Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • 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
  • C09D201/00—Coating compositions based on unspecified macromolecular 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/24—Electrically-conducting paints
• • 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
  • C09D7/45—Anti-settling agents
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2231—Oxides; Hydroxides of metals of tin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/001—Conductive additives

Definitions

• One aspect of the present disclosure relates to a dispersion of chain particles, a film-forming paint, and a method for producing a film-coated substrate.
• a transparent conductive film is formed on the surface of transparent plastic substrates used in LCD displays, organic EL displays, micro LED displays, etc. for antistatic purposes.
• a transparent conductive film in which conductive oxide particles such as antimony-doped tin oxide (ATO) or tin-doped indium oxide (ITO) are blended into the matrix component.
• ATO antimony-doped tin oxide
• ITO tin-doped indium oxide
• conductive oxide particles such as antimony-doped tin oxide (ATO) or tin-doped indium oxide (ITO) are blended into the matrix component.
• ATO antimony-doped tin oxide
• ITO tin-doped indium oxide
• the inventors found chain particles in which ATO particles prepared in a system containing silicon oxide are linked. That is, in the dispersion of chain particles according to one aspect of the present disclosure, the ATO particles have an average particle diameter of 5 to 20 nm, an average number of linkages of 3 to 40, and an isoelectric point of less than pH 2.0. , the chain particles contain silicon oxide.
• Chain particles include silicon oxide, tin oxide, and antimony oxide. It is preferable that silicon oxide is 0.5 to 10% by weight, tin oxide is 70 to 95% by weight, and antimony oxide is 4.5 to 29.5% by weight based on the total of these. Also, the chain particles are dispersed in a solvent (water or organic solvent). When acid (for example, hydrochloric acid) is added to the resulting dispersion to adjust the pH to 1.0, the average particle size of the chain particles becomes 100 nm or less.
• acid for example, hydrochloric acid
• a dispersion liquid of main chain particles can be produced by carrying out the following steps in order.
• a dispersion of ATO particles is prepared by dispersing this suspension in a system containing silicon oxide.
• R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different.
• n is an integer of 0-3.
• Substituents include epoxy groups, (meth)acryloyloxy groups, mercapto groups, amino groups, phenyl groups, and isocyanate groups.
• X is one (or at least one) of an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, or a hydrogen atom.
• a dispersion of chain particles according to one aspect of the present disclosure has good dispersion stability even in a low pH range.
• a film formed using a paint containing this dispersion has a low surface resistance value and is excellent in adhesiveness to a substrate, film strength, etc., even when the content of particles is small.
• the chain-like particles of this embodiment are particles in which ATO (antimony-doped tin oxide) particles are linked, and contain silicon oxide. That is, they are chain ATO (antimony-doped tin oxide) particles containing silicon oxide.
• the average particle size of the ATO particles is 5 to 20 nm.
• the chain particles have an average number of linkages of 3 to 40, and the isoelectric point of the chain particles is less than pH 2.0.
• the average particle size of the ATO particles is not in the range of 5-20 nm, it is difficult to obtain chain-like particles with an average number of connections of 3-40. It is industrially difficult to obtain particles (primary particles) with an average particle size of less than 5 nm, and even if they are obtained, the stability of the primary particles is low. hard to be When the average particle size exceeds 20 nm, contact and aggregation of primary particles are less likely to occur, and many primary particles remain monodisperse. That is, it is difficult to obtain a chain shape with an average number of connections of 3 or more. For this reason, there is a possibility that a low surface resistance value cannot be obtained with a coating having a low particle content.
• the average particle size of the ATO particles is preferably 6-15 nm, more preferably 7-12 nm.
• the average number of chains of chain particles is within the above range, a film with a low surface resistance value can be obtained even if the particle content is small. If the average number of connections is less than 3, it is difficult to obtain a low surface resistance value with a film containing a small amount of particles. It is difficult to obtain chain-like particles with an average number of links exceeding 40. Even if it is obtained, the stability of the paint may be decreased or the haze of the film may be increased.
• the lower limit of the average number of linkages is preferably 5, more preferably 7.
• the upper limit of the average number of linkages is preferably 30, more preferably 20.
• the isoelectric point of chain particles is less than pH 2.0.
• the potential of the particle surface (zeta potential) changes. This potential goes to 0 at a certain pH value.
• the pH value at this time is the isoelectric point.
• the potential of the particle surface disappears, so the electrostatic repulsive force disappears and the particles tend to agglomerate.
• the isoelectric point of ATO particles is around 4.
• the isoelectric point of chain particles according to the present embodiment is less than 2.0. If the isoelectric point is 2.0 or more, the stability in the low pH region is insufficient, so three-dimensional aggregation is likely to occur.
• the isoelectric point is preferably 1.8 or less, more preferably 1.5 or less, and even more preferably 1.0 or less.
• the chain particles contain silicon oxide, tin oxide, and antimony oxide.
• Silicon oxide is preferably contained in an amount of 0.5 to 10% by weight based on the total weight of these three components.
• Tin oxide is preferably contained in an amount of 70 to 95% by weight.
• Antimony oxide is preferably contained in an amount of 4.5 to 29.5% by weight.
• the content of silicon oxide is preferably 10% by weight or less. If the content of silicon oxide is less than 0.5% by weight, the isoelectric point may become greater than 2.0.
• the content of silicon oxide is preferably 0.8 to 8% by weight, more preferably 3.0 to 6.0% by weight.
• the surface resistance of the film may increase because the conductivity of the chain particles decreases.
• the chain particles described above are dispersed in water or an organic solvent.
