Premium Layer Forming Coating Composition

Abstract

To provide a primer layer-forming coating composition capable of forming a primer layer with superior weather resistance.SOLUTION: A primer layer-forming coating composition comprises rutile-type titanium oxide particles that comprise Fe and Zr in a solid phase, with an interplanar spacing of the (110) plane being 0.3250 nm or more, as determined by X-ray diffraction measurement, and the average particle diameter within the range of 5 nm or more and 50 nm or less, and at least one resin selected from the group consisting of polyurethane resin and polyester resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a coating composition for forming a primer layer. [Background technology]

[0002] In recent years, plastic substrates have increasingly replaced inorganic glass substrates as materials for optical lenses, particularly eyeglass lenses. This is because plastic substrates possess superior properties in terms of lightness, impact resistance, processability, and dyeability, and further improvements and developments have been made to the materials themselves as second-generation plastic lenses, resulting in greater lightness and higher refractive index. However, these plastic substrates have the disadvantage of being more easily scratched than inorganic glass substrates.

[0003] Therefore, to avoid this drawback, the surface of optical lenses made from plastic substrates is usually provided with a silicone-based curable coating, i.e., a hard coat layer. Furthermore, when a high refractive index plastic lens substrate is used, in order to avoid light interference (appearing as interference fringes) between the lens and the hard coat layer, metal oxide fine particles are included in the hard coat layer to match its refractive index to that of the lens substrate. For example, Patent Document 1 discloses the use of composite oxide fine particles containing titanium oxide, zirconium oxide, and antimony pentoxide as the metal oxide fine particles. Patent Document 2 also proposes the use of core-shell type metal oxide fine particles, in which titanium oxide-containing metal oxide fine particles are used as core particles and their surfaces are coated with a coating layer made of antimony oxide. It is also known that using titanium oxide can suppress discoloration (yellowing) of the substrate due to ultraviolet light.

[0004] On the other hand, optical lenses in which a hard coat layer is formed on the surface of a plastic lens substrate, and an anti-reflective coating layer is further applied on top of that, have the disadvantage of poor impact resistance. As a means to solve this disadvantage, for example, Patent Document 3 proposes a technique of providing a primer layer between the plastic lens substrate and the hard coat layer.

[0005] In recent years, there has been a demand for plastic lens substrates with higher refractive indices, leading to the use of polythiourethane lenses and polythioepoxy lenses. However, some of these substrates have poor adhesion, further increasing the need for the aforementioned primer layer. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 5-264806 [Patent Document 2] Japanese Patent Publication No. 2002-363442 [Patent Document 3] Special Publication No. 8-505896 [Overview of the project] [Problems that the invention aims to solve]

[0007] According to the inventors' findings, higher weather resistance is required even in the primer layer.

[0008] Therefore, the present invention aims to provide a primer layer forming paint composition that can form a primer layer with excellent weather resistance. [Means for solving the problem]

[0009] According to one aspect of the present invention, the following primer layer forming coating composition is provided. [1] Fe and Zr are in solid solution, The interplanar spacing of the (110) plane obtained by X-ray diffraction measurement is 0.3250 nm or more. The average particle diameter is in the range of 5 nm or more and 50 nm or less. Rutile-type titanium dioxide particles, and, The material comprises at least one resin selected from the group consisting of polyurethane resins and polyester resins. Coating composition for forming a primer layer. [2] The primer layer forming paint composition according to [1], wherein the tensile elongation of the resin is in the range of 100% or more and 2000% or less. [3] The primer layer forming paint composition according to [1] or [2], wherein the glass transition temperature of the resin is 0°C or lower. [4] A primer layer forming paint composition according to any one of [1] to [3], wherein the Ti content of the rutile-type titanium oxide particles is in the range of 40% by mass or more and 90% by mass or less in terms of TiO2 relative to the total amount of the rutile-type titanium oxide particles. [5] A primer layer forming paint composition according to any one of [1] to [4], wherein the Fe content of the rutile-type titanium oxide particles is in the range of 0.01 mol% or more and 5 mol% or less in mol% relative to Ti. [6] A primer layer forming paint composition according to any one of [1] to [5], wherein the Zr content of the rutile-type titanium oxide particles is in the range of 0.1 mol% or more and 15 mol% or less in mol% relative to Ti. [7] A primer layer forming paint composition according to any one of [1] to [6], wherein the Sn content of the rutile-type titanium oxide particles is in the range of 1 mol% or more and 30 mol% or less in mol% relative to Ti. [8] A primer layer forming paint composition according to any one of [1] to [7], wherein the Si content of the rutile-type titanium oxide particles is in the range of 5 mol% or more and 70 mol% or less relative to Ti. [9] The primer layer forming paint composition according to any one of [1] to [8], wherein the Zr / Fe molar ratio of the rutile-type titanium oxide particles is 1 or more. [Effects of the Invention]

[0010] The present invention provides a primer layer forming paint composition that can form a primer layer with excellent weather resistance. [Modes for carrying out the invention]

[0011] The inventors have discovered that by solid-solving Fe and Zr in rutile-type titanium dioxide, particles with low photocatalytic activity can be obtained. Coating films containing these particles exhibit significantly improved weather resistance. Furthermore, the problem of discoloration that often occurs in coating films containing particles obtained by solid-solving Fe in rutile-type titanium dioxide was resolved by the unique combination of elements Fe and Zr. In addition, the inventors have discovered that when a primer layer is formed using a coating composition containing these particles and at least one of polyurethane resin and polyester resin, a primer layer with particularly excellent weather resistance is formed.

[0012] The present invention relates to a primer layer-forming coating composition comprising rutile-type titanium dioxide particles in which Fe and Zr are solid-solved, the interplanar spacing of the (110) plane obtained by X-ray diffraction measurement is 0.3250 nm or more, and the average particle diameter is in the range of 5 nm to 50 nm, as well as at least one resin selected from the group consisting of polyurethane resins and polyester resins.

[0013] The primer layer-forming coating composition of the present invention (hereinafter also referred to as the coating composition) will be described in detail below.

[0014] [Titanium dioxide particles] The coating composition of the present invention contains rutile-type titanium dioxide as a filler. Rutile-type titanium dioxide has lower photocatalytic activity than titanium dioxide having other crystal structures, and is therefore suitable as a material for obtaining a coating film with high weather resistance. In addition, rutile-type titanium dioxide has a higher refractive index than titanium dioxide having other crystal structures, so it can be suitably used, for example, as an optical material. Furthermore, as it has a narrower band gap and is excellent in ultraviolet (UV) absorbing ability compared with titanium dioxide having other crystal structures, it can also be suitably used as a UV absorbing material. When a material having such UV absorbing ability is applied to a substrate, UV degradation of the substrate can be suppressed, and the weather resistance of the substrate with the coating film can be improved. Other crystal structures of titanium dioxide include anatase-type, brookite-type and the like, and these can be distinguished by X-ray diffraction measurement.

[0015] The Ti content of the rutile-type titanium dioxide particles contained in the coating composition of the present invention is preferably in the range of 40% by mass or more and 90% by mass or less in terms of TiO₂, based on the total amount of the rutile-type titanium dioxide particles, more preferably in the range of 45% by mass or more and 80% by mass or less, and particularly preferably in the range of 50% by mass or more and 70% by mass or less. If the Ti content is too low, the refractive index and UV absorbing ability tend to decrease. In addition, if the Ti content is too high, the photocatalytic activity will increase. Therefore, when the Ti content is within the above range, rutile-type titanium dioxide particles having high refractive index and high UV absorbing ability and low photocatalytic activity can be obtained. When the coating composition of the present invention containing such rutile-type titanium dioxide particles is used, a primer layer with high weather resistance can be obtained.

[0016] In the rutile-type titanium oxide particles contained in the coating composition of the present invention, Fe and Zr are solid-dissolved. Generally, solid solution means that two or more elements, which may be metallic or non-metallic, dissolve in each other to form a uniform solid phase as a whole. Such solid solutions are classified into substitutional solid solutions and interstitial solid solutions. Regardless of whether it is a substitutional solid solution or an interstitial solid solution, the crystal lattice of rutile-type titanium oxide changes if Fe and Zr form a solid solution. Such changes in the crystal lattice can be observed by X-ray diffraction measurement. Regarding the titanium oxide particles of the present invention, when Fe and Zr are solid-dissolved, the interplanar spacing of the (110) plane obtained by X-ray diffraction measurement becomes 0.3250 nm or more.

