Coating composition and method for producing the same

Abstract

An object of the present invention is to provide a coating agent composition which forms a coating layer having high transparency, superhydrophilicity, and an antifouling function or an antifogging function even in a low temperature atmosphere. Another object of the present invention is to provide a method for producing the coating agent composition. Still another object of the present invention is to provide a product having a coating layer using the coating agent.SOLUTION: A method for producing a coating agent composition, comprising the steps of: (A) allowing a polymer obtained by polymerizing a silicic acid alkoxide to coexist with cerium hydroxide and / or cerium oxide to obtain an intermediate composition; and (B) allowing the intermediate composition obtained in the step (A) to coexist with acidic colloidal silica to obtain a coating agent composition.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a coating agent composition and a method for producing the same.

Background Art

[0002] Regarding conventional antifouling and anti-fogging coating layers, by imparting water repellency or hydrophilicity to the surface of a substrate, an antifouling function is exerted by preventing the adhesion of contaminants and the self-cleaning effect by water. However, many of the coating agents used for these are solvent-based, which is not preferable from the perspective of environmental protection these days. Therefore, there is a demand for a solvent-free antifouling coating agent. However, regarding water-based coating agents, it has been difficult to form a thin film of 0.4 μm or less. Also, there has been no coating agent that is a one-component type and can be stored for a long time.

[0003] When using a coating agent outdoors, room temperature curing is necessary, but water-based coating agents do not have very good adhesion to the substrate, and particularly have low adhesion to plastic products.

[0004] The imparting of water repellency prevents water from adhering to the coating layer and exhibits an antifouling effect. Also, the imparting of hydrophilicity and water absorbency causes the thin water film or absorbed water on the substrate surface to exhibit hydrophilicity, and by flowing the water, the attached dirt is washed away to exhibit antifouling properties. On the other hand, regarding the anti-fogging effect, a small amount of water vapor adheres to the surface of the substrate in the water repellent film, causing irregular reflection of light and resulting in fogging. Also, in a hydrophilic film, when there is little water, a small amount of dirt adheres to the surface, causing fogging. Also, the attached dirt enters the coating layer due to the static electricity of the coating layer, reducing the anti-fogging property. Also, a coating layer having water absorbency has its water resistance and adhesion reduced by containing water, promoting the deterioration of the coating layer.

[0005] Antifouling and anti-fogging coating agents are known that contain tin oxide-based inorganic ultrafine particles to reduce the surface resistance of the substrate and improve adhesion to the substrate (for example, Patent Document 1). However, reducing the surface resistance of the substrate requires the addition of a large amount of tin oxide-based ultrafine particles, which leads to a decrease in hydrophilicity and adhesion, making it difficult to create a coating layer that combines stable antifouling and anti-fogging properties.

[0006] Furthermore, conventional anti-fog coating layers (for example, Patent Document 2) cause fogging when one side of the transparent substrate is below freezing and the other side is at room temperature. Also, when the temperature of the transparent substrate is lowered below freezing and then returned to room temperature, fogging occurs on the substrate. In addition, if the anti-fouling and anti-fog coating layer applied to the transparent substrate absorbs water, the absorbed water freezes below freezing point, causing fogging due to crystallization. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2008-208241 [Patent Document 2] Japanese Patent Application Publication No. 05-222338 [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention aims to provide a coating agent composition that forms a coating layer that is highly transparent, superhydrophilic, and possesses antifouling and anti-fogging properties even in low-temperature environments. Furthermore, the present invention aims to provide a method for producing this coating agent composition. Finally, the present invention aims to provide a product having a coating layer using this coating agent. [Means for solving the problem]

[0009] The inventors of this invention conducted diligent research to solve the above problems and have now completed the present invention.