• the average particle size of the chain particles becomes 100 nm or less. If the stability on the low pH side is low, the average particle size of the chain particles may exceed 100 nm. That is, when the pH is lowered, the chain particles tend to aggregate, and the average particle size of the chain particles tends to increase. Therefore, the haze of the film may increase.
• the average particle size of the chain particles is preferably 90 nm, more preferably 70 nm or less.
• the acid is preferably an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, or an organic acid such as formic acid and acetic acid.
• the amount of alkali metal contained in this dispersion is preferably 0.05% by weight or less.
• the alkali metal content is more preferably 0.03% by weight or less, and even more preferably 0.01% by weight or less.
• alkali metals represent Li, Na, K, Rb, Cs, and Fr.
• water or an organic solvent is used as the dispersion medium.
• a solvent that can uniformly disperse particles and that can dissolve or disperse additives such as matrix-forming components and polymerization initiators is used.
• the hydrophilic solvents shown in Table 1 are preferred. Water or alcohols are particularly preferred. We may use these alone or in combination of two or more.
• the chain particles of this embodiment can be produced by performing the following steps in order.
• This step promotes chain formation of the ATO particles, resulting in chain particles with a large number of connections.
• n is an integer of 0-3.
• R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different.
• Substituents include epoxy groups, (meth)acryloyloxy groups, mercapto groups, amino groups, phenyl groups, and isocyanate groups.
• X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, or a hydrogen atom.
• ATO particles average particle diameter of 5 to 20 nm
• the chain particles have an average number of linkages of 3 to 40, and the isoelectric point of the chain particles is less than pH 2.0.
• ATO powder is prepared.
• Conventionally known powder of ATO particles can be used.
• the powder of ATO particles (hereinafter referred to as ATO powder) preferably has a specific surface area of 40 m 2 /g to 180 m 2 /g as measured by the BET method. If the specific surface area is less than 40 m 2 /g, the average primary particle size after dispersion may be too large and the chain structure may not be formed. Moreover, when the specific surface area is larger than 180 m 2 /g, it becomes difficult to disperse the ATO particles. Even if the ATO particles can be dispersed, the stability of the ATO particles is low because the ATO particles are small. As a result, the ATO particles tend to aggregate and are less likely to form a chain shape.
• the specific surface area is more preferably 60 to 150 m 2 /g, still more preferably 80 to 140 m 2 /g.
• the weight ratio of tin oxide and antimony oxide contained in the ATO powder is preferably 70:30 to 95:5. If the weight ratio is outside this range (i.e. less than 70% by weight or more than 95% by weight of tin oxide, or less than 5% by weight or more than 30% by weight of antimony oxide) , the conductivity of the ATO particles is reduced, which may increase the surface resistance of the film.
• a suspension is prepared by suspending such ATO powder in an aqueous solution containing 0.05 to 5.0% by weight of an alkali metal hydroxide.
• Alkali metal hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like. If the alkali metal hydroxide concentration is less than 0.05% by weight, the amount of dissolved silicon oxide may be insufficient, and the isoelectric point may exceed 2.0.
• the alkali metal hydroxide concentration is preferably 0.1% by weight or more. On the other hand, when the concentration of the alkali metal hydroxide exceeds 5.0% by weight, it is difficult to remove the alkali metal hydroxide in the subsequent steps.
• the alkali metal hydroxide concentration is preferably 3.0% by weight or less, more preferably 1.0% by weight or less.
• this suspension is dispersed in an environment where silicon oxide exists. That is, a dispersion liquid of ATO particles is prepared by performing dispersion treatment in a system in which silicon oxide exists. At this time, it is sufficient that the silicon oxide raw material is in contact with the suspension. Therefore, the silicon oxide raw material may be added to the suspension in advance or may be added during the dispersion treatment. Alternatively, instruments used for dispersion treatment may contain a silicon oxide component. For example, beads used as a dispersing medium or a container containing a suspension can be used as a source of silicon oxide. ATO powder containing a silicon oxide component may also be used. Examples of silicon oxide raw materials added to the suspension include silicic acid liquid, sodium silicate, silica sol, silica powder, and the like.
• the silicon oxide component When adding silicon oxide to the suspension, it is preferable to add 0.1 to 5% of the silicon oxide component relative to the amount of ATO powder. If the added amount of the silicon oxide component is more than 5%, the silicon oxide component on the surface of the ATO particles increases, which may increase the surface resistance of the film. Moreover, when powder is used as the silicon oxide component, the silicon oxide powder may not be completely dissolved and may remain as a residue, increasing the haze of the coating.
• the silicon oxide is dissolved by the alkali metal component in the suspension, so the same effect as adding silicon oxide can be obtained. Also in this case, the amount of silicon oxide contained in the suspension is preferably 0.1 to 5% with respect to the amount of ATO powder.
• Devices used for dispersion processing include Henschel mixers, homomixers, homogenizers, and bead mills. Among them, a bead mill is preferable because it can industrially carry out a large amount of dispersion treatment.
• Bead mills include Batch SAND manufactured by Sekipe Co., Ltd., MSC mill manufactured by Nippon Coke Kogyo Co., Ltd., Ultra Apex Mill manufactured by Hiroshima Metal & Machinery Co., Ltd., Star Mill manufactured by Ashizawa Fine Tech Co., Ltd., Nano Getter, Neo-Alpha Mill manufactured by Aimex Co., Ltd., and , Dyno Mill manufactured by Shinmaru Enterprises Co., Ltd., and the like.
• beads having a size of 1.0 mm or less are used as a dispersion medium (median), such as zirconia beads (YTZ series manufactured by Tosoh Corporation), alumina beads (TB series manufactured by Taimei Chemical Industry Co., Ltd.), Alternatively, glass beads (L series manufactured by Unitika Ltd.) are used.
