A substrate having particles and a transparent film containing said particles

Abstract

The present invention provides a particle having an outer shell containing silicon having antibacterial properties and a cavity on the inner side thereof. The particle contains 0.5 to 40 mass% of an antibacterial metal component based on oxides and has a cavity on the inner side of the outer shell containing silicon. The porosity of the particle is 10 to 90%, and the ratio of the number of particles having one cavity to the total number of particles is 80% or more. A substrate equipped with a transparent film using the particle has sufficient hardness and strength, and high antibacterial properties, and is particularly useful for anti-reflective applications.

Description

Technology Field

[0001] One aspect of the present disclosure relates to a particle and a substrate having a transparent film comprising said particle. Background Technology

[0002] Conventionally, to prevent surface reflection of substrates such as sheets or lenses formed of glass or plastic, an anti-reflection film is formed on the surface thereof. For example, a coating of a low-refractive-index material, such as fluoropolymer or magnesium fluoride, is formed on the surface of a glass or plastic substrate by a coating method, a deposition method, or a CVD method. However, these methods are expensive in terms of cost. Therefore, the following method is known (for example, see Japanese Patent Publication No. Hei 7-133105). In this method, an anti-reflection film is formed by applying a coating solution containing composite oxide colloid particles with a refractive index of 1.36 to 1.44, comprising silica and inorganic oxides other than silica, to the surface of the substrate.

[0003] In addition, a method for manufacturing particles having an outer shell and an internal cavity is known (see, for example, Japanese Patent Publication No. 2001-233611 and Japanese Patent Publication No. 2013-226539). These particles have a lower refractive index compared to solid particles. A transparent film formed using these particles has a low refractive index and excellent anti-reflective performance.

[0004] In addition, it is known that antibacterial properties are imparted to particles of inorganic oxides such as alumina and silica, or particles of composite oxides such as silica-alumina, by supporting a metal component such as silver or copper on these particles (e.g., see Japanese Patent Publication No. Hei 7-196424 and Japanese Patent Publication No. 2010-273698). Furthermore, an anti-reflective film is known that comprises an anti-reflective layer and a layer having an antibacterial function (see Japanese Patent Publication No. Hei 11-052105). The problem to be solved

[0005] Particles having internal cavities have a lower refractive index compared to particles with solid interiors. For this reason, when particles with internal cavities are used in a coating, the transparency and anti-reflective ability of the coating are improved. However, components requiring transparency and anti-reflective ability include display devices with touch panels, such as smartphones, ATMs, and vending machines. The surfaces of these may be contaminated with fungi, such as E. coli or Staphylococcus aureus, or various viruses. Therefore, antimicrobial properties are required from a hygienic standpoint.

[0006] Conventionally, it is known that an antimicrobial agent is applied to the surface of a film to impart antimicrobial properties to the film. However, for example, if the antimicrobial agent is an organic antimicrobial agent, the application of the antimicrobial agent itself is relatively easy. However, in this case, there is a risk that the film may be invaded by the solvent. Furthermore, if the adhesion and scratch resistance to the film are not good, the sustainability of the antimicrobial performance becomes insufficient. On the other hand, if the antimicrobial agent is an inorganic antimicrobial agent, the sustainability of the antimicrobial performance can be expected as the antimicrobial agent is present within the film. However, it is necessary to separately manufacture a film (antimicrobial layer) containing the antimicrobial agent. However, if the anti-reflective layer and the antimicrobial layer are manufactured separately, there is a risk that the effect of the layer other than the outermost surface will be insufficient, and that productivity will decrease, leading to a surge in production costs. In this regard, if a low-refractive-index component and an antimicrobial component are combined within a single film, there is a risk that the anti-reflective and antimicrobial performance will become insufficient, or that the transparency and strength of the film will become insufficient.

[0007] Therefore, there is a demand for particles that have high transparency and anti-reflective ability when used in films, as well as high antibacterial performance.

[0008] In addition, a substrate equipped with a transparent film (anti-reflection film) using these particles is required to have high transparency and anti-reflection ability, sufficient hardness and strength, and also high antibacterial performance. means of solving the problem

[0009] To solve this problem, the inventors discovered the following particles.

[0010] A particle according to one embodiment of the present disclosure has an outer shell containing silicon and a cavity inside. In addition, the particle contains an antimicrobial metal component in an amount of 0.5 to 40 mass% based on oxides. The proportion of the cavity (porosity) in the particle is 10 to 90%. In addition, the proportion of particles having one cavity relative to the total number of particles is 80% or more.

[0011] These particles possess a low refractive index, along with sufficient hardness and strength, high dispersibility, and high antibacterial performance. A coating solution containing these particles yields a transparent film that has high transparency and anti-reflective ability, along with sufficient hardness (pencil hardness), strength (scratch resistance), and high antibacterial performance. Effects of the invention

[0012] According to particles of one embodiment of the present disclosure, a coating solution capable of producing a film as described below is obtained. This film has high transparency and anti-reflective ability, and excellent adhesion to the substrate. In addition, this film has sufficient hardness and strength, and high antibacterial performance. Specific details for implementing the invention

[0013] The particle according to the present embodiment (hereinafter, the particle according to the present embodiment may be simply referred to as "particle") contains 0.5 to 40 mass% of an antibacterial metal component based on oxides. The shape of the particle has an outer shell containing silicon and a cavity inside it. The proportion of the cavity (porosity) in the particle is 10 to 90%. In addition, the ratio of particles having one cavity inside the outer shell to the total number of particles is 80% or more.

[0014] When the content of the antibacterial metal component of the particles is in the range of 0.5 to 40 mass% based on oxides, by using these particles in a coating, a coating having high antibacterial properties, high transparency, and anti-reflective ability is obtained.

[0015] Here, if the content of the antimicrobial metal component is less than 0.5 mass%, there is a concern that sufficient antimicrobial performance may not be obtained. Conversely, even if the content of the antimicrobial metal component exceeds 40 mass%, the antimicrobial performance is not improved, and in some cases, the antimicrobial metal component becomes unstable, making it prone to breakage from particles and discoloration. In addition, there is a concern that transparency and antireflective ability may be reduced. The content of this antimicrobial metal component is preferably 1 to 30 mass%, and more preferably 3 to 10 mass%.

[0016] Silicon is included in the outer shell of the particle. The silicon-containing material is preferably an oxide. Examples of silicon-containing oxides include silicon oxides containing at least one element of aluminum, zirconium, titanium, zinc, tin, and antimony, and silica. These oxides may be alone, a mixture, or a complex oxide.

[0017] By including silicon in the outer shell, the refractive index of the particles is lowered, and the compatibility between the particles and the matrix-forming components is also improved. For this reason, a transparent film with low reflectivity can be formed. In addition, since the particles can be highly dispersed within the transparent film, the strength of the film is improved. The silicon content included in the particles is preferably 50 mass% or more when silicon is expressed as silica. The silicon content is more preferably 75 mass% or more, even more preferably 85 mass% or more, and particularly preferably 90 mass%.

[0018] The porosity of the particles is 10 to 90%. Here, if the porosity is less than 10%, it is difficult to obtain a coating with sufficient transparency and anti-reflective ability when these particles are used in a coating. Conversely, if the porosity of the particles exceeds 90%, there is a concern that the structure of the particles cannot be maintained because the structure is excessively "porosity," and even if the structure can be maintained, there is a concern that a coating with sufficient hardness and strength cannot be obtained. The porosity is preferably 13 to 80%, and more preferably 20 to 70%.

[0019] The number ratio of particles having one cavity to the total number of particles is 80% or more. If this number ratio is less than 80%, there is a risk that the transparency and anti-reflective ability will be insufficient when these particles are used in a substrate equipped with a film. The number ratio is preferably 95% or more, more preferably 99% or more, and most preferably 100%.

[0020] In addition, it is desirable that the cavity on the inner side of the outer shell follows the shape of the particle. That is, it is preferable that the thickness of the outer shell be as uniform as possible. In this case, depending on the thickness of the outer shell, sufficient hardness and strength can be obtained even when stress is applied to the particle.

[0021] The metal component having antibacterial properties preferably includes an element selected from silver, copper, zinc, lead, tin, bismuth, cadmium, chromium, mercury, nickel, and cobalt. These metal elements may be used alone or in combination. More preferred metal elements are silver, copper, and zinc, and even more preferred metal elements are silver and zinc.

[0022] The density (A1) of the dried particles by the He gas adsorption method is preferably 1.95 to 3.50 g / ml, and the density (B1) of the dried particles by the N2 gas adsorption method is preferably 0.50 to 2.60 g / ml.

[0023] The density obtained by this gas adsorption method is obtained as follows. Specifically, a powder is obtained by drying a dispersion of particles in an evaporator. Subsequently, using a material obtained by heat-treating (drying) this powder in air at 105°C, a dry automatic densimeter (MicroMeritics AccuPyc1340TC) is used to perform measurements using He gas or N2 gas. By doing so, the density obtained by the above gas adsorption method is obtained. In addition, the density (A2) and density (B2) described below are obtained by performing the same measurements using a powder obtained by drying in the above-described evaporator, which is heat-treated (calcined) in air at 400°C.