[0017] The Fe content of the rutile-type titanium oxide particles contained in the coating composition of the present invention, in terms of mol% relative to Ti (when the amount of Ti is taken as 100 mol%), is preferably in the range of 0.01 mol% or more and 5 mol% or less, more preferably in the range of 0.05 mol% or more and 3 mol% or less, and particularly preferably in the range of 0.08 mol% or more and 2 mol% or less. When the Fe content is within the aforementioned range, the photocatalytic activity of the rutile-type titanium oxide particles decreases, and coloration is also reduced. When the coating composition of the present invention containing such rutile-type titanium oxide particles is used, a primer layer having high weather resistance can be obtained.

[0018] The Zr content of the rutile-type titanium oxide particles contained in the coating composition of the present invention, in terms of mol% relative to Ti, is preferably in the range of 0.1 mol% or more and 15 mol% or less, more preferably in the range of 1 mol% or more and 10 mol% or less, and particularly preferably in the range of 3 mol% or more and 7 mol% or less. The titanium oxide particles of the present invention, in which Zr is solid-dissolved together with Fe, have remarkably lower photocatalytic activity compared to titanium oxide particles in which each of Fe and Zr is solid-dissolved alone. This synergistic effect makes it possible to reduce the photocatalytic activity while minimizing the coloration that occurs when Fe is solid-dissolved. When the coating composition of the present invention containing such rutile-type titanium oxide particles is used, a primer layer having high weather resistance can be obtained.

[0019] The molar ratio of Fe to Zr (Zr / Fe) of the rutile-type titanium dioxide particles contained in the paint composition of the present invention is preferably 1 or more, more preferably in the range of 1 to 60, even more preferably in the range of 1 to 30, and particularly preferably in the range of 1 to 15. When the molar ratio of Fe to Zr is within the above range, rutile-type titanium dioxide particles with lower photocatalytic activity and less discoloration can be obtained. When the paint composition of the present invention containing such rutile-type titanium dioxide particles is used, a primer layer with high weather resistance can be obtained.

[0020] The rutile-type titanium dioxide particles contained in the paint composition of the present invention preferably contain elements other than Ti, Fe, and Zr. Specifically, it is preferable to contain at least one element selected from Sn, Si, K, and Al, and particularly preferable to contain Sn or Si. Sn enhances the crystallinity of rutile-type titanium dioxide and suppresses the formation of crystalline structures other than rutile, such as anatase type. This further improves the weather resistance and transparency of the rutile-type titanium dioxide particles. From this viewpoint, the Sn content is preferably in the range of 1 mol% to 30 mol%, more preferably in the range of 3 mol% to 20 mol%, and particularly preferably in the range of 5 mol% to 15 mol% relative to Ti. Furthermore, Si further reduces the photocatalytic activity of the rutile-type titanium dioxide particles. From this viewpoint, the Si content is preferably in the range of 5 mol% to 70 mol%, more preferably in the range of 10 mol% to 50 mol%, and particularly preferably in the range of 15 mol% to 40 mol%, relative to Ti. The content of elements other than Ti, Fe, and Zr is preferably in the range of 5 mol% to 120 mol%, more preferably in the range of 10 mol% to 70 mol%, and particularly preferably in the range of 20 mol% to 50 mol%, relative to Ti. When the content of elements other than Ti, Fe, and Zr is within the above ranges, rutile-type titanium dioxide particles with a high refractive index and low photocatalytic activity can be obtained. When the paint composition of the present invention containing such rutile-type titanium dioxide particles is used, a primer layer with high weather resistance can be obtained.

[0021] The rutile-type titanium dioxide particles contained in the paint composition of the present invention are preferably coated particles with a coating layer formed on their surface. For example, if a coating layer containing at least one element selected from Zr, Si, Al, and Sb is formed, the photocatalytic activity of the rutile-type titanium dioxide particles can be further reduced. In particular, if a coating layer containing either or both Si and Zr is formed, the photocatalytic activity can be further reduced, and dispersibility in polar solvents such as water or alcohol tends to be good. When the paint composition of the present invention containing such rutile-type titanium dioxide particles is used, a primer layer with high adhesion to the substrate can be obtained.

[0022] The surface of the rutile-type titanium oxide particles or the surface of the coating layer contained in the paint composition of the present invention preferably has a surface treatment layer that has been surface-treated with an organosilicon compound such as a silane coupling agent or an amine-based compound. Modifying these surfaces with an organosilicon compound or an amine-based compound improves their dispersibility in the resin and organic solvent components contained in the paint composition.

[0023] The proportion of the coating layer provided by the rutile-type titanium oxide particles in the paint composition of the present invention is preferably in the range of 1% to 30% by mass, more preferably in the range of 1% to 20% by mass, and particularly preferably in the range of 3% to 10% by mass, relative to the total amount of coating particles, in terms of oxide. In the case of a coating layer containing Zr, Si, Al, and Sb, the amount of the coating layer is calculated by converting it to ZrO2, SiO2, Al2O3, or Sb2O5, respectively. If other elements are included, the oxide shall be estimated from the valence of the raw material. For example, if K derived from KOH is included, it shall be converted as K2O. If there are fluctuations in the valence of the raw material during the manufacturing process, the valence of the element shall be determined by performing X-ray photoelectron spectroscopy (XPS measurement) on the finally obtained coating particles. Specifically, from the spectrum obtained by XPS measurement, the peaks attributed to each valence shall be identified, and the oxide shall be estimated based on the valence of the peak with the greatest peak intensity. For example, Cu + , and Cu2+ A peak appears, Cu 2+ The peak of Cu + If the peak intensity is stronger than that, it shall be converted to CuO. Furthermore, the proportion of the surface treatment layer is preferably in the range of 1% by mass or more and 10% by mass or less, more preferably in the range of 2% by mass or more and 9% by mass or less, and particularly preferably in the range of 3% by mass or more and 8% by mass or less, relative to the total amount of coated particles. The proportion of the surface treatment layer shall be calculated by converting the inorganic components contained in the surface treatment layer to oxides. For example, if the surface treatment layer contains a silane coupling agent, the Si contained in the surface treatment layer shall be calculated by converting it to SiO2.

[0024] The average particle size of the rutile-type titanium dioxide particles contained in the paint composition of the present invention is in the range of 5 nm or more and 50 nm or less, preferably in the range of 8 nm or more and 40 nm or less, and more preferably in the range of 10 nm or more and 30 nm or less. When using the paint composition of the present invention in which the average particle size of the rutile-type titanium dioxide particles is in the above range, a dense coating film is easily formed when forming the primer layer. In the present invention, the value of the average particle size is obtained by measuring the size of the primary particles using an electron microscope and taking the average.

[0025] The refractive index of the rutile-type titanium oxide particles contained in the paint composition of the present invention is preferably 1.8 or higher, more preferably 2 or higher, and particularly preferably 2.1 or higher. Rutile-type titanium oxide particles having such a high refractive index can be suitably used for optical materials. The upper limit of the refractive index is not particularly limited, but may be 3 or less.

[0026] The yellowness (YI value) of the titanium dioxide particles contained in the paint composition of the present invention is preferably 58 or less, and more preferably 55 or less. When Fe is solid-solved in rutile-type titanium dioxide, this value increases, and the yellowness intensifies. However, by solid-solving Zr together with Fe, a high photocatalytic activity inhibitory effect can be achieved even with a small amount of Fe, thus achieving both low coloration and high weather resistance. When the paint composition of the present invention containing such rutile-type titanium dioxide particles is used, a highly weather-resistant and transparent primer layer can be obtained.

[0027] The photocatalytic activity of rutile-type titanium dioxide particles contained in the paint composition of the present invention can be determined by irradiating a system of rutile-type titanium dioxide particles and dye with ultraviolet light for 3 hours and measuring the rate of change in absorbance (fading rate) before and after irradiation. The fading rate of rutile-type titanium dioxide particles is preferably 30% or less, more preferably 20% or less, even more preferably 15% or less, and particularly preferably 10% or less. A high photocatalytic activity results in a high fading rate, and a low photocatalytic activity results in a low fading rate. The rutile-type titanium dioxide particles contained in the paint composition of the present invention have a low fading rate, i.e., low photocatalytic activity. Using the paint composition of the present invention containing such rutile-type titanium dioxide particles yields a primer layer with high weather resistance.

[0028] [resin] The paint composition of the present invention comprises at least one of a polyurethane resin and a polyester resin. The paint composition of the present invention, when combined with the aforementioned rutile-type titanium oxide particles and these resins, yields a primer layer with higher weather resistance. Although the reason for this is not clear, it is thought that the combination of rutile-type titanium oxide particles in which Fe and Zr are solid-solved and these resins enhances weather resistance. The mass ratio of resin to filler (resin / filler) in the paint composition of the present invention is preferably in the range of 30 / 70 or more and 90 / 10 or less.