[0010] In other words, the present invention includes the following embodiments. Section 1. A method for producing a coating agent composition, (A) A step of obtaining an intermediate composition by polymerizing silicate alkoxide and coexisting with cerium hydroxide and / or cerium oxide, (B) A step to obtain a coating agent composition by coexisting the intermediate composition obtained in step (A) with acid colloidal silica. A manufacturing method that includes the above. Section 2. Furthermore, the manufacturing method according to item 1, further comprising the step of polymerizing the silicate alkoxide before step (A) to obtain the polymer of 3 polymer to 40 polymer. Section 3. The method for producing the product according to claim 1 or 2, wherein the alkoxide silicate is tetramethoxysilane and / or tetraethoxysilane. Section 4. The manufacturing method according to any one of claims 1 to 3, wherein the cerium hydroxide and / or cerium oxide is a ceria sol having a particle size of 100 nm or less and a cerium concentration of 50% by weight or less in terms of cerium oxide. Section 5. Furthermore, the manufacturing method according to any one of claims 1 to 4, further comprising the step of obtaining a further processed coating agent composition by coexisting the coating agent composition and a surfactant after step (B). Section 6. Furthermore, the manufacturing method according to any one of claims 1 to 5, further comprising the step of obtaining a further processed coating composition by coexisting the coating composition or the further processed coating composition with tin oxide-based fine particles after step (B). Section 7. Furthermore, the manufacturing method according to any one of claims 1 to 6, further comprising the step of obtaining a further processed coating composition by coexisting the coating composition or the further processed coating composition with an aqueous binder resin component after step (B). Section 8. Furthermore, after the step (B), a step of obtaining a further processed coating agent composition by coexisting the coating agent composition or the further processed coating agent composition with a water-soluble solvent and / or water is included, and the production method according to any one of items 1 to 7. Item 9. A coating agent composition containing a polymer obtained by polymerizing an alkoxysilicate, cerium hydroxide and / or cerium oxide, and acidic colloidal silica. Item 10. The coating agent composition according to item 9, wherein the polymer obtained by polymerizing the alkoxysilicate is a trimer to a 40-mer. Item 11. The coating agent composition according to item 9 or 10, wherein the alkoxysilicate is tetramethoxysilane and / or tetraethoxysilane. Item 12. The coating agent composition according to any one of items 9 to 11, wherein the cerium hydroxide and / or cerium oxide is a ceria sol having a particle diameter of 100 nm or less and a cerium concentration of 50% by weight or less in terms of cerium oxide. Item 13. The coating agent composition according to any one of items 9 to 12, having a light transmittance of 80% or more. Item 14. The coating agent composition according to any one of items 9 to 13, further containing a surfactant. Item 15. The coating agent composition according to any one of items 9 to 14, further containing tin oxide-based fine particles. Item 16. The coating agent composition according to any one of items 9 to 15, further containing an aqueous binder resin component. Item 17. The coating agent composition according to any one of items 9 to 16, further containing a water-soluble solvent and / or water. Item 18. A coated article having a coating layer containing the coating agent composition according to any one of items 9 to 17. [2]]

Advantages of the Invention

[0011] According to the present invention, it is possible to provide a coating agent composition that has high transparency, super hydrophilicity, and also has antifouling and anti-fogging functions even in a low-temperature atmosphere. Further, according to the present invention, it is possible to provide a method for producing such a coating agent composition.

Embodiments for Carrying Out the Invention

[0012] <Definition of Terms> In this specification, the term "coating agent composition" means a composition that forms a coating layer when applied to the surface of a substrate such as glass, metal, plastic, etc., and imparts effects such as protection of the substrate surface, polishing effect, antifouling effect, water repellency effect, etc. according to the purpose.

[0013] In this specification, the term "ceria sol" means a sol dispersion containing cerium hydroxide and / or cerium oxide as fine particles.

[0014] In this specification, the term "colloidal silica" means a state in which fine particles of silica (silicon dioxide) are dispersed in a solvent. Usually, silica is amorphous, its particle size is usually about 10 to 300 nm, and it is dispersed in a colloidal state.

[0015] 1. Process (A) The alkoxysilicate used in the present invention is not particularly limited and may have any alkoxy group. Among them, an alkoxysilicate having an alkoxy group with 1 to 4 carbon atoms, such as a methoxy group or an ethoxy group, is preferable because it is liquid at room temperature. Examples of such alkoxysilicate include tetramethoxysilane and tetraethoxysilane.