[0024] The specific reason why the density range varies depending on the gas species used for measurement is unclear. However, it is believed that this is because the difference in adsorption states caused by differences in gas species, resulting from particle surface conditions such as surface irregularities or pores, is expressed numerically.

[0025] Here, if the density (A1) is less than 1.95 g / ml, there is a concern that sufficient antibacterial performance may not be obtained because there is a small amount of antibacterial metal component.

[0026] Conversely, if the density (A1) exceeds 3.50 g / ml, the supported antimicrobial metal component becomes unstable, making it prone to discoloration and separation of the antimicrobial metal component from the particles. Additionally, there is a risk that transparency, antireflective ability, strength, and adhesion may be reduced.

[0027] In addition, in particles with a density (B1) of less than 0.50 g / ml, it is difficult to maintain the outer structure. For this reason, it is difficult to obtain such particles.

[0028] Conversely, if the density (B1) exceeds 2.60 g / ml, the supported antimicrobial metal component becomes unstable, making it prone to discoloration and separation of the antimicrobial metal component from the particles. Additionally, there is a risk that transparency, antireflective ability, hardness, and adhesion may be reduced.

[0029] The density (A1) is more preferably 2.00 to 3.00 g / ml, and even more preferably 2.10 to 2.30 g / ml.

[0030] The density (B1) is more preferably 0.80 to 2.10 g / ml, and even more preferably 0.90 to 1.50 g / ml.

[0031] It is preferable that the density (A2) of particles heat-treated at 400℃ by the He gas adsorption method be 2.17 g / ml or higher.

[0032] Here, if the density (A2) is less than 2.17 g / ml, there is a concern that sufficient antibacterial performance may not be obtained because there is a small amount of antibacterial metal component.

[0033] The upper limit of the density (A2) is not specifically set. However, if the density (A2) is excessively high, depending on the type of antibacterial metal component, there is a risk that the reflectance and haze of the substrate equipped with the formed transparent film may increase, or that the transmittance, strength, and adhesion may decrease. For this reason, for example, the upper limit of the density (A2) may be 3.70 g / ml when the antibacterial metal component is silver, 3.50 g / ml when the antibacterial metal component is copper, and 3.20 g / ml when the antibacterial metal component is zinc.

[0034] The density (A2) is more preferably 2.20 g / ml or higher, and even more preferably 2.24 g / ml or higher.

[0035] It is preferable that the ratio (A2 / B2) of the density (A2) and the density (B2) of particles heat-treated at 400°C by the N2 gas adsorption method be 1.10 or higher.

[0036] Here, if the ratio (A2 / B2) is less than 1.10, the refractive index of the particles increases, so there is a concern that the anti-reflection performance of the film may become insufficient.

[0037] The upper limit of the ratio (A2 / B2) is not specifically set. However, if the ratio (A2 / B2) is excessively large, there is a concern that it will be difficult to maintain the exterior structure. For this reason, the upper limit of the ratio (A2 / B2) is, for example, 4.50.

[0038] The ratio (A2 / B2) is more preferably 1.30 or higher, and even more preferably 1.45 or higher.

[0039] The average particle size of the particles is not particularly limited, but when used on a substrate equipped with a transparent film, it is preferably 20 to 180 nm. When the average particle size is within this range, the particles can exist stably. In addition, in this case, the particles have good dispersibility in the coating solution and in the film, and a film with high transparency, hardness, and strength is obtained. The average particle size is more preferably 30 to 120 nm, and even more preferably 40 to 110 nm.

[0040] The average thickness of the outer shell is preferably 5 to 30 nm. As a result, the structure of the outer shell can be stably maintained, allowing the particles to exist stably. Additionally, a film with high transparency, hardness, and strength is obtained. Here, in the case of a thin outer shell with an average thickness of less than 5 nm, there is a concern that the structure of the particles cannot be maintained. Conversely, if the average thickness of the outer shell exceeds 30 nm, there is a concern that the refractive index of the outer shell may become too high, depending on the type and amount of the antimicrobial metal component. The average thickness of the outer shell is more preferably 5 to 20 nm, and even more preferably 7 to 12 nm.

[0041] It is preferable that the alkali metal content of the particles be less than 1.00 mass% based on oxides.

[0042] Here, if the alkali metal content of the particles is 1.00 mass% or more, there is a risk that the particles will bond together, thereby reducing the dispersibility of the particles in the coating solution and the film, failing to obtain sufficient hardness of the film, or resulting in insufficient transparency. The alkali metal content is more preferably less than 0.10 mass%, and even more preferably less than 0.01 mass%. Most preferably, the particles do not contain alkali metals. However, if the particles contain alkaline earth metals, the aforementioned "alkali metal content" shall be interpreted as the "total content of alkali metals and alkaline earth metals." Furthermore, alkali metals represent Li, Na, K, Rb, Cs, and Fr, and alkaline earth metals represent Be, Mg, Ca, Sr, Ba, and Ra.

[0043] The particles of the present embodiment may be dispersed in organic materials such as organic solvents and organic resins. In that case, it is preferable to surface treat the particles using an organosilicon compound. As the organosilicon compound, it is preferable to use an organosilicon compound represented by the following formula (1) (where n is 1 to 3). Here, when using an organosilicon compound where n is 0, it is preferable to use a partially hydrolyzed product of the organosilicon compound. Through this surface treatment, the particles contain an organic compound having a functional group derived from the organosilicon compound of the following formula (1). The functional group is at least one selected from an alkyl group, an epoxy group, a vinyl group, a (meth)acryloxy group, a mercapto group, an amino group, a phenyl group, and a phenylamino group.

[0044] R n -SiX 4-n ··· Formula (1)

[0045] (However, in the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be identical or different. Examples of substituents include epoxy groups, vinyl groups, (meth)acryloxy groups, mercapto groups, amino groups, and phenylamino groups. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, or a hydrogen atom, and n represents an integer from 0 to 3.)

[0046] As this organosilicon compound, specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, 7-octenyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-Glycidoxypropylmethyldimethoxysilane, γ-Glycidoxypropylmethyldiethoxysilane, γ-Glycidoxypropyltriethoxysilane, 8-Glycidoxyoctyltrimethoxysilane, γ-Methacryloxypropylmethyldimethoxysilane, γ-Methacryloxypropyltrimethoxysilane, γ-Methacryloxypropylmethyldiethoxysilane, γ-Methacryloxypropyltriethoxysilane, γ-Acryloxypropyltrimethoxysilane, 8-Methacryloxyoctyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, Examples include N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-isocyanatepropyltriethoxysilane, trimethylsilanol, n-propyltrimethylsilane, n-propyltriethylsilane, p-styryltrimethoxysilane, methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, trimethylbromosilane, and diethylsilane.

[0047] In the surface treatment of the particles, a dispersion containing the particles and at least one of water and alcohol is prepared. A predetermined amount of an organosilicon compound represented by Formula (1) is added to this dispersion, and water is added as needed to hydrolyze the organosilicon compound. In this way, the surface treatment of the particles is performed. For this hydrolysis, an acid or an alkali is used as a hydrolysis catalyst as needed. Additionally, as needed, impurities may be reduced by ion exchange or ultrafiltration, etc., at least before and after the surface treatment.

[0048] Organosilicon compounds are, R n -SiO (4-n) / 2 It is preferable that 0.1 to 30 mass% of (solid content) be present in the particles. If the particles are surface-treated with an organosilicon compound, the compatibility between the particles and the matrix-forming components is improved.

[0049] Here, if the amount of organosilicon compound is less than 0.1 mass%, the addition effect is not sufficiently obtained. Even if the amount of organosilicon compound is greater than 30 mass%, not only is the dispersibility of the particles not further improved, but there is also a risk that sufficient antibacterial performance may not be obtained. The amount of organosilicon compound is more preferably 1 to 25 mass%, even more preferably 1 to 20 mass%, and particularly preferably 1 to 15 mass%.

[0050] In addition, the shape of the particles is not particularly limited. Examples of particle shapes include spherical, ball-shaped (rugby ball), cocoon-shaped, star candy-shaped, chain-shaped, and dice-shaped particles. Among these, spherical particles are preferred because they have high dispersibility and can be uniformly dispersed within the film.

[0051] [Substance equipped with a transparent film]

[0052] The transparent film-equipped substrate according to the present embodiment comprises a substrate and a transparent film formed on the substrate, comprising the aforementioned particles and a matrix. The matrix is ​​included as a solid component in addition to the particles. Examples of the matrix include additives derived from the coating solution, such as resins, polymerization initiators, and leveling agents. Specifically, a coating solution is applied to the substrate by a known method, followed by drying and ultraviolet irradiation to form a film on the substrate. In the film, the ratio of the solid components of the particles and matrix-forming components to the coating solution is the same as the ratio of the particle components to the matrix in the film.

[0053] Between this transparent film and the substrate, a conventionally known hardcoat layer, anti-glare layer, high refractive index layer, or conductive layer may be disposed depending on the application. It is also possible to combine multiple layers as these layers. For example, when the reflectance of the transparent film-equipped substrate is further reduced in order to use the transparent film-equipped substrate in a display, a combination of a hardcoat layer and a high refractive index layer, or a combination of a hardcoat layer and an anti-glare layer, is used.

