Liquid and / or liquid production method

Abstract

To provide liquid whose viscosity can be reduced by reducing usage of a substance which could give an adverse effect to a human body or without using the substance, and whose viscosity can be easily reduced.SOLUTION: Microbubbles and / or nanobubbles having an average bubble diameter D50 of 10 μm or less, which are formed of predetermined gas, are dissolved into liquid used for coating, printing, adhering, or molding and solidifying, where the viscosity of the liquid is reduced compared with the viscosity of the liquid before dissolving microbubbles and / or nanobubbles of gas into the liquid. The viscosity of the liquid after dissolving microbubbles and / or nanobubbles of gas into the liquid is within the range of 1 mPa s or more and 5000 mPa s or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a liquid having a predetermined gas dissolved therein and a method for producing the liquid. [Background technology]

[0002] A coating agent containing a quaternary ammonium salt having an alkoxysilyl group, a silicate oligomer, and a resin containing an alkoxysilyl group has been disclosed (see Patent Document 1). This coating agent can immobilize a silane-modified quaternary ammonium (a quaternary ammonium salt having an alkoxysilyl group), which is an antibacterial and antiviral agent, by covalent bonding.

[0003] a fluorine-containing polymer and a polymer having a first crosslinkable group and a kinematic viscosity of 30 to 150 mm 2 A coating material containing polydimethylsilicone (1 / 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 has been disclosed (see Patent Document 2). By using this coating material, it is possible to create an antifouling coating film with excellent warm water resistance. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-164186 [Patent Document 2] Japanese Patent Publication No. 2023-52716 Summary of the Invention [Problem to be solved by the invention]

[0005] The coating agent disclosed in Patent Document 1 uses aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene, cumene, cymene, and styrene as organic solvents to adjust the viscosity. The paint disclosed in Patent Document 2 uses lacquer thinner, urethane thinner, epoxy thinner, acrylic thinner, and melamine thinner as organic solvents to adjust the viscosity of the paint. The organic solvents used to adjust the viscosity of coating agents and paints volatilize harmful substances such as toluene, xylene, isopropyl alcohol, 1-butanol, and methanol, which can cause physical symptoms such as numbness in the hands and feet, dizziness, chronic bronchitis, peripheral neuritis, optic atrophy, liver damage, and brain damage in humans who inhale them. Therefore, other methods that can adjust the viscosity of coating agents and paints without using organic solvents or while reducing the amount of organic solvent used are desired. Furthermore, water-based paints use water to adjust the viscosity, which contributes to global water shortages.

[0006] An object of the present invention is to provide a liquid whose viscosity can be easily reduced by reducing or not using any substances that may be harmful to the human body. Another object of the present invention is to provide a liquid whose viscosity can be adjusted without using water, and which does not contribute to the global water shortage. [Means for solving the problem]

[0007] The first premise of the present invention for solving the above problems is a liquid used for coating, printing, bonding, or molding and solidifying.

[0008] The liquid of the present invention in the first premise is characterized in that a predetermined gas is dissolved in the liquid to reduce the viscosity of the liquid.

[0009] In one example of the liquid of the present invention, the viscosity of the liquid before dissolving the gas into the liquid is 10 mPa·s or more and 10,000 mPa·s or less, and the viscosity of the liquid after dissolving the gas into the liquid is reduced to 1 / 2 or more and 1 / 10 or less of the viscosity of the liquid before dissolving the gas into the liquid.

[0010] Another example of the liquid of the present invention is a liquid having a viscosity of 1 mPa·s or more and 5000 mPa·s or less after dissolving a gas in the liquid.

[0011] In another example of the liquid of the present invention, the gas dissolved in the liquid is microbubbles and / or nanobubbles, and the average bubble diameter D 50 is 10 μm or less.

[0012] In another example of the liquid of the present invention, nanobubbles are undergoing Brownian motion inside the liquid.

[0013] Another example of the liquid of the present invention is a liquid containing 10 microbubbles and / or nanobubbles in 1 ml of the liquid. 5 10 pieces / ml or more 12 It is less than 1 / ml.

[0014] In another example of the liquid of the present invention, the gas constituting the microbubbles and / or nanobubbles is one or more selected from 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.

[0015] Another example of the liquid of the present invention is a coating liquid or paint that is applied to the surface of a predetermined substrate.

[0016] Another example of the liquid of the present invention is a coating liquid that is a glass-based coating liquid based on silicon oxide (SiO2), and the paint is any one of a fluororesin paint, a silicone resin paint, an acrylic resin paint, a urethane resin paint, and a water-based paint.

[0017] Another example of the liquid of the present invention is the ink used for printing on the printing surface.

[0018] Another example of the liquid of the present invention is a liquid used for adhesion, such as an adhesive.

[0019] Another example of the liquid used in the present invention is a synthetic resin used for forming a film, which is used for forming and solidifying the liquid.

[0020] A second premise of the present invention for solving the above problem is a liquid manufacturing method for manufacturing the liquid.

[0021] A feature of the liquid producing method of the present invention in the second premise is that the liquid producing method dissolves gas in liquid by using one of the pressurized dissolution method, micropore and porous method, Venturi method, ultrasonic method, static mixer method, cavitation method, swirling liquid flow method, and shear method, or by combining at least two of these methods.

[0022] In one example of the liquid production method of the present invention, the gas is microbubbles and / or nanobubbles, and the liquid production method utilizes any one of these methods or a combination of at least two of these methods to dissolve the microbubbles and / or nanobubbles in the liquid. [Effects of the Invention]

[0023] According to the liquid of the present invention, by dispersing and dissolving a specific gas within the liquid, the gas severs or disrupts the bonds between the molecules of the liquid, thereby weakening the interactions between the molecules of the liquid. This allows the viscosity of liquids used for coating, printing, adhesion, and molding / solidification to be reduced, and the viscosity can be easily adjusted by using the gas. By adjusting the average bubble diameter of the gas dispersed or dissolved in the liquid or the gas content, high-viscosity or medium-viscosity liquids can be converted into low-viscosity liquids, and the degree of viscosity reduction or the degree of low viscosity of the liquid can be adjusted. The viscosity of the liquid can be reduced by reducing the amount of harmful substances such as organic solvents that may have adverse effects on the human body, or by not using harmful substances.

[0024] The viscosity of the liquid before the gas is dispersed and dissolved in it is 10 mPa s or more and 10,000 mPa s or less, and the viscosity of the liquid after the gas is dispersed and dissolved in it is reduced to 1 / 2 or more and 1 / 10 or less of the viscosity of the liquid before the gas is dissolved in it. Therefore, by dispersing and dissolving a specific gas in the liquid, the bonds between the molecules of the liquid are cut or separated by the gas, and the severing or separating of the bonds between the molecules of the liquid can weaken the interactions between the molecules of the liquid, and the viscosity of the liquid used for coating, printing, bonding, and molding and solidifying can be reduced to within the above range.

[0025] The viscosity of the liquid after dissolving and dispersing a gas in it is 1 mPa s or more and 5000 mPa s or less. By dispersing and dissolving a specific gas in the liquid, the gas cuts or separates the bonds between the molecules of the liquid, and the cutting or separation of the bonds between the molecules of the liquid weakens the interactions between the molecules of the liquid, making it possible to reduce the viscosity of liquids used for coating, printing, bonding, and molding and solidifying to within the above range.

[0026] The liquid contains microbubbles and / or nanobubbles dissolved therein, and the average bubble diameter D of the microbubbles and / or nanobubbles is 50Since the average diameter D of the bubbles dispersed and dissolved in the liquid is 10 μm or less, 50 The microbubbles and / or nanobubbles break or disrupt bonds between molecules in the liquid, weakening the interactions between molecules and ensuring that the viscosity of the liquid after dissolving and dispersing microbubbles and / or nanobubbles is lower than that of the liquid before dissolving and dispersing. This makes it easy to reduce the viscosity of liquids used for coating, printing, adhesion, and molding / solidification. By adjusting the average bubble diameter of the microbubbles and / or nanobubbles dispersed and dissolved in the liquid and the content of the microbubbles and / or nanobubbles, high-viscosity or medium-viscosity liquids can be made low-viscosity, and the degree of viscosity reduction or the degree of viscosity reduction of the liquid can be adjusted. The viscosity of the liquid can be reduced by reducing the amount of harmful substances, such as organic solvents, that may have adverse effects on the human body, or by not using harmful substances.

[0027] Because nanobubbles dispersed and dissolved in a liquid undergo Brownian motion within the liquid, the Brownian motion of the nanobubbles within the liquid severs or disrupts the bonds between the liquid's molecules, weakening the interactions between the liquid's molecules. This reliably reduces the viscosity of the liquid after dissolving and dispersing microbubbles and / or nanobubbles compared to the liquid before dissolving and dispersing. This makes it easy to reduce the viscosity of liquids used for coating, printing, adhesion, and molding / solidification. By adjusting the average bubble diameter of the microbubbles and / or nanobubbles undergoing Brownian motion dispersed and dissolved in the liquid, or the content of the microbubbles and / or nanobubbles undergoing Brownian motion, high-viscosity or medium-viscosity liquids can be reduced to low-viscosity liquids, and the degree of viscosity reduction or the degree of viscosity reduction of the liquid can be adjusted. The viscosity of the liquid can be reduced by reducing the amount of harmful substances, such as organic solvents, that may have adverse effects on the human body, or without using harmful substances.

[0028] The liquid contains 10 microbubbles and / or nanobubbles per ml. 5 10 pieces / ml or more 12 Because the concentration is less than 1 / mL, the microbubbles (microbubbles) and / or ultrafine nanobubbles (nanobubbles) dispersed and dissolved in the liquid in large quantities at a predetermined concentration sever or disrupt the bonds between the molecules of the liquid, thereby weakening the interactions between the molecules of the liquid. This reliably reduces the viscosity of the liquid after dissolving and dispersing the microbubbles and / or nanobubbles compared to the liquid before dissolving and dispersing them, thereby easily reducing the viscosity of liquids used for coating, printing, bonding, and molding / solidification. By adjusting the content of the microbubbles and / or nanobubbles dispersed and dissolved in the liquid within the above range, high- or medium-viscosity liquids can be converted to low-viscosity liquids, and the degree of viscosity reduction or the degree of viscosity reduction of the liquid can be adjusted. The viscosity of the liquid can be reduced by reducing the amount of harmful substances, such as organic solvents, that may be harmful to the human body, or by not using harmful substances.

[0029] The microbubbles and / or nanobubbles in a liquid are composed of one or more gases selected from the group consisting 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. The microbubbles and / or nanobubbles of these gases or mixtures of these gases sever or disrupt the bonds between molecules in the liquid, thereby weakening the interactions between molecules. This reliably reduces the viscosity of the liquid after dissolving and dissolving the microbubbles and / or nanobubbles of these gases compared to the liquid before dissolving and dispersing them. This allows for easy reduction in the viscosity of liquids used for coating, printing, bonding, and molding / solidification. The viscosity of a liquid varies depending on the type of gas that forms the microbubbles or nanobubbles, and the viscosity can be finely adjusted by selecting the gas used. The viscosity of the liquid can be reduced by reducing the amount of harmful substances such as organic solvents that may have adverse effects on the human body, or by not using any harmful substances.

[0030] When the liquid is a coating liquid or paint to be applied to the surface of a given substrate, the microbubbles and / or nanobubbles sever or disrupt the bonds between the molecules of the coating liquid or paint, thereby weakening the interactions between the molecules of the coating liquid or paint. This allows the viscosity of the coating liquid or paint after dissolving and dissolving the microbubbles and / or nanobubbles to be lower than that of the coating liquid or paint before dissolving and dissolving, thereby easily reducing the viscosity of the coating liquid or paint to be applied to the surface of the substrate. By adjusting the average bubble diameter of the microbubbles and / or nanobubbles dispersed and dissolved in the coating liquid or paint, or the content of the microbubbles and / or nanobubbles, the coating liquid or paint can be converted from a high- or medium-viscosity coating liquid or paint to a low-viscosity one, and the degree of viscosity reduction or the degree of viscosity reduction of the coating liquid or paint can be adjusted. The viscosity of the coating liquid or paint can be reduced by reducing the amount of harmful substances, such as organic solvents, that may be harmful to the human body, or by not using harmful substances. By using microbubbles and / or nanobubbles to adjust the viscosity of paint, particularly in low-temperature environments where the viscosity of paint is high and where a larger amount of thinner or the like is used to adjust the viscosity, the viscosity of the paint can be reduced without adversely affecting the human body by using paint containing microbubbles and / or nanobubbles that dissolve in large amounts in low-temperature environments.

[0031] When the liquid is a silicon oxide (SiO2)-based glass-based coating liquid, or is any of a fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, and water-based paint, the microbubbles and / or nanobubbles cut or disrupt the bonds between the molecules of the glass-based coating liquid or the paint, and the cutting or disruption of the bonds between the molecules of the glass-based coating liquid or the paint can weaken the interactions between the molecules of the glass-based coating liquid, or the fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, and water-based paint, and the viscosity of the glass-based coating liquid or the paint after the microbubbles and / or nanobubbles have been dispersed and dissolved can be made lower than that of the glass-based coating liquid or the paint before the dispersion and dissolution, making it easy to reduce the viscosity of the glass-based coating liquid, or the fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, and water-based paint to be applied to the surface of a substrate. By adjusting the average bubble size or the content of microbubbles and / or nanobubbles dispersed and dissolved in a glass-based coating liquid, or a fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, or water-based paint, it is possible to convert a high- or medium-viscosity glass-based coating liquid or paint into a low-viscosity one, and to adjust the degree of viscosity reduction or the degree of viscosity reduction of the glass-based coating liquid or paint. The viscosity of the glass-based coating liquid, fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, or water-based paint can be reduced by reducing the amount of harmful substances such as organic solvents that may have adverse effects on the human body, or by reducing the use of harmful substances without using any of the harmful substances.Fluorine resin paints, silicone resin paints, acrylic resin paints, and urethane resin paints use microbubbles and / or nanobubbles to adjust the viscosity of these paints, especially in low-temperature environments where the viscosity of fluororesin paints, silicone resin paints, acrylic resin paints, and urethane resin paints is high, and in situations where more thinner or the like is used to adjust the viscosity, by using fluororesin paints, silicone resin paints, acrylic resin paints, and urethane resin paints containing microbubbles and / or nanobubbles that dissolve in large amounts in low-temperature environments, the viscosity of the fluororesin paints, silicone resin paints, acrylic resin paints, and urethane resin paints can be reduced without adversely affecting the human body. Water-based paints can adjust their viscosity without using water, and because they do not require water for viscosity adjustment, they are useful in areas with water shortages or in environments where water is unavailable, and do not contribute to the global water shortage.