[0029] The tensile elongation of the resin contained in the paint composition of the present invention is preferably in the range of 100% or more and 2000% or less, more preferably in the range of 200% or more and less than 1500%, particularly preferably in the range of 250% or more and less than 1000%, and most preferably in the range of 290% or more and less than 900%. When the tensile elongation of the resin is within the above range, a primer layer with superior impact resistance and adhesion is more easily formed.

[0030] The glass transition temperature of the resin contained in the coating composition of the present invention is preferably 0°C or lower, and more preferably -20°C or lower. When the glass transition temperature of the resin is within the above range, a primer layer with superior impact resistance and adhesion is more easily formed.

[0031] [solvent] The coating composition of the present invention contains a solvent. The solvent is preferably a mixed solvent of water and an organic solvent to ensure good dispersibility of the resin and rutile-type titanium oxide particles. Examples of organic solvents include alcohols such as methanol, ethanol, ethylene glycol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and octanol. Esters such as ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and γ-butyrolactone; Ethers such as diethyl ether, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, and cyclohexanone; Aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; Cyclohexane and other cyclic hydrocarbons; and; Examples include amides such as dimethylformamide, N,N-dimethylacetacetamide, and N-methylpyrrolidone. The content of the solvent is preferably in the range of 60% by mass or more and 99.8% by mass or less, more preferably in the range of 70% by mass or more and 98% by mass or less, and particularly preferably in the range of 80% by mass or more and 90% by mass or less, based on the total amount of the paint composition.

[0032] [Coated substrate including primer layer] The coating composition of the present invention, when applied to various substrates such as glass or plastic, forms a primer layer on the surface of the substrate. In this way, a hard coat layer, anti-reflective layer, UV-cutting layer, etc., can be formed on the primer layer as needed, resulting in a coated substrate. This coated substrate can be used as an optical substrate for eyeglass lenses, various optical lenses such as those for cameras, front panels for optical displays, display cases, window glass, contact glass for photocopiers, automotive light covers, and various UV-blocking filters. A coated substrate containing a primer layer obtained using the coating composition of the present invention has high weather resistance and is therefore suitable for use in the aforementioned applications. Furthermore, when forming a primer layer using the coating composition of the present invention, the substrate is preferably a thiourethane-based or polycarbonate-based substrate.

[0033] [Method for producing the paint composition of the present invention] The paint composition of the present invention can be prepared, for example, by a manufacturing method comprising the following steps (1) to (3). However, the manufacturing method of the paint composition of the present invention is not limited to the following manufacturing method. (1) Preparation of dispersion containing rutile-type titanium dioxide particles (2) Resin dispersion preparation process (3) Mixing process The method for preparing the paint composition of the present invention will be described in detail below.

[0034] [(1) Preparation of dispersion containing rutile-type titanium dioxide particles] In this process, a dispersion containing rutile-type titanium dioxide particles is prepared, in which Fe and Zr are in solid solution, the interplanar spacing of the (110) plane obtained by X-ray diffraction measurement is 0.3250 nm or more, and the average particle diameter is in the range of 5 nm to 50 nm. Such rutile-type titanium dioxide particles can be prepared, for example, by the following steps (A) to (C). (A) Co-precipitation gel preparation process (B) Heat treatment precursor preparation process (C) Hydrothermal treatment process

[0035] (A) Co-precipitation gel preparation process In this step, an aqueous solution containing Ti, Fe, and Zr is neutralized to prepare a coprecipitation gel containing Ti, Fe, and Zr. Preparing a coprecipitation gel containing Ti, Fe, and Zr further promotes the solid solution of Fe and Zr into the final rutile-type titanium oxide.

[0036] Aqueous solutions containing Ti, Fe, and Zr can be prepared by dissolving a Ti source, an Fe source, and a Zr source in water. The Ti source can be conventionally known raw materials such as titanium tetrachloride, titanium sulfate, and titanium alkoxide. The Fe source can be conventionally known raw materials such as iron chloride, iron sulfate, iron nitrate, and iron acetate. Furthermore, the Zr source can be conventionally known raw materials such as zirconium chloride, zirconium carbonate, and zirconium nitrate. The pH of the aqueous solution containing Ti, Fe, and Zr is preferably 3 or less.

[0037] In this process, an alkali with a pH of 10 or higher can be used to neutralize the aforementioned aqueous solution. For example, an alkaline aqueous solution of sodium hydroxide, potassium hydroxide, or ammonia dissolved in water can be used. By mixing the aforementioned aqueous solution and the alkaline aqueous solution until the pH is in the range of 4 to 10, a coprecipitation gel containing Ti, Fe, and Zr is formed. This coprecipitation gel can be recovered by filtration and may be washed with water or other means as necessary.

[0038] (B) Hydrothermal treatment precursor preparation process In this step, the coprecipitation gel obtained in the previous step is redispersed (disintegrated) in water to prepare a hydrothermal treatment precursor. Conventional known methods can be used to disintegrate the coprecipitation gel. For example, a method of dispersing the coprecipitation gel in water and treating it with sonication, or a method of dispersing it in water using an acid or alkali can be used. Alternatively, hydrogen peroxide solution may be used to disintegrate it. At this time, it is preferable to adjust the amount of water so that the concentration of solids in the final hydrothermal treatment precursor is 10% by mass or less.

[0039] The average particle size of the solids contained in the hydrothermal treatment precursor obtained in this process is preferably in the range of 5 nm or more and 50 nm or less, more preferably in the range of 10 nm or more and 40 nm or less, and particularly preferably in the range of 15 nm or more and 30 nm or less. If the average particle size of the solids contained in the coprecipitation gel aqueous dispersion becomes large, the average particle size of the rutile-type titanium dioxide finally obtained also tends to become large. Therefore, it is preferable to adjust the average particle size of the solids contained in the coprecipitation gel dispersion to be close to the average particle size of the rutile-type titanium dioxide particles mentioned above.

[0040] In this step, after disintegrating the coprecipitation gel, specific elemental components may be added. For example, raw materials containing elements such as Sn, Si, or Al may be added. These raw materials are preferably water-soluble. If they are not water-soluble, raw materials dispersed in the form of fine particles such as a sol are preferred. In this case, when using salts containing alkali metals or alkaline earth metals as raw materials, it is preferable to dissolve the raw materials and then remove the alkali metals or alkaline earth metals using a cation exchange resin or the like.

[0041] (C) Hydrothermal treatment process In this step, the hydrothermal treatment precursor obtained in the previous step is subjected to hydrothermal treatment to prepare rutile-type titanium oxide particles in which Fe and Zr are solid-solved. In this step, the hydrothermal treatment precursor can be subjected to hydrothermal treatment using conventionally known equipment such as an autoclave. The temperature of the hydrothermal treatment is preferably in the range of 100°C to 250°C, more preferably in the range of 120°C to 220°C, and particularly preferably in the range of 130°C to 210°C. The holding time in the above temperature range is preferably 1 hour to 48 hours, more preferably 5 hours to 24 hours, and particularly preferably in the range of 10 hours to 20 hours.

[0042] The liquid after hydrothermal treatment contains rutile-type titanium oxide, which may be separated and washed as needed. Furthermore, the separated rutile-type titanium oxide can be calcined to enhance its crystallinity.

[0043] When forming a coating layer on the surface of rutile-type titanium oxide particles, for example, it can be formed by the method described in Japanese Patent Application Publication No. 2009-155496. Furthermore, the surface or the surface of the coating layer can also be hydrophobicized (surface treated) using the method described in the same publication.

[0044] The method for dispersing the aforementioned rutile-type titanium dioxide particles in a solvent can be a conventionally known method. For example, if the titanium dioxide particles are in powder form, a dispersion can be prepared by adding them to water or an organic solvent and then performing a dispersion treatment such as bead milling or ultrasonic treatment. In this case, if the concentration of solids in the dispersion is 10% by mass or less, the titanium dioxide particles will disperse more easily in the solvent. In addition, the zeta potential of the titanium dioxide particles can be measured and the pH can be adjusted to a range suitable for dispersion.

[0045] The solvent used in this process is preferably a mixed solvent of water and an organic solvent. The organic solvents described above can be used.

[0046] [(2) Resin dispersion preparation process] In this step, a resin dispersion is prepared in which at least one of polyurethane resin and polyester resin is dispersed in a solvent. Such a resin dispersion may be prepared by purchasing and using a commercially available resin emulsion, for example, or by dispersing powdered resin in a solvent. The solvent used in this step is not particularly limited, as long as it can disperse the resin.

[0047] [(3) Mixing process] In this step, the paint composition of the present invention is prepared by mixing the dispersion containing rutile-type titanium oxide particles obtained in the previous step with a resin dispersion. A conventionally known method can be used for mixing.