[0054] The thickness of the transparent film can be appropriately selected depending on the application. For example, if the transparent film is an anti-reflective film, the thickness of the transparent film is preferably 80 to 350 nm.

[0055] Here, if the film thickness of the transparent film is less than 80 nm, the strength and scratch resistance of the film may be insufficient, and the film may be too thin to obtain sufficient anti-reflection performance. Conversely, if the film thickness of the transparent film is thicker than 350 nm, the anti-reflection performance may be reduced. In addition, if the shrinkage of the transparent film is very large, there is a risk of cracking. This film thickness is more preferably 85 to 220 nm, and even more preferably 90 to 110 nm.

[0056] In addition, the reflectance of the substrate equipped with the film is preferably 2.0% or less, and more preferably 1.5% or less.

[0057] In addition, the haze of the film-equipped substrate is preferably 3.0% or less, and more preferably 0.3% or less.

[0058] It is preferable that the light transmittance of the substrate equipped with the film be 85.0% or higher.

[0059] Here, if the light transmittance is less than 85.0%, there is a risk that the image clarity in the display device, etc. will be insufficient. This light transmittance is more preferably 90.0% or higher.

[0060] The antibacterial activity test of the film is performed in accordance with JIS Z 2801. It is preferable that the antibacterial activity value be 2.0 or higher. If the antibacterial activity value is 2.0 or higher, it can be determined that the film has antibacterial properties. More preferably, the antibacterial activity value is 4.0 or higher.

[0061] The strength (scratch resistance) of the coating is, using #0000 steel wool, a load of 1000g / cm² 2 It is evaluated by performing a sliding movement in the film. It is desirable that no streaky scratches are observed on the film surface at the point where the number of sliding movements is at least 100. Regarding this scratch resistance, it is more desirable that no scratches are observed at the point where the number of sliding movements is 500, and even more desirable that no scratches are observed at the point where the number of sliding movements is 1000.

[0062] The pencil hardness of the film is preferably H or higher. Here, if the pencil hardness of the film is less than H, the hardness is insufficient as an anti-reflective film. This pencil hardness is more preferably 2H or higher, and even more preferably 4H or higher.

[0063] As for the substrate, known materials may be used. The substrate is preferably a transparent resin substrate, such as glass, polycarbonate, acrylic resin, polyethylene terephthalate (PET), triacetylcellulose (TAC), polyimide, polymethyl methacrylate resin (PMMA), and cycloolefin polymer (COP). These substrates have excellent adhesion to the transparent film formed by the coating solution described above. Therefore, by using these substrates, a substrate with a film having excellent hardness and strength can be obtained. For this reason, a thin substrate is suitably used. The thickness of the substrate is not particularly limited, but is preferably 10 to 100 μm, and more preferably 20 to 80 μm.

[0064] [Method for manufacturing particles]

[0065] The method for manufacturing a particle according to the present embodiment includes a first process for producing a first particle having an outer shell containing silicon and a cavity on the inside, and a second process for supporting an antibacterial metal component on the first particle.

[0066] Here, the first particle of the first process may be manufactured using a conventionally known method (e.g., Japanese Patent Publication No. 2001-233611, Japanese Patent Publication No. 2013-226539). The antimicrobial metal component of the second process can be supported on the particle by adding it as a solution of a metal salt, such as a hydrochloride, nitrate, sulfate, and acetate, or a metal complex ion, or as a solution of a metal alkoxide. Among these, if the antimicrobial metal component is silver, it is more preferable to use silver nitrate. If the antimicrobial metal component is copper, zinc, and tin, it is more preferable to use a hydrochloride, nitrate, sulfate, and acetate.

[0067] Regarding the amount of addition, the addition is carried out so that the antimicrobial metal component in the particles is ultimately 0.5 to 40 mass% based on oxides. When adding, multiple types of antimicrobial metal components may be added separately or simultaneously. In addition, to increase the content, the antimicrobial metal components may be added in multiple stages.

[0068] The conditions for adding the antimicrobial metal component are not particularly limited as long as the final content of the antimicrobial metal component reaches the desired amount. However, the concentration of the dispersion of the first particle is preferably 0.1 to 10 mass% as a solid content. In addition, the pH at the time of adding the antimicrobial metal component is preferably 6 to 13, and more preferably 8 to 10. Here, if the pH is less than 6, the particles become unstable and there is a risk of aggregation. Conversely, if the pH exceeds 13, dissolution of the particles themselves occurs, and there is a risk that the loading of the antimicrobial metal component will be insufficient. In addition, the temperature at the time of adding the antimicrobial metal component is preferably below the boiling point of the solvent. For example, if the solvent is water, this temperature is preferably less than 100°C, and more preferably 30 to 95°C.

[0069] In order to reduce the content of alkali metals and alkaline earth metals in the particles, it is preferable to perform washing using an ion exchange resin or an ultrafiltration membrane after the second process. The total content of the alkali metals and alkaline earth metals is preferably less than 1.0 mass% based on oxides. However, to achieve this content, the first particles may be produced in advance using raw materials with low alkali metal and alkaline earth metal content, or the content of alkali metals and alkaline earth metals in the first particles may be reduced by performing ion exchange, etc., in the first process. In addition, in the second process, it is also possible to use a material containing an antimicrobial metal with low alkali metal and alkaline earth metal content (e.g., a metal alkoxide containing an antimicrobial metal component). Furthermore, these measures may be combined.

[0070] The finally obtained particles may be used as an aqueous dispersion, may be used after substituting with an organic solvent, or may be dried and used as a powder.

[0071] [Film-forming coating solution]

[0072] The particles of the present embodiment may be applied to a coating solution for forming a film. The coating solution comprises particles and a matrix-forming component. In addition to these, the coating solution may also include additives such as an organic solvent, a polymerization initiator, a leveling agent, and a surfactant.

[0073] The concentration of particles in the coating solution is preferably 5 to 95 mass% as solids with respect to the total amount of solids, such as the included particles and matrix-forming components. Here, if the particle concentration is less than 5 mass%, there is a risk that the refractive index of the coating film will not be sufficiently reduced. Conversely, if the particle concentration is higher than 95 mass%, there is a risk that cracks may occur in the coating film, that adhesion to the substrate may become insufficient, and that hardness, strength, transparency, and haze may deteriorate. This particle concentration is more preferably 10 to 85 mass%, and even more preferably 20 to 70 mass%.

[0074] The matrix-forming component is preferably an organic resin-based matrix-forming component. Examples of organic resin-based matrix-forming components include matrix-forming components such as UV-curable resins, thermosetting resins, and thermoplastic resins.

[0075] Examples of UV-curable resins include (meth)acrylic acid resins, γ-glycidyloxy resins, urethane resins, and vinyl resins.

[0076] Examples of thermosetting resins include urethane resin, melamine resin, silicone resin, butyral resin, reactive silicone resin, phenolic resin, epoxy resin, unsaturated polyester resin, and thermosetting acrylic resin.

[0077] Examples of thermoplastic resins include polyester resin, polycarbonate resin, polyamide resin, polyphenylene oxide resin, thermoplastic acrylic resin, vinyl chloride resin, fluoropolymer resin, vinyl acetate resin, and silicone rubber.

[0078] These resins may be copolymers or modified materials of two or more types, or may be used in combination. In addition, these resins may be emulsion resins, water-soluble resins, or hydrophilic resins.

[0079] The components forming these resins are preferably monomers or oligomers due to particle dispersibility and ease of film formation.

[0080] The concentration of the matrix-forming component in the coating solution is preferably 5 to 95 mass% as solids relative to the total amount of solids, such as the included particles and the matrix-forming component. Here, if the concentration of the matrix-forming component is less than 5 mass%, it is difficult to form a film. Furthermore, even if a film is obtained, there is a risk of cracks occurring in the film, insufficient adhesion to the substrate, and deterioration of hardness, strength, transparency, haze, etc. Conversely, if the concentration of the matrix-forming component is higher than 95 mass%, there is a risk that the refractive index will not be sufficiently reduced because the amount of particles is small. The concentration of this matrix-forming component is more preferably 15 to 90 mass%, and even more preferably 30 to 80 mass%.

[0081] As an organic solvent, one capable of uniformly dispersing particles and dissolving or dispersing additives such as matrix-forming components and polymerization initiators is used. Among these, hydrophilic solvents and polar solvents are preferred. Examples of hydrophilic solvents include alcohols, esters, glycols, and ethers. Examples of polar solvents include esters and ketones.

[0082] Examples of alcohols include methanol, ethanol, propanol, 2-propanol, butanol, diacetone alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol.

[0083] Examples of esters include methyl acetate, ethyl acetate, isopropyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, and ethylene glycol monoacetate.

[0084] Examples of glycols include ethylene glycol and hexylene glycol.

[0085] Examples of ethers include diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate.

[0086] Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methylcyclohexanone, dipropyl ketone, methyl pentyl ketone, and diisobutyl ketone.