[0032] When the liquid is ink to be printed on a printing surface, microbubbles and / or nanobubbles sever or disrupt the bonds between the ink molecules, weakening the interactions between the ink molecules and lowering the viscosity of the ink after dispersing and dissolving microbubbles and / or nanobubbles compared to the ink before dispersing and dissolving, thereby reducing the viscosity of the ink to be printed on a printing surface. By adjusting the average bubble diameter of the microbubbles and / or nanobubbles dispersed and dissolved in the ink or the content of microbubbles and / or nanobubbles, high-viscosity or medium-viscosity inks can be made low-viscosity, and the degree of reduction in the viscosity of the ink or the degree of low viscosity of the ink can be adjusted. The viscosity of the ink can be reduced by reducing the amount of harmful substances, such as organic solvents, that may have adverse effects on the human body, or by not using harmful substances.

[0033] When the liquid is an adhesive, the microbubbles and / or nanobubbles can sever or disrupt the bonds between the adhesive molecules, weakening the interactions between the adhesive molecules and lowering the viscosity of the adhesive after dispersing and dissolving the microbubbles and / or nanobubbles compared to the adhesive before dispersing and dissolving them, thereby reducing the viscosity of the adhesive. By adjusting the average bubble diameter of the microbubbles and / or nanobubbles dispersed and dissolved in the adhesive or the content of the microbubbles and / or nanobubbles, the adhesive can be converted from a high-viscosity or medium-viscosity adhesive to a low-viscosity one, and the degree of viscosity reduction or the degree of viscosity reduction of the adhesive can be adjusted. The viscosity of the adhesive can be reduced by reducing the amount of harmful substances, such as organic solvents, that may be harmful to the human body, or by not using harmful substances.

[0034] When the liquid is a synthetic resin used for film formation, the microbubbles and / or nanobubbles sever or disrupt the bonds between the molecules of the synthetic resin, weakening the intermolecular interactions of the synthetic resin. This can lower the viscosity of the synthetic resin after dissolving and dissolving the microbubbles and / or nanobubbles compared to the synthetic resin before dissolving and dispersing, thereby reducing the viscosity of the synthetic resin used for film formation. By adjusting the average bubble diameter of the microbubbles and / or nanobubbles dispersed and dissolved in the synthetic resin for film formation and the content of the microbubbles and / or nanobubbles, high- or medium-viscosity synthetic resins can be made low-viscosity, and the degree of viscosity reduction or the degree of viscosity reduction of the synthetic resin can be adjusted. The viscosity of synthetic resins for film formation can be reduced by reducing the amount of harmful substances, such as organic solvents, that may be harmful to the human body, or by not using harmful substances.

[0035] According to the liquid production method of the present invention, a predetermined gas is dispersed and dissolved in a liquid by using one or at least two of the following methods: pressurized dissolution method, micropore and porous method, Venturi method, ultrasonic method, static mixer method, cavitation method, swirling liquid flow method, and shear method. Therefore, by using these methods, the gas can be reliably dispersed and dissolved inside the liquid, and a liquid can be produced that can have a low viscosity.

[0036] In the liquid production method, the gas is microbubbles and / or nanobubbles, and the microbubbles and / or nanobubbles are dispersed and dissolved in the liquid by using one or at least two of the following methods: pressurized dissolution method, micropore and porous method, Venturi method, ultrasonic method, static mixer method, cavitation method, swirling liquid flow method, and shear method. Therefore, by using these methods, the microbubbles and / or nanobubbles can be reliably dispersed and dissolved inside the liquid, and a liquid with a low viscosity can be produced. [Brief explanation of the drawings]

[0037] [Figure 1] FIG. 1 is a structural diagram showing an example of a gas dissolving device that dissolves and disperses microbubbles and / or nanobubbles in a predetermined liquid. [Figure 2] FIG. 1 is a configuration diagram showing an example of a static fluid mixing device among gas dissolving devices. [Figure 3] An image showing an example of a liquid (glass-based coating liquid, paint, ink, adhesive, synthetic resin for film molding) in which microbubbles and / or nanobubbles are dissolved. [Figure 4] FIG. 2 is an image diagram showing an example of the structure of an inorganic coating film formed on the surface of a substrate. [Figure 5] An image showing an example of the structure of an organic / inorganic hybrid coating film formed on the surface of a substrate. [Figure 6] 1A and 1B are diagrams illustrating the mechanism of viscosity reduction of a liquid. [Figure 7]FIG. 1 is a diagram showing the solubility of gas (microbubbles and / or nanobubbles) depending on the size of the bubbles. [Figure 8] A diagram showing the correlation between viscosity and temperature of liquids (glass-based coating liquids, paints, inks, adhesives, synthetic resins for film molding). [Figure 9] FIG. 1 is a diagram showing the correlation between the solubility of gas (microbubbles and / or nanobubbles) and temperature. [Figure 10] An image showing an example of the structure of a fluororesin paint. [Figure 11] An image showing an example of the structure of silicone resin paint. DETAILED DESCRIPTION OF THE INVENTION

[0038] The liquid and liquid manufacturing method according to the present invention will be described in detail below with reference to the accompanying drawings. FIG. 1 is a structural diagram illustrating an example of a gas dissolving device 15 that dissolves and disperses microbubbles 13 and / or nanobubbles 14 in a predetermined liquid 10. FIG. 2 is a structural diagram illustrating an example of a static fluid mixer 20 included in the gas dissolving device 15. FIG. 3 is a conceptual diagram illustrating an example of a liquid 10 (glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, or synthetic resin for film formation 10e) in which microbubbles 13 and / or nanobubbles 14 have been dissolved. FIG. 4 is a conceptual diagram illustrating an example of the structure of an inorganic coating film 28a formed on the surface 12 of a substrate 11. FIG. 5 is a conceptual diagram illustrating an example of the structure of an organic / inorganic hybrid coating film 28b formed on the surface 12 of a substrate 11. FIG. 6 is a diagram illustrating the mechanism of viscosity reduction in the liquid 10. FIG. 7 is a diagram illustrating the solubility of gas (microbubbles 13 and / or nanobubbles 14) depending on the size of the bubbles. FIG. 8 is a graph showing the correlation between the viscosity of a liquid 10 (glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e) and temperature, and FIG. 9 is a graph showing the correlation between the solubility of a gas (microbubbles 13 and / or nanobubbles 14) and temperature. In FIG. 3, the microbubbles 13 and nanobubbles 14 are illustrated as visible images, but in reality, it is difficult to visually observe the microbubbles 13 and nanobubbles 14. In FIG. 7, the vertical axis represents the amount of dissolved oxygen (DO (mg / L)) and the horizontal axis represents the circulation time (min).

[0039] A gas dissolving device 15 is used to dissolve (introduce) microbubbles 13 and / or nanobubbles 14 of a predetermined gas into a predetermined liquid 10. The liquid 10 includes a coating liquid 10a or paint 10b to be applied to the surface 12 of the substrate 11, and an ink 10c to be printed on the printing surface 12. The liquid 10 also includes an adhesive 10d and a synthetic resin for film formation 10e used to form a film. The coating liquid 10a includes a glass-based coating liquid 10a based on silicon oxide (SiO2), but also includes resin-based coating agents such as nylon coating agents, PVC coating agents (vinyl chloride coating agents), epoxy coating agents, polyethylene coating agents (PE coating agents), fluororesin coating agents, and silicone resin coating agents. The paint 10b includes fluororesin paint, silicone resin paint (silicone resin), acrylic resin paint, urethane resin paint, and water-based paint.

[0040] Before the microbubbles 13 and / or nanobubbles 14 are introduced, the glass-based coating liquid 10a is composed of a siloxane-based solution, an alkyl silicate condensate, and an inert organic solvent as its main components. In the glass-based coating liquid 10a, the siloxane-based solution and the alkyl silicate condensate are diluted with the inert organic solvent. The glass-based coating liquid 10a is prepared by mixing and stirring the siloxane-based solution, the alkyl silicate condensate, and a predetermined inert organic solvent in a predetermined ratio. The microbubbles 13 and / or nanobubbles 14 are introduced into the glass-based coating liquid 10a by a gas dissolving device 15, and the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved (dispersed and mixed) therein (see FIG. 3 ). The glass-based coating liquid 10a may contain only the microbubbles 13, only the nanobubbles 14, or both the microbubbles 13 and the nanobubbles 14.

[0041] The gas that constitutes the microbubbles 13 and / or nanobubbles 14 dissolved in the glass-based coating liquid 10a is selected from the group consisting 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, or a mixed gas of two or more of these gases.

[0042] The viscosity of glass-based coating liquid 10a before the introduction of microbubbles 13 and / or nanobubbles 14 is in the range of 10 mPa·s to 10,000 mPa·s. By dispersing and dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into glass-based coating liquid 10a, the microbubbles 13 and / or nanobubbles 14 sever or disrupt the bonds between molecules of coating liquid 10a, as shown in FIG. 6 , and the severing or disruption of the bonds between molecules of coating liquid 10a weakens the interactions between molecules of coating liquid 10a. The viscosity of glass-based coating liquid 10a after the introduction of microbubbles 13 and / or nanobubbles 14 is reduced to between 1 / 2 and 1 / 10 of that of glass-based coating liquid 10a before the introduction of microbubbles 13 and / or nanobubbles 14. The viscosity of the glass-based coating liquid 10a after the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved is in the range of 1 mPa·s to 5000 mPa·s.

[0043] The microbubbles 13 and / or nanobubbles 14 dispersed and dissolved in the glass-based coating liquid 10a have an average bubble diameter D 50 The microbubbles 13 dispersed and dissolved in the glass-based coating liquid 10a have an average bubble diameter D 50 is 10 μm or less, preferably, the average bubble diameter D 50 is 1 μm or less, and more preferably, the average bubble diameter D 50 The nanobubbles 14, which are ultrafine bubbles dispersed and dissolved in the glass-based coating liquid 10a, have an average bubble diameter D 50The nanobubbles 14 undergo Brownian motion within the glass-based coating liquid 10a. The microbubbles 13 and / or nanobubbles 14 contained in 1 ml of the glass-based coating liquid 10a are in the range of 1 to 800 nm, and preferably in the range of 1 to 300 nm. 5 10 pieces / ml or more 12 The range is less than 1 / ml.

[0044] As shown in Fig. 7, the microbubbles 13 and nanobubbles 14 dispersed and dissolved in the glass-based coating liquid 10a are tiny bubbles, and the microbubbles 13 and nanobubbles 14 dissolve in the glass-based coating liquid 10a to a degree exceeding their saturated solubility at equilibrium. Furthermore, as shown in Fig. 8, the viscosity of the glass-based coating liquid 10a containing the dispersed microbubbles 13 and / or nanobubbles 14 increases as the temperature decreases, and decreases as the temperature increases. Furthermore, as shown in Fig. 9, the solubility of the microbubbles 13 and / or nanobubbles 14 in the glass-based coating liquid 10a increases as the temperature of the glass-based coating liquid 10a decreases, and decreases as the temperature increases.

[0045] The siloxane-based solution that forms the glass-based coating liquid 10a can be an inorganic polysilazane such as a Si-N-based perhydropolysilazane solution (perhydropolysilazane solution), a Si-CN-based organopolysilazane solution, a Si-C-based polycarbosilane solution, a SiC-O-based organopolysilazane solution, a Si-BCN-based organopolysilazane solution, a Si-Ti-N-based organopolysilazane solution, or an organopolysiloxane.

[0046] The inorganic polysilazane is represented by the general formula (Chemical Formula 1).

[0047] [ka] Examples of inorganic polysilazanes include perhydropolysilazanes that include a linear structure having structural units, have a molecular weight of 690 to 2,000, have 3 to 10 SiH groups per molecule, and have element ratios of Si: 59 to 61, N: 31 to 34, and H: 6.5 to 7.5 by weight, as determined by chemical analysis, and have an average molecular weight in the range of 3,000 to 20,000 in terms of polystyrene.

[0048] Perhydropolysilazane contains chain and cyclic portions in its molecule and is represented by the following chemical formula (Chemical Formula 2).

[0049] [ka] An example of the structure of perhydropolysilazane is represented by the following chemical formula (Chemical Formula 3).

[0050] [ka] Another example of the perhydropolysilazane compound group is represented by the following general formula (Chemical Formula 4), which contains a Si-N bond and a functional group (R 1 ~R 3 ) and is a polymer formed from -(SiR1R2-NR3)- units, and at least one of the functional groups R1 and R2 directly bonded to Si is an organic polymer formed from an organic functional group such as an alkyl group having carbon (C).

[0051] [ka] Perhydropolysilazane is an organic compound with a functional group (R 1 ~R 3The content of methyl groups (CH3), which is one of the functional groups, is 50% or more. Furthermore, perhydropolysilazane may not only be a polymer formed from one type of -(SiR1R2-NR3)- unit, but also a polymer formed from multiple types of -(SiR1R2-NR3)- units with different compositions of functional groups (R1 to R3). Furthermore, perhydropolysilazane may be a polymer having a chain, cyclic or crosslinked structure, or may be a polymer having a combination of these structures. R 1 , R 2 , R 3 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a group other than these groups in which the group directly bonded to the silicon atom is carbon, an alkylsilyl group, an alkylamino group, or an alkoxy group. 1 , R 2 , R 3 At least one of the is a hydrogen atom.

[0052] As an example, perhydropolysilazane (A) is a compound having a -(SiH(CH3)-NH)- unit, a -(Si(CH3)2-NH)- unit, a -(SiR 1 It is a polymer containing (CH3)-NR3)- units. 1 (CH3)-NR 3 The functional group R1 in the )-unit is H or CH3, and the functional group R3 directly bonded to N is an organic functional group that promotes the reaction. The inclusion of perhydropolysilazane (A) in the glass-based coating liquid promotes the reaction after the glass-based coating liquid 10a is coated on the surface 12 of the substrate 11, and enables the inorganic coating film 28a or the organic / inorganic hybrid coating film 28b to be formed on the surface 12 of the substrate 11 at an early stage.

[0053] [ka] Another example of perhydropolysilazane (B) is a compound having a -(SiH(CH3)-NH)- unit, a -(SiR 1A polymer containing a (CH3)-NH)-unit, and -(SiR 1 The functional group R of the (CH3)-NH)-unit 1 is an organic functional group that realizes high heat resistance. By including perhydropolysilazane (B) in the glass-based coating liquid 14, the heat resistance of the inorganic coating film 28a or the organic / inorganic hybrid coating film 28b covering the surface 12 of the substrate 11 can be enhanced.

[0054]

Chemical formula

[0055] The organopolysilazane has a hydrogen atom at R 1 and R 2 and an organic group at R 3 . A polysilazane having a cyclic structure with a polymerization degree of 3 to 5 with -(R 2 SiHNH)- as a repeating unit, a polysilazane having both a chain structure and a cyclic structure in a molecule represented by the chemical formula of (R 3 SiHNH) x 〔(R 2 SiH) 1.5 N〕 1-X (0.4 < X < 1), and in the above general formula (Chemical formula 4), R 1 has a hydrogen atom, and R 2 , R 3Polysilazane having an organic group in R 1 and R 2 an organic group, R 3 has a hydrogen atom in -(R 1 R 2 SiNR 3 )- as a repeating unit, there are polysilazanes that mainly have a cyclic structure with a degree of polymerization of 3 to 5.

