Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
  • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
  • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/006—Anti-reflective coatings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
  • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/11—Anti-reflection coatings
  • G02B1/113—Anti-reflection coatings using inorganic layer materials only
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings

Definitions

• One aspect of the present disclosure relates to particles and a substrate with a transparent coating containing the particles.
• an antireflection film is formed on the surface of a base material such as a sheet or lens made of glass or plastic to prevent reflection.
• a film of a substance having a low refractive index, such as fluororesin or magnesium fluoride, is formed on the surface of a glass or plastic substrate by a coating method, a vapor deposition method, a CVD method, or the like.
• these methods are costly. Therefore, the following method is known (see, for example, Japanese Unexamined Patent Publication No. 7-133105).
• an antireflection film is formed by applying a coating liquid containing composite oxide colloidal particles having a refractive index of 1.36 to 1.44, which is composed of silica and inorganic oxides other than silica, on the substrate surface.
• a method for producing particles having an outer shell and a cavity inside thereof is known (see, for example, JP-A-2001-233611 and JP-A-2013-226539).
• the particles have a lower refractive index than solid particles.
• a transparent film formed using these particles has a low refractive index and is excellent in antireflection performance.
• particles of inorganic oxides such as alumina and silica, or particles of composite oxides such as silica-alumina are allowed to carry a metal component such as silver or copper, thereby imparting antibacterial properties to these particles.
• a metal component such as silver or copper
• an antireflection film having an antireflection layer and a layer having an antibacterial function is known (see JP-A-11-052105).
• Particles with internal cavities have a lower refractive index than particles with solid interiors. Therefore, when particles having internal cavities are used for the coating, the transparency and antireflection performance of the coating are improved.
• members requiring transparency and antireflection performance include, for example, display devices having touch panels, such as smartphones, ATMs, and ticket vending machines. These surfaces may be contaminated with fungi such as E. coli or Staphylococcus aureus, or with various viruses. Therefore, antibacterial properties are required from a sanitary point of view.
• an antibacterial agent to the coating surface in order to impart antibacterial properties to the coating.
• the antibacterial agent is an organic antibacterial agent
• the application of the antibacterial agent itself is relatively easy.
• the coating may be attacked by the solvent.
• the fixability to the film and the scratch resistance are not good, the durability of the antibacterial performance will be insufficient.
• the antibacterial agent is an inorganic antibacterial agent
• the presence of the antibacterial agent in the film can be expected to maintain the antibacterial performance.
• a coating containing an antimicrobial agent must be prepared separately.
• the antireflection layer and the antibacterial layer are formed separately, there is a risk that the effect of the layer other than the outermost layer will be insufficient, and that the productivity will decrease and the production cost will increase.
• the antireflection performance and antibacterial performance may be insufficient, or the transparency and strength of the coating may be insufficient.
• a substrate with a transparent coating (antireflection film) using these particles is required to have high transparency and antireflection performance, sufficient hardness and strength, and high antibacterial performance.
• a particle according to one aspect of the present disclosure has an outer shell containing silicon and a cavity inside thereof.
• the particles contain 0.5 to 40% by weight, based on oxide, of an antimicrobial metal component.
• the proportion of voids in the particles (porosity) is 10 to 90%.
• the number ratio of particles having one cavity in the particles to all particles is 80% or more.
• the particles have a low refractive index, sufficient hardness and strength, high dispersibility, and high antibacterial performance.
• a coating liquid containing such particles can provide a transparent film having high transparency and antireflection performance, sufficient hardness (pencil hardness) and strength (scratch resistance), and high antibacterial performance. .
• the particles according to one aspect of the present disclosure it is possible to obtain a coating liquid capable of forming the following coating.
• This coating has high transparency and antireflection performance, and also has excellent adhesion to the substrate. Furthermore, this coating has sufficient hardness and strength as well as high antibacterial performance.
• the particles according to this embodiment (hereinafter, the particles according to this embodiment may be simply referred to as "particles”) contain 0.5 to 40% by mass of the antibacterial metal component based on the oxide.
• the particle shape has an outer shell containing silicon and an inner cavity.
• the proportion of voids in the particles (porosity) is 10 to 90%.
• the number ratio of particles having one cavity inside the outer shell of the particles to all particles is 80% or more.
• the content of the antibacterial metal component of the particles is in the range of 0.5 to 40% by mass based on the oxide, the use of the particles in the coating provides high antibacterial properties and high transparency and antireflection performance. is obtained.
• the content of the antibacterial metal component is less than 0.5% by mass, there is a risk that sufficient antibacterial performance cannot be obtained. Conversely, even if the content of the antibacterial metal component exceeds 40% by mass, the antibacterial performance is not further improved, and in some cases the antibacterial metal component becomes unstable, releasing from the particles, discoloring, etc. becomes more likely to occur. In addition, there is a possibility that the transparency and antireflection performance may be lowered.
• the content of this antibacterial metal component is preferably 1 to 30% by mass, more preferably 3 to 10% by mass.
• the outer shell of the particles contains silicon.
• the substance containing silicon is preferably an oxide.
• Silicon-containing oxides include oxides containing at least one of aluminum, zirconium, titanium, zinc, tin, and antimony and silicon, and silica. These oxides may be used singly, as a mixture, or as composite oxides.
• the silicon content in the particles is preferably 50% by mass or more when silicon is expressed as silica.
• the silicon content is more preferably 75% by mass or more, still more preferably 85% by mass or more, and particularly preferably 90% by mass.
• the porosity of the particles is 10-90%.
• the porosity is preferably 13-80%, more preferably 20-70%.
• the number ratio of particles with one cavity to all particles is 80% or more. If the number ratio is less than 80%, the transparency and antireflection performance may be insufficient when the particles are used in a coated substrate.
• the number ratio is preferably 95% or more, more preferably 99% or more, and most preferably 100%.
• the cavity inside the outer shell has a shape that conforms to the outer shape of the particle. That is, it is preferable that the thickness of the outer shell is uniform. 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 particles.
