurs. When film formation is completed, a coating film 13 is formed on the surface 12 of the substrate 11. The coating film 13 formed from the solvent-based paint 10 has a film thickness in the range of 20 to 110 μm, preferably 30 to 90 μm.

[0141] Inside the coating film 13 formed by drying and curing the solvent-based paint 10B on the surface 12 of the substrate 11 (various articles), the average particle size D of the bubbles 50 is 100 μm or less for microbubbles 14 and / or the average particle size D of the bubbles 50 is 0.5 μm or less, preferably 1 nm or more and 800 nm or less, more preferably 1 nm or more and 300 nm or less for nanobubbles 15. The microbubbles 14 and / or nanobubbles 15 remain trapped without evaporating into the outside air and are dispersed and mixed (dispersed and dissolved) at a predetermined concentration. The microbubbles 14 and / or nanobubbles 15 dispersed and mixed inside the coating film 13 made from the solvent-based paint 10B are mixed in the state of spheres having a high internal bubble pressure, similar to the state in which they were dispersed and mixed in the paint 10B.

[0142] Per 1 cm of the coating film 13 made from the solvent-based paint 10B in which microbubbles 14 and / or nanobubbles 15 are dispersed and mixed 3The total number of microbubbles 14 per hit is 10 5 pieces / cm 3 or more and 10 12 pieces / cm 3 or less, and the total number of nanobubbles 15 per 1 cm 3 of the coating film 13 is 10 5 pieces / cm 3 or more and 10 12 pieces / cm 3 or less.

[0143] The paint 10B (fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, water-based paint) has microbubbles 14 and / or nanobubbles 15 introduced (mixed) therein, and the microbubbles 14 and / or nanobubbles 15 of independent bubbles are dispersed and mixed (dispersed and dissolved) inside the paint 10B at a predetermined concentration. Therefore, the ratio of the paint 10B itself per unit volume of the paint 10B can be reduced by the microbubbles 14 and nanobubbles 15, and when the paint 10B is applied to the surface 12 of the base material 11 to be coated, the coating amount of the paint 10B itself decreases, and the coating amount of the paint 10B on the base material 11 can be reduced.

[0144] The paint 10B (fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, water-based paint) can reduce the unit price of the paint 10B per unit area of the surface 12 of the base material 11 by reducing its coating amount compared to the case where no microbubbles 14 and / or nanobubbles 15 are dispersed and mixed therein, and the paint 10B can be applied at low cost. Even if the base material 11 on which the fluororesin coating film 13 made from the fluororesin paint, the silicone resin coating film 13 made from the silicone resin paint, the acrylic resin coating film 13 made from the acrylic resin paint, the urethane resin coating film 13 made from the urethane resin paint, or the coating film 13 made from the water-based paint is formed is subjected to various damages, the base material 11 can be protected from various damages by those coating films 13 made from the paint 10B, and deterioration of the base material 11 due to those damages can be prevented.

[0145] Figure 9 is a diagram showing an example of the paint 10B of the present invention and comparative examples for the paint 10B of the present invention. As an example of the paint 10B, a one-component curable water-based paint was used as the paint 10B, and a one-component curable water-based paint without nano-bubbles (without nano-bubbles (NB)) and a one-component curable water-based paint containing nano-bubbles (paint 10B) (A method and B method) were prepared. (Without nano-bubbles (NB)) was not diluted with water without introducing nano-bubbles into the one-component curable water-based paint. (A method) was to introduce nano-bubbles into the one-component curable water-based paint without nano-bubbles (NB) by the static mixer method to obtain a one-component curable water-based paint containing nano-bubbles in which nano-bubbles were dispersed and mixed. (B method) was to introduce nano-bubbles into the one-component curable water-based paint without nano-bubbles (NB) by the ultrasonic method to obtain a one-component curable water-based paint containing nano-bubbles in which nano-bubbles were dispersed and mixed.