[0056] For example, an organopolysilazane having a crosslinked structure other than that of the above general formula (Chemical Formula 4) in the molecule is represented by the following general formula (Chemical Formula 7).

[0057] [ka] Also, for example, R 1 Polysilazane R with a crosslinked structure obtained by ammonia decomposition of SiX3 (X: halogen) 1 Si(NH) x , R 1 SiX3 and R 2 The polysilazane structure obtained by co-ammoniolysis of 2SiX2 is represented by the following general formula (Chemical Formula 8).

[0058] [ka] The organopolysiloxane may be, for example, a polysiloxane having an average unit formula (A): (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d There is a polymer having the average unit formula (A): 1 are each independently a monovalent organic group, and are preferably a monovalent ethylenically unsaturated group, a monovalent hydrocarbon group (excluding ethylenically unsaturated groups), or a monovalent substituted hydrocarbon group (excluding ethylenically unsaturated groups). 1The number of carbon atoms in R is preferably 1 or more and 8 or less, more preferably 1 or more and 6 or less. The monovalent substituted hydrocarbon group has a hydrocarbon group as a basic skeleton and contains at least one functional group selected from the group consisting of, for example, a hydroxy group, a mercapto group, an amino group, an isothiocyanate group, a nitro group, and a carbonyl group. 1 is preferably a monovalent ethylenically unsaturated group or a monovalent hydrocarbon group, more preferably a monovalent ethylenically unsaturated group.

[0059] Examples of the monovalent ethylenically unsaturated group include alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl. The number of carbon atoms in the alkenyl group is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, and even more preferably 2 or more and 3 or less. Examples of the monovalent ethylenically unsaturated group include (meth)acryloyloxyalkyl groups, i.e., groups represented by the formula (B): -R 12 -OC(=O)-CR 11 There are also groups represented by =CH2. Specifically, there are acryloyloxypropyl groups and methacryloyloxypropyl groups. R in formula (B) 11 is a hydrogen atom or a methyl group, and R 12 is an alkanediyl group, preferably an alkanediyl group having 1 to 5 carbon atoms. Note that (meth)acrylic is used as a general term for acrylic and methacrylic, and (meth)acryloyl is used as a general term for acryloyl and methacryloyl.

[0060] Among the monovalent ethylenically unsaturated groups, alkenyl groups are preferred, vinyl groups and allyl groups are preferred, and vinyl groups are more preferred. Examples of monovalent hydrocarbon groups include alkyl groups such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, and heptyl groups; aryl groups such as phenyl groups, tolyl groups, and xylyl groups; and aralkyl groups such as benzyl groups and phenethyl groups. The number of carbon atoms in the monovalent hydrocarbon group is preferably 1 to 8, more preferably 1 to 5, and even more preferably 1 to 3.

[0061] Examples of monovalent substituted hydrocarbon groups include a 3-mercaptopropyl group (-(CH2)3-SH) and a 3-aminopropyl group (-(CH2)3-NH2). R 1 From the viewpoint of fine particle formation, each of the groups is preferably an alkyl group or an alkenyl group, more preferably an alkyl group having 1 to 3 carbon atoms, a vinyl group, or an allyl group, and even more preferably a methyl group or a vinyl group.

[0062] In one molecule of organopolysiloxane having the average unit formula (A), at least a portion of R 1 is a group containing a functional group (L) such as a monovalent ethylenically unsaturated group, an aryl group, or an aralkyl group, and is preferably a monovalent ethylenically unsaturated group, more preferably an alkenyl group. The total proportion of the monovalent ethylenically unsaturated group, aryl group, or aralkyl group is determined based on the total R in one molecule of the organopolysiloxane. 1 Based on this, it is preferably 50 mol % or more, more preferably 60 mol % or more, even more preferably 70 mol % or more, still more preferably 80 mol % or more, and particularly preferably 90 mol % or more. The monovalent ethylenically unsaturated group, aryl group, or aralkyl group is a hydrophobic group containing a nonionic functional group capable of coordinating to a metal ion.

[0063] In the average unit formula (A), a, b, c, and d represent the respective constituent units (R 1 3SiO 1 / 2 ), (R 1 2SiO 2 / 2 ), (R 1 SiO 3 / 2 ) and (SiO 4 / 2 The sum of the mole fractions of each structural unit, a, b, c, and d, is 1. a represents the average value of the mole fraction of R 1 3SiO 1 / 2 a is the mole fraction of siloxane units represented by (M units). a is 0 or more and 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less, even more preferably 0.2 or less, and particularly preferably 0.1 or less.

[0064] b is R 1 2SiO2 / 2 b is the mole fraction of siloxane units represented by R (D units). b is 0 or more and 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less, even more preferably 0.2 or less, and particularly preferably 0.1 or less. c is the mole fraction of siloxane units represented by R 1 SiO 3 / 2 is the mole fraction of siloxane units represented by (T units). c is 0.3 or more and 1 or less, preferably 0.4 or more, 0.5 or more, or 0.6 or more, more preferably 0.7 or more, even more preferably 0.8 or more, and particularly preferably 0.9 or more.

[0065] d is SiO 4 / 2 is the mole fraction of siloxane units represented by (Q units). d is 0 or more and 0.7 or less, preferably 0.6 or less, 0.5 or less, or 0.4 or less, more preferably 0.3 or less, even more preferably 0.2 or less, and particularly preferably 0.1 or less. The sum of c and d, which represents the total number of branched structural units, is preferably 0.6 or more, more preferably 0.7 or more, even more preferably 0.8 or more, and particularly preferably 0.9 or more.

[0066] The organopolysiloxane is a polysiloxane having a constitutional unit (R 1 3SiO 1 / 2 When the structural unit (R) in the average unit formula (A) is present, it may contain only one type of structural unit, or may contain two or more types of structural units. 1 2SiO 2 / 2 ) and (R 1 SiO 3 / 2 The same applies to the R 1 At least part of 2 In the average unit formula (A), R may be replaced by O. 2 is a hydrogen atom or an alkyl group. 2 O represents a hydroxy group or an alkoxy group bonded to a silicon atom contained in the organopolysiloxane skeleton. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. The number of carbon atoms in the alkyl group is preferably 1 or more and 3 or less.

[0067] The above R in each of the structural units 1 At least part of 2 The amount of the structural units substituted with O is preferably 0 or more and 0.10 or less, more preferably 0 or more and 0.05 or less, and even more preferably 0 or more and 0.03 or less, relative to the sum of the molar fractions of the structural units, a, b, c, and d, which is 1. The alkoxy group in the structural unit is, for example, an alkoxy group that is a hydrolyzable group contained in an alkoxysilane described below, and remains in the molecule without undergoing hydrolysis and polycondensation. The hydroxy group in this structural unit is, for example, a hydroxy group that remains in the molecule after hydrolysis of an alkoxy group without undergoing polycondensation.

[0068] The organopolysiloxane is preferably a silsesquioxane. Silsesquioxane has a main chain skeleton consisting of Si—O bonds and a main structural unit (R 1 SiO 3 / 2 ) units, and the value of c is 0.7 or greater. Examples of the silsesquioxane structure include a random structure, a complete cage structure, an incomplete cage structure, and a ladder structure. Among these, silsesquioxanes having a random structure are preferred from the viewpoint of ease of production.

[0069] The structural unit (R 1 3SiO 1 / 2 As the alkoxysilane forming R 1 3Si(OR 2 Specific examples thereof include methoxydimethylvinylsilane, ethoxydimethylvinylsilane, methoxydimethylphenylsilane, and ethoxydimethylphenylsilane; and methoxytrimethylsilane and ethoxytrimethylsilane.

[0070] The structural unit (R 1 2SiO 2 / 2 As the alkoxysilane forming R 1 2Si(OR 2) 2. Specific examples thereof include dimethoxymethylvinylsilane, diethoxymethylvinylsilane, and dimethoxybenzylmethylsilane; as well as dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, dipropoxydimethylsilane, and dipropoxydiethylsilane.

[0071] The structural unit (R 1 SiO 3 / 2 As the alkoxysilane forming R 1 Si(OR 2 )3. Specific examples thereof include trimethoxyvinylsilane, triethoxyvinylsilane, trimethoxyallylsilane, triethoxyallylsilane, (3-(meth)acryloyloxypropyl)trimethoxysilane, and (3-(meth)acryloyloxypropyl)triethoxysilane; as well as methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and butyltrimethoxysilane. The structural unit (SiO 4 / 2 As the alkoxysilane that forms Si(OR 2 ) 4. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.

[0072] The alkyl silicate condensate is a condensate (mixture) of one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate, tetra-i-propyl orthosilicate, tetra-n-butyl orthosilicate, tetra-sec-butyl orthosilicate, methyl polysilicate, and ethyl polysilicate. The inert organic solvent is inert to the organic polysilazane, siloxane, and alkyl silicate condensate, and is selected from dibutyl ether, turpentine oil, benzene, toluene, xylene, and propylene glycol monomethyl ether acetate.

[0073] In the glass-based coating liquid 10a, the blending ratio of silicon oxide (inorganic polysilazane, organopolysilazane, organopolysiloxane) to the total mass is in the range of 30 to 60 mass%, the blending ratio of alkyl silicate condensate to the total mass is in the range of 10 to 15 mass%, and the blending ratio of inert organic solvent to the total mass is in the range of 30 to 60 mass%. If the blending ratio of silicon oxide (organosilicon material) is less than 30 mass%, the silicon oxide content is low, and it is not possible to form the desired inorganic coating film 28a or organic / inorganic hybrid coating film 28b with excellent flexibility, impact resistance, and corrosion resistance on the surface 12 of the substrate 11. If the blending ratio of silicon oxide exceeds 60 mass%, the viscosity of the glass-based coating liquid 10a increases more than necessary, and the thickness of the inorganic coating film 28a or organic / inorganic hybrid coating film 28b becomes more than necessary. Since the glass-based coating liquid 10a has a silicon oxide content within the above range relative to its total mass, it is possible to form an appropriate inorganic coating film 28a or organic / inorganic hybrid coating film 28b having excellent flexibility, impact resistance, and corrosion resistance on the surface 12 of the substrate 11.

[0074] If the alkyl silicate condensate content is less than 10% by mass, the alkyl silicate condensate's cross-linking effect is weak, and sufficient cross-linking structures are not formed in the inorganic coating film 28a or the organic / inorganic hybrid coating film 28b. If the alkyl silicate condensate content exceeds 15% by mass, unnecessary cross-linking structures are formed in the inorganic coating film 28a or the organic / inorganic hybrid coating film 28b, resulting in excessive flexibility of the coating films 28a and 28b. Since the glass-based coating liquid 10a has an alkyl silicate condensate content within the above range relative to its total mass, the coating liquid 10a can be used to produce an inorganic coating film 28a or an organic / inorganic hybrid coating film 28b with an appropriate cross-linking structure and flexibility.

[0075] If the blending ratio of the inert organic solvent is less than 30% by mass, the viscosity of the glass-based coating liquid 10a becomes high, resulting in an unnecessarily thick inorganic coating film 28a or organic / inorganic hybrid coating film 28b formed from the coating liquid 10a. If the blending ratio of the inert organic solvent exceeds 60% by mass, the viscosity of the glass-based coating liquid 10a becomes unnecessarily low, making it impossible to form the desired inorganic coating film 28a or organic / inorganic hybrid coating film 28b with excellent flexibility, impact resistance, and corrosion resistance on the surface 12 of the substrate 11. Because the blending ratio of the inert organic solvent to the total mass of the glass-based coating liquid 10a is within the above range, the coating liquid 10a can be used to form an inorganic coating film 28a or organic / inorganic hybrid coating film 28b with the appropriate viscosity and excellent flexibility, impact resistance, and corrosion resistance on the surface 12 of the substrate 11.

[0076] When the glass-based coating liquid 10a is coated onto the surface 12 of the substrate 11 to be coated, it chemically reacts with water to form (deposit) an ultra-thin inorganic coating film 28a or organic / inorganic hybrid coating film 28b. The inorganic coating film 28a or organic / inorganic hybrid coating film 28b is deposited as a coating having an average thickness in the range of 5 nm to 20 μm, preferably 50 nm to 1 μm. The inorganic coating film 28a or organic / inorganic hybrid coating film 28b has high density and high hardness (pencil hardness of approximately 6H to 9H).

[0077] In forming (forming) the inorganic coating film 28a using the glass-based coating liquid 10a, the surface 12 of the substrate 11 is coated with the glass-based coating liquid 10a, and then the surface 12 of the substrate 11 is irradiated with ultraviolet light and infrared light to heat the surface 12 of the substrate 11 to 400°C or higher. In forming (forming) the organic / inorganic hybrid coating film 28b using the glass-based coating liquid 10a, the surface 12 of the substrate 11 is coated with the glass-based coating liquid 10a, and then the surface 12 of the substrate 11 is left at room temperature (normal temperature) for a predetermined time (24 hours or more) without heating. Alternatively, after coating the surface 12 of the substrate 11 with the glass-based coating liquid 10a, the surface 12 of the substrate 11 is left at room temperature (normal temperature) for a predetermined time (24 hours or more) while being irradiated with ultraviolet light. Alternatively, after coating the surface 12 of the substrate 11 with the glass-based coating liquid 10a, the surface 12 of the substrate 11 is irradiated with ultraviolet light and infrared light at the same time to heat the surface 12 of the substrate 11 to a temperature of less than 400°C, and is left for a predetermined time (24 hours or more).

[0078] As a microbubble introduction means (liquid production method) for dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into the glass-based coating liquid 10a (including the paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e), one of the following methods is used: pressurized dissolution method, micropore and porous method, Venturi method, ultrasonic method, static mixer method, cavitation method, swirling liquid flow method, and shear method. Alternatively, at least two of these methods can be combined to dissolve (introduce) the microbubbles 13 and / or nanobubbles 14 into the glass-based coating liquid 10a (including the paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e).

[0079] The pressurized dissolution method uses a pressurized pump (with pressure gauges installed on both the suction and discharge sides) to circulate the glass-based coating liquid 10a stored in the reservoir, while drawing in gas (one or more of the following: 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) from the pump's suction line. The gas is drawn in by attaching a valve to the flow path, which generates negative pressure and allows the gas to be self-drawn. The gas-liquid multiphase flow with the glass-based coating liquid 10a that has drawn in the gas is agitated by the pump and pressurized in the dissolution tank via the discharge line, resulting in dissolution. Any excess gas that has not dissolved is released into the atmosphere.

[0080] In the micropore and porous method, a porous body or porous membrane made by sintering or weakly bonding glass, metal, ceramic, or the like to form micropores, or a porous body or membrane made by stretching a glass tube, etc., is placed in a pressurized glass-based coating liquid 10a, and pressurized gas is pumped into the porous body or membrane, causing the gas to be ejected as bubbles from the micropore outlets. Furthermore, by applying a liquid flow, the bubbles are broken down to generate fine bubbles of microbubbles 13 and ultrafine bubbles of nanobubbles 14, which are dissolved (mixed) into the glass-based coating liquid 10a. In the micropore and porous method, the bubble size can be adjusted by adjusting the liquid flow rate and the gas supply pressure.