• the antibacterial metal component preferably contains an element selected from silver, copper, zinc, lead, tin, bismuth, cadmium, chromium, mercury, nickel, and cobalt. These metal elements may be used alone, or may be used in combination. More preferred metal elements are silver, copper and zinc, and more preferred metal elements are silver and zinc.
• the density (A1) of the dried particles by the He gas adsorption method is preferably 1.95 to 3.50 g/ml
• the density (B1) of the dried particles by the N 2 gas adsorption method is preferably 0.95 to 3.50 g/ml. It is preferably between 50 and 2.60 g/ml.
• the density by this gas adsorption method is obtained as follows. That is, powder is obtained by drying the dispersion liquid of the particles with an evaporator. Next, using the substance obtained by heat-treating (drying) this powder at 105 ° C. in the air, a dry automatic density meter (AccuPyc 1340TC manufactured by Micromeritics) is used to measure He gas or Measurements are performed using N2 gas. This gives the density obtained by the gas adsorption method described above. In addition, the density (A2) and density (B2) described later are measured in the same manner using the powder obtained by drying with the evaporator described above and heat-treated (calcined) at 400 ° C. in the air. obtained by
• the reason for this is that the difference in the adsorption state due to the difference in the gas species according to the surface state of the particles such as unevenness or pores on the particle surface appears as a numerical value.
• the density (A1) is less than 1.95 g/ml, the antibacterial metal component is small, so there is a possibility that sufficient antibacterial performance cannot be obtained. Conversely, if the density (A1) exceeds 3.50 g/ml, the supported antibacterial metal component becomes unstable, and the release of the antibacterial metal component from the particles, discoloration, and the like tend to occur. In addition, transparency, antireflection performance, strength and adhesion may deteriorate.
• the density (B1) exceeds 2.60 g/ml, the supported antibacterial metal component becomes unstable, so that the antibacterial metal component is easily liberated from the particles and discolored. In addition, transparency, antireflection performance, hardness and adhesion may decrease.
• Density (A1) is more preferably 2.00 to 3.00 g/ml, still more preferably 2.10 to 2.30 g/ml.
• the density (B1) is more preferably 0.80 to 2.10 g/ml, still more preferably 0.90 to 1.50 g/ml.
• the density (A2) of the particles heat-treated at 400°C by the He gas adsorption method is preferably 2.17 g/ml or more.
• the antibacterial metal component is small, so there is a risk that sufficient antibacterial performance cannot be obtained.
• the upper limit of density (A2) is not set in particular. However, if the density (A2) is too large, depending on the type of the antibacterial metal component, the reflectance and haze of the formed substrate with a transparent film may increase, or the transmittance, strength and adhesion may decrease. There is a risk.
• the upper limit of density (A2) may be 3.70 g/ml when the antimicrobial metal component is silver, and 3.50 g/ml when the antimicrobial metal component is copper. or 3.20 g/ml when the antimicrobial metal component is zinc.
• the density (A2) is more preferably 2.20 g/ml or more, and still more preferably 2.24 g/ml or more.
• the ratio (A2/B2) between the density (A2) and the density (B2) of the particles heat-treated at 400° C. by the N 2 gas adsorption method is preferably 1.10 or more.
• the ratio (A2/B2) is less than 1.10, the refractive index of the particles increases, and the antireflection performance of the coating may become insufficient.
• the upper limit of the ratio (A2/B2) is not particularly set. However, if the ratio (A2/B2) is too large, it may become difficult to maintain the outer shell structure. Therefore, the upper limit of the ratio (A2/B2) is, for example, 4.50.
• the ratio (A2/B2) is more preferably 1.30 or more, still more preferably 1.45 or more.
• the average particle size of the particles is not particularly limited, it is preferably 20 to 180 nm when used for a substrate with a transparent film. When the average particle size is within this range, the particles can stably exist. In this case, the particles are well dispersed in the coating liquid and in the coating, and a coating having high transparency, hardness and strength can be obtained.
• the average particle size is more preferably 30-120 nm, still more preferably 40-110 nm.
• the average thickness of the outer shell is preferably 5-30 nm.
• the structure of the outer shell can be stably maintained, so that the particles can stably exist.
• a coating with high transparency, hardness and strength is obtained.
• the average thickness of the outer shell exceeds 30 nm, the refractive index of the outer shell may become too high, depending on the type and amount of the antibacterial metal component.
• the average thickness of the outer shell is more preferably 5-20 nm, still more preferably 7-12 nm.
• the alkali metal content of the particles is preferably less than 1.00% by mass based on oxides.
• the alkali metal content of the particles is 1.00% by mass or more, the particles coalesce, the dispersibility of the particles in the coating liquid and the coating decreases, and the film does not have sufficient hardness. It may not be obtained, or the transparency may be insufficient.
• the alkali metal content is more preferably less than 0.10% by weight, even more preferably less than 0.01% by weight. Most preferably, the particles do not contain alkali metals.
• Alkali metals represent Li, Na, K, Rb, Cs, and Fr
• alkaline earth metals represent Be, Mg, Ca, Sr, Ba, and Ra.
• the particles of this embodiment can also be dispersed in organic substances such as organic solvents and organic resins.
• the particles are preferably surface-treated using an organosilicon compound.
• an organosilicon compound it is preferable to use an organosilicon compound represented by the following formula (1) (where n is 1 to 3).
• n is 1 to 3
• the particles contain an organic compound having a functional group derived from the organosilicon compound of formula (1) below.
• 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.
• R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different.
• substituents include epoxy group, vinyl group, (meth)acryloxy group, mercapto group, amino group, and phenylamino group
• X is an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, a halogen atom, or a hydrogen atom
• n is 0 to indicates an integer of 3.
• organosilicon compound examples include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, Silane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris( ⁇ -methoxyethoxy)silane, 7-octenyltrimethoxysilane 3,3,3-trifluoro propyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)eth,
• a dispersion containing particles and at least one of water and alcohol is prepared.
• a predetermined amount of the organosilicon compound represented by formula (1) is added to this dispersion, and water is added as necessary to hydrolyze the organosilicon compound.
• surface treatment of the particles is performed.
• an acid or alkali is used as a hydrolysis catalyst, if necessary.