• a dispersion medium such as zirconia beads (YTZ series manufactured by Tosoh Corporation), alumina beads (TB series manufactured by Taimei Chemical Industry Co., Ltd.), Alternatively, glass beads (L series manufactured by Unitika Ltd.) are used.
• the dispersion of ATO particles is hydrothermally treated.
• Hydrothermal treatment tends to lower the isoelectric point to 2.0 or less.
• the dissolved oxygen content in the dispersion is preferably 3 mg/L or more. Hydrothermal treatment with a dissolved oxygen content of less than 3 mg/L does not sufficiently lower the isoelectric point. Therefore, when the pH is lowered, the particles may aggregate, and it may be difficult to form a uniform chain structure. Even if a chain-like shape is obtained, the average number of connections may exceed 40.
• the dissolved oxygen content in the dispersion is preferably 10 mg/L or more, more preferably 20 mg/L or more.
• the dissolved oxygen content of the dispersion obtained in step a is 3 mg/L or more, this dispersion can be hydrothermally treated as it is.
• the dissolved oxygen content is less than 3 mg/L, the dissolved oxygen content of the dispersion is increased by bubbling oxygen gas or adding hydrogen peroxide.
• the hydrothermal treatment is preferably carried out at 100-300°C for 1-64 hours. If the treatment temperature is less than 100° C., antimony doping does not progress and the surface resistance of the film does not sufficiently decrease. On the other hand, even if the processing temperature exceeds 300° C., the doping does not proceed any further, and expensive heat-resistant and pressure-resistant equipment is required. If the treatment time is less than 1 hour, the antimony doping will be insufficient and the surface resistance value of the film will not sufficiently decrease. Even if the treatment time is longer than 64 hours, antimony doping does not proceed any further, resulting in a decrease in productivity.
• Step c Next, after step b, an alkaline component is added while the solid content concentration of the dispersion is less than 10% by weight. Thereby, the pH of this dispersion is adjusted to 4 or higher. When the pH of the dispersion is 4 or higher, the solid content concentration can be stably increased thereafter. If the pH of the dispersion is less than 4, the particles tend to aggregate while increasing the solid content concentration, so there is a risk that a chain structure with an average number of linkages of 3 to 40 will not be formed.
• the pH of the dispersion is preferably 6 or higher, more preferably 7-10.
• Alkaline components added here include sodium hydroxide, potassium hydroxide, aqueous ammonia, TMAH, and the like.
• the alkali component is preferably aqueous ammonia or TMAH.
• the solid content concentration of the dispersion is adjusted to 15% or more.
• Known methods distillation, filtration, etc. can be used to adjust the solid content concentration. If the solid content concentration is less than 15%, subsequent chain formation of the particles becomes difficult, and the number of connections tends to be less than 3.
• the solid content concentration is preferably 15 to 30% by weight. If the solid content concentration is 30% by weight or more, the average number of linkages may exceed 40.
• the solid content concentration is more preferably in the range of 18-25% by weight.
• the pH of the dispersion is lowered to between 1 and 3. That is, the pH is adjusted while the solid content concentration is 15% by weight or more.
• the pH can be lowered by the addition of acid or dealkalization.
• the ion exchange resin an H-type cation exchange resin is suitable. If the pH of the dispersion is less than 1, the average number of chain-like particles linked may exceed 40. On the other hand, when the pH of the dispersion liquid is higher than 3, the average number of linkages may be less than 3 without progressing chain formation.
• n is an integer of 0-3.
• R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different.
• Substituents include epoxy groups, (meth)acryloyloxy groups, mercapto groups, amino groups, phenyl groups, and isocyanate groups.
• X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, or a hydrogen atom. At this time, it is preferable to add alcohol to the dispersion.
• the amount of the organosilicon compound added is preferably 10 to 35% with respect to the amount of ATO particles present in the dispersion. If the amount of the organosilicon compound added is less than 10%, chain particles with an average number of linkages of 3 to 40 in the dispersion may become chain particles with an average number of linkages of less than 3 in the paint. Moreover, even if the number of connections is maintained, the dispersibility of the chain particles in the paint may become insufficient, resulting in an increase in the haze of the film and an increase in the surface resistance value. If the amount of the organosilicon compound added exceeds 35% by weight, the surface of the ATO particles may be thickly covered with the organosilicon compound, which may increase the surface resistance of the coating. More preferably, the amount of the organosilicon compound added is 15 to 25% by weight. The appropriate addition amount varies depending on the type of organosilicon compound, the particle size of the ATO particles, the number of bonds, and the like.
• organosilicon compounds are shown in Table 2. We can use these organosilicon compounds singly or in combination of two or more. Those in which n is 0 or 1 are preferably used.
• the alcohols added in this step are preferably the alcohols shown in Table 1. We can use these alone or in combination of two or more.
• the amount of alcohol added is preferably 10 to 1000% of the total amount of the chain-like particle dispersion. If the amount of alcohol added is less than 10%, the organosilicon compound added is difficult to dissolve, and there is a risk that a uniform coating will not be formed on the chain particles. In this case, the average number of chain-like particles connected exceeds 40, or the chain-like particles are partially covered with a large thickness, which may increase the surface resistance value of the film. In addition, when the amount of alcohol added exceeds 1000%, the chain particles may be disconnected due to dilution, and the average number of chain particles connected may be less than 3. The amount of alcohol added is more preferably 30 to 500%, even more preferably 50 to 200%.