[0081] In the Venturi method, glass-based coating liquid 10a and gas are simultaneously flowed through a Venturi tube that has a narrowed portion called a throat midway through the fluid flow path, and shock waves generated by a sudden change in the liquid flow rate shatter the bubbles, generating fine bubbles such as microbubbles 13 and ultrafine bubbles such as nanobubbles 14, and the microbubbles 13 and / or nanobubbles 14 are mixed into the glass-based coating liquid 10a. In the Venturi method, the flow rate of the bubbles dissolved in the glass-based coating liquid 10a accelerates at the contraction section (smallest constriction section), and the pressure is suddenly reduced (cavitation occurs when the pressure falls below the saturated vapor pressure of the paint), causing the bubbles to temporarily expand, but then collapse (crush) due to a sudden increase in pressure in the expansion section downstream, resulting in the bubbles becoming finer. In the Venturi tube method (gas-liquid two-phase flow), the flow velocity accelerates at the contraction (narrowed part) of the Venturi tube, reducing the pressure and causing the bubbles to expand. In the downstream expansion section, the flow becomes even more supersonic, further reducing the pressure and causing the bubbles to expand. However, in the downstream expansion section, the pressure suddenly increases, causing the bubbles to contract, collapse, and form shock waves, generating micro-nano bubbles 13 and nanobubbles 14. In order for the Venturi method to achieve bubble miniaturization, a sufficient pressure reduction at the contraction section of the Venturi tube is required for the bubbles to expand, followed by a rapid pressure recovery that leads to their violent collapse. Therefore, a sufficiently fast flow velocity at the inlet is required. Furthermore, a certain flow velocity must be exceeded to efficiently achieve atomization.

[0082] The ultrasonic method is composed of a hollow ultrasonic horn, an ultrasonic vibrator, a vibration circuit, and a gas supply means. The hollow ultrasonic horn has a stepped cylindrical structure with a gas flow path inside, and ultrasonic vibrations are amplified according to the area ratio between the large end face and the small end face. Gas passes through the hollow ultrasonic horn from a gas inlet on the side and is released into the glass-based coating liquid 10a from a gas outlet on the ultrasonic vibration surface. The gas supply means adjusts the supply amount and pressure of gas from a gas cylinder using a regulator, valve, and flow meter. In the ultrasonic method, the tip of the hollow ultrasonic horn is inserted into the paint, and the hollow ultrasonic horn is ultrasonically vibrated while supplying gas. The gas-liquid interface formed at the tip of the hollow ultrasonic horn is micronized by the ultrasonic disturbance, and microbubbles 13 and / or nanobubbles 14 are dissolved (mixed) into the glass-based coating liquid 10a.

[0083] The static mixer method generates a high-speed rotating fluid by passing a gas-liquid mixture (or a fluid in which gas is dissolved at a high concentration under pressure) through a specially designed nozzle with a guide vane or screw that generates a strong swirling flow inside and a mushroom-shaped projection array (current cutter) on the inner wall. The high-speed rotating fluid collides with the projections (current cutter) protruding from the inner wall of the pipe, generating cavitation and shock waves due to the strong shearing action and large negative pressure. A recirculation region of the negative pressure area is formed in the center of the high-speed rotating fluid, which is subdivided by the cavitation and shock waves behind the projections. These flows are then recirculated, promoting turbulent mixing of the gas-liquid two-phase flow, generating fine bubbles of microbubbles 13 and ultrafine bubbles of nanobubbles 14, which are then dissolved (mixed) into the glass-based coating liquid 10a.

[0084] The cavitation method is a method in which a gas-liquid mixture is sent into a pump and cavitation is used to generate bubbles, and the microbubbles 13 and nanobubbles 14 generated by the cavitation are dissolved (mixed) into the glass-based coating liquid 10a. In the cavitation method, when the flow path is suddenly expanded or hits an obstacle, the boundary layer behind it separates and a negative pressure region is formed, and when this negative pressure exceeds a certain limit, it overcomes the intermolecular forces of the fluid and creates cavities (voids), from which fine bubbles of microbubbles 13 and ultrafine bubbles of nanobubbles 14 are generated.

[0085] The swirling liquid flow method generates a large negative pressure in the center of the cylindrical container by swirling a high-speed water flow of glass-based coating liquid 10a in the tangential direction of the container at the speed of light, causing turbulence by the shearing action of the gas sucking and entraining flow, which atomizes the gas and generates fine bubbles of microbubbles 13 and ultrafine bubbles of nanobubbles 14, and these microbubbles 13 and / or nanobubbles 14 are mixed into the glass-based coating liquid 10a. The swirling liquid flow method generates even finer bubbles by its structure, accompanied by collapse and shock waves.

[0086] In the shearing method (mechanical shearing method), gas is drawn in by rotating rotors installed in a cylindrical casing and mixed with the glass-based coating liquid 10a. As the rotors rotate, the shearing action of the rotors agitates and refines the bubbles, generating fine microbubbles 13 and ultrafine nanobubbles 14. The glass-based coating liquid 10a containing the microbubbles 13 and / or nanobubbles 14 is then discharged toward the outlet. One example of this method is to suck in the glass-based coating liquid 10a as the rotor rotates and expel it through the stator, drawing in gas according to Bernoulli's law, and creating turbulence through the action of two types of blades, the fixed blades and the rotating blades, shearing and refineing the bubbles. Another example is to automatically draw in the decompressed gas using a turbo mixer with a vortex turbo pump, drawing in the gas, and dissolving it in the glass-based coating liquid 10a all at once, simultaneously and continuously pressurizing and mixing the gas.

[0087] A specific example of a gas introduction device 15 that dissolves (introduces) microbubbles 13 and / or nanobubbles 14 into a glass-based coating liquid 10a (including paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e) using a static mixer system is described below. As shown in FIG. 1 , the gas introduction device 15 is composed of a storage tank 16 having a predetermined volume, a gas supply tank 17, a water supply pump 18, an air supply pump 19, a static fluid mixer 20 (static mixer), a storage tank 21 having a predetermined volume and containing the glass-based coating liquid 10a in which the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved (dispersed and mixed), a cooling device (not shown), and a controller (not shown). Electric power is supplied to the gas introduction device 15 from a power source (not shown). The storage tank 16 stores the above-mentioned glass-based coating liquid 10a (the coating liquid 10a (including paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e) before the microbubbles 13 and nanobubbles 14 are dispersed and dissolved).

[0088] The gas to be dispersed and mixed into the glass-based coating liquid 10a is stored at a predetermined pressure in the gas supply tank 17. As described above, the gas to be dispersed and mixed into the glass-based coating liquid 10a may be one single gas selected from 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, or a mixed gas of two or more gases.

[0089] The gas supply tank 17 is connected to a mixing line 24 (mixing pipe) via an air supply line 23 (air supply pipe). Although not shown, a barometer, a check valve, and an air supply solenoid valve are installed in the air supply line 24. The barometer is connected to a controller via a signal line, measures the air pressure of the gas stored in the gas supply tank 17, and transmits the measured air pressure to the controller. The control unit of the air supply solenoid valve is connected to the controller via a signal line, and its on / off (opening and closing) is controlled by the controller. An air supply pump 19 is installed in the air supply line 23. The control unit of the air supply pump 19 is connected to the controller via a signal line. The on / off and output of the air supply pump 19 are controlled by the controller.

[0090] The water supply pump 18 is installed in a water supply pipe 22, and its control unit is connected to the controller via a signal line. The start / stop and output of the water supply pump 18 are controlled by the controller. The water supply pump 18 is connected to a static fluid mixer 20 via a mixing pipe 24. The static fluid mixer 20 is connected to a storage tank 21 of a predetermined volume via a supply pipe 25. A level meter (not shown) is installed in the storage tank 21. The level meter is connected to the controller via a signal line, measures the level (reserved volume) of the glass-based coating liquid 10a in which the microbubbles 13 and nanobubbles 14 are dispersed and mixed and stored in the storage tank 21, and transmits the measured level to the controller.

[0091] As shown in Fig. 2, the static fluid mixer 20 (static mixer) is composed of a cylindrical unit 26 having an inlet and an outlet, and a plurality of honeycomb structure elements 27 (agitating blades) arranged inside the cylindrical unit 26. The honeycomb structure elements 27 are arranged in series inside the cylindrical unit 26. The static fluid mixer 20 passes the glass-based coating liquid 10a and gas through the honeycomb structure elements 27 by centrifugal force generated by high-speed rotation, thereby finely pulverizing the gas to the micro-level and ultra-finely pulverizing to the nano-level to generate microbubbles 13 and nanobubbles 14, and then dissolves (mixes) the generated microbubbles 13 and / or nanobubbles 14 evenly and uniformly in the glass-based coating liquid 10a, producing the glass-based coating liquid 10a in which the microbubbles 13 and / or nanobubbles 14 are evenly and uniformly dispersed and mixed (dispersed and dissolved) throughout.

[0092] In the static fluid mixer 20, the glass-based coating liquid and gas pass through the honeycomb structure element 27 many times, thereby causing the gas to become finer (micro-level) and ultra-fine (nano-level) particles, and the finer and ultra-fine gases dissolve more readily in the glass-based coating liquid 10a. The cooling device cools the cylindrical unit 26 of the static fluid mixer 20 to a set temperature by circulating a refrigerant (e.g., hydrofluorocarbon). The control unit of the cooling device is connected to a controller via a signal line. The start / stop and output of the cooling device are controlled by the controller.

[0093] The controller is a physical computer that has a central processing unit (CPU or MPU) and memory (main memory and cache memory), runs on an independent operating system (OS), and is equipped with a large-capacity storage area. Input devices such as a keyboard and mouse, and output devices such as a display and printer are connected to the controller via interfaces. The central processing unit of the controller starts a nanobubble mixing application stored in the memory under the control of the operating system (OS), and performs a dissolution operation to disperse and dissolve (disperse and mix) microbubbles 13 and nanobubbles 14 in a glass-based coating liquid 10a (including paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e) according to the application.

[0094] When the gas introduction device 15 is switched on, a dissolving (mixing) operation begins, in which microbubbles 13 and nanobubbles 14 are dissolved (mixed) into the glass-based coating liquid 10a stored in the storage tank 16. A predetermined amount of the glass-based coating liquid 10a is poured into the storage tank 16, and the gas supply tank 17 contains a predetermined pressure of 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, or carbon dioxide, or a mixture of two or more of these gases). When the gas introduction device 15 is switched on, the controller sends a water supply signal to the control unit of the water supply pump 18, an air supply signal to the control unit of the air supply pump 19, and a cooling signal to the control unit of the cooling device. Furthermore, the controller sends an open signal to the control section of the water supply electromagnetic valve, sends an open signal to the control section of the air supply electromagnetic valve, and sends measurement signals to the level meter, flow meter, and barometer.

[0095] Upon receiving the water supply signal, the control unit of the water supply pump 18 starts the water supply pump 18 at a predetermined output (set output), and upon receiving the air supply signal, the control unit of the air supply pump 19 starts the air supply pump 19 at a predetermined output (set output). Upon receiving the cooling signal, the control unit of the cooling device starts the cooling device at a predetermined output (set output). Upon receiving the open signal, the control unit of the water supply solenoid valve opens the water supply solenoid valve, and upon receiving the open signal, the control unit of the air supply solenoid valve opens the air supply solenoid valve. Upon receiving the measurement signal, the level meter starts measuring the level of the glass-based coating liquid 10a stored in the storage tank 16, and upon receiving the measurement signal, the flow meter starts measuring the flow rate of the glass-based coating liquid 10a flowing through the water supply pipe 22. Upon receiving the measurement signal, the barometer starts measuring the air pressure of the gas flowing through the air supply pipe 23.

[0096] Glass-based coating 10a stored in storage tank 16 is forcibly supplied from storage tank 16 to static fluid mixer 20 by starting water supply pump 18 (coating liquid supply step). Glass-based coating 10a flows from water supply pipe 22 through water supply pump 18 into mixing pipe 24, and then flows through mixing pipe 24 into static fluid mixer 20. Gas stored in gas supply tank 17 is forcibly supplied from gas supply tank 17 to static fluid mixer 20 by starting air supply pump 19 (gas supply step). The gas flows from air supply pipe 23 through air supply pump 19 into mixing pipe 24, is mixed with glass-based coating 10a in mixing pipe 24, and then flows into static fluid mixer 20 together with glass-based coating 10a. In the mixing pipeline 24, the glass-based coating 10a supplied by the water supply pump 18 is mixed with the gas supplied by the air supply pump 19, to produce the glass-based coating 10a mixed with the gas (gas mixing step). The glass-based coating 10a mixed with the gas flows into the static fluid mixer 20.

[0097] The controller receives the measured level measured by the level meter of the storage tank 16 and outputs (displays) an injection message on the display when the measured level drops to the storage level. The controller receives the measured flow rate measured by the flow meter and adjusts the output of the feedwater pump 18 so that the measured flow rate becomes the target flow rate. The controller receives the measured air pressure measured by the barometer and adjusts the output of the air supply pump 19 so that the measured air pressure becomes the target air pressure.

[0098] The cooling device continuously cools the cylindrical unit 26 of the static fluid mixer 20 using a refrigerant while the gas introduction device 15 is running (cooling process). The cooling device maintains the temperature of the cylindrical unit 26 at a set temperature (e.g., 10 to 20°C). In the static fluid mixer 20, a glass-based coating liquid 10a mixed with gas flows in through an inlet, and the glass-based coating 10a mixed with gas is transformed into a continuous phase fluid and a dispersed phase fluid by a plurality of honeycomb structure elements 27 (agitating blades). The continuous phase and dispersed phase fluids of the glass-based coating 10a flow in a serpentine manner through the honeycomb structure elements 27. The shear force applied at this time atomizes the dispersed phase fluid (gas), generating an atomized mixed fluid.

[0099] Next, the flow of the generated atomized mixed fluid is rectified, and then the rectified atomized mixed fluid flows while meandering through the honeycomb structure element 27 arranged on the downstream side, and the atomized mixed fluid (gas) as a dispersed phase is further atomized by the shear force it receives at that time. Finally, the gas mixed in the glass-based coating liquid 10a is atomized to the micro-level or nano-level, and micro-level or nano-level bubbles (microbubbles 13 and / or nanobubbles 14) are dispersed and dissolved in the glass-based coating liquid 10a, and bubbles with an average bubble diameter D 50 is 10 μm or less, preferably, the average bubble diameter D 50 is 1 μm or less, and more preferably, the average bubble diameter D 50 Microbubbles 13 and / or average bubble diameter D 50A glass-based coating liquid 10a is prepared in which nanobubbles 14, which are independent ultrafine bubbles having a size in the range of 1 to 800 nm, preferably in the range of 1 to 300 nm, are dispersed and dissolved at a predetermined concentration (microbubble and / or nanobubble-containing paint manufacturing process).