[0016] When polymerizing the silicate alkoxide used in the present invention, one or a mixture of two or more types may be used. The condensation reaction may be carried out by known methods, for example, by a dehydration reaction or dealcoholization reaction after hydrolysis. Water, organic solvents, catalysts, etc. may be used as appropriate for these reactions. The degree of polymerization of the polymer after the reaction is not particularly limited, but it is preferable that the polymer be a 3- to 40 polymer to obtain a viscosity suitable for a coating agent composition. It may also be mixed with water-soluble solvents, water, etc. as appropriate.

[0017] The form of cerium hydroxide and / or cerium oxide used in the present invention is not particularly limited; for example, it may be in powder form, but from the viewpoint of dispersibility, it is preferable to use a ceria sol form dispersed in a water-soluble solvent or water. When cerium hydroxide and / or cerium oxide is in the form of a ceria sol, sol formation may be carried out by known methods. A suitable ceria sol can be obtained when the cerium hydroxide and / or cerium oxide has a particle size of 100 nm or less and the cerium concentration is 50% by weight or less in terms of cerium oxide.

[0018] In step (A), the coating agent composition or the further processed coating agent composition may be further processed by coexisting it with other metal alkoxides. Examples of metal alkoxides include aluminum compounds, titanium compounds, and zirconium compounds. These compounds are thought to act as curing catalysts.

[0019] In the present invention, the mixing means can be appropriately employed according to the reaction scale, including methods such as stirring, shaking, and ultrasonic dispersion.

[0020] 2. Process (B) The colloidal silica used in this invention can be, for example, a water-soluble solvent or a form dispersed in water. While the particle size is not particularly limited, from the viewpoint of dispersibility, it is preferable that the particles be spherical with a diameter of 100 nm or less, or nanoparticles in which spherical particles are linked in a chain. Furthermore, to maintain the stability of the coating composition, it is preferable to use acidic colloidal silica.

[0021] When acidic colloidal silica is directly mixed with cerium hydroxide and / or cerium oxide, a white gel substance is formed, impairing transparency; therefore, only about 0.5% to 3% of cerium hydroxide and / or cerium oxide can be mixed in terms of solid content. In this regard, the present inventors have found that by coexisting a composition containing a polymer obtained by polymerizing silicate alkoxide and cerium hydroxide and / or cerium oxide with acidic colloidal silica, the amount of cerium hydroxide and / or cerium oxide that can be incorporated can be increased without impairing the transparency of the coating composition. According to the present invention, a coating composition containing up to about 30% of cerium hydroxide and / or cerium oxide in terms of solid content can be produced depending on the application.

[0022] 3. Additional process The manufacturing method of the present invention may further include dilution steps, steps involving the coexistence of further additives, etc., in order to produce a coating composition suited to the application. The additional steps are not particularly limited as long as the properties of the coating composition of the present invention are not impaired, and the manufacturing method of the present invention may include multiple identical or different additional steps, and their order is not limited. The following are examples of additional steps, but the present invention is not limited in any way by these examples.

[0023] The manufacturing method of the present invention may further include a step after step (B) to obtain a further processed coating composition by coexisting the coating composition or a further processed coating composition with a surfactant. The surfactant improves the wettability of the coating composition of the present invention with respect to the substrate. The form of the surfactant is not particularly limited and may be a solid, liquid, a water-soluble solvent and / or a mixture with water. If the water content of the coating composition of the present invention is high, the surface tension increases and the wettability with respect to the substrate deteriorates. In particular, if the water content is 70% or more, it is preferable that the coating composition contains a surfactant.

[0024] The surfactant used in the present invention is not particularly limited, and both ionic and nonionic surfactants can be used. However, it is preferable to use a surfactant that can improve the wettability of the coating composition and maintain transparency when present in an amount of 0.5% by weight or less relative to the coating composition. Furthermore, it is particularly preferable to use a nonionic surfactant because it does not affect the dispersibility of the solid components of the coating composition. Among these, acetylene glycol-based surfactants are particularly preferred because they not only improve wettability in small amounts but also improve the antifouling and antifogging properties of the coating composition.