• the dispersion to which the alcohol has been added it is preferable to heat the dispersion to which the alcohol has been added at a temperature of 30°C or higher and at a temperature lower than the boiling point of the solvent used. If the heating temperature is low, the reaction may take a long time or the organosilicon compound may remain unreacted, depending on the types and amounts of the organosilicon compound and alcohol added. The greater the amount of unreacted organosilicon compound, the more likely the stability of the paint and the hardness of the film will decrease.
• Acid catalysts include inorganic acids (such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid) or organic acids (such as formic acid and acetic acid).
• a dispersion of chain-like particles obtained by such a process can be used as it is to form a coating material for forming a transparent film.
• water or an organic solvent may be used for solvent replacement.
• Equipment used for solvent displacement includes rotary evaporators and ultrafiltration membranes. Solvent replacement improves the compatibility of the particles with the matrix component in the paint. Therefore, streaky unevenness and defects are suppressed during coating, and the appearance can be improved.
• a paint for forming a transparent film can be prepared by blending the above-described chain-like particle dispersion, a matrix-forming component, and an organic solvent.
• the solid content of chain particles in the paint is preferably in the range of 0.06 wt% to 7.5 wt%. If the solid content is less than 0.06% by weight, the chain particles in the film are too small and the surface resistance of the film increases. On the other hand, if the solid content exceeds 7.5% by weight, the coloring of the film becomes conspicuous. More preferably, the solid content is 0.1 to 6.0% by weight. Further, the total concentration of chain particles and matrix-forming components in the paint is preferably in the range of 3 to 50% by weight as solid content. If the total concentration is less than 3% by weight, the film thickness may be too thin to obtain sufficient surface resistance and scratch resistance.
• the total concentration exceeds 50% by weight, the viscosity of the paint will increase and the fluidity will decrease, resulting in deterioration of coatability. Furthermore, since the dispersibility of the chain particles in the paint is lowered, it is difficult to obtain a uniform film thickness. Therefore, appearance defects such as coating unevenness are likely to occur. More preferably, the total concentration is 5-40% by weight.
• the organic solvent used in the paint may be any solvent that can dissolve or disperse the matrix-forming component while dispersing the chain-like particles.
• organic solvents include water, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methylcyclohexanone, dipropyl ketone, methylpentyl ketone, diisobutyl ketone, acetylacetone, acetoacetate, and the like. ), and the hydrophilic solvents shown in Table 1. These may be used alone or in combination of two or more.
• thermosetting resins thermoplastic resins
• thermoplastic resins include polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, and silicone rubbers.
• Thermosetting resins include urethane resins, melamine resins, silicone resins, butyral resins, reactive silicone resins, phenolic resins, epoxy resins, unsaturated polyester resins, and thermosetting acrylic resins.
• the thermosetting resin may be ultraviolet curable or electron beam curable.
• the thermosetting resin may contain a curing catalyst.
• the matrix component may be a copolymer or a modified product of two or more of the above resins. These resins may be emulsion resins, water-soluble resins, and hydrophilic resins.
• Alkylene oxide-modified acrylic resins such as ethylene oxide-modified acrylic resins, propylene oxide-modified acrylic resins, and butylene oxide-modified acrylic resins are suitable as the ultraviolet curable resin used as the matrix component.
• Alkylene oxide modification means having an alkylene oxide block structure such as ethylene oxide ( --CH.sub.2--CH.sub.2--O--) and propylene oxide ( --CH.sub.2 -- CH.sub.2 -- CH.sub.2 --O--).
• the ATO particles are surface-treated in the coating liquid, and the ATO particles are highly dispersed without agglomeration. Therefore, it is possible to obtain a film having a low surface resistance value and excellent transparency, light transmittance, hardness, and the like.
• Non-modified acrylic resins include pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
• the base material known materials such as sheets, films, or panels made of materials such as glass, polycarbonate, acrylic resin, polyethylene terephthalate (PET), or triacetyl cellulose (TAC) are used.
• Suitable materials for the substrate include TAC, polycarbonate, acrylic resin, and the like.
• interference fringes can be suppressed by forming a transparent film composed of chain particles and matrix components on the TAC substrate.
• the content of chain particles in the coating is preferably 3 to 15% by weight. If the content of the chain-like particles is less than 3% by weight, the amount of chain-like particles in the coating is too small, and the coating may have a high surface resistance value. If the content of the chain-like particles exceeds 15% by weight, the coloring of the coating is likely to be conspicuous. More preferably, the content of chain particles is 4 to 10% by weight.
• the surface resistance value of the film-coated substrate is preferably in the range of 10 7 to 10 12 ⁇ / ⁇ . In order to make the surface resistance value less than 10 7 ⁇ / ⁇ , it is necessary to include a large amount of chain-like particles in the coating film, which results in insufficient coloring and hardness. If the surface resistance value of the film-coated substrate exceeds 10 12 ⁇ / ⁇ , the antistatic performance will be insufficient. More preferably, the film-coated substrate has a surface resistance value of 10 8 to 10 12 ⁇ / ⁇ .
• the thickness of the coating is preferably 0.5-30 ⁇ m. If the film thickness is less than 0.5 ⁇ m, it is difficult to obtain sufficient surface resistance and hardness. If the film thickness exceeds 30 ⁇ m, the film may crack, curl (curve or warp), or be colored. More preferably, the film thickness is 1 to 15 ⁇ m.
• a film-coated substrate is produced by applying a paint onto a substrate, drying, and curing.
• coating methods include well-known methods such as a dip method, a spray method, a spinner method, a roll coat method, a bar coat method, a slit coater printing method, a gravure printing method, and a micro gravure printing method. Drying is carried out at temperatures ranging from ambient temperature to about 90°C.