[0100] When the microbubbles 13 and nanobubbles 14 are dissolved (introduced) into the glass-based coating liquid 10a, friction between the glass-based coating liquid 10a and the microbubbles 13 and nanobubbles 14 causes the temperature of the glass-based coating liquid 10a in the cylindrical unit 26, in which the microbubbles 13 and / or nanobubbles 14 are dispersed and mixed, to rise. However, the cooling device cools the cylindrical unit 26, so that the temperature of the glass-based coating liquid 10a in the cylindrical unit 26 is maintained at 10 to 20°C. The glass-based coating liquid 10a in which the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved, is stored in the storage tank 21 through the supply pipe 25. The controller receives the measured level measured by the level meter of the storage tank 21 and outputs (displays) the measured level on a display.

[0101] The coating liquid manufacturing method (liquid manufacturing method) can reliably dissolve (introduce) microbubbles 13 and / or nanobubbles 14 into glass-based coating liquid 10a by using such methods (pressure dissolution method, micropore and porous method, Venturi method, ultrasonic method, static mixer method, cavitation method, swirling liquid flow method, shear method), and can produce glass-based coating liquid 10a whose viscosity is reduced by microbubbles 13 and / or nanobubbles 14.

[0102] In glass-based coating liquid 10a, the bonds between molecules of coating liquid 10a are cut or separated by microbubbles 13 and / or nanobubbles 14, and the cutting or separation of the bonds between molecules of coating liquid 10a can weaken the interactions between molecules of coating liquid 10a, so that the viscosity of glass-based coating liquid 10a after microbubbles 13 and / or nanobubbles 14 have been dispersed and dissolved can be made lower than that of coating liquid 10a before being dispersed and dissolved, and the viscosity of glass-based coating liquid 10a to be coated on surface 12 of substrate 11 can be easily reduced.

[0103] The glass-based coating liquid 10a can be converted from a high-viscosity or medium-viscosity coating liquid 10a to a low-viscosity one, and the degree of viscosity reduction or the degree of viscosity reduction of the coating liquid 10a can be adjusted by adjusting the average bubble diameter of the microbubbles 13 and / or nanobubbles 14 dispersed or dissolved in the glass-based coating liquid 10a or the content of the microbubbles 13 and / or nanobubbles 14. The glass-based coating liquid 10a does not use harmful substances such as organic solvents to reduce its viscosity, or the amount of harmful substances such as organic solvents used can be reduced when reducing the viscosity, making it possible to reduce the viscosity of the liquid without adversely affecting the human body.

[0104] FIG. 10 is a schematic diagram showing an example of the structure of a fluororesin paint, and FIG. 11 is a schematic diagram showing an example of the structure of a silicone resin paint. Before the microbubbles 13 and / or nanobubbles 14 are introduced into the paint 10b, any of fluororesin paint, silicone resin paint (silicone resin), acrylic resin paint, urethane resin paint, and water-based paint is used. Microbubbles 13 and / or nanobubbles 14 are introduced into the paint 10b by the gas dissolving device 15 described above, and the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved (dispersed and mixed) therein (see FIG. 3 ). The gases constituting the microbubbles 13 and / or nanobubbles 13 dissolved in the paint 10b are the same as those dissolved in the glass-based coating liquid 10a. Note that the paint 10b may contain only microbubbles 13 dispersed and dissolved (dispersed and mixed), only nanobubbles 14 dispersed and dissolved (dispersed and mixed), or both microbubbles 13 and nanobubbles 14.

[0105] The viscosity of the paint 10b before the microbubbles 13 and / or nanobubbles 14 are introduced is in the range of 10 mPa·s to 10,000 mPa·s. By dispersing and dissolving (introducing) the microbubbles 13 and / or nanobubbles 14 into the paint 10b, the microbubbles 13 and / or nanobubbles 14 sever or disrupt the bonds between the molecules of the paint 10b, and the severing or disruption of the bonds between the molecules of the paint 10b weakens the interactions between the molecules of the paint 10b (see FIG. 6). The viscosity of the paint 10b into which the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved (introduced) is reduced to between 1 / 2 and 1 / 10 of that of the paint 10b before the microbubbles 13 and / or nanobubbles 14 are introduced. The viscosity of the paint 10b after the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved is in the range of 1 mPa·s to 5,000 mPa·s.

[0106] The microbubbles 13 and / or nanobubbles 14 dispersed and dissolved in the paint 10b have an average bubble diameter D 50 The microbubbles 13 that are fine bubbles dispersed and dissolved in the paint 10b have an average bubble diameter D 50is 10 μm or less, preferably, the average bubble diameter D 50 is 1 μm or less, and more preferably, the average bubble diameter D 50 The nanobubbles 14, which are ultrafine bubbles dispersed and dissolved in the paint 10b, have an average bubble diameter D 50 The nanobubbles 14 are in the range of 1 to 800 nm, preferably in the range of 1 to 300 nm. The nanobubbles 14 are undergoing Brownian motion inside the paint 10b. The microbubbles 13 and / or nanobubbles 14 contained in 1 ml of the paint 10b are 5 10 pieces / ml or more 12 The range is less than 1 / ml.

[0107] The microbubbles 13 and nanobubbles 14 dispersed and dissolved in the paint 10b are tiny bubbles, and the microbubbles 13 and nanobubbles 14 dissolve in the paint 10b at a level exceeding the saturated solubility at equilibrium (see FIG. 7). Furthermore, the viscosity of the paint 10b in which the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved increases as the temperature decreases, and decreases as the temperature increases (see FIG. 8). Furthermore, the solubility of the microbubbles 13 and / or nanobubbles 14 in the paint 10b increases as the temperature of the paint 10b decreases, and decreases as the temperature increases (see FIG. 9).

[0108] The fluororesin paint (paint 10b) is applied to the surface 12 of the substrate 11 and then hardens to form a fluororesin coating film having a predetermined thickness. The silicone resin paint (paint 10b) is applied to the surface 12 of the substrate 11 and then hardens to form a silicone resin coating film having a predetermined thickness. The acrylic resin paint (paint 10b) is applied to the surface 12 of the substrate 11 and then hardens to form an acrylic resin coating film having a predetermined thickness. The urethane resin paint (paint 10b) is applied to the surface 12 of the substrate 11 and then hardens to form a urethane resin coating film having a predetermined thickness.

[0109] Fluorine resin paint is a paint whose main component is fluororesin. The fluororesin that is the main component of fluororesin paint is a solution of one or a blend of two or more of the following: PTFT (polytetrafluoroethylene), PFA (perfluoroalkoxyalkane polymer), FEP (perfluoroethylenepropene copolymer), and ETFE (ethylene-tetrafluoroethylene copolymer). It is possible to use a high-temperature modified fluororesin that increases adhesion to the surface 12 of the substrate 11 and improves abrasion resistance without reducing its heat resistance, or a low-temperature modified fluororesin that can be processed at low temperatures while taking advantage of the low friction and non-stick properties of fluororesin.

[0110] The molecular structure of PTFT (polytetrafluoroethylene) is represented by the following general formula (1).

[0111] [ka] PTFT has a molecular structure in which carbon atoms (C) and fluorine atoms (F) are bonded in a linear chain, and the bonds between the carbon atoms are tightly covered with fluorine atoms, providing protection. The arrangement of atoms within the PTFT molecule is tightly packed and symmetrical, resulting in very little charge polarization. Furthermore, it is a polymer made up of extremely long molecular chains with a molecular weight of one million to tens of millions. Stable due to this unique molecular structure, PTFT forms a coating film 13 with excellent non-adhesive properties, water and oil repellency, low friction, heat resistance, chemical resistance, electrical properties, flame retardancy, and weather resistance. PTFT has a density of 2.13 to 2.20 g / cm. 3 The range is 110-115 / 45-50, its room temperature hardness is F to 2H, and its water repellency angle (°) water / oil (nHD) is 110-115 / 45-50.

[0112] The molecular structure of PFA (perfluoroalkoxyalkane polymer) is represented by the following general formula (2).

[0113] [ka] PFA is a copolymer of tetrafluoroethylene (TFE) and perfluoroalkyl vinyl ether (PFVE). Its key features include low viscosity when molten and properties comparable to those of PTFT. Like PTFT, it has excellent heat resistance, with a continuous use temperature of 260°C, and is resistant to most chemicals, including strong acids, strong alkalis, and organic solvents. PFA forms an organic coating film with excellent non-stick properties, heat resistance, cold resistance, water repellency, chemical resistance, electrical properties, flame retardancy, and weather resistance. PFA's room temperature hardness is F-H, and its water / oil repellency angle (°) is 110-115 / 45-50.

[0114] The molecular structure of FEP (perfluoroethylene propene copolymer) is represented by the following general formula (3).

[0115] [ka] FEP is a copolymer of tetrafluoroethylene (TFE) and hexafluoropropylene (HFP), and has the trifluoromethyl group CF3 in its molecular chain, giving it the same non-stickiness and chemical resistance as PTFE, while also having a low melting point. Because FEP has a low melt viscosity, when used in coatings, it can produce a continuous film without pinholes. FEP has a density of 2.15 to 2.17 g / cm. 3 The range is 100-115°, its room temperature hardness is F to H, and its water repellency angle (°) water / oil (nHD) is 110-115 / 45-50.

[0116] The molecular structure of ETFE (ethylene-tetrafluoroethylene copolymer) is represented by the following general formula (4).

[0117] [ka] ETFE is a copolymer of tetrafluoroethylene and ethylene, and contains hydrogen atoms (H) in its molecular structure. Therefore, compared to PTFE and FEP, it has lower chemical resistance and heat resistance, with a continuous use temperature of 150°C. On the other hand, it has high mechanical strength and can be processed at a low melting point. ETFE has a density of 1.73 to 1.75 g / cm 3 is in the range.

[0118] Silicone resin paint is a paint whose main component is silicone resin. The molecular structure of silicone resin (silicone resin), the main component of silicone resin paint, is represented by the following general formula (5).

[0119] [ka] Silicone resin paints have excellent durability, water resistance, chemical resistance, and flexibility, and form a coating film 13 (a three-dimensional glass skeleton coating) with high adhesion to the surface 12 of the substrate 11. Silicone resin coatings 13 made from silicone resin paints are composed of siloxane bonds (Si-O, silicon-oxygen) and contain several silicates (SiO4 / 2) or silsesquioxanes (R-SiO3 / 2). R represents various alkyl or aryl groups, with typical functional groups being methyl or phenyl. Compared to organic resins composed of carbon bonds (CC), they exhibit greater resistance to decomposition by heat and radiation. The resistance of silicone resin coatings is due to the strength of their oxygen-hydrogen bonds (82.6 kcal / mole for carbon-carbon bonds, compared to 108 kcal / mole for silicon-oxygen bonds), their transparency to visible and ultraviolet light, and their inherently partially oxidized structure.

[0120] By adding organic functional groups, siloxane polymers have a more linear structure, and are endowed with physical properties (such as flexibility) and performance derived from the organic functional groups. The introduction of phenyl groups into the siloxane backbone improves compatibility with organic resins, increases toughness, and maintains thermal stability at medium temperatures (250°C). On the other hand, methyl groups improve curing properties, resist thermal shock, and reduce weight loss under extreme humidity conditions. Silicone polymer coating solutions (silicone resins) are produced by hydrolyzing chlorosilanes or alkoxysilanes, and highly reactive silanol groups (Si-OH) are formed during this process. RSiC 13 + 3H2O RSi(OH)3 + 3HCl, RSi(OR')3 + 3H2O RSi(OH)3 + 3R'OH. In the initial condensation reaction, siloxane oligomer structures are formed. 2 RSi(OH)3RSi(OH)2- O - SiR(OH)2 + H2O. Further condensation leads to the formation of three-dimensional crosslinked siloxane structures. Adding heat and catalysts during the condensation reaction increases the molecular weight and improves physical properties. On the other hand, the viscosity of the polymer increases, necessitating dilution in a solvent. Similarly, in cases requiring specific application properties, the reaction of hydroxyl groups (e.g., polyester) with silanol and alkoxy groups forms a silicone-organic composite resin, improving performance depending on the degree of siloxane modification. Cold blending of the resin intermediate with the organic resin can be achieved using a small amount of solvent. However, to advance the reaction and ensure complete cure, a higher and longer thermal curing process is required. In addition to selecting the optimum silicone resin, other ingredients in the formulation play an important role in application performance.

[0121] When creating a prototype silicone resin paint, the first step is to determine the required characteristics for the intended application and then determine which resin binder can be used. The heat, chemicals, and UV rays to which the silicone resin paint will be exposed during curing, as well as the required physical properties, also influence the choice of resin binder. Silicone resin paint (silicone resin) contributes to improving the heat resistance, chemical resistance, and UV resistance of the silicone resin coating, but other performance and physical properties can also be imparted by combining silicone with specific organic binders (coat hardness: phenolic and melamine resins; room temperature drying: acrylic resins; corrosion resistance: epoxy resins; toughness: alkyd resins). The amount of silicone in the coating formulation is determined based on the performance requirements for the application.

[0122] Silicone resin coatings contain a catalyst and curing conditions. Silanol-functional resins heat cure without the addition of a catalyst. However, the addition of metal driers (e.g., zinc, iron, or cobalt octoate) accelerates the cure. Typical catalyst loadings are 0.1–0.2% metal based on resin solids. Silicone resin coatings formulated with silanol-functional silicone resins require heat curing for optimal film performance, but the cure time varies depending on the silicone content and the curing conditions of the other major ingredients. The cure time for 100% silicone resin systems is 232°C (450°F) for 30 minutes or 204°C (400°F) for 60 minutes.

[0123] Acrylic resin paint is a paint whose main component is acrylic resin. Acrylic resin paint forms an acrylic resin coating film 13 with excellent weather resistance, gloss, transparency, water resistance, adhesion, and corrosion resistance. Water-based acrylic resins and solvent-based acrylic resins can be used. Water-based acrylic resins include acrylic emulsions, acrylic-styrene emulsions, hydroxyl-containing acrylic emulsions, room-temperature-drying water-soluble acrylic resins, baking acrylic dispersions, and hydroxyl-containing acrylic dispersions. Solvent-based acrylic resins include isocyanate-curing acrylic resins, room-temperature / forced-drying acrylic resins, melamine-baking acrylic resins, and moisture-curing silicone acrylic resins.

[0124] The urethane resin paint is composed of a polyol having multiple hydroxyl groups and a polyisocyanate as the main component. The urethane resin paint may be an acrylic urethane paint containing an acrylic polyol as the main component. The urethane resin paint may also contain an acrylic polyol and cellulose acetate butyrate. The urethane resin paint forms a urethane resin coating film 10b with excellent coating performance, finish, weather resistance, adhesion, flexibility, and chemical resistance. The urethane resin paint can be diluted with an organic solvent.

[0125] Examples of polyols that can be used include 1,6-hexanediol, cyclohexyldimethanol, neopentyl glycol, butylethylpropanediol, trimethylolethane, trimethylolpropane, polycaprolactone triol, ditrimelylpropane, pentaerythritol, polycaprolactone tetraol, dipentaerythritol, sorbitol, and mannitol. Also, a mixture of at least two of these may be used.