[0025] The manufacturing method of the present invention may further include a step after step (B) to obtain a further processed coating composition by coexisting the coating composition or a further processed coating composition with tin oxide-based fine particles. The form of the tin oxide-based fine particles is not particularly limited and may be a solid, a water-soluble solvent and / or a mixture with water, etc. The tin oxide-based fine particles improve the adhesion of the coating composition to the substrate and suppress the adhesion of dirt due to their antistatic effect.

[0026] The tin oxide-based fine particles used in the present invention are not particularly limited, but preferably include antimond-doped tin oxide and / or indium-doped tin oxide. In order to maintain the transparency of the coating composition, the particle size of the tin oxide-based fine particles is preferably 100 nm or less, and particularly preferably 50 nm or less.

[0027] The manufacturing method of the present invention may further include a step after step (B) of obtaining a further processed coating composition by coexisting the coating composition or a further processed coating composition with an aqueous binder resin component. The form of the aqueous binder resin component is not particularly limited and may be a solid, a water-soluble solvent and / or a mixture with water, etc. When the coating composition contains an aqueous binder resin component, it exhibits excellent adhesion to the resin substrate and becomes difficult to peel off. The aqueous binder resin is selected according to the type of resin of the substrate, and one with excellent adhesion to the substrate should be selected. For example, for polyethylene terephthalate film, vinyl chloride film, polyolefin film, polypropylene film, and various other films, water-dispersible polyester resin emulsion, water-soluble self-reacting acrylic resin, water-dispersible chlorinated propylene resin emulsion, etc., can be used.

[0028] It is known that the dispersibility of water-based binder resin components improves in the presence of tin oxide-based fine particles. In such cases, it is preferable that the water-based binder resin component be present in an amount of 0.3 to 10 parts by mass, and more preferably 0.8 to 8 parts by mass, per 100 parts by mass of tin oxide-based fine particles. If the amount of water-based binder resin component is less than 0.3 parts by mass, adhesion to the substrate and water resistance will decrease, and the substrate will become more prone to peeling.

[0029] Since the stability of the coating composition of the present invention decreases when the concentration of solid components is high, the manufacturing method of the present invention may further include a step of obtaining a further processed coating composition by coexisting the coating composition or a further processed coating composition with a water-soluble solvent and / or water.

[0030] The water-soluble solvent used in the present invention is not particularly limited, and examples include alcohols such as ethanol and glycol ethers. Its form is also not particularly limited, and it may be water or a mixture with a different water-soluble solvent. Since a high content of water-soluble solvent in the coating composition restricts storage and handling as a hazardous material, it is preferable to have a low content of water-soluble solvent and a high content of water. The water content is preferably 50% or more, more preferably 70% or more, and particularly preferably 80% or more, relative to the coating composition.

[0031] The manufacturing method of the present invention may further include a step of obtaining a further processed coating composition by coexisting the coating composition or a further processed coating composition with a dye, antioxidant, lubricant, stabilizer, thickener, pH adjuster, ultraviolet absorber, flame retardant, etc., to the extent that the properties of the coating composition of the present invention are not impaired. The types of these additives are not particularly limited. Furthermore, the form of these additives is not particularly limited and may be solid, liquid, water-soluble solvent and / or a mixture with water, etc.

[0032] 4. Coating composition Furthermore, the present invention encompasses a coating composition comprising a polymer obtained by polymerizing silicate alkoxide, cerium hydroxide and / or cerium oxide, and acidic colloidal silica.

[0033] The coating layer formed by the coating composition of the present invention preferably has high transparency and does not reduce the transmittance of the transparent substrate. The transmittance is preferably 80% or more, more preferably 90% or more, even more preferably 95% or more, and particularly preferably 98% or more for a 0.4 μm thin film. Furthermore, the coating composition of the present invention contains ceriasol with a high refractive index, which has the effect of increasing reflectance, so when the coating composition is applied to a black substrate, it has little effect on the color of the substrate. On the other hand, the coating layer formed by the coating composition of the present invention may have low transparency as long as its antifouling and antifogging properties are maintained, and may be colored with dyes or the like.

[0034] The coating layer formed by the coating composition of the present invention has very high hydrophilicity and exhibits antifouling and anti-fogging properties. Therefore, the contact angle of the coating layer with water is preferably 30° or less, more preferably 15° or less, and particularly preferably 5° or less.