• an ultraviolet curable resin the resin is cured by ultraviolet irradiation of 100 to 1000 mJ/cm 2 .
• a curing treatment may be performed by heating.
• the coating film applied on the substrate is heated at 150° C. or higher during or after drying.
• the dried coating film is irradiated with electromagnetic waves such as electron beams, X-rays, or ⁇ -rays, which have shorter wavelengths than visible light. This accelerates the hardening of the matrix-forming component, so that the hardness of the obtained coating is increased.
• the film formed in this way has a low surface resistance value, excellent adhesion to the substrate, transparency, and haze, and is less likely to crack.
• Example 1 ⁇ Preparation of ATO powder> A mixed solution was prepared by dissolving 10.4 kg of potassium stannate trihydrate and 2.2 kg of potassium antimonyl tartrate in 32 kg of pure water. This mixed solution was added to 75 kg of pure water in which 91 g of ammonium nitrate and 88 g of 85% potassium hydroxide were dissolved at 30° C. over 24 hours with stirring to carry out hydrolysis. At this time, a 10% nitric acid aqueous solution was added at the same time so that the pH of this solution was maintained at 9.0. The generated precipitate was filtered, washed, and then dispersed again in water to prepare a precursor hydroxide dispersion (solid concentration: 20% by weight).
• Step a 1875 g of this ATO powder was suspended in 4740 g of an aqueous potassium hydroxide solution having a concentration of 0.42% by weight. Subsequently, a bead mill filled with glass beads was used to disperse the suspension for 9 hours. The suspension was kept at 30° C. during the dispersing process. The ATO concentration of the resulting dispersion was 28.3% by weight. The amount of silicon oxide contained in the dispersion was 1.0% of the amount of ATO. The amount of alkali metal contained in the dispersion was 1.1% of the amount of ATO.
• the dispersion After adding 18000 g of pure water to 6000 g of this dispersion, the dispersion was held at 95°C for 5 hours and then cooled to room temperature. The dispersion was then centrifuged at 15200G for 10 minutes. After that, the supernatant was collected. Thereby, coarse particles are removed.
• Step b Pure water was added to the collected supernatant to prepare a dispersion having a solid concentration of 6% by weight. After that, the dispersion was subjected to hydrothermal treatment (175° C., 24 hours). The dissolved oxygen concentration before hydrothermal treatment was 8 mg/L. A cation exchange resin was added to 3200 g of this dispersion until the pH reached 3.0, and the mixture was stirred for 60 minutes. The resin was then separated by filtering the dispersion.
• Step c 15% aqueous ammonia was added to 3000 g of this dispersion (solid concentration: 5.5% by weight) so as to adjust the pH to 8.0.
• This dispersion was subjected to centrifugation (15200 G, 10 minutes), and then the supernatant was collected. As a result, a dispersion liquid from which coarse particles were removed was obtained.
• the solid content concentration of the dispersion was adjusted to 20% by weight.
• a cation exchange resin was added to the dispersion so that the pH was 3, and the dispersion was stirred for 30 minutes. After that, the resin was separated from this dispersion, and the dispersion was allowed to stand at 35° C. for 12 hours.
• Step d Next, 28 g of tetraethoxysilane (orthoethyl silicate manufactured by Tama Chemical Co., Ltd., SiO 2 concentration: 28.8% by weight) was added to 800 g of this dispersion (solid concentration: 20.0% by weight) over 10 minutes. The dispersion was stirred for 30 minutes. Furthermore, 800 g of ethanol was added to the dispersion, and the dispersion was stirred at 50° C. for 15 hours. As a result, the solid content concentration was 10.3% by weight.
• tetraethoxysilane orthoethyl silicate manufactured by Tama Chemical Co., Ltd., SiO 2 concentration: 28.8% by weight
• Table 3 shows the conditions for preparing an ethanol dispersion of chain particles. Moreover, the physical properties were measured by the following methods. Table 4 also shows the results of other examples and comparative examples.
• the isoelectric point of the chain-like particles of this example was 0.8, and the average particle diameter when the pH was adjusted to 1.0 was 18 nm.
• Isoelectric point The dispersion of this example was diluted with pure water to 0.1% by weight. Hydrochloric acid (5% by weight) is added to the dispersion to give pHs of 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, and 4.0. so I adjusted. This produced each sample having the pH described above.
• the zeta potential of each sample was measured using a zeta potential measurement device (Zetasizer Nano ZS manufactured by Spectris). A graph showing the relationship between zeta potential and pH was prepared, the pH at which the zeta potential was 0 was obtained from the graph, and the obtained value was defined as the isoelectric point.
• a dispersion having a pH of 1.0 was prepared by adding hydrochloric acid (5% by weight) to the dispersion according to this example. This dispersion was measured using a dynamic light scattering particle size distribution analyzer (NANOTRAC-WAVE II manufactured by Microtrac Bell) to determine the average particle size.
• NANOTRAC-WAVE II manufactured by Microtrac Bell
• Average number of links 1,000 chain-like particles were selected in the same manner as in the measurement of the average particle size described above, and the major axis of each was determined.
• the average number of connections is a value obtained by dividing the "average value of major diameters" by the above-mentioned "average value of minor diameters (average particle diameter)".
• Table 4 shows integers obtained by rounding off.
• the paint was prepared by thoroughly mixing 94 g of Kayarad KS-HDDA manufactured by Yakusha), 16 g of photoinitiator (Omnirad-184 manufactured by IGM Resins B.V.), 490 g of isopropanol, 140 g of isopropyl glycol, and 140 g of butyl cellosolve. made.