• impurities may be reduced by ion exchange, ultrafiltration, or the like before and/or after the surface treatment.
• the organosilicon compound is preferably present in the particles at 0.1 to 30% by mass as R n —SiO (4-n)/2 (solid content). If the particles are surface-treated with an organosilicon compound, the compatibility between the particles and the matrix-forming component is improved.
• the amount of the organosilicon compound is less than 0.1% by mass, the addition effect cannot be sufficiently obtained. Even if the amount of the organosilicon compound is more than 30% by mass, the dispersibility of the particles is not further improved, and there is also the possibility that sufficient antibacterial performance cannot be obtained.
• the amount of the organosilicon compound is more preferably 1 to 25% by mass, still more preferably 1 to 20% by mass, and particularly preferably 1 to 15% by mass.
• the shape of the particles is not particularly limited.
• Examples of the shape of the particles include spherical, ellipsoidal (rugby ball)-like, cocoon-like, confetti-like, chain-like, and dice-like shapes.
• spherical particles are preferable because they have high dispersibility and can be uniformly dispersed in the coating.
• the base material with a transparent coating includes a base material and a transparent coating containing the particles and the matrix described above, on which the base material is formed.
• the matrix is contained as a solid content other than particles. Examples of the matrix include resins derived from the coating solution, polymerization initiators, and additives such as leveling agents.
• a coating is formed on the substrate by applying the coating liquid to the substrate by a known method and then drying and irradiating the substrate with ultraviolet rays. In the coating, the ratio of the solid content of the particles and the matrix-forming component in the coating liquid directly becomes the ratio of the particle component and the matrix in the coating.
• a conventionally known hard coat layer, anti-glare layer, high refractive index layer, conductive layer, or the like may be placed between the transparent coating and the base material, depending on the application.
• these layers it is also possible to combine a plurality of layers. For example, in order to further reduce the reflectance of the substrate with a transparent film in order to use the substrate with a transparent film in a display, a combination of a hard coat layer and a high refractive index layer, or a hard coat layer and an anti-glare layer is used in combination with
• the film thickness of the transparent coating can be appropriately selected according to the application.
• the thickness of the transparent coating is preferably 80 to 350 nm.
• 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 antireflection performance. Conversely, if the film thickness of the transparent coating is thicker than 350 nm, the antireflection performance may deteriorate. Also, if the shrinkage of the transparent coating is very large, cracks may occur.
• This film thickness is more preferably 85 to 220 nm, still more preferably 90 to 110 nm.
• the reflectance of the coated substrate is preferably 2.0% or less, more preferably 1.5% or less.
• the haze of the film-coated substrate is preferably 3.0% or less, more preferably 0.3% or less.
• the light transmittance of the coated base material is preferably 85.0% or more.
• the light transmittance is less than 85.0%, there is a risk that the definition of an image will be insufficient in a display device or the like.
• This light transmittance is more preferably 90.0% or more.
• the antibacterial test of the coating is conducted according to JIS Z 2801. This antibacterial activity value is preferably 2.0 or more. If the antibacterial activity value is 2.0 or more, it can be determined that the film has antibacterial properties. This antibacterial activity value is more preferably 4.0 or more.
• the strength (abrasion resistance) of the film is evaluated by sliding with #0000 steel wool under a load of 1000 g/cm 2 . It is preferable that no streak-like damage is observed on the film surface when the number of times of sliding is at least 100 times. With regard to the scratch resistance, it is more preferable that no scratches are observed after 500 sliding cycles, and it is even more preferable that no scratches are observed after 1000 sliding cycles.
• the pencil hardness of the coating is preferably H or higher.
• the hardness as an antireflection coating is insufficient.
• the pencil hardness is more preferably 2H or higher, and still more preferably 4H or higher.
• a known material can be used as the base material.
• Substrates are transparent materials such as, for example, glass, polycarbonate, acrylic, polyethylene terephthalate (PET), triacetylcellulose (TAC), polyimide, polymethyl methacrylate (PMMA), and cycloolefin polymer (COP).
• a resin substrate is preferred. These substrates are excellent in adhesion to the transparent film formed from the coating liquid described above. Therefore, by using these substrates, it is possible to obtain coated substrates having excellent hardness, strength, and the like. Therefore, a thin base material is preferably used.
• the thickness of the substrate is not particularly limited, but preferably 10 to 100 ⁇ m, more preferably 20 to 80 ⁇ m.
• the method for producing particles according to the present embodiment includes a first step of producing first particles having an outer shell containing silica and an inner cavity; and two steps.
• the first particles in the first step may be produced by conventionally known methods (for example, JP-A-2001-233611, JP-A-2013-226539).
• the antibacterial metal component is supported on the particles by being added as a solution of metal salts such as hydrochloride, nitrate, sulfate, and acetate, or as a solution of metal complex ions, or as a solution of metal alkoxide. It is possible. Among them, when the antibacterial metal component is silver, it is more preferable to use silver nitrate. More preferably, hydrochlorides, nitrates, sulfates and acetates are used when the antimicrobial metal components are copper, zinc and tin.
• the addition is carried out so that the final antibacterial metal component in the particles is 0.5 to 40% by mass based on the oxide.
• multiple types of antibacterial metal components may be added separately or simultaneously.
• the antibacterial metal component may be added in multiple batches.
• the conditions for adding the antibacterial metal component are not particularly limited as long as the final content of the antibacterial metal component reaches the desired content.
• the concentration of the dispersion liquid of the first particles is preferably 0.1 to 10% by mass in terms of solid content.
• the pH at the time of adding the antibacterial metal component is preferably 6-13, more preferably 8-10.
• the temperature at which the antibacterial metal component is added is preferably below the boiling point of the solvent.
• the temperature is preferably below 100°C, more preferably between 30 and 95°C.
• the first particles are prepared in advance using raw materials with less alkali metals and alkaline earth metals, or ion exchange or the like is performed in the first step.
• the content of alkali metals and alkaline earth metals in the particles may be reduced.
• a material containing an antibacterial metal with a low alkali metal and alkaline earth metal content for example, a metal alkoxide containing an antibacterial metal component. Furthermore, these measures may be combined.