[0035] The composition ratio of the coating agent composition of the present invention is not limited to a range that does not impair its properties, and the composition ratio of the polymer obtained by polymerizing silicate alkoxide, cerium hydroxide and / or cerium oxide, and acidic colloidal silica is preferably 460:3:537 to 385:167:448 in terms of solid content, and more preferably 459:6:535 to 448:30:522.

[0036] Furthermore, from the viewpoint of safety and stability of the coating composition of the present invention, a high water content is preferable. The water content is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more, relative to the coating composition.

[0037] Furthermore, the coating composition of the present invention preferably contains a surfactant in order to improve wettability. The amount of surfactant is not limited as long as the properties of the coating composition of the present invention are not impaired, but is preferably 1% by weight or less, and particularly preferably 0.5% by weight or less, relative to the coating composition.

[0038] The coating composition of the present invention may further contain tin oxide-based fine particles. The amount of these particles is not limited as long as the properties of the coating composition of the present invention are not impaired, and is preferably 1% to 20% by weight, and particularly preferably 3% to 10% by weight, relative to the coating composition.

[0039] The coating composition of the present invention may further contain a water-based binder resin component. The amount thereof is not limited as long as the properties of the coating composition of the present invention are not impaired, and is preferably 0.3% to 20% by weight, and particularly preferably 0.5% to 3% by weight relative to the coating composition.

[0040] 5. Painted products Furthermore, the present invention includes coated articles having a coating layer containing the coating composition of the present invention. The substrate used for the coated article is not particularly limited and includes, for example, plastic films, plastic resin sheets and their molded products, metals, and ceramics such as glass and cement and their ceramic molded products.

[0041] The method of applying the coating composition to the substrate is not particularly limited and includes, for example, spray coating, dip coating, brush coating, gravure roll coating, reverse roll coating, lip coating, air knife coating, wire bar coating, curtain flow coating, etc. Furthermore, it also includes laminating a plastic film with an adhesive applied to one side to the substrate and then applying the coating composition to it. It also includes applying an undercoat of another coating composition to the substrate and then applying the coating composition of the present invention on top of that.

[0042] The coating composition of the present invention can usually be cured at room temperature between 10°C and 40°C. At room temperature, the coating layer is usually formed after drying for 3 hours or more. Heat curing may also be performed to accelerate the curing time. In that case, it is preferable to heat treat to 40°C or higher within the range that the substrate can withstand. If it is difficult to form the coating layer, it is preferable to heat treat to 80°C or higher within the range that the substrate can withstand. In that case, treatment at 100°C or higher for about 30 seconds to 2 minutes is preferable. On the other hand, it is necessary to select a heating temperature and heating time within a range that does not impair the properties of the coating layer, and the heating temperature is preferably 120°C or lower. [Examples]

[0043] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way to these examples.

[0044] 1.Light transmittance Light transmittance was measured using a UV-Vis spectrophotometer V-530 (manufactured by JASCO Corporation). 2. Contact angle and hydrophilicity The contact angle and water content were evaluated using a portable contact angle meter PG-X+ (manufactured by Matsubo Co., Ltd.). 3. Antifouling Test The antifouling test was commissioned to the Japan Civil Engineering Research Center and conducted in accordance with the Accelerated Test Method III for the Evaluation of Antifouling Materials. In this test, a material is judged to conform to the Class III antifouling material standard for civil engineering applications if the brightness difference ΔL is -3.20 or higher and the post-test transmittance is 66.0% or higher. 4. Adhesion Adhesion was evaluated using a 10x10 grid test and a pencil scratch test in accordance with JIS K 5400:1990. 5. Anti-fog properties The anti-fogging properties against steam from hot water were evaluated by placing the sample over a container filled with hot water at 90°C or higher and observing the resulting fogging. Next, the anti-fogging properties against temperature changes from low temperature to room temperature were evaluated by cooling the sample to below -20°C and observing the resulting fogging when it was removed and brought to room temperature of 20°C.