[0146] As comparative examples for the paint 10B, a one-component curable water-based paint without nano-bubbles (NB) that was not diluted with water (one-component curable water-based paint without nano-bubbles (NB) before dilution), a one-component curable water-based paint without nano-bubbles (NB) diluted with 1% equivalent of water (one-component curable water-based paint without nano-bubbles (NB) with 1% water added), a one-component curable water-based paint without nano-bubbles (NB) diluted with 5% equivalent of water (one-component curable water-based paint without nano-bubbles (NB) with 5% water added), a one-component curable water-based paint without nano-bubbles (NB) diluted with 10% equivalent of water (one-component curable water-based paint without nano-bubbles (NB) with 10% water added), a one-component curable water-based paint without nano-bubbles (NB) diluted with 15% equivalent of water (one-component curable water-based paint without nano-bubbles (NB) with 15% water added), and a one-component curable water-based paint without nano-bubbles (NB) diluted with 20% equivalent of water (one-component curable water-based paint without nano-bubbles (NB) with 20% water added) were prepared.

[0147] Viscosity (mPa·s) of the nano-bubble-free one-component curable aqueous paint of the example, the nano-bubble-containing one-component curable aqueous paint of Method A, the nano-bubble-containing one-component curable aqueous paint of Method B, the nano-bubble-free one-component curable aqueous paint before water dilution of the comparative example, the nano-bubble-free one-component curable aqueous paint with 1% water added, the nano-bubble-free one-component curable aqueous paint with 5% water added, the nano-bubble-free one-component curable aqueous paint with 10% water added, the nano-bubble-free one-component curable aqueous paint with 15% water added, and the nano-bubble-free one-component curable aqueous paint with 20% water added was measured at room temperature of 20°C.

[0148] Furthermore, viscosity (mpa·s) of the nano-bubble-free one-component curable aqueous paint before heating (20°C), the nano-bubble-free one-component curable aqueous paint heated to 25°C, the nano-bubble-free one-component curable aqueous paint heated to 30°C, the nano-bubble-free one-component curable aqueous paint heated to 40°C, the nano-bubble-free one-component curable aqueous paint heated to 50°C, and the nano-bubble-free one-component curable aqueous paint heated to 60°C was measured.

[0149] As a result of the viscosity measurement, the viscosity of the nano-bubble-free one-component curable aqueous paint of the example was 718 (mpa·s), the viscosity of the nano-bubble-containing one-component curable aqueous paint of Method A of the example was 682 (mpa·s), and the viscosity of the nano-bubble-containing one-component curable aqueous paint of Method B of the example was 99 (mpa·s). The viscosity of the nano-bubble-free one-component curable aqueous paint before water dilution of the comparative example was 718 (mpa·s), the viscosity of the nano-bubble-free one-component curable aqueous paint with 1% water added of the comparative example was 665 (mpa·s), the viscosity of the nano-bubble-free one-component curable aqueous paint with 5% water added of the comparative example was 414 (mpa·s), the viscosity of the nano-bubble-free one-component curable aqueous paint with 10% water added of the comparative example was 258 (mpa·s), the viscosity of the nano-bubble-free one-component curable aqueous paint with 15% water added of the comparative example was 172 (mpa·s), and the viscosity of the nano-bubble-free one-component curable aqueous paint with 20% water added of the comparative example was 102 (mpa·s).

[0150] Furthermore, the viscosity of the one-component curable aqueous paint without nanobubbles before heating (20°C) in the comparative example was 718 (mPa·s), the viscosity of the one-component curable aqueous paint without nanobubbles heated to 25°C in the comparative example was 583 (mPa·s), the viscosity of the one-component curable aqueous paint without nanobubbles heated to 30°C in the comparative example was 385 (mPa·s), the viscosity of the one-component curable aqueous paint without nanobubbles heated to 40°C in the comparative example was 319 (mPa·s), the viscosity of the one-component curable aqueous paint without nanobubbles heated to 50°C in the comparative example was 186 (mPa·s), and the viscosity of the one-component curable aqueous paint without nanobubbles heated to 60°C in the comparative example was 89 (mPa·s).

[0151] As a result of the above, the one-component curable aqueous paint containing nanobubbles of the A method can reduce the water dilution by 1% in the one-component curable aqueous paint by dispersing and mixing nanobubbles in the aqueous paint. The viscosity (99 mPa·s) of the one-component curable aqueous paint containing nanobubbles of the B method greatly exceeds 5% of the recommended dilution amount of the one-component curable aqueous paint, corresponds to a water dilution amount of 20%, and is comparable to the viscosity of the one-component curable aqueous paint heated to 60°C. It was found that the one-component curable aqueous paint of the B method containing more nanobubbles than the one-component curable aqueous paint of the A method has a large decrease in viscosity due to the dispersion and mixing of a large amount of nanobubbles in the aqueous paint. It is considered that the more nanobubbles are introduced into the one-component curable aqueous paint, the lower the viscosity of the aqueous paint will be.