• the finally obtained particles may be used as an aqueous dispersion, substituted with an organic solvent, or further dried and used as a powder.
• the particles of the present embodiment can be applied to a coating liquid for film formation.
• This coating liquid contains particles and a matrix-forming component.
• the coating liquid may contain additives such as an organic solvent, a polymerization initiator, a leveling agent, and a surfactant.
• the concentration of the particles in the coating liquid is preferably 5 to 95% by mass as solid content with respect to the total amount of solid content such as particles and matrix-forming components.
• the particle concentration is less than 5% by mass, the refractive index of the coating may not be reduced sufficiently.
• the particle concentration is higher than 95% by mass, cracks may occur in the coating, adhesion to the substrate may be insufficient, and hardness, strength, transparency, haze, etc. may deteriorate.
• the concentration of the particles is more preferably 10-85% by weight, more preferably 20-70% by weight.
• the matrix-forming component is preferably an organic resin-based matrix-forming component.
• organic resin-based matrix-forming component include matrix-forming components such as UV-curable resins, thermosetting resins, and thermoplastic resins.
• UV-curable resins examples include (meth)acrylic acid-based resins, ⁇ -glycyloxy-based resins, urethane-based resins, and vinyl-based resins.
• Thermosetting resins include urethane resins, melamine resins, silicone resins, butyral resins, reactive silicone resins, phenol resins, epoxy resins, unsaturated polyester resins, and thermosetting acrylic resins.
• thermoplastic resins examples include polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, and silicone rubbers.
• These resins may be copolymers or modified products of two or more kinds, and may be used in combination. These resins may also be emulsion resins, water-soluble resins, or hydrophilic resins.
• the components forming these resins are preferably monomers or oligomers in terms of particle dispersibility and ease of coating.
• the concentration of the matrix-forming component in the coating liquid is preferably 5 to 95% by mass as a solid content with respect to the total solid content of the particles and the matrix-forming component.
• concentration of the matrix-forming component is less than 5% by mass, it is difficult to form a coating. Moreover, even if a coating is obtained, cracks may occur in the coating, adhesion to the substrate may become insufficient, and hardness, strength, transparency, haze, etc. may deteriorate.
• the concentration of the matrix-forming component is higher than 95% by mass, the amount of particles is so small that the refractive index may not be reduced sufficiently.
• the concentration of this matrix-forming component is more preferably 15 to 90% by mass, more preferably 30 to 80% by mass.
• organic solvent one that can uniformly disperse the particles and that can dissolve or disperse additives such as matrix-forming components and polymerization initiators is used.
• hydrophilic solvents and polar solvents are preferred.
• Hydrophilic solvents include, for example, alcohols, esters, glycols, and ethers.
• Polar solvents include, for example, esters and ketones.
• Alcohols include methanol, ethanol, propanol, 2-propanol, butanol, diacetone alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol.
• 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. is mentioned.
• Glycols include ethylene glycol and hexylene glycol.
• 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.
• Ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methylcyclohexanone, dipropyl ketone, methylpentyl ketone, and diisobutyl ketone.
• polar solvents include dimethyl carbonate and toluene.
• any additive that can be conventionally used for forming an antireflection film can be used as the additive.
• a polymerization initiator, a leveling agent, or the like is used to accelerate the polymerization of the matrix-forming component and improve the film-forming properties.
• 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-diphenylethan-1-one, 1-hydroxycyclohexylphenylketone, and 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinopropan-1-one.
• leveling agents examples include acrylic leveling agents, silicone leveling agents, and acrylic silicone leveling agents. Those having a fluorine group are preferably used as these leveling agents.
• the solid content concentration of the coating liquid (percentage of the total solid content of the solid content of the particles and the solid content of the matrix-forming component with respect to the coating liquid) is preferably 0.1 to 100% by mass.
• a coating liquid having a solid concentration of 100% by mass means that no organic solvent is present in the coating liquid.
• the solid content concentration of the coating liquid is more preferably 1 to 50% by mass.
• Example 1 ⁇ Preparation of first particles (first step)> 430 g of silica alumina sol (Fine Cataloid USBB-120 manufactured by Nikki Shokubai Kasei Co., Ltd., average particle diameter 25 nm, solid content concentration 23% by mass) was mixed with 9.6 kg of pure water, and the resulting mixture was heated to 98 ° C. was warmed to A sodium hydroxide aqueous solution having a concentration of 1% by mass was added to this mixed liquid to adjust the pH to 12.5.
• silica alumina sol Feine Cataloid USBB-120 manufactured by Nikki Shokubai Kasei Co., Ltd., average particle diameter 25 nm, solid content concentration 23% by mass
• Concentrated hydrochloric acid having a concentration of 35.5% by mass was added dropwise to 50 kg of the silica-alumina particle dispersion to adjust the pH to 1.0, thereby performing a dealumination treatment.
• the dissolved aluminum salt was separated by an ultrafiltration membrane and washed to obtain 10 kg of a dispersion liquid of silica-based particles having a solid content concentration of 5% by mass.
• 131 g of an aqueous sodium hydroxide solution having a concentration of 10% by 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 Na 2 O content of these particles was 0.2% by mass.
• 500 g of an aqueous dispersion of the first particles diluted to 1.5% by mass with pure water was adjusted to 30° C., and 70.8 g of a 1.0% by mass silver nitrate aqueous solution was added to the aqueous dispersion. Addition was carried out over 30 minutes while stirring, and heat treatment was performed at 95° C. for 3 hours. After the 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 having a solid concentration of 1.5% by mass.
• a cation exchange resin (Diaion SK1B, manufactured by Mitsubishi Chemical Corporation) was used for 500 g of the aqueous dispersion of silica-based particles to perform ion exchange for 3 hours, followed by an anion exchange resin. Ion exchange was carried out for 3 hours using 100 g of (Diaion SA20A manufactured by Mitsubishi Chemical Corporation). After that, ion exchange was performed at 80° C. for 3 hours using 100 g of a cation exchange resin (Diaion SK1B manufactured by Mitsubishi Chemical Corporation) to produce 160 g of an aqueous dispersion of the particles of the present embodiment. The solid content concentration of this dispersion was 5% by mass, and the Na 2 O content of the particles was 50 ppm.