[0087] Examples of polar solvents include dimethyl carbonate and toluene.

[0088] These may be used individually or in combination of two or more types.

[0089] As additives, those conventionally available for forming anti-reflective films may be optionally used. For example, polymerization initiators or leveling agents are used to promote the polymerization of matrix-forming components and improve film formation properties.

[0090] Examples of polymerization initiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)2,4,4-trimethyl-pentylphosphine oxide, 2-hydroxymethyl-2-methylphenyl-propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one.

[0091] Examples of leveling agents include acrylic leveling agents, silicone leveling agents, and acrylic-silicone leveling agents. It is preferable to use these leveling agents having fluorine groups.

[0092] Regarding the concentration of these additives in the coating solution, those included as solid components upon film formation are, for convenience, counted as matrix-forming components, and those after film formation are counted as the matrix.

[0093] The solid content concentration of the coating solution (the ratio of the total solid content of the particles and the matrix-forming components to the coating solution) is preferably 0.1 to 100 mass%.

[0094] Here, if the solid content concentration of the coating solution is less than 0.1 mass%, the concentration stability of the paint is low, which makes coating difficult and may result in difficulty in obtaining a uniform film. In addition, in this case, haze or poor appearance may occur, which may lead to a decrease in productivity and manufacturing reliability. A solid content concentration of 100 mass% of the coating solution means that no organic solvent is present in the coating solution. More preferably, the solid content concentration of the coating solution is 1 to 50 mass%.

[0095] Hereinafter, embodiments of the present embodiment will be described.

[0096] [Example 1]

[0097] <Production of the First Particle (Process 1)>

[0098] 430g of silica alumina sol (Fine Cataloid USBB-120 manufactured by Nikki Shokubai Kasei Co., Ltd., average particle size 25nm, solid content concentration 23 mass%) and 9.6kg of pure water were mixed, and the resulting mixture was heated to 98℃. To this mixture, an aqueous sodium hydroxide solution with a concentration of 1 mass% was added to adjust the pH to 12.5.

[0099] To this mixture, 10.2 kg of an aqueous sodium silicate solution (SiO2 concentration 3.0 mass%) and 10.2 kg of an aqueous sodium aluminate solution (Al2O3 concentration 1.0 mass%) were added simultaneously. Subsequently, 37.5 kg of an aqueous sodium silicate solution (SiO2 concentration 3.0 mass%) and 12.5 kg of an aqueous sodium aluminate solution (Al2O3 concentration 1.0 mass%) were added simultaneously to this mixture (reaction solution). During this process, the temperature of the reaction solution was maintained at 98°C. Subsequently, by washing this reaction solution with an ultrafiltration membrane, a dispersion of silica-alumina particles with a solid content concentration of 3 mass% was obtained.

[0100] To 50 kg of this silica-alumina particle dispersion, concentrated hydrochloric acid with a concentration of 35.5 mass% was added dropwise to adjust the pH to 1.0, and dealaluminization treatment was performed. The dissolved aluminum salt was separated using an ultrafiltration membrane, and by washing, 10 kg of a silica-based particle dispersion with a solid content of 5 mass% was obtained. Subsequently, 131 g of an aqueous sodium hydroxide solution with a concentration of 10 mass% was added to this dispersion. This dispersion was heat-treated in an autoclave at 195°C for 24 hours to obtain an aqueous dispersion of the first particle. The Na2O content of this particle was 0.2 mass%.

[0101] <Impregnation of antimicrobial metal components (Process 2)>

[0102] Next, 500g of an aqueous dispersion of the first particles, diluted to 1.5 mass% with pure water, was adjusted to 30°C, and 70.8g of a 1.0 mass% silver nitrate aqueous solution was added to this aqueous dispersion over 30 minutes while stirring, followed by heat treatment at 95°C for 3 hours. After heat treatment, the aqueous dispersion was cooled to room temperature, washed with an ultrafiltration membrane, and concentrated to obtain an aqueous dispersion of silica-based particles with a solid content concentration of 1.5 mass%.

[0103] Next, ion exchange was performed for 3 hours using 200g of cation exchange resin (Diion SK1B, Mitsubishi Chemical Corporation) on 500g of the aqueous dispersion of the silica-based particles, and then ion exchange was performed for 3 hours using 100g of anion exchange resin (Diion SA20A, Mitsubishi Chemical Corporation). After that, 160g of the aqueous dispersion of the particles of the present embodiment was prepared by performing ion exchange at 80°C for 3 hours using 100g of cation exchange resin (Diion SK1B, Mitsubishi Chemical Corporation). The solid content concentration of this dispersion was 5 mass%, and the Na2O content of the particles was 50 ppm.

[0104] Measurements were performed on the particles using the following methods. The characteristics and properties of the particles at each manufacturing process are shown in Table 1 (the same applies to the following examples. Additionally, the characteristics and properties of the comparative examples are shown in Table 2).

[0105] The physical properties of the particles were measured using image analysis.

[0106] Specifically, first, the dispersion of particles was diluted to 0.01 mass% and then dried on a collodion film of a copper cell for an electron microscope. Subsequently, the powder obtained by this was photographed at a magnification of 1 million times using a field emission transmission electron microscope (HF5000 manufactured by Hitachi High Technologies Inc.). For any 1,000 particles of the obtained photographic projection (SEM image, TEM image), each item was measured by the following methods (1) to (4).

[0107] (1) particle size

[0108] The particle area was determined from the SEM image processing, and the circle equivalent diameter was calculated from that area. The average value of the circle equivalent diameters was taken as the particle diameter.

[0109] (2) Outer thickness

[0110] For particles having a cavity on the inner side of the outer shell from TEM images, the thickness of the outer shell was determined, and the average value was taken as the outer shell thickness.

[0111] (3) Porosity

[0112] The volume of each particle was calculated using the particle diameter obtained for the particle having a cavity on the inner side of the outer shell and the outer shell thickness obtained in (2) above. Then, the ratio of the internal volume of the particle to the total particle volume was calculated, and the average value was taken as the porosity.

[0113] (4) Ratio of particles with one cavity to the total number of particles

[0114] The number of cavities within the particles was measured from TEM images, and the ratio of particles with one cavity to the total number of particles was calculated.

[0115] (5) Content of antimicrobial metal elements, metal elements other than silicon constituting the outer shell, alkali metals and alkaline earth metals

[0116] The content of antimicrobial metal elements (Ag, Cu, Zn, Pb, Sn, Bi, Cd, Cr, Hg, Ni, and Co) in the particles, metal elements other than silicon constituting the outer shell (Al, Zr, Ti, Zn, Sn, and Sb), alkali metals, and alkaline earth metals was measured as follows. Specifically, the particles were dissolved in hydrofluoric acid, heated to remove the hydrofluoric acid, and then pure water was added as necessary to obtain a solution. Measurements were performed on the obtained solution using an ICP inductively coupled plasma emission spectromass spectrometer (ICPM-8500 manufactured by Shimadzu Seisakusho Inc.).

[0117] (6) Silica content

[0118] The dispersion of particles was dried at 120°C for 12 hours, and the silica (SiO2) content was determined by measuring the powder obtained by this process using a fluorescent X-ray analyzer (EA600VX manufactured by Hitachi High-Tech Science Corp.).

[0119] (7) Density obtained by He gas adsorption method (A1) and density obtained by N2 gas adsorption method (B1)

[0120] The dispersion of particles was dried in an evaporator and then dried at 105°C. The powder obtained by this process was placed in a cell, and measurements were performed using a dry automatic densimeter (MicroMeritics AccuPyc1340TC) with He gas or N2 gas, under conditions of 10 measurements and a gas introduction pressure of 134 kPa.

[0121] (8) Density (A2) obtained by the He gas adsorption method of a heat-treated product at 400℃ and the ratio (A2 / B2) of density (A2) and density (B2) obtained by the N2 gas adsorption method

[0122] After drying the dispersion of particles in an evaporator, it was heat-treated (calcined) in air at 400°C for 1 hour. The powder obtained by this process was placed in a cell, and measurements were taken using a dry automatic densimeter (MicroMeritics AccuPyc1340TC) with He gas or N2 gas, under conditions of 10 measurements and a gas introduction pressure of 134 kPa. By doing so, the ratio (A2 / B2) was determined.

[0123] (9) Organic compounds having functional groups

[0124] The presence or absence of functional groups included in the particles and their types were determined by the following method.

[0125] First, the dispersion of particles was dried in an evaporator and then dried at 105°C. For the powder obtained thereby, a Fourier Transform Infrared Spectrometer (FT-IR) (FT / IR-6100 manufactured by Nihon Bunko Inc.) was used to analyze the wavenumber range by diffuse reflection with a wavenumber range of 700 cm⁻¹. -1 up to 4000cm -1 Set to , using TGS as the detector, with a resolution of 4.0 cm -1 Measurements were performed with the number of integrated measurements set to 50. Peaks were detected by these measurements, and functional groups were identified by referring to the organic compound spectrum database SDBS (https: / / sdbs.db.aist.go.jp (National Institute of Advanced Industrial Science and Technology, 2021.01)).