[0048] [Method for manufacturing a coated substrate including a primer layer] A conventionally known method can be used to produce a coated substrate containing a primer layer using the coating composition of the present invention. For example, the primer layer-forming coating composition of the present invention can be applied to a substrate by a conventionally known method such as dipping, spraying, spinning, roll coating, or bar coating, dried, and cured by heat treatment or ultraviolet irradiation.

[0049] Examples of substrates include various substrates made of glass or plastic, and a specific example is a plastic substrate used as an optical lens. In the present invention, a thiourethane-based substrate or a polycarbonate-based substrate is preferred. The thickness of the primer layer formed on the substrate is preferably in the range of 0.2 μm or more and 5 μm or less, and more preferably in the range of 0.4 μm or more and 3 μm or less. [Examples]

[0050] The present invention will be described in more detail using preparation examples, reference examples, and examples, but the present invention is not limited thereto. [Measurement or evaluation method for rutile-type titanium dioxide particles obtained in the preparation example and reference example] Various measurements and evaluations were performed using the following methods [1] to

[10] .

[0051] [1] Average particle size The shape of the sample was observed using a scanning electron microscope (SEM) (Hitachi High-Technologies Corporation, S-5500) at an accelerating voltage of 30 kV. The sample for observation was prepared as follows: The aqueous dispersion sol of the sample was diluted with water to a solid content concentration of 0.05 mass%, then coated onto a collodion film-coated metal grid (Oken Shoji Co., Ltd.), and the solvent was evaporated by irradiating it with a 250 W infrared lamp for 30 minutes to prepare the sample for observation. The obtained SEM image was printed, and the particle diameter of 100 primary particles was measured with calipers, and the average value was taken as the average particle diameter. If the particle shape was anisotropic, the longest axis was taken as the particle diameter.

[0052] [2] Solid content concentration After removing the solvent contained in the sample by infrared irradiation or the like, the residue was calcined at 1000°C for 1 hour to obtain the ignition residue (solid content). The ratio of the mass of the ignition residue to the mass of the sample was defined as the solid content concentration.

[0053] [3] Method for measuring particle composition (Titanium, tin, silicon, iron, and antimony) An aqueous dispersion of the sample (inorganic oxide particles such as titanium dioxide particles) was collected in a zirconia crucible, and after removing the water by infrared irradiation, the resulting dried material was heated with Na2O2 and NaOH to melt it. Sulfuric acid and hydrochloric acid were then added to the resulting molten material, and water was added for dilution. Using an ICP instrument (ICPS-8100, manufactured by Shimadzu Corporation), the amounts of titanium, tin, silicon, iron, and antimony in the obtained solution were measured in terms of oxides (TiO2, SnO2, SiO2, Fe2O3, and Sb2O5).

[0054] (Zirconium, molybdenum, and aluminum) A water dispersion of the sample was placed in a platinum dish, hydrofluoric acid and sulfuric acid were added and heated, and then water was added to dissolve the inorganic oxide particles. After further dilution with water, the amounts of zirconium, molybdenum, and aluminum were measured in oxide equivalents (ZrO2, MoO3, and Al2O3) using an ICP instrument (Shimadzu Corporation, ICPS-8100). (potassium) An aqueous dispersion of the sample was placed in a platinum dish, hydrofluoric acid and sulfuric acid were added and heated, and hydrochloric acid was added to dissolve the solid components. After further dilution with water, the amount of potassium was measured in oxide equivalent (K2O) using an atomic absorption spectrometer (Hitachi, Ltd., Z-5300).

[0055] [4] Crystal structure analysis of particles A 2g solid weight portion of the aqueous dispersion of the sample was taken and placed in a porcelain crucible (Type B-2). After drying at 110°C for 12 hours, the residue was placed in a desiccator and cooled to room temperature. Next, the residue was mixed with a small amount of strontium titanate (manufactured by Kojun Chemical Laboratory Co., Ltd.) and ground for 15 minutes. Powder X-ray diffraction was then measured using a SmartLab X-ray diffractometer (manufactured by Rigaku Corporation). The obtained diffraction pattern was analyzed using PDXL2 version 2.7.2.0 software to identify peak positions, and the peak (2θ) originating from the (110) plane of the mixed strontium titanate was corrected to 32.374 degrees. The measurement conditions and details of the data analysis are as follows. • Measurement conditions Measurement device: Powder X-ray diffraction analyzer SmartLab (manufactured by Rigaku Corporation) X-ray generator: 9kW open tube (CuKα source, voltage 45kV, current 200mA) Soller / PSC:5.0deg IS length: 10.0mm PSA: None Soller: 5.0deg IS:1 / 2 RS1: 13mm RS2: 20mm Scan step: 0.02deg Scan range: 5-70deg Scan speed: 5deg / min X-ray detector: High-speed one-dimensional X-ray detector (D / TeXUltra250) Measurement atmosphere: Under atmospheric pressure Sample stage: Al2O3 sample holder (bottomless) • Data analysis Analysis software: Integrated powder X-ray diffraction analysis software PDXL2 Version 2.7.2.0 (manufactured by Rigaku Corporation) Smoothing: Smoothing using B-Splne (X threshold 1.5) Background removal: Fitting method Kα2 removal: intensity ratio 0.497 Peak search: Second derivative method, σ-cut value = 3, σ-cut range 0.5~20.0 Profile fitting method: Fitting to measurement data Profile fitting peak shape: Split type pseudo-Voigt function

[0056] [5] Evaluation of the photocatalytic activity inhibitory effect of titanium dioxide particles (measurement of fading rate) A solvent was added to the titanium dioxide particle dispersion so that the mass concentration of Ti (in TiO2 equivalent) was 0.335% and the water / methanol ratio was 1 / 1 (mass ratio). Next, the obtained dispersion was mixed with a glycerin solution of sunset yellow FCF dye with a solid content of 0.02% by mass in a mass ratio (mass of dispersion / mass of glycerin solution) of 1 / 3 to prepare a sample, which was placed in a quartz cell measuring 1 mm in depth, 1 cm in width, and 5 cm in height. Then, using an ultraviolet lamp (LUV-6, manufactured by AS ONE Corporation) with a selected wavelength range of I-line (wavelength 365 nm), an intensity of 0.4 mW / cm was applied to a 1 cm wide × 5 cm high surface of the quartz cell. 2 The distance was adjusted to achieve a wavelength equivalent to 365 nm, and ultraviolet light was irradiated.

[0057] The absorbance of the aforementioned sample at a wavelength of 490 nm before UV irradiation (A0) and the absorbance after n hours of UV irradiation (An) were measured using a UV-Vis spectrophotometer (JASCO Corporation, V-550), and the dye fading rate (SY fading rate) at 3 hours of UV irradiation was calculated using the following formula. Fading rate=(An-A0) / A0×100(%)

[0058] [6] Method for measuring the film thickness and refractive index of a coating film The reflectance spectra of the coating film and the coated substrate were measured using an optical measuring device (Olympus Corporation, USPM-RUIII), and the film thickness and refractive index of the coating film were calculated.

[0059] [7] Method for measuring particle refractive index Multiple coating films with different ratios of titanium oxide particles to matrix were prepared using the method described in

[0105] to

[0110] of Japanese Patent Publication No. 2010-168266. The refractive index of each coating film was determined using the method described above, and the particle refractive index was calculated from these.

[0060] [8] Weather resistance evaluation of thermosetting coatings Weathering tests were conducted on thermosetting coated substrates using a weathering tester (Q-Lab, UV fluorescent lamp type accelerated weathering tester QUV), and the time until cracks could be visually observed was evaluated. The weathering test conditions consisted of the following steps 1, 2, and 3, with one cycle (12 hours), and the presence or absence of cracks was visually observed. [Weather resistance test conditions] Step 1: UV irradiation (light source: UVA-340, radiant intensity: 0.70 W / m²) 2 (Temperature: 60℃, Time: 8 hours) Step 2: Condensation (Light source: None, Temperature: 50°C, Time: 4 hours) Step 3: Return to Step 1. [Evaluation Method] • Environment: Below 10 lux Observation method: An LED light was shone from the side onto the substrate with the thermosetting coating, and the presence or absence of cracks was visually observed.