• the particles were measured using the following method.
• the characteristics and properties of the particles in each production process are shown in Table 1 (the same applies to the following examples; the characteristics and properties of the comparative examples are shown in Table 2).
• the physical properties of the particles were measured by image analysis.
• the particle dispersion was diluted to 0.01% by mass, and then dried on a collodion film of a copper cell for an electron microscope.
• the powder thus obtained was photographed with a field emission transmission electron microscope (HF5000, manufactured by Hitachi High-Technologies Corporation) at a magnification of 1,000,000. 1000 arbitrary particles in the obtained photographic projections (SEM images, TEM photographs) were measured for each item by the following methods (1) to (4).
• Particle Size The area of the particles was determined from the image processing of the SEM image, and the equivalent circle diameter was determined from the area. The average value of the equivalent circle diameters was taken as the particle size.
• Antibacterial metal elements in particles (Ag, Cu, Zn, Pb, Sn, Bi, Cd, Cr, Hg, Ni, and Co) content, metal elements other than silicon constituting the outer shell (Al, Zr, Ti, Zn, Sn, and Sb), alkali metal content, and alkaline earth
• the metal content 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. The resulting solution was subjected to measurement using an ICP inductively coupled plasma emission spectrometry mass spectrometer (ICPM-8500 manufactured by Shimadzu Corporation).
• Density (A1) determined by He gas adsorption method and density (B1) determined by N2 gas adsorption method The particle dispersion was dried in an evaporator and then dried at 105°C. The powder thus obtained is placed in a cell, and measured 10 times with a dry automatic density meter (AccuPyc1340TC manufactured by Micromeritics, Inc.) using He gas or N2 gas under conditions of a gas introduction pressure of 134 kPa. and took measurements.
• the particle dispersion was dried in an evaporator and then dried at 105°C.
• a Fourier transform infrared spectrometer (FT-IR) (FT/IR-6100 manufactured by JASCO Corporation) is used to determine the wavenumber region by the diffuse reflection method. Measurement was performed at 700 cm ⁇ 1 to 4000 cm ⁇ 1 , using TGS as a detector, with a resolution of 4.0 cm ⁇ 1 and with 50 integration times. A peak is detected by this measurement, and the organic compound spectrum database SDBS (https://sdbs.db.aist.go.jp (National Institute of Advanced Industrial Science and Technology, 2021.01)) is referenced to perform functionalization. identified the base.
• SDBS https://sdbs.db.aist.go.jp (National Institute of Advanced Industrial Science and Technology, 2021.01)
• a coating liquid for forming a film having a solid content concentration of 4% by mass was produced.
• the matrix-forming components used were 2.30 g of dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd. DPE-6A, solid content concentration 100% by mass), 1,6-hexanediol diacrylate (Shin-Nakamura Chemical Co., Ltd. A-HD-N, solid content concentration 100 mass%) 0.58 g, reactive silicone oil for water repellent material (manufactured by Shin-Etsu Chemical Co., Ltd.
• Hard coat paint (ELCOM HP-1004 manufactured by Nikki Shokubai Kasei Co., Ltd.), TAC film (FT-PB80UL-M manufactured by Panac Co., Ltd., thickness 80 ⁇ m, refractive index 1.51), bar coater method (# 18 ) and the applied paint was dried at 80° C. for 120 seconds. After that, the applied and dried paint was cured by irradiating ultraviolet rays of 300 mJ/cm 2 to prepare a hard coat film. The film thickness of the hard coat film was 8 ⁇ m.
• the prepared coating liquid was applied to the TAC film with the hard coat film formed thereon by a bar coater method (#4), and the applied paint was dried at 80° C. for 120 seconds.
• the coated base material was produced by curing the paint by irradiating 400 mJ/cm 2 ultraviolet rays under N 2 atmosphere.
• Q Ut-At Expression (2) (However, Q indicates the antibacterial activity value, Ut indicates the average value of the logarithmic value of the number of viable bacteria per 1 cm 2 of the unprocessed test piece after 24 hours, and At is 1 cm after 24 hours of the antibacterial processed test piece. Shows the average logarithmic value of the number of viable bacteria per 2. )
• Staphylococcus aureuse NBRC 12732 and Escherichia coli NBRC 3972 were used as test bacteria.
• Nutrient broth at 1/20 concentration (meat extract 150 mg/L + peptone 250 mg/L) was used as nutrition.
• test piece was prepared by covering this with a 4 cm square PE film. did.
• the test bacteria on the test piece were cultured for 24 hours at 35°C ⁇ 1°C and a relative humidity of 90% or higher. Next, the test bacteria on the test piece were washed out and recovered, and the number of viable bacteria per 1 cm 2 was measured.
• Adhesion 100 squares were made by making 11 parallel scratches on the surface of the film-coated substrate with a knife at intervals of 1 mm in length and width. A cellophane tape was adhered to this, and then the cellophane tape was peeled off. After that, the number of squares remaining without peeling of the film was counted. Adhesion was evaluated by classifying the number of squares into the following three grades. Number of remaining squares 95 or more: ⁇ Number of remaining squares 90-94: ⁇ Number of remaining squares 85-89: ⁇ Number of remaining squares 84 or less: ⁇
• Example 2 In the same manner as in Example 1, 128 g of an ethanol dispersion of particles having a solid content concentration of 5% by 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. Thereafter, the solvent was replaced with methyl isobutyl ketone (MIBK) in an evaporator to produce an MIBK dispersion of particles having a solid concentration of 5% by mass. The Na 2 O content of this particle was 50 ppm. Next, a coating liquid and a base material with a film were produced in the same manner as in Example 1 except that an MIBK dispersion of particles was used, and each characteristic was evaluated.
• MIBK methyl isobutyl ketone
• Example 3 An MIBK dispersion of particles having a solid content concentration of 5% by mass was produced in the same manner as in Example 2, except that 7.8 g of the silver nitrate aqueous solution was used in the second step. The Na 2 O content of this particle was 50 ppm. Next, a coating liquid and a base material with a film were produced in the same manner as in Example 1 except that an MIBK dispersion of particles was used, and each characteristic was evaluated.