[0045] Example 1 Coating agent composition A 150 g (20% solids by weight) of a 10-polymer siloxane polymer was prepared by condensing 100 g of tetraethoxysilane in water, ethanol, and hydrochloric acid. 60 g of ethanol was added to the polymer, and 150 g (15% solids by weight) of acidic colloidal silica (ST-OUP, Nissan Chemical Corporation) was added to prepare a coating agent composition through partial reaction. 0.2% by weight of the nonionic surfactant orphine (Shin-Etsu Chemical Co., Ltd.) was added to the coating agent composition. Further water was added to obtain a room-temperature curing coating agent composition A with a solids content of 1.5%.

[0046] Coating agent composition B 150 g (20% solids) of a 10-polymer siloxane polymer was prepared by condensing 100 g of tetraethoxysilane in water, ethanol, and hydrochloric acid. 3 g of ceria sol aqueous solution (30% solids) (Daiichi Kigenso Kagaku Kogyo) was added to this polymer, and 150 g (15% solids) of acidic colloidal silica was added to partially react and prepare a coating agent composition. 0.2% by weight of the nonionic surfactant orphine was added to this coating agent composition. Further water was added to obtain a room-temperature curing coating agent composition B with a solids content of 1.5%.

[0047] A sample was prepared by applying either the above coating agent composition A or B to float glass (blue plate glass) used in residential and building windows, door glass, etc., to form a coating layer.

[0048] Various evaluations were performed on the obtained samples. The results are shown in Table 1. Untreated glass had low hydrophilicity, resulting in poor stain resistance and poor anti-fogging. Glass coated with coating agent A had a transparent, hydrophilic coating layer, but poor anti-fogging. The coating layer with coating agent B was superhydrophilic, resulting in a coating layer that combined excellent stain resistance and anti-fogging. Similarly, the above coating agents were applied to the windshield, rear window, and window glass of laminated automotive glass, and the results were almost the same. In particular, glass used in automobiles requires low-temperature anti-fogging properties, and the coating layer with coating agent B is optimal.

[0049] [Table 1]

[0050] Example 2 Coating agents A and B used in Example 1 were applied to a mirror. Because mirrors reflect light, fogging occurs even with the adhesion of a small amount of water droplets. The results are shown in Table 2. Untreated mirrors fog up because steam adheres to the surface as water droplets. Mirrors coated with coating agent A fog up slightly when steam adheres to them due to diffuse reflection of light. However, when a large amount of water was applied, a uniform water film was formed on the surface of the mirror, and even when exposed to steam, the water film absorbed the steam, maintaining anti-fogging properties for about an hour. Mirrors coated with coating agent B had very high hydrophilicity, and even when exposed to steam, water droplets did not form, maintaining anti-fogging properties.

[0051] [Table 2]

[0052] Example 3 A room-temperature curing coating composition with a solid content of 1% was prepared, similar to coating agent B in Example 1. The coating composition was applied to the exterior painted surface of a detached house using an air sprayer after the paint had dried completely, and then dried at room temperature. A crane truck was used for painting. No discoloration was observed on the exterior paint (white) after it was left outdoors for three years after application. Conventional coating agents that combine colloidal silica with siloxane polymer have a low refractive index of 1.43, and in dark-colored paints such as black, light absorption increases, causing discoloration. This coating composition contains ceriasol, which has a high refractive index, and was found to have the effect of increasing light reflectivity. Therefore, this coating composition does not cause discoloration when applied to black surfaces.

[0053] Example 4 A room-temperature curing coating agent composition with a solid content of 1% was prepared, similar to coating agent B in Example 1. The coating agent composition was placed in a dip tank, and an air conditioning equipment component consisting of aluminum fins and copper pipes was immersed and then removed. After that, the coating agent liquid was applied thinly and evenly by rotation and vibration. To shorten the curing time, hot air drying at 100°C was performed. As a result, hydrophilicity was imparted, and the adhesion of water droplets to the aluminum fins was suppressed by a thin water film. Therefore, the evaporation of the water film was accelerated, and the cooling efficiency of the air conditioner was improved.