• Table 5 shows the paint preparation conditions. Unless otherwise specified, paints were similarly prepared and evaluated in the following examples and comparative examples.
• film-coated substrates were measured and evaluated as follows. The results are shown in Table 5. Unless otherwise specified, film-coated substrates were similarly prepared and evaluated in the following examples and comparative examples.
• the surface resistance of the film-coated substrate was measured with a surface resistance meter (Hiresta UX MCP-HT800, manufactured by Nitto Seiko Analyticc Co., Ltd.).
• Coloring A fluorescent lamp was applied to the film-coated substrate, and the film-coated substrate was visually observed. The presence or absence of coloration in transmission was evaluated according to the following criteria. Colorless and transparent, no coloration observed: A Very light coloring is slightly observed : B Light coloring is observed: C Dark coloring is observed :D
• 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. A cellophane tape was adhered to this, and the cellophane tape was peeled off. After that, the number of squares remaining without peeling of the film (remaining squares) was measured. Based on the number of remaining squares, adhesion was evaluated according to the following criteria. Number of remaining squares: 100: A Number of remaining squares 90 to 99: B Number of remaining squares 85 to 89: C Number of remaining squares 84 or less: D
• Example 2 ATO powder was prepared in the same manner as in Example 1. 1875 g of this ATO powder was suspended in 4740 g of an aqueous potassium hydroxide solution having a concentration of 0.42% by weight. To this suspension, 18.3 g of silica sol (Cataloid SI-550 manufactured by Nikki Shokubai Kasei Co., Ltd., SiO 2 concentration: 20.5% by weight) was added as silicon oxide. Subsequently, a bead mill filled with zirconia beads was used to disperse the suspension for 8 hours. The suspension was kept at 30° C. during the dispersion process. The ATO concentration of the resulting dispersion was 28.3% by weight.
• silica sol Cataloid SI-550 manufactured by Nikki Shokubai Kasei Co., Ltd., SiO 2 concentration: 20.5% by weight
• the amount of silicon oxide contained in the dispersion was 0.2% of the amount of ATO.
• the amount of alkali metal contained in the dispersion was 1.1% of the amount of ATO. Then, after centrifugation treatment was performed in the same manner as in Example 1, the supernatant was recovered.
• Example 2 After that, in the same manner as in Example 1, an ethanol dispersion of chain particles with a solid content concentration of 30% by weight was prepared.
• the chain particles had an isoelectric point of 1.6 and an average particle diameter of 45 nm when the pH was adjusted to 1.0.
• Example 3 An ethanol dispersion of chain particles having a solid content concentration of 30% by weight was prepared in the same manner as in Example 2, except that the amount of silica sol added as silicon oxide in step a of Example 2 was changed to 457.3 g. .
• the chain particles had an isoelectric point of 0.5 and an average particle diameter of 15 nm when the pH was adjusted to 1.0.
• the ATO concentration of the dispersion after the dispersion treatment was 26.5% by weight.
• the amount of silicon oxide contained in the dispersion was 5.0% of the amount of ATO.
• the amount of alkali metal contained in the dispersion was 1.2% of the amount of ATO.
• Example 4 An ethanol dispersion of chain particles with a solid content concentration of 30% by weight was prepared in the same manner as in Example 1, except that an aqueous potassium hydroxide solution with a concentration of 7.0% by weight was used in step a of Example 1. .
• the chain particles had an isoelectric point of 0.4 and an average particle diameter of 15 nm when the pH was adjusted to 1.0.
• the ATO concentration of the dispersion after the dispersion treatment was 28.3% by weight.
• the amount of silicon oxide contained in the dispersion was 4.9% of the amount of ATO.
• the amount of alkali metal contained in the dispersion was 17.7% of the amount of ATO.
• Example 5 Dispersion treatment was performed in the same manner as in Example 2, except that 100.6 g of silica sol added as silicon oxide in step a of Example 2 was changed.
• the ATO concentration of the dispersion after dispersion treatment was 27.9% by weight.
• the amount of silicon oxide contained in the dispersion was 1.1% of the amount of ATO.
• the amount of alkali metal contained in the dispersion was 1.1% of the amount of ATO.
• the supernatant was recovered.
• this supernatant liquid was adjusted with an ultrafiltration membrane so that the solid content concentration was 10% by weight. Thereafter, this dispersion was subjected to hydrothermal treatment (175° C., 24 hours). The dissolved oxygen concentration before hydrothermal treatment was 3 mg/L. Thereafter, in the same manner as in Example 1, an ethanol dispersion of chain particles having a solid content concentration of 30% by weight was prepared.
• the chain particles had an isoelectric point of 0.5 and an average particle diameter of 95 nm when the pH was adjusted to 1.0.
• Example 6 In step a of Example 2, 24.4 g of Rheolosil QS-20 (manufactured by Tokuyama, SiO 2 concentration of 99.9% by weight or more) was added as silicon oxide. Otherwise, in the same manner as in Example 2, a dispersion of ATO particles was prepared. The ATO concentration of the dispersion after dispersion treatment was 28.2% by weight. The amount of silicon oxide contained in the dispersion was 1.3% of the amount of ATO. The amount of alkali metal contained in the dispersion was 1.1% of the amount of ATO. Next, after performing the centrifugation process similarly to Example 1, the supernatant liquid was collect
• this supernatant was adjusted to a solid content concentration of 15% by weight with an ultrafiltration membrane. Furthermore, bubbling with O 2 gas was performed. After that, the dispersion was subjected to hydrothermal treatment (175° C., 24 hours). The dissolved oxygen concentration before hydrothermal treatment was 20 mg/L or higher. A cation exchange resin was added to 3200 g of the hydrothermally treated dispersion until the pH reached 3.0, and the mixture was stirred for 60 minutes. The resin was then separated by filtering the dispersion.