• Example 4 In the second step, an MIBK dispersion of particles having a solid content concentration of 5% by mass was produced in the same manner as in Example 2, except that 920 g of the silver nitrate aqueous solution was used and the addition time was set to 90 minutes. The Na 2 O content of this particle was 50 ppm. Next, a coating liquid and a base material with a film were produced in the same manner as in Example 1 except that an MIBK dispersion of particles was used, and each characteristic was evaluated.
• Example 5 ⁇ Preparation of first particles (first step)> 10 g of silica sol (Cataloid SI-550 manufactured by Nikki Shokubai Kasei Co., Ltd., average particle diameter 5 nm, SiO concentration 20.5% by mass) and 10.0 kg of pure water were mixed, and the resulting mixture was heated to 50°C. I warmed up. A sodium hydroxide aqueous solution having a concentration of 1% by mass was added to this mixed liquid to adjust the pH to 10.5.
• silica sol Cataloid SI-550 manufactured by Nikki Shokubai Kasei Co., Ltd., average particle diameter 5 nm, SiO concentration 20.5% by mass
• Concentrated hydrochloric acid having a concentration of 35.5% by mass was added dropwise to 50 kg of the silica-alumina particle dispersion to adjust the pH to 1.0, thereby performing a dealumination treatment.
• the dissolved aluminum salt was separated by an ultrafiltration membrane and washed to obtain 18 kg of a dispersion liquid of silica-based particles having a solid content concentration of 5% by mass.
• 236 g of an aqueous sodium hydroxide solution with a concentration of 10% by weight 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 Na 2 O content of these particles was 0.3 mass %.
• an MIBK dispersion of particles having a solid concentration of 5% by mass was produced in the same manner as in Example 2, except that the first particles diluted to 1.5% by mass with pure water were used. .
• the Na 2 O content of this particle was 90 ppm.
• a coating liquid and a base material with a film were produced in the same manner as in Example 1 except that an MIBK dispersion of particles was used, and each characteristic was evaluated.
• first particles Preparation of first particles (first step)> 10 g of silica sol (cataloid SI-50 manufactured by Nikki Shokubai Kasei Co., Ltd., average particle diameter 25 nm, SiO 2 concentration 48% by mass) and 5.0 kg of pure water were mixed, and the resulting mixture was heated to 98°C. . A sodium hydroxide aqueous solution having a concentration of 1% by mass was added to this mixed liquid to adjust the pH to 12.5.
• silica sol catalog SI-50 manufactured by Nikki Shokubai Kasei Co., Ltd., average particle diameter 25 nm, SiO 2 concentration 48% by mass
• a sodium hydroxide aqueous solution having a concentration of 1% by mass was added to this mixed liquid to adjust the pH to 12.5.
• Concentrated hydrochloric acid having a concentration of 35.5% by mass was added dropwise to 50 kg of the silica-alumina particle dispersion to adjust the pH to 1.0, thereby performing a dealumination treatment.
• the dissolved aluminum salt was separated by an ultrafiltration membrane and washed to obtain 5 kg of a dispersion liquid of silica-based particles having a solid content concentration of 5% by mass.
• 66 g of an aqueous sodium hydroxide solution having a concentration of 10% by 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 Na 2 O content of these particles was 0.2% by weight.
• an MIBK dispersion of particles having a solid concentration of 5% by mass was produced in the same manner as in Example 2, except that the first particles diluted to 1.5% by mass with pure water were used. .
• the Na 2 O content of this particle was 30 ppm.
• a coating liquid having a solid concentration of 4 mass % was obtained by mixing a matrix-forming component and an organic solvent with 32 g of the MIBK dispersion liquid of the 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 material, 0.85 g of silicone-modified polyurethane acrylate, and 0.29 g of a photopolymerization initiator.
• the organic solvents used are 80.4 g isopropyl alcohol, 48.2 g methyl isobutyl ketone and 32.1 g isopropyl glycol.
• a coated base material was produced in the same manner as in Example 1 except that this coating liquid was used, and each characteristic was evaluated.
• Example 7 ⁇ Preparation of first particles (first step)> 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. A sodium hydroxide aqueous solution having a concentration of 1% by mass was added to this mixed liquid to adjust the pH to 12.5.
• Concentrated hydrochloric acid having a concentration of 35.5% by mass was added dropwise to 50 kg of the silica-alumina particle dispersion to adjust the pH to 1.0, thereby performing a dealumination treatment.
• the dissolved aluminum salt was separated by an ultrafiltration membrane and washed to obtain 9 kg of a dispersion liquid of silica-based particles having a solid content concentration of 5% by mass.
• 118 g of an aqueous sodium hydroxide solution having a concentration of 10% by weight 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 Na 2 O content of these particles was 0.1 mass %.
• an MIBK dispersion of particles having a solid concentration of 5% by mass was produced in the same manner as in Example 2, except that the first particles diluted to 1.5% by mass with pure water were used. .
• the Na 2 O content of this particle was 30 ppm.
• a coating liquid and a base material with a film were produced in the same manner as in Example 1 except that an MIBK dispersion of particles was used, and each characteristic was evaluated.
• Example 8 ⁇ Preparation of first particles (first step)> 63 g of silica sol (Cataloid SI-50 manufactured by Nikki Shokubai Kasei Co., Ltd.) and 29.9 kg of pure water were mixed, and the resulting mixture was heated to 98°C. A sodium hydroxide aqueous solution having a concentration of 1% by mass was added to this mixed liquid to adjust the pH to 12.5.
• Concentrated hydrochloric acid having a concentration of 35.5% by mass was added dropwise to 40 kg of the silica-alumina particle dispersion to adjust the pH to 1.0, thereby performing a dealumination treatment.
• the dissolved aluminum salt was separated by an ultrafiltration membrane and washed to obtain 13 kg of a dispersion liquid of silica-based particles having a solid content concentration of 5% by mass.
• 170 g of an aqueous sodium hydroxide solution having a concentration of 10% by 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 Na 2 O content of these particles was 0.2% by mass.