[0054] Example 5 Coating agent composition C Similar to coating composition B, a coating composition was prepared by partially reacting a siloxane polymer of tetraethoxysilane 10 polymer with a ceriasol aqueous solution and acidic colloidal silica. In addition, a composition (solid content 10% by weight) containing a polyester resin emulsion and water-dispersed tin oxide ultrafine particles (Unitika Ltd.) was diluted with water to prepare an aqueous composition with a solid content of 2% by weight. To the above coating composition, 0.2% by weight of the nonionic surfactant orphine and 20% by weight of the above aqueous composition were added. Further water was added to obtain a room-temperature curing coating composition C with a solid content of 1.5%.

[0055] The above coating agent composition C was applied to one side of a 50 μm thick PET film and heated at 110°C for 20 minutes to accelerate curing and form a coating layer. An adhesive was applied to the other side, and release paper was attached. By laminating this transparent, stain-resistant, and anti-fogging PET film to a transparent substrate, it becomes possible to provide a transparent functional product with stain-resistant and anti-fogging properties.

[0056] Coating agent composition D Similar to coating composition B, a coating composition was prepared by partially reacting a siloxane polymer of tetraethoxysilane 10 polymer with a ceriasol aqueous solution and acidic colloidal silica. Furthermore, an aqueous composition was prepared by diluting a composition (Unitika Ltd.) containing a polyether ester amide resin component and water-dispersible tin oxide ultrafine particles with water. To the above coating composition, 0.2% by weight of the nonionic surfactant orphine (Nisshin Chemical Industry) and 20% by weight of the aqueous composition were added. Further water was added to obtain coating composition D with a solid content of 3%. Coating composition D was applied to a PET film and heated at 110°C for 1 minute to form an excellent anti-fogging coating layer. However, it could not be cured at room temperature.

[0057] Table 3 shows the results of applying coating composition C to a PET film, with coating composition A used as a control. When coating composition A was applied directly to the PET film, it was found to have poor adhesion, be easily peeled off, and have low anti-fogging properties. Coating composition C, which contains tin oxide ultrafine particles with a low surface resistance, has good adhesion to the PET film and exhibits excellent anti-fogging properties.

[0058] [Table 3]

[0059] Furthermore, Table 4 shows the results of evaluating the performance of PET films coated with coating composition C, which were then laminated onto various pieces of equipment.

[0060] [Table 4]

[0061] Example 6 The performance of agricultural vinyl film after applying a coating composition was investigated.

[0062] Agricultural polyvinyl chloride film (PVC film) is susceptible to plasticizer bleed-out. Therefore, acidic colloidal silica (20% solids content) was added to a water-based acrylic resin (U-Double, Nippon Shokubai Co., Ltd.) at a solids content ratio of 30%, and then diluted to prepare an aqueous solution with a solids content of 3%, which was applied to the PVC film as an undercoat. After drying the film at 50°C for 10 minutes, coating composition B was applied as a topcoat and heated at 50°C for 10 minutes to form a coating layer.

[0063] Polyolefin film (PO film) exhibits poor adhesion to coating composition B. Therefore, a composition containing acid-modified polyolefin / ether block polymer and tin oxide (10% solids content) (Unitika Ltd.) was prepared by adding 30% acidic colloidal silica and 0.2% nonionic surfactant, diluting with water to prepare an aqueous solution with 3% solids content, which was used as the undercoat agent. Furthermore, a coating agent composition with 3% solids content was prepared in the same manner as coating agent composition B, and this was added to the undercoat agent at a solids ratio of 30%, which was then diluted with water to obtain a coating agent composition with 1.5% solids content. The undercoat agent was applied to the PO film and heated at 110°C for 30 seconds. Furthermore, the coating agent composition was applied again and heated at 110°C for 30 seconds to form a coating layer.

[0064] The evaluation results are shown in Table 5. This coating composition imparted antifouling and anti-fogging properties to agricultural films. As a result, the reduction in light transmittance due to contamination is suppressed, and the falling of water droplets is also suppressed, thus not affecting agricultural crops.

[0065] [Table 5]

[0066] Example 7 Regarding the preparation of the coating agent composition, the relationship between the order of raw material addition and the amount of ceriasol that can be added was evaluated. The composition ratios other than ceriasol were the same as those of coating agent composition B.