[0126] However, for this particle, no peaks attributable to functional groups were observed. This is because surface treatment of the particle with an organosilicon compound such as 3-methacryloxypropyltrimethoxysilane, as in other examples, was not performed.

[0127] <Preparation of coating solution for coating formation>

[0128] By replacing the solvent of 160 g of the aqueous dispersion of particles with ethanol using an ultrafiltration membrane, a particle ethanol dispersion with a solid content of 5 mass% was obtained. The Na2O content of these particles was 50 ppm.

[0129] A coating solution for forming a film with a solid content of 4 mass% was prepared by mixing a matrix-forming component and an organic solvent with 96 g of an ethanol dispersion of these particles. The matrix-forming components used are dipentaerythritol hexaacrylate (DPE-6A, manufactured by Kyoesha Chemical Co., Ltd., with a solid content of 100 mass%) 2.30 g, 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shinnakamura Chemical Co., Ltd., with a solid content of 100 mass%) 0.58 g, reactive silicone oil for water-repellent agents (X-22-174DX, manufactured by Shin-Etsu Chemical Co., Ltd., with a solid content of 100 mass%) 0.19 g, silicone-modified polyurethane acrylate (Shiko UT-4314, manufactured by Nippon Kose Chemical Co., Ltd., with a solid content of 30 mass%) 0.43 g, and a photopolymerization initiator (Omnirad TPO, manufactured by IGM Resins BV, with a solid content of 100 mass%) 0.14 g. The organic solvents used are 50.2g isopropyl alcohol, 30.1g methyl isobutyl ketone, and 20.1g isopropyl glycol.

[0130] <Manufacture of a substrate equipped with a film>

[0131] A hardcoat paint (ELCOM HP-1004 manufactured by Nikki Shokubai Kasei Co., Ltd.) was applied to a TAC film (FT-PB80UL-M manufactured by Fanuc Co., Ltd., thickness 80 μm, refractive index 1.51) using the bar coater method (#18), and the applied paint was dried at 80°C for 120 seconds. Afterward, the applied and dried paint was dried at 300 mJ / cm² 2 A hardcoat film was produced by curing it through irradiation with ultraviolet light. The thickness of the hardcoat film was 8 μm.

[0132] Next, the prepared coating solution was applied to the TAC film with the hardcoat film using the bar coater method (#4), and the applied paint was dried at 80°C for 120 seconds. Afterwards, under an N2 atmosphere, 400 mJ / cm² 2 A substrate equipped with a film was manufactured by curing the paint by irradiating it with ultraviolet rays.

[0133] Measurements regarding the following items were performed on the substrates equipped with the coating. The measurement results are shown in Table 3 (the same applies to the following examples and comparative examples).

[0134] (10) Appearance

[0135] The presence or absence of foreign matter defects was confirmed by visually inspecting the obtained coated substrate.

[0136] No foreign matter defects are detected : ◎

[0137] Slight foreign matter defects are observed: ○

[0138] Numerous foreign matter defects are identified: △

[0139] Foreign matter defects present throughout: ×

[0140] (11) Film thickness, reflectance

[0141] Using an ellipsometer (ULVAC EMS-1), the film thickness and reflectance at a wavelength of 550 nm of the film-equipped substrate were measured.

[0142] (12) Haze, total light transmittance

[0143] Using a haze meter (manufactured by Suga Shikenki Co., Ltd.), the haze and total light transmittance of the coated substrate were measured.

[0144] (13) Antibacterial test

[0145] The antibacterial test was performed in accordance with JIS Z 2801. The antibacterial activity value was calculated using the following formula (2).

[0146] Q=Ut-At ···· Equation (2)

[0147] (where Q represents the antibacterial activity value, and Ut is 1 cm after 24 hours of the untreated specimen) 2 It represents the average logarithmic value of the viable cell count, and At is the 1 cm² value of the antimicrobial treated specimen after 24 hours. 2 Represents the average value of the logarithmic value of the number of viable cells.

[0148] Staphylococcus aureus NBRC 12732 and Escherichia coli NBRC3972 were used as test bacteria. As nutrition, a 1 / 20 concentration of nutrient broth (meat extract 150 mg / L + peptone 250 mg / L) was used.

[0149] For measurement, test specimens were prepared by dropping 0.4 mL of bacterial suspension onto a coated substrate and an untreated film, both cut into squares with sides of 5 cm, and covering them with a square PE film with sides of 4 cm. The test bacteria on the specimens were cultured for 24 hours at 35°C ± 1°C and a relative humidity of 90% or higher. Subsequently, the test bacteria on the specimens were washed away and recovered, and then 1 cm 2 The number of viable bacteria in the sugar was measured.

[0150] (14) Measurement of scratch resistance

[0151] Using #0000 steel wool, load 1000g / cm² 2 100 sliding movements were performed. The surface of the film-equipped substrate after the sliding movement was observed visually and evaluated according to the following criteria.

[0152] metewand;

[0153] No striped scratches are observed : ◎

[0154] Slight striped scratches are observed : ○

[0155] Numerous striped scratches are observed: △

[0156] The entire surface is beveled : ×

[0157] (15) Adhesion

[0158] On the surface of a substrate equipped with a film, 100 grids were created by making 11 parallel incisions with a knife at intervals of 1 mm in the horizontal and vertical directions. Cellophane tape was adhered to these, and then the cellophane tape was peeled off. Afterward, the number of grids remaining without peeling off the film was counted. Adhesion was evaluated by classifying this number of grids into the following four stages.

[0159] Number of remaining grid lines 95 or more: ◎

[0160] Number of remaining grid lines 90 to 94: ○

[0161] Number of remaining grid lines 85 to 89: △

[0162] Number of remaining grid lines 84 or less: ×

[0163] [Example 2]

[0164] In the same manner as in Example 1, 128 g of an ethanol dispersion of particles with a solid content concentration of 5 mass% was obtained. To this, 0.32 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and heat treatment was performed at 30°C for 24 hours. Subsequently, an MIBK dispersion of particles with a solid content concentration of 5 mass% was prepared by replacing the solvent with methyl isobutyl ketone (MIBK) in an evaporator. The Na2O content of these particles was 50 ppm. Next, a coating solution and a substrate equipped with a film were prepared in the same manner as in Example 1, except that the MIBK dispersion of particles was used, and each characteristic was evaluated.

[0165] [Example 3]

[0166] In the second process, an MIBK dispersion of particles with a solid content concentration of 5 mass% was prepared in the same manner as in Example 2, except that 7.8 g of an aqueous silver nitrate solution was used. The Na2O content of these particles was 50 ppm. Subsequently, a coating solution and a substrate equipped with a film were prepared in the same manner as in Example 1, except that the MIBK dispersion of particles was used, and each characteristic was evaluated.

[0167] [Example 4]

[0168] In the second process, an MIBK dispersion of particles with a solid content concentration of 5 mass% was prepared in the same manner as in Example 2, except that 920 g of an aqueous silver nitrate solution was used and the addition time was 90 minutes. The Na2O content of these particles was 50 ppm. Subsequently, a coating solution and a substrate equipped with a film were prepared in the same manner as in Example 1, except that the MIBK dispersion of particles was used, and each characteristic was evaluated.

[0169] [Example 5]

[0170] <Production of the First Particle (Process 1)>

[0171] 10 g of silica sol (cataloid SI-550 manufactured by Nikki Shokubai Kasei Co., Ltd., average particle size 5 nm, SiO2 concentration 20.5 mass%) and 10.0 kg of pure water were mixed, and the resulting mixture was heated to 50°C. To this mixture, an aqueous sodium hydroxide solution with a concentration of 1 mass% was added to adjust the pH to 10.5.

[0172] To this mixture, 7.9 kg of an aqueous sodium silicate solution (SiO2 concentration 3.0 mass%) and 7.9 kg of an aqueous sodium aluminate solution (Al2O3 concentration 1.0 mass%) were added simultaneously. Subsequently, 51.8 kg of an aqueous sodium silicate solution (SiO2 concentration 3.0 mass%) and 17.1 kg of an aqueous sodium aluminate solution (Al2O3 concentration 1.0 mass%) were added simultaneously to this mixture (reaction solution). During this process, the temperature of the reaction solution was maintained at 50°C. Subsequently, by washing this reaction solution with an ultrafiltration membrane, a dispersion of silica-alumina particles with a solid content concentration of 3 mass% was obtained.

[0173] To 50 kg of this silica-alumina particle dispersion, concentrated hydrochloric acid with a concentration of 35.5 mass% was added dropwise to adjust the pH to 1.0, and dealalumination treatment was performed. The dissolved aluminum salt was separated using an ultrafiltration membrane, and by washing, 18 kg of a silica-based particle dispersion with a solid content of 5 mass% was obtained. Subsequently, 236 g of an aqueous sodium hydroxide solution with a concentration of 10 mass% was added to this dispersion. This dispersion was heat-treated in an autoclave at 195°C for 24 hours to obtain an aqueous dispersion of the first particle. The Na2O content of this particle was 0.3 mass%.