[0061] [9] Evaluation of the amount of color of titanium dioxide particles (YI value) Titanium oxide particles were dispersed in an aqueous solution to a solid content concentration of 5% by mass, placed in a quartz cell with a path length of 10 mm, and their absorption spectrum was measured using a UV-Vis spectrophotometer (V-750, manufactured by JASCO Corporation). The spectrum was then converted to the XYZ color system using the standard illuminant D65. From this XYZ color system, the YI value was calculated using the following formula, following the method for determining the YI value when using the XYZ color system with the standard illuminant D65 as defined in JIS K7373:2006. YI = 100(1.2985X - 1.1335Z) / Y

[0062]

[10] Bayer trial A wear tester BTE (manufactured by COLTS Laboratories) and a haze value measuring device (Nippon Denshoku Industries Co., Ltd., NDH5000) were used to calculate the Bayer value based on the change in haze value between a plastic lens substrate (test piece described later; hereinafter also referred to as "the lens under test") and a reference lens. As the reference lens, a commercially available plastic lens substrate CR-39 (diethylene glycol bisallyl carbonate, using monomers manufactured by PPG, substrate refractive index 1.50) was used. Specifically, the haze value of each lens was first measured, and the initial haze value of the reference lens was defined as D(std0), and the initial haze value of the lens under test as D(test0). Each lens was placed in the pan of the abrasion testing machine described above, 500g of special sand (Kryptoniteβ) was filled on top of it, and the pan was vibrated from side to side at 150 times / minute for 4 minutes (600 times in total). The haze value of the lenses after vibration was measured, and the haze value of the reference lens was defined as D(stdf), and the haze value of the lens under test as D(testf). The Bayer test value (R) was calculated using the following formula. R=[D(stdf)-D(std0)] / [D(testf)-D(test0)]

[0063] [Preparation Example 1: Titanium Oxide Particles 1] [Preparation of an aqueous dispersion sol containing titanium dioxide particles] (A) Co-precipitation gel preparation process A white slurry with a pH of 9.5 was prepared by mixing 668 g of an aqueous titanium tetrachloride solution containing 7.75% by mass of Ti (in TiO2 equivalent) (manufactured by Osaka Titanium Technologies Co., Ltd.), 6.03 g of an aqueous ferric chloride solution containing 7.75% by mass of Fe (in Fe2O3 equivalent) (manufactured by Toagosei Co., Ltd., high-grade superferrous iron), 54.7 g of zirconium oxychloride containing 7.75% by mass of Zr (in ZrO2 equivalent) (manufactured by Taiyo Mining Co., Ltd.), and aqueous ammonia solution containing 15% by mass of ammonia (manufactured by Ube Industries, Ltd.). The slurry was then filtered, and the filtrate was washed with water to obtain 560 g of a coprecipitation gel containing Fe, Zr, and Ti with a solid content of 10% by mass.

[0064] (B) Hydrothermal treatment precursor preparation process To 202 g of the coprecipitation gel obtained in the aforementioned process, 347 g of hydrogen peroxide solution containing 35% by mass of hydrogen peroxide (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 1145 g of water were added. The mixture was then stirred at 80°C for 1 hour, and 328 g of water was added to obtain 2020 g of the lysis solution of the coprecipitation gel. This lysis solution was yellow and transparent, with a pH of 8.5, and the average particle size of the particles in the lysis solution (calculated using cumulant analysis from particle size distribution data obtained using dynamic scattering method (ELSZ, manufactured by Otsuka Electronics Co., Ltd.)) was 25 nm.

[0065] After mixing cation exchange resin (manufactured by Mitsubishi Chemical Corporation) with this dissolving solution (2020 g), 273 g of potassium stannate aqueous solution containing 1% by mass of potassium stannate (manufactured by Showa Chemical Co., Ltd.) in terms of SnO2 was gradually added under stirring.

[0066] After separating the cation exchange resin contained in the obtained dissolving solution, a silica sol containing 0.4% by mass of aluminum (in terms of Al2O3) was obtained (average particle size 16 nm (value obtained using dynamic scattering method), specific surface area 375 m²). 2 A hydrothermal treatment precursor was prepared by mixing 32.5 g of silica (prepared according to the method described in Example 1 "Preparation of silica sol" of Japanese Patent Publication No. 2009-197078) with 508 g of water.

[0067] (C) Hydrothermal treatment process The hydrothermal treatment precursor obtained in the aforementioned process was heated in an autoclave (manufactured by Pressure Glass Industry Co., Ltd., 5 L) at 165°C for 18 hours. This was cooled to room temperature, and the sol-like reaction product was recovered. This reaction product was concentrated using an ultrafiltration membrane apparatus (manufactured by Asahi Kasei Corporation, SIP-1013, SIP-0013) to obtain 270 g of an aqueous dispersion sol with a solid content of 10% by mass.

[0068] The particles contained in the obtained aqueous dispersion sol were titanium oxide particles with a rutile-type crystalline structure, containing iron, zirconium, tin, silicon, aluminum, and potassium. The composition of these titanium oxide particles (Ti content (in TiO2 equivalent), content of added elements (mol %) relative to Ti, Zr / Fe molar ratio), various physical properties, and evaluation results are shown in Table 1. When the content of each element was calculated using iron, zirconium, tin, and silicon as added elements, the results were 0.07 mol% for Fe, 4.0 mol% for Zr, 5.3 mol% for Sn, and 19.7 mol% for Si, respectively.

[0069] [Preparation of coatings for film formation] To 2.63 kg of an aqueous zirconium oxychloride solution containing 2% by mass of zirconium oxychloride (manufactured by Taiyo Mining Co., Ltd.) in terms of ZrO2, ammonia water containing 15% by mass of ammonia was gradually added under stirring to obtain a slurry with a pH of 8.5. Next, the slurry was filtered, and the resulting solid was washed with water to obtain 526 g of zirconia cake containing 10% by mass of zirconium oxychloride in terms of ZrO2.

[0070] To 20g of the aforementioned cake, 180g of water was added, and then 4.0g of potassium hydroxide granules containing 85% by mass of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added to make the system alkaline. Then, 40g of hydrogen peroxide solution containing 35% by mass of hydrogen peroxide was added, and the mixture was heated to 50°C to dissolve the cake. Furthermore, 156g of water was added to obtain 400g of an aqueous solution of zirconic acid peroxide containing 0.5% by mass in terms of ZrO2. The pH of this aqueous solution of zirconic acid peroxide was 12.9.

[0071] The aqueous dispersion sol containing titanium dioxide particles obtained in the aforementioned process was diluted with water to prepare 700 g of a sol with a solid content of 2% by mass. 196 g of the aqueous zirconate peroxide solution obtained in the aforementioned process was added to this sol at room temperature and stirred to obtain an aqueous zirconate peroxide solution mixture.

[0072] The aqueous zirconic acid peroxide mixture obtained in the aforementioned process was heat-treated at 60°C for 6 hours and then cooled to room temperature. This was diluted with water to a solid content concentration of 0.1% by mass, and then subjected to hydrothermal treatment in an autoclave at 165°C for 18 hours. After removing the reaction product, it was concentrated using an ultrafiltration membrane apparatus (Asahi Kasei Corporation, SIP-1013, SIP-0013) to obtain 145 g of an aqueous dispersion of zirconia-coated titanium oxide particles with a solid content concentration of 10% by mass.

[0073] 140 g of the aqueous dispersion obtained in the aforementioned process was added under stirring to a methanol solution in which 10.7 g of tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd.) was dissolved as a surface treatment agent. Next, the resulting mixture was heated at 50°C for 6 hours, then cooled to room temperature. After that, the dispersion medium in the mixture was replaced from water to methanol using an ultrafiltration membrane apparatus (manufactured by Asahi Kasei Corporation, SIP-0013), and then further concentrated to obtain a methanol dispersion with a solid content of 20% by mass.

[0074] 6.63 g of the methanol dispersion obtained in the aforementioned process was stirred, and 1.97 g of purified water and 3.02 g of γ-glycidoxypropyltrimethoxysilane (manufactured by Momentive Performance Materials Japan LLC) were added. The mixture was then stirred at room temperature for one hour to co-hydrolyze the methanol dispersion and γ-glycidoxypropyltrimethoxysilane.

[0075] Next, 6.92 g of propylene glycol monomethyl ether (manufactured by Dow Chemical Japan Ltd.), 0.071 g of acetylacetone aluminum (manufactured by Kishida Chemical Co., Ltd.), and 0.071 g of a silicone-based surfactant (manufactured by Toray Dow Corning Ltd., L-7001) as a leveling agent were added to this mixture, and the mixture was stirred at room temperature for one hour, after which it was left to stand at room temperature for 48 hours. This prepared a paint for forming a thermosetting coating film.

[0076] [Preparation of coated substrates] [Pretreatment of plastic lens substrates] A required number of commercially available plastic lens substrates with a refractive index of 1.60 (monomer name: MR-8, thiourethane type, manufactured by Mitsui Chemicals, Inc.) were prepared and etched by immersion in an 8% by mass NaOH aqueous solution maintained at 40°C for 10 minutes. After that, the substrates were removed, washed with water, and thoroughly dried.