• Example 2 After that, in the same manner as in Example 1, an ethanol dispersion of chain particles with a solid content concentration of 30% by weight was prepared.
• the chain particles had an isoelectric point of 0.2 and an average particle diameter of 13 nm when the pH was adjusted to 1.0.
• Example 7 By performing the steps up to the hydrothermal treatment in step b in the same manner as in Example 1, a dispersion liquid after the hydrothermal treatment was obtained. 15% aqueous ammonia was added to 3000 g of this dispersion so that the pH was 4.0. This dispersion was subjected to centrifugal separation (15200 G, 10 minutes), and then the supernatant was collected to obtain a dispersion. Next, using an ultrafiltration membrane, the solid content concentration of the dispersion was adjusted to 15% by weight. Furthermore, a cation exchange resin was added to the dispersion so that the pH was 3, and the dispersion was stirred for 30 minutes. After that, the resin was separated from this dispersion, and the dispersion was allowed to stand at 35° C. for 12 hours.
• the dispersion liquid was concentrated.
• an ethanol dispersion of chain-like particles (solid concentration: 30% by weight) according to this example was obtained.
• the chain particles had an isoelectric point of 0.8 and an average particle size of 15 nm when the pH was adjusted to 1.0.
• Example 8 By performing the steps up to the hydrothermal treatment in step b in the same manner as in Example 1, a dispersion liquid after the hydrothermal treatment was obtained. 15% aqueous ammonia was added to 3000 g of this dispersion so that the pH was 10.0. This dispersion was subjected to centrifugal separation (15200 G, 10 minutes), and then the supernatant was collected to obtain a dispersion. Next, using an ultrafiltration membrane, the solid content concentration of the dispersion was adjusted to 30% by weight. Furthermore, a cation exchange resin was added to the dispersion so that the pH was 3, and the dispersion was stirred for 30 minutes. After that, the resin was separated from this dispersion, and the dispersion was allowed to stand at 35° C. for 12 hours.
• the dispersion liquid was concentrated.
• an ethanol dispersion of chain particles (solid concentration: 30% by weight) according to this example was obtained.
• the chain particles had an isoelectric point of 0.8 and an average particle diameter of 38 nm when the pH was adjusted to 1.0.
• Example 9 In step c of Example 1, after adjusting the solid content concentration of the dispersion liquid to 20% by weight using an ultrafiltration membrane, the ethanol dispersion liquid of chain-like particles according to this example (solid content concentration 30% by weight ).
• the chain particles had an isoelectric point of 0.8 and an average particle diameter of 55 nm when the pH was adjusted to 1.0.
• step d 18.8 g of tetraethoxysilane was added to 300 g of the dispersion obtained in step c of Example 1 (solid concentration: 20.0% by weight) over 10 minutes. Stirred for 1 minute. Furthermore, 300 g of ethanol was added to the dispersion, and the dispersion was stirred at 50° C. for 15 hours. As a result, the solid content concentration was 10.6% by weight. Except for this, in the same manner as in Example 1, an ethanol dispersion of chain particles (solid content concentration: 30% by weight) according to this example was obtained. The chain particles had an isoelectric point of 0.6 and an average particle diameter of 21 nm when the pH was adjusted to 1.0.
• step d 12.4 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 300 g of the dispersion obtained in step c of Example 1 (solid concentration: 20.0% by weight). was added over 10 minutes and the dispersion was stirred for 30 minutes. Furthermore, 1500 g of ethanol was added to the dispersion, and the dispersion was stirred at 50° C. for 15 hours. This resulted in a solid concentration of 3.8% by weight. Except for this, in the same manner as in Example 1, an ethanol dispersion of chain particles (solid content concentration: 30% by weight) according to this example was obtained. The chain particles had an isoelectric point of 0.7 and an average particle diameter of 28 nm when the pH was adjusted to 1.0.
• KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.
• Example 12 By performing the steps up to step b in the same manner as in Example 6, a dispersion having a solid concentration of 14.6% by weight was obtained. To 3000 g of this dispersion, 500 g of anion exchange resin was added and the dispersion was stirred for 1 hour. After separating the resin from this dispersion, 1000 g of a cation exchange resin was added to the dispersion again, and the dispersion was heated to 80° C. and stirred. After cooling the dispersion to room temperature, the resin was separated from the dispersion.
• Example 13 A mixed solution was prepared by dissolving 15.3 kg of potassium stannate trihydrate and 1.9 kg of potassium antimonyl tartrate in 43 kg of pure water. This mixed solution was added to 108 kg of pure water in which 131 g of ammonium nitrate and 93 g of 29% ammonia water were dissolved at 30° C. over 24 hours with stirring to carry out hydrolysis. At this time, a 10% nitric acid aqueous solution was added at the same time so that the pH of this solution was maintained at 8.5. After filtering and washing the generated precipitate, it was dispersed again in water to obtain a precursor hydroxide dispersion (solid concentration: 20% by weight).
• Example 2 Thereafter, the same procedure as in Example 1 was repeated except that the amount of tetraethoxysilane added in step d was changed to 16.0 g. ) was made.
• the chain particles had an isoelectric point of 1.2 and an average particle diameter of 62 nm when the pH was adjusted to 1.0.