[0174] In the second process, an MIBK dispersion of particles with a solid content concentration of 5 mass% was prepared in the same manner as in Example 2, except that the first particles diluted with pure water to 1.5 mass% were used. The Na2O content of these particles was 90 ppm. Subsequently, a coating solution and a substrate equipped with a film were prepared in the same manner as in Example 1, except that the MIBK dispersion of particles was used, and each characteristic was evaluated.

[0175] [Example 6]

[0176] <Production of the First Particle (Process 1)>

[0177] 10 g of silica sol (Cataloid SI-50 manufactured by Nikki Shokubai Kasei Co., Ltd., average particle size 25 nm, SiO2 concentration 48 mass%) and 5.0 kg of pure water were mixed, and the resulting mixture was heated to 98°C. To this mixture, an aqueous sodium hydroxide solution with a concentration of 1 mass% was added to adjust the pH to 12.5.

[0178] To this mixture, 65 kg of an aqueous sodium silicate solution (SiO2 concentration 1.5 mass%) and 65 kg of an aqueous sodium aluminate solution (Al2O3 concentration 0.5 mass%) were added simultaneously. Subsequently, 37 kg of an aqueous sodium silicate solution (SiO2 concentration 1.5 mass%) and 12 kg of an aqueous sodium aluminate solution (Al2O3 concentration 0.5 mass%) were added simultaneously to this mixture (reaction solution). During this process, the temperature of the reaction solution was maintained at 98°C. Subsequently, by washing this reaction solution with an ultrafiltration membrane, a dispersion of silica-alumina particles with a solid content concentration of 3 mass% was obtained.

[0179] To 50 kg of the dispersion of silica-alumina particles, concentrated hydrochloric acid with a concentration of 35.5 mass% was added dropwise to adjust the pH to 1.0, and dealaluminization treatment was performed. The dissolved aluminum salt was separated using an ultrafiltration membrane, and by washing, 5 kg of a dispersion of silica-based particles with a solid content of 5 mass% was obtained. Subsequently, 66 g of an aqueous sodium hydroxide solution with a concentration of 10 mass% was added to this dispersion. This dispersion was heat-treated in an autoclave at 195°C for 24 hours to obtain an aqueous dispersion of the first particles. The Na2O content of these particles was 0.2 mass%.

[0180] In the second process, an MIBK dispersion of particles with a solid content concentration of 5 mass% was prepared in the same manner as in Example 2, except that the first particles diluted to 1.5 mass% with pure water were used. The Na2O content of these particles was 30 ppm.

[0181] <Manufacture of substrates equipped with coating solution and film>

[0182] A coating solution with a solid content of 4 mass% was obtained by mixing a matrix-forming component and an organic solvent with 32 g of a dispersion of MIBK particles. The matrix-forming components used were 4.61 g of dipentaerythritol hexaacrylate, 1.15 g of 1,6-hexanediol diacrylate, 0.38 g of reactive silicone oil for water-repellent agents, 0.85 g of silicone-modified polyurethane acrylate, and 0.29 g of a photopolymerization initiator. The organic solvents used were 80.4 g of isopropyl alcohol, 48.2 g of methylisobutyl ketone, and 32.1 g of isopropyl glycol. Subsequently, a substrate equipped with a coating was prepared in the same manner as in Example 1, except that this coating solution was used, and each characteristic was evaluated.

[0183] [Example 7]

[0184] <Production of the First Particle (Process 1)>

[0185] 313 g of silica alumina sol (Fine Cataloid USBB-120 manufactured by Nikki Shokubai Kasei Co., Ltd.) and 29.7 kg of pure water were mixed, and the resulting mixture was heated to 98°C. To this mixture, an aqueous sodium hydroxide solution with a concentration of 1 mass% was added to adjust the pH to 12.5.

[0186] To this mixture, 30.0 kg of an aqueous sodium silicate solution (SiO2 concentration 3.0 mass%) and 30.0 kg of an aqueous sodium aluminate solution (Al2O3 concentration 1.0 mass%) were added simultaneously. Subsequently, 70.0 kg of an aqueous sodium silicate solution (SiO2 concentration 1.5 mass%) and 23.3 kg of an aqueous sodium aluminate solution (Al2O3 concentration 0.5 mass%) were added simultaneously to this mixture (reaction solution). During this process, the temperature of the reaction solution was maintained at 98°C. Subsequently, by washing the reaction solution with an ultrafiltration membrane, a dispersion of silica-alumina particles with a solid content concentration of 3 mass% was obtained.

[0187] To 50 kg of the dispersion of these silica-alumina particles, concentrated hydrochloric acid with a concentration of 35.5 mass% was added dropwise to adjust the pH to 1.0, and dealaluminization treatment was performed. The dissolved aluminum salt was separated using an ultrafiltration membrane, and by washing, 9 kg of a dispersion of silica-based particles with a solid content of 5 mass% was obtained. Subsequently, 118 g of an aqueous sodium hydroxide solution with a concentration of 10 mass% was added to this dispersion. This dispersion was heat-treated in an autoclave at 195°C for 24 hours to obtain an aqueous dispersion of the first particles. The Na2O content of these particles was 0.1 mass%.

[0188] In the second process, an MIBK dispersion of particles with a solid content concentration of 5 mass% was prepared in the same manner as in Example 2, except that the first particles diluted with pure water to 1.5 mass% were used. The Na2O content of these particles was 30 ppm. Subsequently, a coating solution and a substrate equipped with a film were prepared in the same manner as in Example 1, except that the MIBK dispersion of particles was used, and each characteristic was evaluated.

[0189] [Example 8]

[0190] <Production of the First Particle (Process 1)>

[0191] 63g of silica sol (Cataloid SI-50 manufactured by Nikki Shokubai Kasei Co., Ltd.) and 29.9kg of pure water were mixed, and the resulting mixture was heated to 98℃. To this mixture, an aqueous sodium hydroxide solution with a concentration of 1 mass% was added, and the pH was adjusted to 12.5.

[0192] To this mixture, 10.7 kg of an aqueous sodium silicate solution (SiO2 concentration 3.0 mass%) and 10.7 kg of an aqueous sodium aluminate solution (Al2O3 concentration 1.0 mass%) were added simultaneously. Subsequently, 86 kg of an aqueous sodium silicate solution (SiO2 concentration 3.0 mass%) and 28.6 kg of an aqueous sodium aluminate solution (Al2O3 concentration 1.0 mass%) were added simultaneously to this mixture (reaction solution). During this process, the temperature of the reaction solution was maintained at 98°C. Subsequently, by washing this reaction solution with an ultrafiltration membrane, a dispersion of silica-alumina particles with a solid content concentration of 3 mass% was obtained.

[0193] To 40 kg of the dispersion of silica-alumina particles, concentrated hydrochloric acid with a concentration of 35.5 mass% was added dropwise to adjust the pH to 1.0, and dealaluminization treatment was performed. The dissolved aluminum salt was separated using an ultrafiltration membrane, and by washing, 13 kg of a dispersion of silica-based particles with a solid content of 5 mass% was obtained. Subsequently, 170 g of an aqueous sodium hydroxide solution with a concentration of 10 mass% was added to this dispersion. This dispersion was heat-treated in an autoclave at 195°C for 24 hours to obtain an aqueous dispersion of the first particles. The Na2O content of these particles was 0.2 mass%.

[0194] In the second process, an MIBK dispersion of particles with a solid content concentration of 5 mass% was prepared in the same manner as in Example 2, except that the first particles diluted with pure water to 1.5 mass% were used. The Na2O content of these particles was 0.018 mass%.

[0195] <Manufacture of substrates equipped with coating solution and film>

[0196] A coating solution with a solid content of 4 mass% was prepared by mixing a matrix-forming component and an organic solvent with 56 g of a dispersion of MIBK particles. The matrix-forming components used were 3.74 g of dipentaerythritol hexaacrylate, 0.94 g of 1,6-hexanediol diacrylate, 0.31 g of reactive silicone oil for water-repellent agents, 0.69 g of silicone-modified polyurethane acrylate, and 0.23 g of a photopolymerization initiator. The organic solvents used were 69.0 g of isopropyl alcohol, 41.4 g of methylisobutyl ketone, and 27.6 g of isopropyl glycol. Subsequently, a substrate equipped with a coating was prepared in the same manner as in Example 1, except that this coating solution was used, and each characteristic was evaluated.

[0197] [Example 9]

[0198] <Production of the First Particle (Process 1)>

[0199] 52g of silica sol (Cataloid SI-50 manufactured by Nikki Shokubai Kasei Co., Ltd.) and 4.9kg of pure water were mixed, and the resulting mixture was heated to 98℃. To this mixture, an aqueous sodium hydroxide solution with a concentration of 1 mass% was added to adjust the pH to 12.5.

[0200] To this mixture, 77 kg of an aqueous sodium silicate solution (SiO2 concentration 1.0 mass%) and 86 kg of an aqueous sodium aluminate solution (Al2O3 concentration 0.3 mass%) were added simultaneously. Subsequently, 92 kg of an aqueous sodium silicate solution (SiO2 concentration 1.0 mass%) and 34 kg of an aqueous sodium aluminate solution (Al2O3 concentration 0.3 mass%) were added simultaneously to this mixture (reaction solution). During this process, the temperature of the reaction solution was maintained at 98°C. Subsequently, by washing this reaction solution with an ultrafiltration membrane, a dispersion of silica-alumina particles with a solid content concentration of 3 mass% was obtained.