[0077] The thermosetting coating paint obtained in the aforementioned process was applied to the surface of the plastic lens substrate obtained in the aforementioned process to form a coating film. A spin coating method was used for applying the paint, and the conditions were adjusted so that the film thickness after curing was 2.5 μm. The coating film was cured by heat treatment at a temperature of 80°C for 10 minutes, and then at a temperature of 120°C for 1 hour to obtain a substrate with a thermosetting coating film. The evaluation results of this substrate with a thermosetting coating film are shown in Table 1.

[0078] [Preparation Example 2: Titanium Oxide Particles 2] In the coprecipitation gel preparation step of the rutile-type titanium dioxide particle preparation (A) in Preparation Example 1, an aqueous dispersion sol was obtained in the same manner as in Preparation Example 1, except that 17.7 g of ferric chloride aqueous solution was added. The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 1. Furthermore, a thermosetting coated substrate was obtained in the same manner as the preparation of the coating-forming paint and the thermosetting coated substrate in Preparation Example 1, except that this aqueous dispersion sol was used. The evaluation results of this thermosetting coated substrate are shown in Table 1.

[0079] [Preparation Example 3: Titanium Oxide Particles 3] In the coprecipitation gel preparation step of Preparation Example 1 for rutile-type titanium dioxide particle preparation (A), 60.3 g of ferric chloride aqueous solution (manufactured by Toagosei Co., Ltd., high-grade superferrous chloride) was added, except that an aqueous dispersion sol was obtained in the same manner as in Preparation Example 1. The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 1. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1 for coating-forming paint and thermosetting coated substrate preparation, except that this aqueous dispersion sol was used. The evaluation results of this thermosetting coated substrate are shown in Table 1.

[0080] [Preparation Example 4: Titanium Oxide Particles 4] In the coprecipitation gel preparation step of Preparation Example 1 for rutile-type titanium dioxide particle preparation (A), 106 g of ferric chloride aqueous solution (manufactured by Toagosei Co., Ltd., high-grade superferrous chloride) was added, except that an aqueous dispersion sol was obtained in the same manner as in Preparation Example 1. The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 1. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1 for coating-forming paint and thermosetting coated substrate preparation, except that this aqueous dispersion sol was used. The evaluation results of this thermosetting coated substrate are shown in Table 1.

[0081] [Preparation Example 5: Titanium Oxide Particles 5] In the hydrothermal treatment precursor preparation step for rutile-type titanium oxide particle preparation (B) in Preparation Example 3, an aqueous dispersion sol was obtained in the same manner as in Preparation Example 3, except that 205 g of an aqueous potassium stannate solution containing 1% by mass of potassium stannate (manufactured by Showa Chemical Co., Ltd.) on an SnO2 basis was added to the dissolving solution (2020 g). The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 1. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1, except that this aqueous dispersion sol was used for coating preparation and thermosetting coated substrate preparation. The evaluation results of this thermosetting coated substrate are shown in Table 1.

[0082] [Preparation Example 6: Titanium Oxide Particles 6] In Preparation Example 3, in the hydrothermal treatment precursor preparation step for rutile-type titanium oxide particle preparation (B), an aqueous dispersion sol was obtained in the same manner as in Preparation Example 3, except that 410 g of an aqueous potassium stannate solution containing 1% by mass of potassium stannate (manufactured by Showa Chemical Co., Ltd.) on an SnO2 basis was added to the dissolving solution (2020 g). The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 1. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1, except that this aqueous dispersion sol was used for coating preparation and thermosetting coated substrate preparation. The evaluation results of this thermosetting coated substrate are shown in Table 1.

[0083] [Preparation Example 7: Titanium Oxide Particles 7] In the coprecipitation gel preparation step of Preparation Example 1 for rutile-type titanium oxide particle preparation (A), an aqueous dispersion sol was obtained in the same manner as in Preparation Example 1, except that the amount of zirconium oxychloride (manufactured by Taiyo Kogyo Co., Ltd.) containing 7.75% by mass of Zr (calculated as ZrO2) was set to 5.47 g. The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 1. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1 for coating-forming paint preparation and thermosetting coated substrate preparation, except that this aqueous dispersion sol was used. The evaluation results of this thermosetting coated substrate are shown in Table 1.

[0084] [Preparation Example 8: Titanium Oxide Particles 8] In the coprecipitation gel preparation step of the rutile-type titanium oxide particle preparation (A) in Preparation Example 1, an aqueous dispersion sol was obtained in the same manner as in Preparation Example 1, except that the amount of zirconium oxychloride (manufactured by Taiyo Mining Co., Ltd.) containing 7.75% by mass of Zr (calculated as ZrO2) was set to 9.30 g. The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 1. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1, except that this aqueous dispersion sol was used for the preparation of the coating-forming paint and the thermosetting coated substrate. The evaluation results of this thermosetting coated substrate are shown in Table 1.

[0085] [Preparation Example 9: Titanium Oxide Particles 9] In the coprecipitation gel preparation step of the rutile-type titanium oxide particle preparation (A) in Preparation Example 1, an aqueous dispersion sol was obtained in the same manner as in Preparation Example 1, except that the amount of zirconium oxychloride (manufactured by Taiyo Mining Co., Ltd.) containing 7.75% by mass of Zr (calculated as ZrO2) was 27.4 g. The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 1. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1, except that this aqueous dispersion sol was used for coating preparation and thermosetting coated substrate preparation. The evaluation results of this thermosetting coated substrate are shown in Table 1.

[0086] [Preparation Example 10: Titanium Oxide Particles 10] In the coprecipitation gel preparation step of the rutile-type titanium oxide particle preparation (A) in Preparation Example 1, an aqueous dispersion sol was obtained in the same manner as in Preparation Example 1, except that the amount of zirconium oxychloride (manufactured by Taiyo Mining Co., Ltd.) containing 7.75% by mass of Zr (calculated as ZrO2) was 82.1 g. The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 1. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1, except that this aqueous dispersion sol was used for the preparation of the coating-forming paint and the thermosetting coated substrate. The evaluation results of this thermosetting coated substrate are shown in Table 1.

[0087] [Preparation Example 11: Titanium Oxide Particles 11] In the hydrothermal treatment precursor preparation step for rutile-type titanium oxide particle preparation (B) in Preparation Example 3, an aqueous dispersion sol was obtained in the same manner as in Preparation Example 3, except that 1483 g of an aqueous potassium stannate solution containing 1% by mass of potassium stannate (manufactured by Showa Chemical Co., Ltd.) on an SnO2 basis was added to the dissolving solution (809 g). The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 1. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1, except that this aqueous dispersion sol was used for coating preparation and thermosetting coated substrate preparation. The evaluation results of this thermosetting coated substrate are shown in Table 1.

[0088] [Preparation Example 12: Titanium Oxide Particles 12] In the (B) hydrothermal treatment precursor preparation step of the rutile-type titanium oxide particle preparation of Preparation Example 3, an aqueous dispersion sol was obtained by the same method as in Preparation Example 3, except that 1943 g of an aqueous potassium stannate solution containing potassium stannate (manufactured by Showa Kako Co., Ltd.) in an amount of 1% by mass in terms of SnO₂ was added to 353 g of the peptized liquid. Table 1 shows the composition, various physical properties, and respective evaluation results of the particles contained in the obtained aqueous dispersion sol. Further, a substrate with a thermosetting coating film was obtained in the same manner as the preparation of the coating material for coating film formation and the preparation of the substrate with a thermosetting coating film in Preparation Example 1, except that this aqueous dispersion sol was used. Table 1 shows the evaluation results of this substrate with a thermosetting coating film.

[0089] [Preparation Example 13: Titanium Oxide Particles 13] In the (B) hydrothermal treatment precursor preparation step of the rutile-type titanium oxide particle preparation of Preparation Example 3, silica sol containing 0.4% by mass of aluminum in terms of Al₂O₃ (average particle diameter: 16 nm (value obtained by dynamic scattering method), specific surface area: 375 m 2 / g, pH 2.2, solid content concentration: 16% by mass, prepared with reference to the method described in Example 1 "Preparation of silica sol" of Japanese Unexamined Patent Publication No. 2009-197078), an aqueous dispersion sol was obtained by the same method as in Preparation Example 3, except that the addition amount of the silica sol was changed to 24.8 g and the amount of water to be added subsequently was changed to 388 g. Table 1 shows the composition, various physical properties, and respective evaluation results of the particles contained in the obtained aqueous dispersion sol. Further, a substrate with a thermosetting coating film was obtained in the same manner as the preparation of the coating material for coating film formation and the preparation of the substrate with a thermosetting coating film in Preparation Example 1, except that this aqueous dispersion sol was used. Table 1 shows the evaluation results of this substrate with a thermosetting coating film.