[0126] For the polyisocyanate, a difunctional or higher isocyanate compound is used. Examples of difunctional isocyanate compounds include hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and 4,4-dicyclohexyl diisocyanate. Examples of trifunctional or higher isocyanate compounds are those synthesized using diisocyanate compounds as starting materials, such as biuret compounds, trimethylolpropane adduct compounds, isocyanurate compounds, and allophanate compounds. In order to increase the crosslink density of urethane resin coating films made from urethane resin paints and improve the weather resistance and stain resistance of the coating films, it is preferable that the polyisocyanate be a trifunctional or higher isocyanate compound.

[0127] Examples of trifunctional or higher isocyanate compounds include biuret hexamethylene diisocyanate, adduct hexamethylene diisocyanate, isocyanurate hexamethylene diisocyanate, blocked isocyanate, trimethylolpropane adduct 1,3-bis(isocyanatomethyl)cyclohexane, isocyanurate 1,3-bis(isocyanatomethyl)cyclohexane, trimethylolpropane adduct isophorone diisocyanate, and allophanate hexamethylene diisocyanate. Also, a mixture of at least two of these isocyanate compounds can be used. For water-based paints, emulsions, emulsions containing aggregates, or water-soluble resins can be used.

[0128] Fluorocarbon resin paints, silicone resin paints, acrylic resin paints, urethane resin paints, and water-based paints contain various additives and pigments as needed. Additives include matting agents to reduce the gloss of the paint film, surfactants to prevent a decrease in surface tension, anti-sagging agents to prevent paint from running off, color-stabilizing agents to prevent uneven color caused by pigment mixing, preservatives and mildew inhibitors to prevent corrosion of the paint film, plasticizers to improve the paint's flexibility and adhesion, anti-skinning agents to prevent the formation of a skin on the surface during paint storage, and leveling agents to ensure the paint film's fluidity. Additives include curing agents that harden the paint film and improve its weather resistance, water resistance, chemical resistance, and heat resistance. Curing agents include blocked isocyanates such as hexamethylene isocyanate trimer or their emulsion dispersions, melamine resins such as methylated melamine, methylolated melamine, and butylolated melamine, and urea resins such as methylated urea and butylated urea. Pigments include inorganic color pigments, organic color pigments, and extender pigments. Fluorocarbon resin paints, silicone resin paints, acrylic resin paints, and urethane resin paints are either water-based or oil-based, and either one-component or two-component. Other additives may also be added, such as film-forming aids, thickeners, light stabilizers, design agents, surface conditioners, and aqueous media. Aqueous media are used to dilute aqueous dispersions. Thickeners used include urethane-based thickeners, polyacrylic-based thickeners, polyamide-based thickeners, cellulose-based thickeners, and clay mineral thickeners such as bentonite.

[0129] As with the glass-based coating liquid 10a, the microbubble introduction means (liquid production method) for dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into the coating material 10b can be any one of the previously described pressurized dissolution method, micropore and porous method, Venturi method, ultrasonic method, static mixer method, cavitation method, swirling liquid flow method, and shear method. Alternatively, the microbubbles 13 and / or nanobubbles 14 can be dissolved (introduced) into the coating material 10b by combining at least two of these methods. The gas introduction device 15 for dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into the coating material 10b using the static mixer method is the same as the previously described gas introduction device 15 for dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into the glass-based coating liquid 10a (see Figures 1 and 2).

[0130] The paint manufacturing methods (liquid manufacturing methods) can reliably dissolve (introduce) microbubbles 13 and / or nanobubbles 14 into the paint 10b by using the methods (pressure dissolution method, micropore and porous method, Venturi method, ultrasonic method, static mixer method, cavitation method, swirling liquid flow method, shear method), and can produce paint 10b whose viscosity is reduced by the microbubbles 13 and / or nanobubbles 14.

[0131] In paint 10b, the microbubbles 13 and / or nanobubbles 14 cut or fragment the bonds between the molecules of the fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, or water-based paint, and the cutting or fragmenting of the bonds between the molecules of the paint can weaken the interactions between the molecules of the paint, and the viscosity of the paint after microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved can be made lower than that of the paint before being dispersed and dissolved, and the viscosity of the fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, or water-based paint to be applied to surface 12 of substrate 11 can be easily reduced.

[0132] By adjusting the average bubble diameter of the microbubbles 13 and / or nanobubbles 14 dispersed and dissolved in the fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, or water-based paint, or the content of the microbubbles 14 and / or nanobubbles 14, the high-viscosity or medium-viscosity paint 10b can be made low-viscosity, and the degree of viscosity reduction or the degree of viscosity reduction of the paint 10b can be adjusted. The paint 10b does not use harmful substances such as organic solvents to reduce the viscosity of the fluororesin paint, silicone resin paint, acrylic resin paint, urethane resin paint, or water-based paint, or the amount of harmful substances such as organic solvents used when reducing the viscosity can be reduced, thereby reducing the viscosity of these paints without adversely affecting the human body.

[0133] The paint 10b uses microbubbles 13 and / or nanobubbles 14 to adjust its viscosity. This allows the use of fluororesin paint, silicone resin paint, acrylic resin paint, or urethane resin paint, which contains microbubbles 13 and / or nanobubbles 14 that dissolve in large amounts in low-temperature environments, to lower the viscosity of the resin paint without adversely affecting the human body, particularly in situations where fluororesin paint, silicone resin paint, acrylic resin paint, or urethane resin paint has a high viscosity and requires the use of a larger amount of thinner or the like in low-temperature environments. If the paint 10b is a water-based paint, the viscosity can be adjusted without using water. Since there is no need to use water for viscosity adjustment, the paint 10b is useful in areas with water shortages or in environments where water is unavailable, and does not contribute to the global water shortage.

[0134] Next, we will explain the ink 10c in which microbubbles 14 and / or nanobubbles 15 are dissolved. Examples of ink 10c before the microbubbles 13 and / or nanobubbles 14 are introduced include lithographic ink (offset ink) used in lithographic printing (offset printing), gravure ink used in gravure printing, a type of intaglio printing, newspaper ink used for printing newspapers, resin letterpress ink (flexographic ink) used in letterpress printing using flexible resin plates, screen ink used in stencil printing (screen printing), and UV ink that instantly hardens and dries the ink by irradiating it with ultraviolet light, creating a strong ink film.

[0135] Microbubbles 13 and / or nanobubbles 14 are introduced into the ink 10c by the gas dissolving device 15 described above, and the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved (dispersed and mixed) in the ink 10c (see FIG. 3). The gas constituting the microbubbles 13 and / or nanobubbles 14 dissolved in the ink 10c is the same as that dissolved in the glass-based coating liquid 10a. Note that the ink 10c may contain only microbubbles 13 dispersed and dissolved (dispersed and mixed), only nanobubbles 14 dispersed and dissolved (dispersed and mixed), or both microbubbles 13 and nanobubbles 14 dispersed and dissolved (dispersed and mixed).

[0136] The viscosity of the ink 10c before the microbubbles 13 and / or nanobubbles 14 are introduced is in the range of 10 mPa·s to 10,000 mPa·s. By dispersing and dissolving (introducing) the microbubbles 13 and / or nanobubbles 14 into the ink 10c, the microbubbles 13 and / or nanobubbles 14 sever or disrupt the bonds between the molecules of the ink 10c, and the severing or disruption of the bonds between the molecules of the ink 10c weakens the interactions between the molecules of the ink 10c (see FIG. 6). The viscosity of the ink 10c after the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved (introduced) is reduced to between 1 / 2 and 1 / 10 of that of the ink 10c before the microbubbles 13 and / or nanobubbles 14 are introduced. The viscosity of the ink 10c after the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved is in the range of 1 mPa·s to 5,000 mPa·s.

[0137] The microbubbles 13 and / or nanobubbles 14 dispersed and dissolved in the ink 10c have an average bubble diameter D 50 The microbubbles 13, which are fine bubbles dispersed and dissolved in the ink 10c, have an average bubble diameter D 50 is 10 μm or less, preferably, the average bubble diameter D 50 is 1 μm or less, and more preferably, the average bubble diameter D 50 The nanobubbles 14, which are ultrafine bubbles dispersed and dissolved in the ink 10c, have an average bubble diameter D 50 The nanobubbles 14 are in the range of 1 to 800 nm, preferably in the range of 1 to 300 nm. The nanobubbles 14 are undergoing Brownian motion inside the ink 10c. The microbubbles 13 and / or nanobubbles 14 contained in 1 ml of the ink 10c are 5 10 pieces / ml or more 12 The range is less than 1 / ml.

[0138] The microbubbles 13 and nanobubbles 14 dispersed and dissolved in the ink 10c are tiny bubbles, and the microbubbles 13 and nanobubbles 14 dissolve in the ink 10c to a degree exceeding the saturated solubility at equilibrium (see FIG. 7). Furthermore, the viscosity of the ink 10c in which the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved increases as the temperature decreases, and decreases as the temperature increases (see FIG. 8). Furthermore, the solubility of the microbubbles 13 and / or nanobubbles 14 in the ink 10c increases as the temperature of the ink 10c decreases, and decreases as the temperature increases (see FIG. 9).

[0139] As with the glass-based coating liquid 10a, the microbubble introduction means (liquid production method) for dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into the ink 10c can be any one of the previously described pressurized dissolution method, micropore and porous method, Venturi method, ultrasonic method, static mixer method, cavitation method, swirling liquid flow method, and shear method. Alternatively, the microbubbles 13 and / or nanobubbles 14 can be dissolved (introduced) into the ink 10c by combining at least two of these methods. The gas introduction device 15 for dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into the ink 10c using the static mixer method is the same as the previously described gas introduction device 15 for dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into the glass-based coating liquid 10a (see Figures 1 and 2).

[0140] The ink production method (liquid production method) can reliably dissolve (introduce) microbubbles 13 and / or nanobubbles 14 into the ink 10c by using the methods (pressure dissolution method, micropore and porous method, Venturi method, ultrasonic method, static mixer method, cavitation method, swirling liquid flow method, shear method), and can produce ink 10c whose viscosity is reduced by the microbubbles 13 and / or nanobubbles 14.

[0141] The microbubbles 13 and / or nanobubbles 14 sever or disrupt the bonds between the molecules of the ink 10c, which weakens the interactions between the molecules of the ink 10c, thereby making it possible to lower the viscosity of the ink 10c after the microbubbles 13 and / or nanobubbles 14 have been dispersed and dissolved therein compared to the ink 10c before the dispersion and dissolution, thereby reducing the viscosity of the ink 10c printed on the printing surface 12. By adjusting the average bubble diameter of the microbubbles 13 and / or nanobubbles 14 dispersed and dissolved in the ink 10c and the content of the microbubbles 13 and / or nanobubbles 14, the ink 10c can be made from a high- or medium-viscosity ink 10c to a low-viscosity ink 10c, and the degree of reduction in the viscosity of the ink 10c and the degree of low viscosity of the ink 10c can be adjusted. Ink 10c does not use harmful substances such as organic solvents to reduce its viscosity, or the amount of harmful substances such as organic solvents used when reducing viscosity can be reduced, making it possible to reduce the viscosity of the ink without adversely affecting the human body.

[0142] Next, the adhesive 10d in which the microbubbles 13 and / or nanobubbles 14 have been dissolved will be described. The adhesive 10d before the microbubbles 13 and / or nanobubbles 14 are introduced includes natural adhesives and organic adhesives. Natural adhesives include starch-based adhesives, protein-based adhesives, natural rubber-based adhesives, and asphalt-based adhesives. Organic adhesives include thermoplastic resin-based adhesives, thermosetting resin-based adhesives, and elastomer-based adhesives.

[0143] Thermoplastic adhesives include vinyl acetate, polyvinyl acetal, ethylene vinyl acetate (EVA), vinyl chloride, acrylic, polyamide, cellulose, and alpha-olefin adhesives. Thermosetting adhesives include urea (water-based), melamine, phenolic, resorcinol, epoxy, structural acrylic, polyester, polyurethane, and polyaromatic. Elastomer adhesives include chloroprene, nitrile, styrene butadiene (SBR), polysulfide, butyl, silicone, acrylic, modified silicone, urethane, silylated urethane, and telechelic polyacrylate.

[0144] Microbubbles 13 and / or nanobubbles 14 are introduced into the adhesive 10d by the gas dissolving device 15, and the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved (dispersed and mixed) therein (see FIG. 3). The gas constituting the microbubbles 13 and / or nanobubbles 14 dissolved in the adhesive 10d is the same as that dissolved in the glass-based coating liquid 10a. Note that the adhesive 10d may contain only microbubbles 13 dispersed and dissolved (dispersed and mixed), only nanobubbles 14 dispersed and dissolved (dispersed and mixed), or both microbubbles 13 and nanobubbles 14 dispersed and dissolved (dispersed and mixed).

[0145] The adhesive 10d before the microbubbles 13 and / or nanobubbles 14 are introduced has a viscosity in the range of 10 mPa·s to 10,000 mPa·s. By dispersing and dissolving (introducing) the microbubbles 13 and / or nanobubbles 14 into the adhesive 10d, the microbubbles 13 and / or nanobubbles 14 cut or disrupt the bonds between the molecules of the adhesive 10d, and the cutting or disruption of the bonds between the molecules of the adhesive 10d weakens the interactions between the molecules of the adhesive 10d (see FIG. 6). The viscosity of the adhesive 10d after the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved (introduced) is reduced to between 1 / 2 and 1 / 10 of that of the adhesive 10d before the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved. The viscosity of the adhesive 10d after the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved is in the range of 1 mPa·s to 5,000 mPa·s.

[0146] The microbubbles 13 and / or nanobubbles 14 dispersed and dissolved in the adhesive 10d have an average bubble diameter D 50 The microbubbles 13, which are fine bubbles dispersed and dissolved in the adhesive 10d, have an average bubble diameter D 50 is 10 μm or less, preferably, the average bubble diameter D 50 is 1 μm or less, and more preferably, the average bubble diameter D 50 The nanobubbles 14, which are ultrafine bubbles dispersed and dissolved in the adhesive 10d, have an average bubble diameter D 50 The nanobubbles 14 are in the range of 1 to 800 nm, preferably in the range of 1 to 300 nm. The nanobubbles 14 are undergoing Brownian motion inside the adhesive 10d. The microbubbles 13 and / or nanobubbles 14 contained in 1 ml of the adhesive 10d are 5 10 pieces / ml or more 12 The range is less than 1 / ml.

[0147] The microbubbles 13 and nanobubbles 14 dispersed and dissolved in the adhesive 10d are tiny bubbles, and the microbubbles 13 and nanobubbles 14 dissolve in the adhesive 10d beyond their saturated solubility at equilibrium (see FIG. 7). Furthermore, the viscosity of the adhesive 10d in which the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved increases as the temperature decreases, and decreases as the temperature increases (see FIG. 8). Furthermore, the solubility of the microbubbles 13 and / or nanobubbles 14 in the adhesive 10d increases as the temperature of the adhesive 10d decreases, and decreases as the temperature increases (see FIG. 9).