[0201] To 50 kg of the dispersion of these silica-alumina particles, concentrated hydrochloric acid with a concentration of 35.5 mass% was added dropwise to adjust the pH to 1.0, and dealaluminization treatment was performed. The dissolved aluminum salt was separated using an ultrafiltration membrane, and by washing, 9 kg of a dispersion of silica-based particles with a solid content of 5 mass% was obtained. Subsequently, 118 g of an aqueous sodium hydroxide solution with a concentration of 10 mass% was added to this dispersion. This dispersion was heat-treated in an autoclave at 195°C for 24 hours to obtain an aqueous dispersion of the first particles. The Na2O content of these particles was 0.2 mass%.

[0202] In the second process, an MIBK dispersion of particles with a solid content concentration of 5 mass% was prepared in the same manner as in Example 2, except that the first particles diluted to 1.5 mass% with pure water were used. The Na2O content of these particles was 40 ppm.

[0203] <Manufacture of substrates equipped with coating solution and film>

[0204] A coating solution with a solid content of 4 mass% was prepared by mixing a matrix-forming component and an organic solvent with 64 g of a dispersion of MIBK particles. The matrix-forming components used were 3.46 g of dipentaerythritol hexaacrylate, 0.86 g of 1,6-hexanediol diacrylate, 0.29 g of reactive silicone oil for water-repellent agents, 0.64 g of silicone-modified polyurethane acrylate, and 0.22 g of a photopolymerization initiator. The organic solvents used were 65.3 g of isopropyl alcohol, 39.2 g of methylisobutyl ketone, and 26.1 g of isopropyl glycol. Subsequently, a substrate equipped with a coating was prepared in the same manner as in Example 1, except that this coating solution was used, and each characteristic was evaluated.

[0205] [Example 10]

[0206] In the second process, 500g of an aqueous dispersion of silica-based particles was ion-exchanged for 3 hours using 100g of cation exchange resin. However, subsequent ion exchange with an anion exchange resin and re-ion exchange with a cation exchange resin were not performed. Except for this, an MIBK dispersion of particles with a solid content concentration of 5 mass% was prepared in the same manner as in Example 2. The Na2O content of these particles was 0.09 mass%. Subsequently, a coating solution and a substrate equipped with a film were prepared in the same manner as in Example 1, except for the use of the MIBK dispersion of particles, and each characteristic was evaluated.

[0207] [Example 11]

[0208] In the second process, an aqueous dispersion of particles was obtained in the same manner as in Example 1, except that 42.5 g of an aqueous silver nitrate solution was used. The Na2O content of these particles was 60 ppm. Subsequently, an MIBK dispersion of particles with a solid content of 5 mass% was prepared in the same manner as in Example 2, except that 1.92 g of 3-methacryloxypropyltrimethoxysilane was added to the ethanol dispersion of particles with a solid content of 5 mass% prepared in the same manner as in Example 1. The Na2O content of these particles was 50 ppm. Subsequently, a coating solution and a substrate equipped with a film were prepared in the same manner as in Example 1, except that the MIBK dispersion of particles was used, and each characteristic was evaluated.

[0209] [Example 12]

[0210] Dealanium treatment was performed by adding concentrated hydrochloric acid with a concentration of 35.5 mass% dropwise to 50 kg of a dispersion of silica-alumina particles prepared in the same manner as in Example 1 to adjust the pH to 1.0. The dissolved aluminum salt was separated using an ultrafiltration membrane and washed, and then dealanium treatment was performed again by adding concentrated hydrochloric acid with a concentration of 35.5 mass% dropwise to adjust the pH to 0.3. By separating the dissolved aluminum salt using an ultrafiltration membrane and washing, 10 kg of a dispersion of silica-based particles with a solid content concentration of 5 mass% was obtained. Subsequently, 131 g of an aqueous sodium hydroxide solution with a concentration of 10 mass% was added to this dispersion. This dispersion was heat-treated in an autoclave at 195°C for 24 hours to obtain an aqueous dispersion of the first particles. The Na2O content of these particles was 0.2 mass%, and the Al2O3 content was 0.00 mass%.

[0211] In the second process, an MIBK dispersion of particles with a solid content of 5 mass% was prepared in the same manner as in Example 1, except that 14.2 g of an aqueous silver nitrate solution was added to the first particles diluted to 1.5 mass% with pure water. The Na2O content of these particles was 30 ppm. Subsequently, a coating solution and a substrate equipped with a film were prepared in the same manner as in Example 2, except that the MIBK dispersion of particles was used, and each characteristic was evaluated.

[0212] [Example 13]

[0213] In the second process, an MIBK dispersion of particles with a solid content concentration of 5 mass% was prepared in the same manner as in Example 2, except that 132.8 g of an aqueous copper nitrate solution was used instead of an aqueous silver nitrate solution. The Na2O content of these particles was 50 ppm. Subsequently, a coating solution and a substrate equipped with a film were prepared in the same manner as in Example 1, except that the MIBK dispersion of particles was used, and each characteristic was evaluated.

[0214] [Example 14]

[0215] In the second process, an MIBK dispersion of particles with a solid content concentration of 5 mass% was prepared in the same manner as in Example 2, except that 130.3 g of an aqueous zinc nitrate solution was used instead of an aqueous silver nitrate solution. The Na2O content of these particles was 50 ppm. Subsequently, a coating solution and a substrate equipped with a film were prepared in the same manner as in Example 1, except that the MIBK dispersion of particles was used, and each characteristic was evaluated.

[0216] [Example 15]

[0217] <Manufacture of substrates equipped with coating solution and film>

[0218] A coating solution with a solid content of 4 mass% was prepared by mixing a matrix-forming component and an organic solvent with 64 g of the MIBK dispersion of the particles prepared in Example 9. The matrix-forming component used was 3.11 g of dipentaerythritol hexaacrylate, 0.77 g of 1,6-hexanediol diacrylate, 2.16 g of fluorine-based resin (Optool DAC-HP, manufactured by Daikin Kogyo Co., Ltd., with a solid content of 20 mass%), 0.48 g of fluorine-based additive (Megapac F477, manufactured by DIC Co., Ltd., with an active ingredient of 100%), and 0.22 g of photopolymerization initiator. The organic solvent used was 65.3 g of isopropyl alcohol, 39.2 g of methylisobutyl ketone, and 24.8 g of isopropyl glycol. Next, a substrate equipped with a film was prepared in the same manner as in Example 1, except that this coating solution was used, and each characteristic was evaluated.

[0219] [Example 16]

[0220] <Preparation of Coating Solution for Forming High Refractive Index Layer>

[0221] A coating solution for forming a high refractive index layer with a solid content of 5 mass% was obtained by mixing a matrix-forming component and an organic solvent with 26 g of titania-based sol (ELCOM V-9108 manufactured by Nikki Shokubai Kasei Co., Ltd., particle size 15 nm, solid content concentration 30.5 mass%). The matrix-forming components used were 1.44 g of dipentaerythritol hexaacrylate, 0.36 g of 1,6-hexanediol diacrylate, and 0.1 g of photopolymerization initiator. The organic solvent used was 172 g of propylene glycol monomethyl ether.

[0222] <Manufacture of a substrate equipped with a film>

[0223] The aforementioned coating solution for forming a high refractive index layer was applied by the bar coater method (#8) onto the hardcoat layer of a TAC film having a hardcoat film prepared in the same manner as in Example 1, and the applied paint was dried at 80°C for 120 seconds. Thereafter, the applied and dried paint was subjected to 1200 mJ / cm² 2 A high-refractive-index layer was fabricated on a hardcoat layer by curing it through irradiation with ultraviolet light. The film thickness of the high-refractive-index layer was 220 nm.

[0224] Next, the coating solution prepared in Example 9 was applied onto the high-refractive-index layer of a TAC film having a high-refractive-index layer using a bar coater method (#4), and the applied coating was dried at 80°C for 120 seconds. Afterwards, under an N2 atmosphere, 400 mJ / cm² 2 By curing the paint by irradiating it with ultraviolet rays, a substrate equipped with a film was manufactured, and each characteristic was evaluated.

[0225] [Example 17]

[0226] Preparation of a coating solution for forming an anti-glare layer

[0227] By mixing 10g of silica powder (silica micro beads P-500 manufactured by Nikki Shokubai Kasei Co., Ltd.) with a matrix-forming component and an organic solvent, a coating solution for forming an anti-glare layer with a solid content concentration of 35 mass% was obtained. The matrix-forming component used was 30.2g of dipentaerythritol hexaacrylate, 7.6g of 1,6-hexanediol diacrylate, and 1.9g of photopolymerization initiator. The organic solvent used was 78.2g of propylene glycol monomethyl ether.