[0090] [Preparation Example 14: Titanium Oxide Particles 14] In the (B) hydrothermal treatment precursor preparation step of the rutile-type titanium oxide particle preparation of Preparation Example 3, silica sol containing 0.4% by mass of aluminum in terms of Al₂O₃ (average particle diameter: 16 nm (value obtained by dynamic scattering method), specific surface area: 375 m 2A water-dispersed sol was obtained in the same manner as in Preparation Example 3, except that the amount of silica (prepared according to the method described in Example 1 "Preparation of Silica Sol" of Japanese Patent Publication No. 2009-197078) added was 53.8 g, followed by the addition of 841 g of water. The composition and physical properties of the particles contained in the obtained water-dispersed sol, and the evaluation results are shown in Table 1. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1, except that this water-dispersed sol was used for the preparation of the coating-forming paint and the thermosetting coated substrate. The evaluation results of this thermosetting coated substrate are shown in Table 1.

[0091] [Preparation Example 15: Titanium Oxide Particles 15] A thermosetting coating-forming paint obtained in the same manner as in Preparation Example 3 was used, and a thermosetting coated substrate was obtained in the same manner except that the spin-coating conditions were adjusted so that the cured film thickness was 0.1 μm. The evaluation results of this thermosetting coated substrate are shown in Table 1.

[0092] [Reference Example 1: Reference Titanium Oxide Particles 1] A thermosetting coated substrate was obtained in the same manner as in Preparation Example 1, except that titanium dioxide particles (titanium(IV) dioxide, rutile type, -5 μm, 99.9% (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)) were used instead of the titanium dioxide particles obtained in Preparation Example 1. The evaluation results of these titanium dioxide particles and thermosetting coated substrates are shown in Table 2.

[0093] [Reference Example 2: Reference Titanium Oxide Particles 2] In Preparation Example 1, a water-dispersed sol was obtained in the same manner as in Preparation Example 1, except that ferric chloride aqueous solution and zirconium oxychloride were not added in the coprecipitation gel preparation step (A). The composition and physical properties of the particles contained in the obtained water-dispersed sol, and the evaluation results are shown in Table 2. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1, except that this water-dispersed sol was used for the preparation of the coating-forming paint and the thermosetting coated substrate. The evaluation results of this thermosetting coated substrate are shown in Table 2.

[0094] [Reference Example 3: Reference Titanium Oxide Particles 3] In the coprecipitation gel preparation step for rutile-type titanium oxide particles (A) in Preparation Example 1, an aqueous dispersion sol was obtained in the same manner as in Preparation Example 1, except that zirconium oxychloride was not added. The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 2. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1 for coating-forming paint and thermosetting coated substrate preparation, except that this aqueous dispersion sol was used. The evaluation results of this thermosetting coated substrate are shown in Table 2.

[0095] [Reference Example 4: Reference Titanium Oxide Particles 4] In the coprecipitation gel preparation step of Preparation Example 1 for rutile-type titanium oxide particle preparation (A), an aqueous dispersion sol was obtained in the same manner as in Preparation Example 1, except that zirconium oxychloride was not added and 177 g of ferric chloride aqueous solution was added. The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 2. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1 for coating film formation paint preparation and thermosetting coated substrate preparation, except that this aqueous dispersion sol was used. The evaluation results of this thermosetting coated substrate are shown in Table 2.

[0096] [Reference Example 5: Reference Titanium Oxide Particles 5] In the coprecipitation gel preparation step of the rutile-type titanium oxide particle preparation (A) in Preparation Example 1, an aqueous dispersion sol was obtained in the same manner as in Preparation Example 1, except that an aqueous solution of ferric chloride (manufactured by Toagosei Co., Ltd., high-grade superferrous chloride) containing 7.75% by mass of Fe on an Fe2O3 basis was not added. The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 2. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1, except that this aqueous dispersion sol was used for the preparation of the coating-forming paint and the thermosetting coated substrate. The evaluation results of this thermosetting coated substrate are shown in Table 2.

[0097] [Reference Example 6: Reference Titanium Oxide Particles 6] In the coprecipitation gel preparation step for rutile-type titanium dioxide particle preparation (A) in Preparation Example 1, 109 g of molybdenum(V) chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) containing 7.75% by mass of Mo (MoO3 equivalent) was added instead of an aqueous solution of ferric chloride (manufactured by Toagosei Co., Ltd., high-grade superferrous acid). An aqueous dispersion sol was obtained in the same manner as in Preparation Example 1. The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 2. Furthermore, a thermosetting coated substrate was obtained in the same manner as in Preparation Example 1, except that this aqueous dispersion sol was used for coating preparation and thermosetting coated substrate preparation. The evaluation results of this thermosetting coated substrate are shown in Table 2.

[0098] [Reference Example 7: Reference Titanium Oxide Particles 7] In the coprecipitation gel preparation step of the rutile-type titanium dioxide particle preparation (A) in Preparation Example 1, 13.4 g of antimony(III) chloride was added instead of an aqueous solution of ferric chloride (manufactured by Toagosei Co., Ltd., high-grade superferrous chloride) to obtain an aqueous dispersion sol in the same manner as in Preparation Example 1. The composition and various physical properties of the particles contained in the obtained aqueous dispersion sol, and the evaluation results are shown in Table 2. Furthermore, a thermosetting coated substrate was obtained in the same manner as in the preparation of the coating-forming paint and thermosetting coated substrate in Example 1, except that this aqueous dispersion sol was used. The evaluation results of this thermosetting coated substrate are shown in Table 2.

[0099] [Table 1]

[0100] [Table 2]

[0101] [Method for measuring or evaluating the coating composition obtained in the example and the coated substrate containing the primer layer obtained using the same] Various measurements and evaluations were performed using the following methods

[11] to

[19] .

[0102]

[11] Appearance (interference fringes) A fluorescent lamp, "Product Name: Mellow 5N" (manufactured by Toshiba Lighting & Technology Corporation, a three-wavelength daylight-white fluorescent lamp), was installed inside a box with a black interior wall. The light from the fluorescent lamp was reflected off the surface of the coated substrate described in each example, and the occurrence of rainbow patterns (interference fringes) due to light interference was visually confirmed and evaluated according to the following criteria. A: There are almost no interference fringes. B: Interference fringes are not noticeable. C: Interference fringes are prominent. D: There are glare-like interference fringes.

[0103]

[12] Exterior (cloudy) A fluorescent lamp, "Product Name: Mellow 5N" (manufactured by Toshiba Lighting & Technology Corporation, tri-wavelength daylight white fluorescent lamp), was installed in a box with a black interior wall. The coated substrates described in each example were placed vertically directly beneath the fluorescent lamp, and their transparency (degree of cloudiness) was visually inspected and evaluated according to the following criteria. A: It's clear. B: It is slightly cloudy. C: There is clear cloudiness. D: There is significant cloudiness.

[0104]

[13] Scratch resistance test The surface of the coated substrate described in each example was rubbed by hand with Bonstar Steel Wool #0000 (manufactured by Nippon Steel Wool Co., Ltd.), and the degree of scratching was visually determined and evaluated according to the following criteria. A: It hardly gets scratched. B: There are some minor scratches. C: It gets quite scratched. D: Scratches appear over almost the entire surface of the rubbed area.

[0105]

[14] Adhesion test Using a knife, cuts were made at 1 mm intervals on the surface of the coated substrate described in each example, forming 100 square mm grids. Cellophane adhesive tape was then firmly pressed onto the grid, and the tape was pulled sharply in a direction 90 degrees to the in-plane direction of the coated substrate. This operation was repeated a total of 5 times and evaluated according to the following criteria. ◎: No peeling. ○: There is very slight peeling. △: There is some peeling. ×: There is obvious peeling. ××: There is significant peeling.

[0106]

[15] Hot water resistance test After immersing the coated substrates described in each example in hot water maintained at 80°C for 10 minutes, the same adhesion test as described above was performed and evaluated according to the following criteria. ◎: No peeling. ○: There is very slight peeling. △: There is some peeling. ×: There is obvious peeling. ××: There is significant peeling.

[0107]

[16] Weathering test The coated substrates described in each example were exposed to a xenon weathermeter (Suga Test Instruments Co., Ltd., X-75 model) for 60 or 120 hours, and then subjected to the same adhesion test as described above, and evaluated according to the following criteria. ◎: No peeling. ○: There is very slight peeling. △: There is some peeling. ×: There is obvious peeling. ××: There is significant peeling.

[0108]

[17] Impact resistance test An anti-reflective film was formed on the coated substrate described in each example by vacuum deposition using an inorganic oxide component. A 17g hard ball was dropped from a height of 127cm onto the center of this coated substrate and evaluated according to the following criteria. ○: The anti-reflective coating does not crack. ×: The anti-reflective coating cracks.