• an MIBK dispersion of particles having a solid concentration of 5% by mass was produced in the same manner as in Example 2, except that the first particles diluted to 1.5% by mass with pure water were used. .
• the Na 2 O content of these particles was 0.018 mass %.
• a coating liquid having a solid concentration of 4% by mass was prepared by mixing 56 g of the MIBK dispersion liquid of the particles with the matrix-forming component and the organic solvent.
• 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 material, 0.69 g of silicone-modified polyurethane acrylate, and 0.23 g of a photopolymerization initiator.
• the organic solvents used are 69.0 g of isopropyl alcohol, 41.4 g of methyl isobutyl ketone and 27.6 g of isopropyl glycol.
• a coated base material was produced in the same manner as in Example 1 except that this coating liquid was used, and each characteristic was evaluated.
• Example 9 ⁇ Preparation of first particles (first step)> 52 g of silica sol (manufactured by Nikki Shokubai Kasei Co., Ltd., Cataloid SI-50) and 4.9 kg of pure water were mixed, and the resulting mixture was heated to 98°C. A sodium hydroxide aqueous solution having a concentration of 1% by mass was added to this mixed liquid to adjust the pH to 12.5.
• Concentrated hydrochloric acid having a concentration of 35.5% by mass was added dropwise to 50 kg of the silica-alumina particle dispersion to adjust the pH to 1.0, thereby performing a dealumination treatment.
• the dissolved aluminum salt was separated by an ultrafiltration membrane and washed to obtain 9 kg of a dispersion liquid of silica-based particles having a solid content concentration of 5% by mass.
• 118 g of an aqueous sodium hydroxide solution having a concentration of 10% by weight 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 Na 2 O content of these particles was 0.2% by weight.
• an MIBK dispersion of particles having a solid concentration of 5% by mass was produced in the same manner as in Example 2, except that the first particles diluted to 1.5% by mass with pure water were used. .
• the Na 2 O content of this particle was 40 ppm.
• a coating liquid having a solid concentration of 4% by mass was prepared by mixing 64 g of the MIBK dispersion liquid of the particles with the matrix-forming component and the organic solvent.
• 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 material, 0.64 g of silicone-modified polyurethane acrylate, and 0.22 g of a photopolymerization initiator.
• the organic solvents used are 65.3 g of isopropyl alcohol, 39.2 g of methyl isobutyl ketone and 26.1 g of isopropyl glycol.
• a coated base material was produced in the same manner as in Example 1 except that this coating liquid was used, and each characteristic was evaluated.
• Example 10 In the second step, 500 g of an aqueous dispersion of silica-based particles was ion-exchanged with 100 g of a cation exchange resin for 3 hours. However, the subsequent ion exchange with an anion exchange resin and the second ion exchange with a cation exchange resin were not performed. Except for this, in the same manner as in Example 2, an MIBK dispersion of particles having a solid content concentration of 5% by mass was produced. The Na 2 O content of these particles was 0.09 mass %. Next, a coating liquid and a base material with a film were produced in the same manner as in Example 2 except that an MIBK dispersion of particles was used, and each characteristic was evaluated.
• Example 11 An aqueous dispersion of particles was obtained in the same manner as in Example 1, except that 42.5 g of the silver nitrate aqueous solution was used in the second step. The Na 2 O content of this particle was 60 ppm.
• Example 2 in the same manner as in Example 2 except that 1.92 g of 3-methacryloxypropyltrimethoxysilane was added to the ethanol dispersion of particles having a solid content concentration of 5% by mass produced in the same manner as in Example 1, A MIBK dispersion of particles with a solids concentration of 5% by weight was prepared. The Na 2 O content of this particle was 50 ppm.
• a coating liquid and a base material with a film were produced in the same manner as in Example 1 except that an MIBK dispersion of particles was used, and each characteristic was evaluated.
• Example 12 Concentrated hydrochloric acid having a concentration of 35.5% by mass was added dropwise to 50 kg of a dispersion liquid of silica-alumina particles prepared in the same manner as in Example 1 to adjust the pH to 1.0, thereby performing a dealumination treatment. After the dissolved aluminum salt was separated by an ultrafiltration membrane and washed, concentrated hydrochloric acid having a concentration of 35.5% by mass was added dropwise to adjust the pH to 0.3, and dealumination treatment was performed. The dissolved aluminum salt was separated by an ultrafiltration membrane and washed to obtain 10 kg of a dispersion liquid of silica-based particles having a solid content concentration of 5% by mass.
• aqueous sodium hydroxide solution having a concentration of 10% by 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 Na 2 O content of the particles was 0.2% by weight and the Al 2 O 3 content was 0.00% by weight.
• Particles having a solid concentration of 5% by mass were 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% by mass with pure water in the second step. of MIBK dispersion was prepared. The Na 2 O content of this particle was 30 ppm. Next, a coating liquid and a base material with a film were produced in the same manner as in Example 1 except that an MIBK dispersion of particles was used, and each characteristic was evaluated.
• Example 13 An MIBK dispersion of particles having a solid content concentration of 5% by mass was produced in the same manner as in Example 2, except that 132.8 g of an aqueous copper nitrate solution was used in place of the aqueous silver nitrate solution in the second step. The Na 2 O content of this particle was 50 ppm. Next, a coating liquid and a base material with a film were produced in the same manner as in Example 1 except that an MIBK dispersion of particles was used, and each characteristic was evaluated.
• Example 14 An MIBK dispersion of particles having a solid content concentration of 5% by mass was produced in the same manner as in Example 2, except that 130.3 g of an aqueous zinc nitrate solution was used in place of the aqueous silver nitrate solution in the second step. The Na 2 O content of this particle was 50 ppm. Next, a coating liquid and a base material with a film were produced in the same manner as in Example 1 except that an MIBK dispersion of particles was used, and each characteristic was evaluated.
• Example 15 ⁇ Production of Coating Liquid and Coated Substrate>
• a coating solution having a solid concentration of 4% by mass was produced.
• the matrix-forming components used were 3.11 g of dipentaerythritol hexaacrylate, 0.77 g of 1,6-hexanediol diacrylate, fluorine-based resin (Optool DAC-HP manufactured by Daikin Industries, Ltd., solid content concentration of 20% by mass).