[0228] <Manufacture of a film-equipped substrate (17)>

[0229] The aforementioned anti-glare layer forming coating solution was applied by the bar coater method (#9) onto the hardcoat layer of a TAC film having a hardcoat film, prepared in the same manner as in Example 1, and the applied paint was dried at 80°C for 120 seconds. Thereafter, the applied and dried paint was dried at 800 mJ / cm² 2 An anti-glare layer was produced on the hardcoat layer by curing it through irradiation with ultraviolet rays.

[0230] Next, the coating solution prepared in Example 9 was applied onto the anti-glare layer of a TAC film having an anti-glare layer using the bar coater method (#4), and the applied coating was dried at 80°C for 120 seconds. Afterwards, under an N2 atmosphere, 400 mJ / cm² 2 A substrate equipped with a film was manufactured by curing the paint by irradiating it with ultraviolet rays, and each characteristic was evaluated.

[0231] [Comparative Example 1]

[0232] In the second process, an MIBK dispersion of particles with a solid content concentration of 5 mass% was prepared in the same manner as in Example 2, except that an aqueous silver nitrate solution was not used and 0.34 g of 3-methacryloxypropyltrimethoxysilane was added to 128 g of an ethanol dispersion of particles. The Na2O content of these particles was 50 ppm. Subsequently, a coating solution and a substrate equipped with a film were prepared in the same manner as in Example 1, except that the MIBK dispersion of particles was used, and each characteristic was evaluated.

[0233] [Comparative Example 2]

[0234] By diluting silica sol (cataloids SI-45P manufactured by Nikki Shokubai Kasei Co., Ltd., particle size 60 nm, solid content 40.5 mass%) with pure water, 10 kg of silica sol with a solid content of 5 mass% was obtained. Subsequently, 131 g of an aqueous sodium hydroxide solution with a concentration of 10 mass% was added to this silica sol, and by heat-treating it in an autoclave at 195°C for 24 hours, an aqueous dispersion of the first silica-based particles was obtained. The Na2O concentration of these silica-based particles was 0.2 mass%. Furthermore, these silica-based particles were so-called "solid particles" that did not have internal cavities.

[0235] In the second process, an MIBK dispersion of silica-based particles with a solid content of 5 mass% was prepared in the same manner as in Example 2, except that the first silica-based particles diluted to 1.5 mass% with pure water were used. The Na2O content of these particles was 80 ppm. Subsequently, a coating solution and a substrate equipped with a film were prepared in the same manner as in Example 1, except that the MIBK dispersion of silica-based particles was used, and each characteristic was evaluated.

[0236] [Comparative Example 3]

[0237] Preparation of silver nanoparticles

[0238] 65g of 25 mass% iron(II) sulfate was added to 729g of a 30 mass% aqueous sodium citrate solution while bubbling nitrogen gas. After stirring for 30 minutes, 24g of 10 mass% silver nitrate was added to the mixture at once, and stirring was performed for 6 hours. Centrifugation was performed at 5000 rpm for 10 minutes to recover the precipitate, and the recovered precipitate was suspended by ultrasound in 270g of pure water to obtain an aqueous dispersion of silver nanoparticles. Subsequently, the solvent of 200g of the aqueous dispersion of silver nanoparticles was replaced with IPA using an ultrafiltration membrane to prepare an IPA dispersion of silver nanoparticles with a solid content concentration of 5.0 mass%. The particle size of these silver nanoparticles was 10 nm, and the Na2O concentration was 0 ppm. In addition, the particle characteristics shown in Table 2 are the characteristics obtained when the particles prepared in Comparative Example 1 and silver nanoparticles are mixed in a mass ratio of 95.4:4.6. However, regarding the measurement of the outer thickness and porosity, only particles having a cavity on the inner side of the outer shell were selected. Furthermore, the mixing ratio of the particles prepared in Comparative Example 1 and the silver nanoparticles is adjusted so that the apparent porosity and antibacterial metal content of the mixture correspond to the particles of Example 2.

[0239] <Manufacture of substrates equipped with coating solution and film>

[0240] A coating solution and a substrate equipped with a film were prepared in the same manner as in Example 1, except that a solution was used in which 91.6 g of an MIBK dispersion of particles prepared in Comparative Example 1 that does not contain antibacterial metal components and 4.4 g of an IPA dispersion of silver nanoparticles were mixed, and each characteristic was evaluated.

[0241] [Comparative Example 4]

[0242] In the second process, an MIBK dispersion of particles with a solid content of 5 mass% was prepared in the same manner as in Example 2, except that 2120 g of an aqueous silver nitrate solution was used and the addition time was 90 minutes. The Na2O content of these particles was 50 ppm. Subsequently, a coating solution and a substrate equipped with a film were prepared in the same manner as in Example 1, except that the MIBK dispersion of particles was used, and each characteristic was evaluated.

[0243] [Comparative Example 5]

[0244] <Production of the First Particle (Process 1)>

[0245] 188 g of silica alumina sol (Fine Cataloid USBB-120 manufactured by Nikki Shokubai Kasei Co., Ltd.) and 89.8 kg of pure water were mixed, and the resulting mixture was heated to 98°C. To this mixture, an aqueous sodium hydroxide solution with a concentration of 1 mass% was added, and the pH was adjusted to 12.5.

[0246] To this mixture, 23.0 kg of an aqueous sodium silicate solution (SiO2 concentration 3.0 mass%) and 23.0 kg of an aqueous sodium aluminate solution (Al2O3 concentration 1.0 mass%) were added simultaneously. Subsequently, 15.0 kg of an aqueous sodium silicate solution (SiO2 concentration 3.0 mass%) and 5.0 kg of an aqueous sodium aluminate solution (Al2O3 concentration 1.0 mass%) were added simultaneously to this mixture (reaction solution). During this process, the temperature of the reaction solution was maintained at 98°C. Subsequently, by washing this reaction solution with an ultrafiltration membrane, a dispersion of silica-alumina particles with a solid content concentration of 3 mass% was obtained.

[0247] To 50 kg of the dispersion of these silica-alumina particles, concentrated hydrochloric acid with a concentration of 35.5 mass% was added dropwise to adjust the pH to 1.0, and dealaluminization treatment was performed. The dissolved aluminum salt was separated using an ultrafiltration membrane, and by washing, 9 kg of a dispersion of silica-based particles with a solid content of 5 mass% was obtained. Subsequently, 118 g of an aqueous sodium hydroxide solution with a concentration of 10 mass% was added to this dispersion. This dispersion was heat-treated in an autoclave at 195°C for 24 hours to obtain an aqueous dispersion of the first particles. The Na2O concentration of these particles was 0.1 mass%.

[0248] In the second process, an MIBK dispersion of particles with a solid content concentration of 5.0 mass% was prepared in the same manner as in Example 2, except that the first particles diluted to 1.5 mass% with pure water were used. The Na2O content of these particles was 40 ppm. Subsequently, a coating solution and a substrate equipped with a film were prepared in the same manner as in Example 1, except that the MIBK dispersion of particles was used, and each characteristic was evaluated.

[0249]

[0250]

[0251]

Claims

Claim 1 The particle comprises 0.5 to 40 mass% of an antimicrobial metal component based on oxide, has an outer shell containing silicon and an inner cavity, the ratio of the cavity to the particle (porosity) is 10 to 90%, and furthermore, the ratio of particles having one cavity to the total number of particles is 80% or more, the average particle diameter of the particle is 20 to 180 nm, the density (A1) of the particle dried at 105°C by He gas adsorption method is 1.95 to 3.50 g / ml, the density (B1) by N2 gas adsorption method is 0.50 to 2.60 g / ml, the density (A2) of the particle heat-treated at 400°C by He gas adsorption method is 2.17 g / ml or more, and the ratio (A2 / B2) of the density (B2) of the particle heat-treated at 400°C by N2 gas adsorption method is 1.10 Particles of up to 4.

50. Claim 2 In claim 1, the particle wherein the antimicrobial metal component comprises at least one element selected from silver, copper, zinc, lead, tin, bismuth, cadmium, chromium, mercury, nickel, and cobalt. Claim 3 A particle according to claim 1, wherein the density (A1) of the dried product of the particle at 105°C by the He gas adsorption method is 2.10 to 2.30 g / ml, and the density (B1) of the dried product of the particle by the N2 gas adsorption method is 0.80 to 2.10 g / ml. Claim 4 A particle according to claim 1, wherein the density (A2) of the heat-treated product of the particle at 400°C by the He gas adsorption method is 2.17 g / ml or higher, and the ratio (A2 / B2) of the density (A2) and the density (B2) of the heat-treated product of the particle at 400°C by the N2 gas adsorption method is 1.30 to 4.

50. Claim 5 In claim 1, the particle having an average thickness of the outer shell of the particle of 5 to 30 nm. Claim 6 In claim 1, the particle having an alkali metal content of less than 1.00 mass% based on oxide. Claim 7 In claim 1, the particle comprises an organic compound having a functional group. Claim 8 A transparent film-equipped substrate comprising a substrate and a transparent film formed on the substrate, the transparent film comprising the particles and matrix described in claim 1. Claim 9 A substrate having a transparent film according to claim 8, further comprising at least one layer selected from a hardcoat layer, a high refractive index layer, an anti-glare layer, and a conductive layer disposed between the transparent film and the substrate.

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