[0109]

[18] Tensile elongation A resin emulsion was dried at 80°C for 20 hours to create a film with a thickness of approximately 40 μm. Next, a sample was created by punching it out with a No. 4 dumbbell as specified in JIS K6301. Then, the elongation of the sample was measured using a tensile property measuring device (Tensilon UTA-500, manufactured by Orientec Co., Ltd.) set to a tensile speed of 200 mm / min and a measurement temperature of 25°C. Here, the elongation measured just before the sample was cut was defined as the tensile elongation. This measurement method conforms to JIS K6251.

[0110]

[19] Glass transition temperature A resin emulsion was dried at 80°C for 20 hours to create a film with a thickness of approximately 40 μm. Next, the dynamic viscoelasticity of this sample was measured using a dynamic viscoelasticity analyzer (Orientec Co., Ltd., Rheovibron DDV-0.1FP) set to a heating rate of 2°C / min and a frequency of 35 Hz. Here, the temperature at which the storage modulus E in dynamic viscoelasticity is maximized is defined as the glass transition temperature of the polyurethane compound. This measurement method conforms to JIS K7244.

[0111] [Example 1] 132 g of a commercially available urethane emulsion (Superflex 460, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 38% solids by mass, 62% water by mass, tensile elongation 750%, glass transition temperature -21°C) was mixed with water and methanol to prepare 500 g of a resin dispersion. Additionally, 250 g of a titanium dioxide particle dispersion (20% solids by mass, 80% methanol by mass), in which the aforementioned titanium dioxide particles 3 were dispersed in methanol, was mixed with water and methanol to prepare 500 g of a dispersion containing rutile-type titanium dioxide. Next, the resin dispersion and the dispersion containing rutile-type titanium dioxide particles were mixed. Furthermore, 5 g of polyether-modified silicone (DOWSILL-7001, manufactured by Dow-Toray Industries, Inc.) was added as a leveling agent to prepare 1005 g of a primer layer-forming coating composition. The composition of each component in this coating composition, by mass ratio, was resin / titanium dioxide particles / water / methanol = 5 / 5 / 40 / 50. The properties of the primer layer-forming paint composition obtained in this process are shown in Table 3.

[0112] [Paint composition for forming a hard coat layer] 145 g of γ-glycidoxypropyltrimethoxysilane (SILQIEST A-187, manufactured by Momentive Performance Materials Japan LLC) was mixed with 25 g of methanol, and 45 g of 0.01 N hydrochloric acid was added dropwise while stirring. Hydrolysis was then carried out by stirring at room temperature overnight.

[0113] Next, 585g of commercially available titanium dioxide sol (Optlake 1120Z (8RX-7·A15) manufactured by JGC Catalysts & Chemicals Co., Ltd.), 25g of itaconic acid (manufactured by Kishida Chemical Co., Ltd.) as a curing agent, 10g of dicyandiamide (manufactured by Kishida Chemical Co., Ltd.), and 5g of polyether-modified silicone ("DOWSILL-7001" manufactured by Dow-Toray Industries, Inc.) as a leveling agent were added to the hydrolyzed liquid, and the mixture was stirred overnight at room temperature to prepare a coating composition for forming a hard coat layer.

[0114] [Coated substrate including primer layer] As a substrate, we prepared "Monomer name: MR-8" (plastic lens substrate with a refractive index of 1.60) manufactured by Mitsui Chemicals, Inc. Next, we immersed this substrate in a 10 wt% KOH aqueous solution maintained at a temperature of 40°C for 2 minutes to perform an etching treatment. Furthermore, we removed the substrate, washed it with water, and then dried it thoroughly.

[0115] Next, the aforementioned primer layer-forming coating composition was applied to the surface of the substrate using the dipping method (pulling speed 100 mm / min). Afterward, the primer layer was pre-cured by heating at 100°C for 10 minutes. At this time, the pre-cured film thickness of the formed primer layer was approximately 0.8 to 1.0 μm.

[0116] Furthermore, the aforementioned hard coat layer forming coating composition was applied to the surface of the pre-cured primer layer using the dipping method (pulling speed 300 mm / min). The substrate was then dried at 100°C for 10 minutes, followed by heat treatment at 120°C for 2 hours to cure the hard coat layer. The primer layer was also cured simultaneously. The hard coat layer thickness after curing was approximately 2.4–2.8 μm. The properties of the coated substrate obtained in this process are shown in Table 4. The results of evaluation using the methods described in

[11] –

[19] are also shown in Table 4.

[0117] [Example 2] A coated substrate was prepared in the same manner as in Example 1, except that the commercially available titanium dioxide particles in the hard coat layer forming coating composition were replaced with titanium dioxide particles 3. The coated substrate was also evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4, respectively.

[0118] [Example 3] In the process of preparing the paint composition for forming the primer layer, 132 g of a commercially available urethane emulsion (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 460, 38% solids by mass, 62% water by mass, tensile elongation 750%, glass transition temperature -21°C) was replaced with 156 g of another commercially available urethane emulsion (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 420, 32% solids by mass, 68% water by mass, tensile elongation 290%, glass transition temperature -10°C) in the step of preparing the paint composition for forming the primer layer. The coated substrate was prepared in the same manner as in Example 1. The coated substrate was also evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4, respectively.

[0119] [Example 4] In the process of preparing the paint composition for forming the primer layer, 132 g of a commercially available urethane emulsion (Superflex 460, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 38% solids by mass, 62% water by mass, tensile elongation 750%, glass transition temperature -21°C) was replaced with 200 g of a commercially available polyester emulsion (Pesresin A-160P, manufactured by Takamatsu Oil & Fat Co., Ltd., 25% solids by mass, 75% water by mass, tensile elongation 800%, glass transition temperature -30°C). The coated substrate was prepared in the same manner as in Example 1. The coated substrate was also evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4, respectively.

[0120] [Comparative Example 1] In the process of preparing the paint composition for forming the primer layer, 132 g of commercially available urethane emulsion (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 460, 38% solids by mass, 62% water by mass, tensile elongation 750%, glass transition temperature -21°C) was replaced with 89 g of commercially available ethylene vinyl acetate emulsion (Sumika Chemtex Co., Ltd., Sumikaflex S-201HQ, 56% solids by mass, 44% water by mass, tensile elongation 1000%, glass transition temperature -20°C). The coated substrate was prepared in the same manner as in Example 1. The coated substrate was also evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4, respectively.

[0121] [Comparative Example 2] In the process of preparing the paint composition for forming the primer layer, 132 g of a commercially available urethane emulsion (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 460, solids content 38% by mass, water 62% by mass, tensile elongation 750%, glass transition temperature -21℃) was replaced with 83 g of a commercially available ethylene acrylic special ester emulsion (Sumika Chemtex Co., Ltd., Sumikaflex S-3950, solids content 60% by mass, water 40% by mass, over 1500%, -50℃) in the process of preparing the paint composition for forming the primer layer. The coated substrate was prepared in the same manner as in Example 1. The coated substrate was also evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4, respectively.

[0122] [Table 3]

[0123] Table 4

Claims

1. Fe and Zr are in solid solution. The interplanar spacing of the (110) planes obtained by X-ray diffraction measurement is 0.3250 nm or more. The average particle diameter is in the range of 5 nm or more and 50 nm or less. Zirconia-coated titanium oxide particles, and, The material comprises at least one resin selected from the group consisting of polyurethane resins and polyester resins. Coating composition for forming a primer layer.

2. The primer layer forming paint composition according to claim 1, wherein the tensile elongation of the resin is in the range of 100% or more and 2000% or less.

3. The primer layer forming paint composition according to claim 1, wherein the glass transition temperature of the resin is 0°C or lower.

4. The Ti content of the zirconia-coated titanium oxide particles is such that, relative to the total amount of the zirconia-coated titanium oxide particles, TiO ２ A primer layer-forming coating composition according to claim 1, wherein the amount is in the range of 40% by mass or more and 90% by mass or less.

5. The primer layer forming paint composition according to claim 1, wherein the Fe content of the zirconia-coated titanium oxide particles is in the range of 0.01 mol% or more and 5 mol% or less in mol% relative to Ti.

6. The primer layer forming paint composition according to claim 1, wherein the Zr content of the zirconia-coated titanium oxide particles is in the range of 0.1 mol% or more and 15 mol% or less in mol% relative to Ti.

7. The primer layer forming paint composition according to claim 1, wherein the Sn content of the zirconia-coated titanium oxide particles is in the range of 1 mol% or more and 30 mol% or less in terms of mol% relative to Ti.

8. The primer layer forming paint composition according to claim 1, wherein the Si content of the zirconia-coated titanium oxide particles is in the range of 5 mol% or more and 70 mol% or less relative to Ti.

9. The primer layer forming paint composition according to claim 1, wherein the Zr / Fe molar ratio of the zirconia-coated titanium oxide particles is 1 or more.

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