• a coated base material was produced in the same manner as in Example 1 except that this coating liquid was used, and each characteristic was evaluated.
• Example 16 ⁇ Preparation of coating solution for forming high refractive index layer> A matrix-forming component and an organic solvent were mixed with 26 g of titania-based sol (ELCOM V-9108 manufactured by Nikki Shokubai Kasei Co., Ltd., particle diameter 15 nm, solid content concentration 30.5 mass%) to give a solid content concentration of 5 mass%. to obtain a coating liquid for forming a high refractive index layer.
• the matrix-forming ingredients used were 1.44 g of dipentaerythritol hexaacrylate, 0.36 g of 1,6-hexanediol diacrylate, and 0.1 g of photoinitiator.
• the organic solvent used is 172 g of propylene glycol monomethyl ether.
• the coating solution for forming a high refractive index layer was applied by a bar coater method (#8).
• the paint was dried at 80°C for 120 seconds. After that, the applied and dried paint was cured by irradiating with ultraviolet rays of 1200 mJ/cm 2 to form a high refractive index layer on the hard coat layer.
• the film thickness of the high refractive index layer was 220 nm.
• Example 9 the coating liquid produced in Example 9 was applied by the bar coater method (#4), and the applied paint was heated at 80°C at 120°C. Let dry for seconds. After that, the paint was cured by irradiating ultraviolet rays of 400 mJ/cm 2 in an N 2 atmosphere to produce a coated base material, and each property was evaluated.
• Example 17 ⁇ Preparation of coating solution for forming anti-glare layer> 10 g of silica powder (Silica Microbead P-500 manufactured by Nikki Shokubai Kasei Co., Ltd.) was mixed with a matrix-forming component and an organic solvent to obtain an anti-glare layer-forming coating liquid having a solid content of 35% by mass.
• the matrix-forming ingredients used were 30.2 g dipentaerythritol hexaacrylate, 7.6 g 1,6-hexanediol diacrylate, and 1.9 g photoinitiator.
• the organic solvent used is 78.2 g of propylene glycol monomethyl ether.
• Example 9 the coating liquid produced in Example 9 was applied onto the antiglare layer of the TAC film having the antiglare layer by the bar coater method (#4), and the applied paint was dried at 80°C for 120 seconds. rice field. After that, the paint was cured by irradiating ultraviolet rays of 400 mJ/cm 2 in an N 2 atmosphere to produce a coated base material, and each property was evaluated.
• Example 1 In the second step, a solid was prepared in the same manner as in Example 2 except that the silver nitrate aqueous solution was not used and 0.34 g of 3-methacryloxypropyltrimethoxysilane was added to 128 g of the ethanol dispersion of particles. A MIBK dispersion of particles with a concentration of 5% by weight was prepared. The Na 2 O content of this particle was 50 ppm. Next, a coating liquid and a base material with a film were produced in the same manner as in Example 1 except that an MIBK dispersion of particles was used, and each characteristic was evaluated.
• silica sol manufactured by Nikki Shokubai Kasei Co., Ltd., Cataloid SI-45P, particle diameter 60 nm, solid content concentration 40.5% by mass
• silica sol manufactured by Nikki Shokubai Kasei Co., Ltd., Cataloid SI-45P, particle diameter 60 nm, solid content concentration 40.5% by mass
• 131 g of an aqueous sodium hydroxide solution having a concentration of 10% by mass was added to this silica sol, and the mixture was heat treated in an autoclave at 195° C. for 24 hours to obtain a first aqueous dispersion of silica-based particles.
• the Na 2 O concentration of this silica-based particle was 0.2% by mass.
• the silica-based particles were so-called "solid particles" without cavities inside.
• a liquid was produced.
• the Na 2 O content of this particle was 80 ppm.
• a coating liquid and a substrate with a film were produced in the same manner as in Example 1 except that an MIBK dispersion of silica-based particles was used, and each characteristic was evaluated.
• the solvent of 200 g of the aqueous dispersion of silver nanoparticles was replaced with IPA using an ultrafiltration membrane to produce an IPA dispersion of silver nanoparticles with a solid concentration of 5.0% by mass.
• the silver nanoparticles had a particle diameter of 10 nm and a Na 2 O concentration of 0 ppm.
• the particle properties shown in Table 2 are properties when the particles produced in Comparative Example 1 and the silver nanoparticles were mixed at a mass ratio of 95.4:4.6. However, for measurements of shell thickness and porosity, only particles with cavities inside the shell were considered. The mixing ratio of the particles produced in Comparative Example 1 and the silver nanoparticles was adjusted so that the apparent porosity and the amount of the antibacterial metal in the mixture were equivalent to the particles of Example 2.
• Example 4 An MIBK dispersion of particles having a solid concentration of 5% by mass was produced in the same manner as in Example 2, except that 2120 g of an aqueous solution of silver nitrate was used in the second step and the addition time was set to 90 minutes. . The Na 2 O content of this particle was 50 ppm. Next, a coating liquid and a base material with a film were produced in the same manner as in Example 1 except that an MIBK dispersion of particles was used, and each characteristic was evaluated.
• Concentrated hydrochloric acid having a concentration of 35.5% by mass was added dropwise to 50 kg of the silica-alumina particle dispersion to adjust the pH to 1.0, thereby performing a dealumination treatment.
• the dissolved aluminum salt was separated by an ultrafiltration membrane and washed to obtain 9 kg of a dispersion liquid of silica-based particles having a solid content concentration of 5% by mass.
• 118 g of an aqueous sodium hydroxide solution having a concentration of 10% by weight 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 Na 2 O concentration of these particles was 0.1% by mass.
• an MIBK dispersion of particles having a solid content concentration of 5.0% by mass was prepared in the same manner as in Example 2, except that the first particles diluted to 1.5% by mass with pure water were used. manufactured. The Na 2 O content of this particle was 40 ppm.
• a coating liquid and a base material with a film were produced in the same manner as in Example 1 except that an MIBK dispersion of particles was used, and each characteristic was evaluated.

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