Explanation of symbols

[0152] 10A Paint 10B Paint in which microbubbles and / or nanobubbles are dispersed and mixed 11 Substrate 12 Surfaces (outer surface, inner surface) 13 Coating film 14 Microbubbles 15 Nanobubbles 16 Microbubble-nanobubble mixing device 17 Coating liquid storage water tank 18 Gas supply tank 19 Water supply pump 20 Air supply pump 21 Stationary fluid mixing device (microbubble / nanobubble generator) 22 Coating liquid storage tank 23 Water supply pipeline 24 Air supply pipeline 25 Mixing pipeline 26 Supply pipeline 27 Cylindrical unit 28 Honeycomb structure element (stirring blade)

Claims

1. A paint that is applied to the surface of a substrate to be coated and forms a coating film on the surface of the substrate, wherein microbubbles and / or nanobubbles are introduced into the paint, and the microbubbles and / or the nanobubbles are dispersed and mixed inside the paint at a predetermined concentration. A paint characterized by this.

2. The average particle size D of the microbubbles and / or the nanobubbles ５０ The paint according to claim 1, wherein the average particle size D is 100 μm or less.

3. The average particle size D of the microbubbles and / or the nanobubbles ５０ The paint according to claim 2, wherein the average particle size D is 0.5 μm or less.

4. The microbubbles and / or the nanobubbles contained in 1 ml of the paint are 10 ５ or more and 10 １２ or less per ml. The paint according to claim 3.

5. The paint according to claim 4, wherein the microbubbles and / or the nanobubbles are performing Brownian motion inside the paint.

6. The paint according to claim 5, wherein the viscosity of the paint after introducing the microbubbles and / or the nanobubbles is lower than that of the paint before introducing the microbubbles and / or the nanobubbles.

7. The paint according to claim 6, wherein the viscosity of the paint after introducing the microbubbles and / or the nanobubbles is in the range of 1 to 1000 mPa·s.

8. The gas forming the microbubbles and / or the nanobubbles is any one of air, nitrogen, argon, helium, xenon, neon, krypton, radon, hydrogen, oxygen, ozone, methane, ethylene, propane, butane, acetylene, ethanol, fluorine, chlorine, bromine, iodine, ammonia, hydrogen sulfide, sulfur dioxide, carbon monoxide, carbon dioxide, or a mixed gas obtained by mixing two or more of them. The paint according to claim 7.

9. The paint according to claim 8, wherein the paint is any one of a fluororesin paint, a silicone resin paint, an acrylic resin paint, a urethane resin paint, and an aqueous paint.

10. A paint manufacturing method for manufacturing the paint according to any one of claims 1 to 8, wherein the paint manufacturing method uses any one of a pressure dissolution method, a micropore and porous method, an ejector method, a Venturi method, an ultrasonic method, a static mixer method, a cavitation method, a swirling liquid flow method, a shear method, or combines these methods to introduce the microbubbles and / or the nanobubbles into the paint. A paint manufacturing method characterized by this.

11. The object to be coated with the paint according to any one of claims 1 to 9 is a building, and the paint is applied to the surface of the building, and a coating film is formed on the surface of the building by the cured paint. A building characterized by this.

12. The object to be coated with the paint according to any one of claims 1 to 9 is a moving body, the paint is applied to the surface of the moving body, and a paint film is formed on the surface of the moving body by the cured paint. A moving body characterized by this.

13. The object to be coated with the paint according to any one of claims 1 to 9 is an industrial product, the paint is applied to the surface of the industrial product, and a paint film is formed on the surface of the industrial product by the cured paint. An industrial product characterized by this.

14. The object to be coated with the paint according to any one of claims 1 to 9 is furniture and equipment, the paint is applied to the surface of the furniture and equipment, and a paint film is formed on the surface of the furniture and equipment by the cured paint. Furniture and equipment characterized by this.

Images