• Example 14 A mixed solution was prepared by dissolving 10.4 kg of potassium stannate trihydrate and 2.5 kg of potassium antimonyl tartrate in 32 kg of pure water. This mixed solution was added to 75 kg of pure water in which 91 g of ammonium nitrate and 88 g of 85% potassium hydroxide were dissolved at 30° C. over 24 hours with stirring to carry out hydrolysis. At this time, a 10% nitric acid aqueous solution was added at the same time so that the pH of this solution was maintained at 11.0. The generated precipitate was filtered, washed, and then dispersed again in water to prepare a precursor hydroxide dispersion (solid concentration: 20% by weight).
• Example 2 Thereafter, the same procedure as in Example 1 was repeated except that the amount of tetraethoxysilane added in step d was changed to 40.0 g. ) was made.
• the chain particles had an isoelectric point of 1.2 and an average particle diameter of 62 nm when the pH was adjusted to 1.0.
• Example 15 50 g of an ethanol dispersion of chain particles prepared in the same manner as in Example 1, 500 g of ethylene oxide-modified acrylic resin (NK Ester ATM-4E manufactured by Shin Nakamura Chemical Co., Ltd.), 1.6 hexanediol diacrylate (non-modified acrylic Resin, Kayarad KS-HDDA manufactured by Nippon Kayaku) 214 g, photoinitiator (Omnirad-184 manufactured by IGM Resins B.V.) 36 g, isopropanol 1470 g, isopropyl glycol 140 g, and butyl cellosolve 140 g are thoroughly mixed.
• a paint was prepared by
• Example 16 100 g of an ethanol dispersion of chain particles prepared in the same manner as in Example 1, 113 g of ethylene oxide-modified acrylic resin (NK Ester ATM-4E manufactured by Shin Nakamura Chemical Co., Ltd.), 1.6 hexanediol diacrylate (non-modified acrylic Resin, Kayarad KS-HDDA manufactured by Nippon Kayaku Co., Ltd.) 49 g, photoinitiator (Omnirad-184 manufactured by IGM Resins B.V.) 8 g, isopropanol 117 g, isopropyl glycol 140 g, and butyl cellosolve 140 g are thoroughly mixed.
• a paint was prepared by
• step a of Example 1 a bead mill filled with zirconia beads was used to disperse the suspension for 8 hours.
• the ATO concentration of the resulting dispersion was 28.3% by weight.
• the amount of silicon oxide contained in this dispersion was 0% of the amount of ATO.
• the amount of alkali metal contained in the dispersion was 1.1% of the amount of ATO. Then, in the same manner as in Example 1, the supernatant was collected.
• step b an ultrafiltration membrane was used to adjust the solid content concentration of the supernatant to 15% by weight.
• the dispersion was subjected to hydrothermal treatment (175° C., 24 hours).
• the dissolved oxygen concentration before the hydrothermal treatment was 2 mg/L or higher.
• a cation exchange resin was added until the pH reached 3.0, followed by stirring for 60 minutes. The resin was then separated by filtering the dispersion.
• step c and subsequent steps were performed in the same manner as in Example 1 to prepare an ethanol dispersion of chain particles (solid concentration: 30% by weight).
• the chain particles had an isoelectric point of 2.7 and an average particle size of 181 nm when the pH was adjusted to 1.0.
• step a of Example 1 an aqueous potassium hydroxide solution with a concentration of 6.5% by weight was used. Except for this, the same procedure as in Example 1 was performed up to step a.
• the ATO concentration of the dispersion after dispersion treatment was 28.3% by weight.
• the amount of silicon oxide contained in this dispersion was 7.1% of the amount of ATO, and the amount of alkali metal contained in the dispersion was 25.3% of the amount of ATO.
• the content of silicon oxide in the supernatant liquid recovered in step a was 5.5% relative to the amount of ATO.
• Example 2 After that, in the same manner as in Example 1, an ethanol dispersion of chain particles (solid concentration: 30% by weight) was prepared.
• the particles had an isoelectric point of 0.4 and an average particle diameter of 14 nm when the pH was adjusted to 1.0.
• step c of Example 1 the solid content concentration of the supernatant recovered after centrifugation was adjusted to 13% by weight. Except for this, in the same manner as in Example 1, an ethanol dispersion of chain particles (solid concentration: 30% by weight) was prepared. The particles had an isoelectric point of 0.8 and an average particle diameter of 18 nm when the pH was adjusted to 1.0.
• step c of Example 1 the solid content concentration of the supernatant collected after centrifugation was adjusted to 20% by weight. A cation exchange resin was added to the resulting dispersion so as to adjust the pH to 4. Except for this, in the same manner as in Example 1, an ethanol dispersion of chain particles (solid concentration: 30% by weight) was prepared. The isoelectric point of this particle was 0.8, and the average particle diameter when the pH was adjusted to 1.0 was 20 nm.
• step c of Example 1 the solid content concentration of the supernatant collected after centrifugation was adjusted to 35% by weight. A cation exchange resin was added to the resulting dispersion so that the pH was 3. This dispersion liquid was subjected to stirring, resin separation, and standing in the same manner as in Example 1. The dispersion was gelled by standing still. Therefore, it was not possible to proceed to the next step.
• step d of Example 1 64 g of tetraethoxysilane was added to 800 g of the dispersion liquid (solid concentration: 20.0% by weight) obtained in step c over 10 minutes. The dispersion was stirred for 30 minutes. Furthermore, 800 g of ethanol was added to the dispersion, and the dispersion was stirred at 50° C. for 15 hours. As a result, the solid content concentration was 10.7% by weight. Thereafter, in the same manner as in Example 1, an ethanol dispersion of chain particles (solid concentration: 30% by weight) was prepared. The chain particles had an isoelectric point of 0.4 and an average particle diameter of 16 nm when the pH was adjusted to 1.0.

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