[0067] (a) A siloxane polymer was prepared by condensing tetraethoxysilane in water, ethanol, and hydrochloric acid. To this polymer, an aqueous ceriasol solution and acidic colloidal silica were added in that order. Further, water was added to dilute the mixture.

[0068] (b) Tetraethoxysilane was condensed in water, ethanol, and hydrochloric acid to prepare a siloxane polymer. Acidic colloidal silica and ceria sol aqueous solution were added to the polymer in that order. Further, water was added to dilute the mixture.

[0069] (c) Tetraethoxysilane, water, ethanol, hydrochloric acid, ceriasol aqueous solution, and acidic colloidal silica were reacted simultaneously. Further, water was added to dilute the mixture.

[0070] (d) Tetraethoxysilane was condensed in water, ethanol, and hydrochloric acid to prepare a siloxane polymer. Acidic colloidal silica was added to the polymer, and then water was added to dilute it. An aqueous ceria sol solution was then added to this.

[0071] The amount of ceriasol that could be added to each composition (a) to (d) was 30%, 3%, 1%, and 0.5% in terms of solid content, respectively. Composition (a) can accommodate more ceriasol than the other compositions, and the amount added can be adjusted according to the application. Furthermore, a stable composition can be produced during the manufacturing process. If the solid content ratio is higher than the above, there is a higher possibility of yellow precipitate forming in the final composition, and the stability decreases.

Claims

1. A method for producing a coating agent composition, (A) A step of obtaining an intermediate composition by polymerizing silicate alkoxide and coexisting with cerium hydroxide and / or cerium oxide, (B) A step to obtain a coating agent composition by coexisting the intermediate composition obtained in step (A) with acid colloidal silica. A manufacturing method that includes the above.

2. Furthermore, the manufacturing method according to claim 1, further comprising a step of polymerizing the silicate alkoxide before step (A) to obtain the polymer of 3 polymer to 40 polymer.

3. The method for producing the product according to claim 1, wherein the alkoxide silicate is tetramethoxysilane and / or tetraethoxysilane.

4. The manufacturing method according to claim 1, wherein the cerium hydroxide and / or cerium oxide is a ceria sol having a particle size of 100 nm or less and a cerium concentration of 50% by weight or less in terms of cerium oxide.

5. Furthermore, the manufacturing method according to claim 1, further comprising the step of obtaining a further processed coating agent composition by coexisting the coating agent composition and a surfactant after step (B).

6. Furthermore, the manufacturing method according to claim 1, further comprising the step of obtaining a further processed coating agent composition by coexisting the coating agent composition or the further processed coating agent composition with tin oxide-based fine particles after step (B).

7. Furthermore, the manufacturing method according to claim 1, further comprising the step of obtaining a further processed coating agent composition by coexisting the coating agent composition or the further processed coating agent composition with an aqueous binder resin component after step (B).

8. Furthermore, the manufacturing method according to any one of claims 1 to 7, further comprising the step of obtaining a further processed coating agent composition by coexisting the coating agent composition or the further processed coating agent composition with a water-soluble solvent and / or water after step (B).

9. A coating composition comprising a polymer obtained by polymerizing silicate alkoxide, cerium hydroxide and / or cerium oxide, and acidic colloidal silica, obtained by the manufacturing method described in claim 1.

10. The coating composition according to claim 9, wherein the polymer obtained by polymerizing the alkoxide silicate is a 3-polymer to a 40-polymer.

11. The coating composition according to claim 9, wherein the alkoxide silicate is tetramethoxysilane and / or tetraethoxysilane.

12. The coating composition according to claim 9, wherein the cerium hydroxide and / or cerium oxide is a ceria sol having a particle size of 100 nm or less and a cerium concentration of 50% by weight or less in terms of cerium oxide.

13. The coating composition according to claim 9, wherein the light transmittance is 80% or more.

14. Furthermore, the coating composition according to claim 9, comprising a surfactant.

15. Furthermore, the coating composition according to claim 9 further comprises tin oxide-based fine particles.

16. Furthermore, the coating composition according to claim 9 further comprises a water-based binder resin component.

17. Furthermore, the coating composition according to claim 9 comprises a water-soluble solvent and / or water.

18. A painted article having a coating layer containing the coating agent composition according to any one of claims 10 to 17.

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