[0148] As with the glass-based coating liquid 10a, the microbubble introduction means (liquid production method) for dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into the adhesive 10d can be any one of the previously described pressurized dissolution method, micropore and porous method, Venturi method, ultrasonic method, static mixer method, cavitation method, swirling liquid flow method, and shear method. Alternatively, the microbubbles 13 and / or nanobubbles 14 can be dissolved (introduced) into the adhesive 10d by combining at least two of these methods. The gas introduction device 15 for dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into the adhesive 10d using the static mixer method is the same as the previously described gas introduction device 15 for dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into the glass-based coating liquid 10a (see FIGS. 1 and 2).

[0149] The adhesive manufacturing method (liquid manufacturing method) can reliably dissolve (introduce) microbubbles 13 and / or nanobubbles 14 into the adhesive 10d by using such methods (pressure dissolution method, micropore and porous method, Venturi method, ultrasonic method, static mixer method, cavitation method, swirling liquid flow method, shear method), and can produce an adhesive 10d whose viscosity is reduced by the microbubbles 13 and / or nanobubbles 14.

[0150] The microbubbles 13 and / or nanobubbles 14 sever or disrupt the bonds between the molecules of the adhesive 10d, thereby weakening the intermolecular interactions of the adhesive 10d. The viscosity of the adhesive 10d after dispersing and dissolving the microbubbles 13 and / or nanobubbles 14 can be lowered compared to the viscosity of the adhesive 10d before dispersing and dissolving the microbubbles 13 and / or nanobubbles 14, thereby reducing the viscosity of the adhesive 10d. By adjusting the average bubble diameter of the microbubbles 13 and / or nanobubbles 14 dispersed and dissolved in the adhesive 10d or the content of the microbubbles 13 and / or nanobubbles 14, the adhesive 10d can be changed from a high-viscosity or medium-viscosity adhesive 10d to a low-viscosity adhesive 10d, and the degree of viscosity reduction or the degree of viscosity reduction of the adhesive 10d can be adjusted. The adhesive 10d does not use harmful substances such as organic solvents to reduce its viscosity, or the amount of harmful substances such as organic solvents used can be reduced when reducing the viscosity, thereby reducing the viscosity of the adhesive 10d without adversely affecting the human body.

[0151] Next, the synthetic resin 10e used for forming the film will be described. The synthetic resin 10e used for forming the film before the introduction of the microbubbles 13 and / or nanobubbles 14 is, for example, polyvinyl alcohol (PVA). A polyvinyl alcohol film using polyvinyl alcohol is produced by dissolving the polyvinyl alcohol resin in a solvent such as water to prepare a polyvinyl alcohol stock solution, forming the solution into a film by a solution casting method, and drying the solution using a metal heating roll or the like.

[0152] Microbubbles 13 and / or nanobubbles 14 are introduced into polyvinyl alcohol stock solution 10e, which is obtained by dissolving polyvinyl alcohol in a solvent, by the gas dissolving device 15 described above, and the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved (dispersed and mixed) therein (see FIG. 3). The gas constituting the microbubbles 13 and / or nanobubbles 14 dissolved in polyvinyl alcohol stock solution 10e is the same as that dissolved in glass-based coating liquid 10a. Note that in polyvinyl alcohol stock solution 10e (synthetic resin for film formation 10e), only microbubbles 13 may be dispersed and dissolved (dispersed and mixed), only nanobubbles 14 may be dispersed and dissolved (dispersed and mixed), or both microbubbles 13 and nanobubbles 14 may be dispersed and dissolved (dispersed and mixed).

[0153] The viscosity of polyvinyl alcohol stock solution 10e before the introduction of microbubbles 13 and / or nanobubbles 14 is in the range of 10 mPa·s to 10,000 mPa·s. By dispersing and dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into polyvinyl alcohol stock solution 10e, the microbubbles 13 and / or nanobubbles 14 sever or disrupt the intermolecular bonds of polyvinyl alcohol (synthetic resin 10e for film formation), and the severing or disruption of the intermolecular bonds of polyvinyl alcohol weakens the intermolecular interactions of polyvinyl alcohol (see FIG. 6 ). The viscosity of polyvinyl alcohol stock solution 10e into which microbubbles 13 and / or nanobubbles 14 have been dispersed and dissolved (introduced) is reduced to between one-half and one-tenth of that of polyvinyl alcohol stock solution 10e before the introduction of microbubbles 13 and / or nanobubbles 14. The viscosity of the polyvinyl alcohol stock solution 10e after the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved is in the range of 1 mPa·s to 5000 mPa·s.

[0154] The microbubbles 13 and / or nanobubbles 14 dispersed and dissolved in the polyvinyl alcohol stock solution 10e (synthetic resin for film formation 10e) have an average bubble diameter D 50 The microbubbles 13, which are fine bubbles dispersed and dissolved in the polyvinyl alcohol stock solution 10e, have an average bubble diameter D50 is 10 μm or less, preferably, the average bubble diameter D 50 is 1 μm or less, and more preferably, the average bubble diameter D 50 The nanobubbles 14, which are ultrafine bubbles dispersed and dissolved in the polyvinyl alcohol stock solution 10e, have an average bubble diameter D 50 The nanobubbles 14 are undergoing Brownian motion inside the polyvinyl alcohol stock solution 10e. The microbubbles 13 and / or nanobubbles 14 contained in 1 ml of the polyvinyl alcohol stock solution 10e are in the range of 1 to 800 nm, and preferably in the range of 1 to 300 nm. 5 10 pieces / ml or more 12 The range is less than 1 / ml.

[0155] The microbubbles 13 and nanobubbles 14 dispersed and dissolved in the polyvinyl alcohol stock solution 10e (synthetic resin 10e for film formation) are tiny bubbles, and the microbubbles 13 and nanobubbles 14 dissolve in the polyvinyl alcohol stock solution 10e in an amount exceeding the saturated solubility at equilibrium (see FIG. 7). Furthermore, the viscosity of the polyvinyl alcohol stock solution 10e in which the microbubbles 13 and / or nanobubbles 14 are dispersed and dissolved increases as the temperature decreases, and decreases as the temperature increases (see FIG. 8). Furthermore, the solubility of the microbubbles 13 and / or nanobubbles 14 in the polyvinyl alcohol stock solution 10e increases as the temperature of the polyvinyl alcohol stock solution 10e decreases, and decreases as the temperature increases (see FIG. 9).

[0156] As with the glass-based coating liquid 10a, the microbubble introduction means (liquid production method) for dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into the polyvinyl alcohol stock solution 10e (synthetic resin for film formation 10e) can be any one of the previously described pressurized dissolution method, micropore and porous method, Venturi method, ultrasonic method, static mixer method, cavitation method, swirling liquid flow method, and shear method. Alternatively, the microbubbles 13 and / or nanobubbles 14 can be dissolved (introduced) into the polyvinyl alcohol stock solution 10e by combining at least two of these methods. The gas introduction device 15 for dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into the polyvinyl alcohol stock solution 10e (synthetic resin for film formation 10e) using the static mixer method is the same as the previously described gas introduction device 15 for dissolving (introducing) microbubbles 13 and / or nanobubbles 14 into the glass-based coating liquid 10a (see FIGS. 1 and 2).

[0157] The polyvinyl alcohol stock solution manufacturing method (liquid manufacturing method) can reliably dissolve (introduce) microbubbles 13 and / or nanobubbles 14 into the polyvinyl alcohol stock solution 10e (synthetic resin for film molding 10e) by using such methods (pressure dissolution method, micropore and porous method, Venturi method, ultrasonic method, static mixer method, cavitation method, swirling liquid flow method, shear method), and can produce polyvinyl alcohol stock solution 10e whose viscosity has been reduced by the microbubbles 13 and / or nanobubbles 14.

[0158] The microbubbles 13 and / or nanobubbles 14 cut or sever the bonds between the molecules of the synthetic resin 10e for film formation (polyvinyl alcohol stock solution 10e), and the severance or severance of the bonds between the molecules of the synthetic resin 10e for film formation can weaken the interactions between the molecules of the synthetic resin 10e. This makes it possible to lower the viscosity of the synthetic resin 10e for film formation after the microbubbles 13 and / or nanobubbles 14 have been dispersed and dissolved therein compared to the synthetic resin 10e for film formation before the dispersion and dissolution, thereby reducing the viscosity of the synthetic resin 10e for film formation (polyvinyl alcohol stock solution 10e). By adjusting the average bubble diameter of the microbubbles 13 and / or nanobubbles 14 dispersed and dissolved in the film-forming synthetic resin 10e (polyvinyl alcohol stock solution 10e) or the content of the microbubbles 13 and / or nanobubbles 14, the high-viscosity or medium-viscosity film-forming synthetic resin 10e can be converted to a low-viscosity one, and the degree of viscosity reduction or the degree of viscosity reduction of the film-forming synthetic resin 10e can be adjusted. The film-forming synthetic resin 10e (polyvinyl alcohol stock solution 10e) does not require the use of harmful substances such as organic solvents to reduce its viscosity, or the amount of harmful substances such as organic solvents used can be reduced when reducing the viscosity, thereby reducing the viscosity of the film-forming synthetic resin 10e for film formation without adversely affecting the human body.

[0159] The microbubbles 13 and nanobubbles 14 dispersed and dissolved within the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) are negatively charged and are mixed into the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e in the form of spheres with high internal bubble pressure. The particle sizes of the microbubbles 13 dispersed and dissolved (dispersed and mixed) within the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) were measured using visualization methods, light scattering methods, laser diffraction / scattering methods, and interference imaging methods. The content and total number of microbubbles 13 dispersed and mixed inside the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) were measured using an electrical detection zone method and an image analysis method.

[0160] The visualization method uses a digital microscope or CCD camera imaging device to capture images of microbubbles 13, converting them to black and white through image processing to measure particle size (bubble diameter). The light scattering method uses a laser particle size distribution analyzer to irradiate the interior of glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, or synthetic resin for film molding 10e (polyvinyl alcohol) containing microbubbles 13 with a beam of laser light. The scattered light is detected with a photomultiplier tube, and particle size (bubble diameter) is measured based on Mie scattering theory. The laser diffraction and scattering method measures particle size (bubble diameter) by irradiating laser light onto microbubbles, which instantaneously scatter diffracted and scattered light forward, backward, and to the side. The scattered light pattern is correlated with the bubble diameter, allowing particle size (bubble diameter) to be measured. The interference imaging method obtains a scattering pattern when laser light is irradiated onto spherical bubbles, but interference fringes are observed on out-of-focus surfaces. The particle size (bubble diameter) is determined from the number of interference fringes detected by a CCD camera.

[0161] The rising speed of the microbubbles 13 at room temperature within the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) containing dispersed microbubbles 13 is in the range of 0.00005 mm / min to 0·0005 mm / min (0·0005 to 0.00005 mm / min). Because the microbubbles 13 have a small volume, their rising speed within the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e is extremely slow. If the rising speed of microbubbles 13 inside glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, or synthetic resin for film molding 10e exceeds 0·0005 mm / min, it becomes difficult to keep microbubbles 14 inside glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, or synthetic resin for film molding 10e for a long period of time, and microbubbles 14 may volatilize prematurely from glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, or synthetic resin for film molding 10e. Since the rising speed of microbubbles 13 inside glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e (polyvinyl alcohol) at room temperature is within the above-mentioned range, microbubbles 13 are less likely to volatilize from glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e, and microbubbles 13 can be retained inside glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e for a long period of time.

[0162] The particle size, content, and total number of nanobubbles 14 dispersed within glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) were measured using nanoparticle tracking analysis (NTA). Nanoparticle tracking analysis can measure the particle size (particle size distribution), content, total number (particle number concentration), and aggregation state of nanobubbles 14 within glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) with high resolution. In nanoparticle tracking analysis, glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e are placed in a sample chamber and irradiated with laser light. Nanoparticle tracking analysis uses a highly sensitive CMOS camera to detect the 90° scattered light from each nanobubble 15 irradiated with laser light. The Brownian motion of the detected particles is observed and tracked as the movement of bright spots on the camera image. By tracking this movement, the diffusion coefficient is calculated, and the particle size of the nanobubbles 14 is determined using the Stokes-Einstein equation. The particle distribution (concentration) is calculated by counting all particles within the camera's field of view, which has a known volume, to determine the number of nanobubbles 14 per ml. This determines the nanobubble 14 content in the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol), as well as the total number of nanobubbles 14 per ml of the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e. In nanoparticle tracking analysis, the zeta potential of the particles is determined by measuring the electrophoretic mobility when a constant voltage is applied to the cell.The volume of the nanobubbles 14 dispersed and mixed inside the glass-based coating liquid 10a, the paint 10b, the ink 10c, the adhesive 10d, and the synthetic resin for film formation 10e (polyvinyl alcohol) can also be measured by a laser diffraction / scattering method, and the number of the nanobubbles 14 dispersed and mixed inside the glass-based coating liquid 10a, the paint 10b, the ink 10c, the adhesive 10d, and the synthetic resin for film formation 10e can also be measured by an electrical detection zone method or an image analysis method.

[0163] In the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e (polyvinyl alcohol) containing dispersed nanobubbles 14, the rising speed of the nanobubbles 14 within the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e is in the range of 0.000005 mm / min to 0·00005 mm / min (0·00005 to 0.000005 mm / min) at room temperature. Because the nanobubbles 14 have an extremely small volume, their rising speed within the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e (polyvinyl alcohol) is extremely slow. If the rising speed of nanobubbles 14 inside glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) exceeds 0·00005 mm / min, it becomes difficult to retain nanobubbles 14 inside glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e for a long period of time, and nanobubbles 14 may volatilize prematurely from glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e. Since the rising speed of nanobubbles 14 inside glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e (polyvinyl alcohol) at room temperature is within the above-mentioned range, nanobubbles 14 are unlikely to volatilize from glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e, and nanobubbles 14 can be retained inside glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e for a long period of time.

[0164] The nanobubbles 14 are spherical bubbles with a diameter of less than 1 μm and a Reynolds number Re of approximately 1 inside the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol).

[0165] The rising speed of nanobubbles 14 inside glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) is extremely slow. The rising speed of nanobubbles 14 inside glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e depends on the liquid properties of glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e. In water, the Reynolds number Re becomes approximately 1 at a diameter of approximately 100 μm, and they become spherical bubbles. The rising speed U of a spherical bubble with diameter d is calculated using Stokes' equation: U=pgd 2 / 18μ, where p is the liquid density, g is the gravitational acceleration, and μ is the liquid viscosity.

[0166] Nanobubbles 14 dissolved (mixed) inside glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) have high internal bubble pressure (self-pressurizing effect). The internal bubble pressure is higher than the pressure around the bubble by ΔP according to the Young-Laplace equation: ΔP = 4σ / d, due to the influence of surface tension σ. The relationship between the diameter d of the bubble inside glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e and the internal bubble pressure is such that the smaller the bubble, the higher the internal bubble pressure (3.87 "atm" for 1 μm, 29.7 "atm" for 100 nm, assuming the surface tension σ of water: 72.8 mN / m (20°C), and the pressure around the bubble: 1 "atm"). Therefore, when the bubbles contract, the partial pressure of the dissolved gas components, i.e., the driving force for dissolution, increases, and by reducing the gas to nano-size, the gas becomes more easily dissolved in the paint 10B, and a large amount of nanobubbles 14 dissolves in the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e.

[0167] The nanobubbles 14 mixed (dissolved) inside the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) have a large gas-liquid interfacial area. The gas-liquid interfacial area per unit volume, A / V, is expressed by the formula: A / V = 6d. A / V increases as the bubble diameter d decreases, and contributes greatly to the amount of gas mixed (dissolved) inside the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e. The amount of gas mixed (dissolved) in the nanobubbles 14 is extremely large. The mass transfer rate N (mol / s) of the bubbles into the paint 10B is expressed by the formula: N = K G A(pp*) where KG is the gas phase reference overall mass transfer coefficient (mol / m 2 sPa”, A is the surface area of ​​the bubble [m 2 ], p is the partial pressure of the dissolved component in the bubble (Pa), and p* is the partial pressure of the gas phase in equilibrium with the dissolved component in the liquid phase (Pa).

[0168] When nanobubbles 14 are dissolved (mixed) into a glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, or synthetic resin for film molding 10e (polyvinyl alcohol), the overall mass transfer resistance 1 / K is calculated based on the double boundary film theory consisting of a gas boundary film and a liquid boundary film sandwiching the gas-liquid interface. L or 1 / K G H is the liquid phase resistance 1 / k L and gas phase resistance 1 / k G Ohm's law of electrical resistance as a sum of H and K: 1 / K L =1 / K G H=1 / k L +1 / k G H. Here, K L is the liquid phase reference overall mass transfer coefficient, H is Henry's constant (p = HC), formula: 1 / K L =1 / K G H=1 / k L +1 / k G If the gas-side mass transfer resistance 1 / kGH can be substantially ignored at H, the liquid-phase reference overall mass transfer coefficient KL and the liquid-side mass transfer coefficient kL become substantially equal.

[0169] For spherical bubbles, the Reynolds number Re<1 and the rising velocity is the Stokes equation: U=pgd 2 Liquid-side mass transfer coefficient k when expressed as / 18μ L is the formula: k L =D L / d[l+(1+dU / D L ) 1 / 3 ] where 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, the equation: k L =D L +dl+[(1+dU / D L ) 1 / 3 ] is the bubble diameter and the liquid-side mass transfer coefficient k of the oxygen-water system. L When the bubble diameter d is 100 μm, k L is 1.817 10 -4 "m / s", k when the bubble diameter d is 10 μm L is 5.37·10 -4 "m / s", k when the bubble diameter d is 1 μm L is 5.20·10 -3 The diffusion coefficient of oxygen inside the paint 10 is D L is 2.60·10 -9 "m 2 / s" was used.

[0170] k for the bubble diameter d L Using the value of N = K and the pressure inside the bubble (atm) for the bubble diameter d, G The mass transfer rate N was calculated using A(pp*) and rearranged. As a result, when the bubble diameter d was 10 μm, the rising rate U was 3.26·10 -3 "m / min", pressure difference ΔP is 2.91·10 4 , bubble number ratio is 1.0 10 6 , area ratio is 100, mass transfer rate ratio is 6.15·10 4 "mol / s" and 1.0 10 8 When the bubble diameter d is 100 nm, the rising speed U is 3.15·10 -7 "m / min", pressure difference ΔP is 2.91·10 6 , bubble number ratio is 1.0 10 12, area ratio is 1.0 10 4 , mass transfer rate ratio is 5.95·10 10 "mol / s" and 1.0 10 18 "mol / mm".

[0171] If a spherical bubble with a diameter of 1 mm is divided into bubbles with a diameter of 10 μm, the number of bubbles will be 10 6 If a spherical bubble with a diameter of 1 mm is divided into bubbles with a diameter of 100 nm, the number of bubbles will increase to 10 12 The surface area of ​​a bubble with a diameter of 1 mm is 1, and the surface area is 10 4 Therefore, if the mass transfer rate (dissolution rate) per unit time of a bubble with a diameter of 1 mm is 1, then the mass transfer rate (dissolution rate) of a bubble with a diameter of 10 μm is 6·10 4 The mass transfer rate (dissolution rate) per unit time for a bubble with a diameter of 1 mm is 1, and for a bubble with a diameter of 100 nm, the mass transfer rate (dissolution rate) is 6·10 10 In this way, when the bubbles become nano-sized, the surface area and the partial pressure inside the bubbles increase, and the rate of increase decreases, which causes a sudden increase in the mass transfer rate (dissolution rate) for the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e.

[0172] The surface potential of nanobubbles 14 was measured using electrophoresis experimental equipment. The nanobubbles 14 generated in the container were subjected to zigzag motion by switching the electric field direction of the electrodes introduced into the electrophoresis cell (thickness 1 mm, height 23.0 mm, width 75.0 mm) every 1 second. The bubble diameter was calculated using the Stokes equation based on the measurement of the rising speed, and the zeta potential of the bubbles was calculated using the Smoluchowski equation: ζ = μu / ε based on the horizontal speed. Here, ζ is the zeta potential "V", μ is the viscosity "kg / ms" of the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e, and u is the mobility of the bubbles "m 2 / sV”, ε is the dielectric constant of the paint 10, s 2 C2 / kgm 3 "

[0173] Nanobubbles 13 are negatively charged at -30 to -40 mV regardless of their bubble diameter (microbubbles 14 are similar). The cluster structures of glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) are formed from molecules of glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e and ionized positive and negative ions, and while positive and negative ions tend to settle within the structures, negative ions in particular tend to accumulate at interfaces, resulting in negative charges. Because the nanobubbles 14 are negatively charged, the nanobubbles 14 and the microbubbles 13 inside the glass-based coating liquid 10a, the paint 10b, the ink 10c, the adhesive 10d, and the synthetic resin for film molding 10e repel each other, and the nanobubbles 14 and the microbubbles 13 repel each other, and the nanobubbles 14 and the microbubbles 13 are unlikely to bond (unite) with each other or with the microbubbles 13 due to electrostatic repulsion.

[0174] The nanobubbles 13 (microbubbles 14) dissolved (mixed) in the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) are negatively charged, so that the nanobubbles 13 dispersed and dissolved in the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e repel each other, the microbubbles 14 repel each other, and the nanobubbles 14 repel each other. 3, the nanobubbles 14 and the microbubbles 13 do not bond (unite), and it is possible to prevent the nanobubbles 14 and the microbubbles 13 from becoming large bubbles due to bonding between the nanobubbles 14 and between the microbubbles 13, or between the nanobubbles 14 and the microbubbles 13, and it is possible to maintain the dispersed and mixed state of the microbubbles 13 that are fine bubbles and the dispersed and dissolved (mixed) state of the nanobubbles 14 that are ultrafine bubbles in the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e.

[0175] In the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e (polyvinyl alcohol), the microbubbles 13 (fine bubbles) and / or the nanobubbles 14 (ultrafine bubbles) are dispersed and dissolved (dispersed and mixed) within the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e without bonding (coalescing) with each other, with each other, or with each other. Therefore, the nanobubbles 14 and the microbubbles 13 are less likely to volatilize from the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e, and the nanobubbles 14 and the microbubbles 13 can remain within the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e for a long period of time.

[0176] The forces acting on the nanobubbles 14 inside the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) include buoyancy and drag. Buoyancy is proportional to the volume of the nanobubbles 14 (proportional to the cube of the radius of the nanobubbles 14). Drag is proportional to the cross-sectional area of ​​the nanobubbles 14 (proportional to the square of the radius of the nanobubbles 14) and proportional to the square of the rising speed of the nanobubbles 14. Specifically, when the radius of the nanobubbles 14 is r, the density of the glass-based coating liquid 10a, the paint 10b, the ink 10c, the adhesive 10d, and the synthetic resin for film molding 10e (polyvinyl alcohol) is ρ, the acceleration of gravity is g, the viscosity of the glass-based coating liquid 10a, the paint 10b, the ink 10c, the adhesive 10d, and the synthetic resin for film molding 10e is η, and the moving speed of the nanobubbles 14 is u, the buoyancy acting on the nanobubbles 14 (the density of the nanobubbles 14 is ignored) is expressed by Archimedes' principle as follows: F = 4πr 3 It is expressed by ρg / 3.

[0177] Furthermore, the resistance force acting on the nanobubbles 14 is expressed by the formula (2): F = 6πηru according to Stokes' theorem. From the formulas (1) and (2), the movement speed u of the nanobubbles 14 inside the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) is expressed by the formula (3): u = (2 / 9)r 2 The upward movement velocity of the nanobubbles 14 within the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e was calculated using equation (3). As is clear from equation (3), the larger the radius r (particle size) of the nanobubbles 14, the higher the movement velocity u of the nanobubbles 14 within the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e.

[0178] When the radius r of the nanobubble 14 under 1 atmosphere is a, the radius r and the water depth h are calculated by the following formula (4): r = a × {101325 / (ρgh + 101325)} 1 / 3As is clear from formulas (3) and (4), the nanobubbles 14 have larger particle sizes and rise faster as the water depth of the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film molding 10e (polyvinyl alcohol) becomes shallower.

[0179] When nanobubbles 14 and larger microbubbles 13 are mixed in the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, or synthetic resin for film formation 10e (polyvinyl alcohol), the nanobubbles 14 may float up due to the influence of the latter larger microbubbles 13 or may be affected by cavitation collapse due to external pressure, which may shorten the lifespan of the nanobubbles 14. However, in the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e that contain only nanobubbles 14, the lifespan of the nanobubbles 14 inside the glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, and synthetic resin for film formation 10e is long.

[0180] The liquid 10 (glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, synthetic resin for film formation 10e) contains gas dissolved therein as microbubbles 13 and / or nanobubbles 13 undergoing Brownian motion, and the average bubble diameter D 50 is 10 μm or less (average bubble diameter D 50 is 10 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and the average bubble diameter D of the nanobubbles 14 is 50 The diameter of the microbubbles 13 and / or nanobubbles 14 contained in 1 ml of the solution is in the range of 1 to 800 nm, preferably in the range of 1 to 300 nm. 5 10 pieces / ml or more 12 1 / ml or less, the average bubble diameter D 50The microbubbles 13 and / or nanobubbles 14 cut or disrupt the bonds between the molecules of the liquid 10, and the cutting or disruption of the bonds between the molecules of the liquid 10 weakens the interactions between the molecules of the liquid 10, so that the viscosity of the liquid 10 after the microbubbles 13 and / or nanobubbles 14 have been dispersed and dissolved can be reliably made lower than that of the liquid 10 before being dispersed and dissolved, and the viscosity of the glass-based coating liquid 10a (liquid 10) or paint 10b (liquid 10) used for application, the ink 10c (liquid 10) used for printing, the adhesive 10d (liquid 10) used for adhesion, and the synthetic resin for film molding 10e (liquid 10) used for molding and solidifying can be easily reduced.

[0181] The liquid 10 (glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, synthetic resin for film formation 10e) can be converted from a high-viscosity or medium-viscosity liquid 10 to a low-viscosity liquid 10 by adjusting the average bubble diameter of the microbubbles 13 and / or nanobubbles 14 dispersed or dissolved therein, the content of the microbubbles 13 and / or nanobubbles 14, and by selecting the gas that constitutes the microbubbles 13 or nanobubbles 14, and the degree of reduction in the viscosity of the liquid 10 or the degree of low viscosity of the liquid 10 can be adjusted. The viscosity of the liquid 10 (glass-based coating liquid 10a, paint 10b, ink 10c, adhesive 10d, synthetic resin for film formation 10e) can be reduced by reducing the amount of harmful substances, such as organic solvents, that may be harmful to the human body, or by not using any harmful substances. [Explanation of symbols]

[0182] 10 liquid 10a Glass-based coating liquid 10b paint 10c ink 10d adhesive 10e Synthetic resin for film molding (polyvinyl alcohol) 11 Base material 12 sides 13 Microbubbles 14 Nanobubbles 15 Nanobubble mixing device 16 Coating liquid storage tank 17 Gas supply tank 18 Water Pump 19 Air supply pump 20 Static fluid mixing device (microbubble / nanobubble generator) 21 Coating liquid storage tank 22 Water supply pipeline 23 Air supply line 24 Mixing line 25 Supply pipeline 26 Cylindrical unit 27 Honeycomb structure element (mixing blade) 28a Inorganic coating film 28b Organic / inorganic hybrid coating film

Claims

1. A liquid used for coating, printing, bonding, or molding and solidifying, A liquid characterized in that the viscosity of the liquid is reduced by dissolving a predetermined gas in the liquid.

2. 2. The liquid according to claim 1, wherein the viscosity of the liquid before dissolving the gas in the liquid is 10 mPa·s or more and 10,000 mPa·s or less, and the viscosity of the liquid after dissolving the gas in the liquid is reduced to 1 / 2 or more and 1 / 10 or less of the viscosity of the liquid before dissolving the gas in the liquid.

3. 3. The liquid according to claim 2, wherein the viscosity of the liquid after dissolving the gas in the liquid is 1 mPa·s or more and 5000 mPa·s or less.

4. The gas dissolved in the liquid is microbubbles and / or nanobubbles, and the average bubble diameter D ５０ The liquid according to claim 2 or 3, wherein the particle size is 10 μm or less.

5. The liquid according to claim 4 , wherein the nanobubbles are undergoing Brownian motion within the liquid.

6. The microbubbles and / or nanobubbles contained in 1 ml of the liquid are 10 ５ pcs / ml or more 10 １２ The liquid according to claim 4 or claim 5, wherein the concentration is not more than 1 / ml.

7. 7. The liquid according to claim 6, wherein the gas constituting the microbubbles and / or the nanobubbles is one or more selected from the group consisting 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.

8. The liquid according to claim 7, wherein the liquid used for application is a coating liquid or paint to be applied to the surface of a predetermined substrate.

9. The coating liquid contains silicon oxide (SiO ２ 9. The liquid according to claim 8, wherein the coating material is a glass-based coating liquid based on fluororesin paint, silicon resin paint, acrylic resin paint, urethane resin paint, or water-based paint.

10. The liquid according to claim 7, wherein the liquid used for printing is an ink to be printed on a printing surface.

11. The liquid according to claim 7, wherein the liquid used for adhesion is an adhesive.

12. 8. The liquid according to claim 7, wherein the liquid used for molding and solidifying is a synthetic resin used for molding a film.

13. A liquid producing method for producing the liquid according to any one of claims 1 to 12, comprising: The liquid production method is characterized in that the gas is dissolved in the liquid by using one of a pressurized dissolution method, a micropore and porous method, a Venturi method, an ultrasonic method, a static mixer method, a cavitation method, a swirling liquid flow method, and a shear method, or by combining at least two of these methods.

14. 14. The liquid producing method according to claim 13, wherein the gas is microbubbles and / or nanobubbles, and the liquid producing method uses one of those methods or a combination of at least two of those methods to dissolve the microbubbles and / or nanobubbles in the liquid.

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