WO2017115637A1 - Matériau stratifié particulaire pour former des charges sur une surface de substrat et liquide de mise en forme de film pour former des charges sur une surface de substrat - Google Patents

Matériau stratifié particulaire pour former des charges sur une surface de substrat et liquide de mise en forme de film pour former des charges sur une surface de substrat Download PDF

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WO2017115637A1
WO2017115637A1 PCT/JP2016/086757 JP2016086757W WO2017115637A1 WO 2017115637 A1 WO2017115637 A1 WO 2017115637A1 JP 2016086757 W JP2016086757 W JP 2016086757W WO 2017115637 A1 WO2017115637 A1 WO 2017115637A1
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substance
titanium oxide
silicon oxide
charge
dielectric
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PCT/JP2016/086757
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English (en)
Japanese (ja)
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緒方　四郎
義光 松井
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サスティナブル・テクノロジー株式会社
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Priority to JP2017558920A priority Critical patent/JPWO2017115637A1/ja
Publication of WO2017115637A1 publication Critical patent/WO2017115637A1/fr

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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • B08B17/02—Preventing deposition of fouling or of dust
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides

Definitions

  • the present invention forms a particulate laminate that charges the substrate surface on the substrate surface or substrate surface layer, and repels or adsorbs on the substrate surface contaminants that float in the atmosphere and adversely affect the substrate.
  • the present invention relates to a technique for protecting the substrate surface or reducing the influence of the contaminant on the substrate by separating the substrate and changing the contaminant into a safety material.
  • Patent Document 1 generates a positive charge on the surface of the substrate by disposing a composite of a conductor and a dielectric or semiconductor on the surface of the substrate or the substrate surface layer.
  • a technique for protecting a substrate surface by electrostatically attracting or repelling is disclosed.
  • the applicant arranges a positively charged substance and a negatively charged substance on the substrate surface or the substrate surface layer, and positively and negatively charges the substrate surface, so that contaminants from the outside are introduced into the substrate.
  • a technique for protecting a substrate surface by electrostatically attracting or repelling the surface is disclosed.
  • the charged voltage on the substrate surface due to the positively charged substance and / or the negatively charged substance arranged on the substrate surface or the substrate surface layer exhibits the function for protecting the substrate as described above. Even if this technology is applied to the surface of an electronic device, the voltage is so weak that the function of the electronic device itself is not impaired.
  • Patent Document 1 and Patent Document 2 what kind of substance can be selected as a positively charged substance or a negatively charged substance in order to arrange a positively charged substance and / or a negatively charged substance on the substrate surface or the substrate surface layer. It is disclosed. Further, in the above document, as one of means for disposing a positively charged substance or a negatively charged substance on a substrate surface or a substrate surface layer, a film-forming solution having a positively charged substance and / or a negatively charged substance is used. It is disclosed that forming a coating or layer on the surface is an effective means.
  • a dielectric or semiconductor for stably forming charges is appropriately interposed between the conductive materials.
  • the dielectric or semiconductor an appropriate substance is selected from the viewpoint of function and cost, and further, a charge substance and a dielectric or semiconductor for stably functioning formation and fixation of charges on the substrate surface or surface layer.
  • a method for forming a functionally excellent coating film or layer of the particulate laminate on the substrate surface or the substrate surface layer must be solved.
  • the present invention provides a substrate protection technique in which contaminants from the outside are electrostatically repelled or adsorbed by positively and / or negatively charging the substrate surface or the substrate surface layer. It is an object of the present invention to provide means for forming charges efficiently and stably without uneven distribution.
  • the particulate laminate for forming a substrate surface charge according to the present invention includes a titanium oxide as a dielectric or semiconductor between a substance having a positive charge and / or a substance having a negative charge on the surface of the substrate or the surface layer of the substrate. It is characterized by interposing silicon oxide (including titanium oxide and / or silicon oxide compounds).
  • One embodiment of the particulate laminate includes particles made of a substance having a positive charge and / or a substance having a negative charge, and titanium oxide and / or silicon oxide (dioxide or semiconductor oxide as a dielectric or semiconductor). It is characterized in that it is formed by adjoining and adhering to a particle comprising the above compound.
  • the substance having a positive charge and / or the substance having a negative charge includes titanium oxide and / or silicon oxide (a compound of titanium oxide and / or silicon oxide) as a dielectric or semiconductor. It is characterized in that colloidal particles encapsulated in (1) are joined.
  • Still another embodiment of the particulate laminate includes a positively charged substance and / or a negatively charged substance and titanium oxide and / or silicon oxide as a dielectric or semiconductor (a compound of titanium oxide and / or silicon oxide). And the like) are bonded as particles of a complex at a molecular level.
  • the substrate surface charge forming film forming liquid according to the present invention includes a positively charged substance and / or a negatively charged substance, and titanium oxide and / or silicon oxide (titanium oxide and / or oxide) as a dielectric or semiconductor. Including a compound of silicon).
  • the above-mentioned film forming solution for forming a surface charge on a substrate includes titanium oxide and / or silicon oxide (including a compound of titanium oxide and / or silicon oxide) as the dielectric or semiconductor, a substance having the positive charge, and
  • titanium oxide including a titanium oxide compound
  • the ratio of the negative charge to the substance having a negative charge is 1: 0.01 to 1: 0.3 when silicon oxide (including a titanium oxide compound) is used.
  • silicon oxide including a titanium oxide compound
  • a compound of silicon 1: 0.03 to 1: 2.7
  • titanium oxide and silicon oxide (including these compounds) 1: 0.01 to 1: 0.
  • a ratio of 3 is preferable.
  • the substance having a positive charge and / or the substance having a negative charge is (1) Cation (2) Conductor having positive charge, composite of conductor having positive charge and dielectric, composite of conductor having positive charge and semiconductor, two or more kinds having positive charge A dielectric or / and a composite made of a semiconductor, a positively charged conductor or a composite (3) an anion (4) a negatively charged conductor, a negatively charged conductor and a dielectric Conductor or composite having negative charge of composite, composite of conductor having negative charge and semiconductor, composite of two or more kinds of dielectric having negative charge or / and semiconductor (5) ) Substance having photocatalytic function (6) Dielectric or semiconductor excluding titanium oxide and / or silicon oxide (including titanium oxide and / or silicon oxide compound) selected from the group consisting of (1) to (6) above A substance having at least one positive charge It is preferably a substance having a beauty / or negative charge.
  • particles that positively and / or negatively charge the substrate surface or the substrate surface layer by arranging and charging a substance having a positive charge and / or a substance having a negative charge on the substrate or the substrate surface layer.
  • a substance having a positive charge and / or a substance having a negative charge on the substrate or the substrate surface layer can be formed efficiently and stably without uneven distribution of charges, so that external contaminants can be electrostatically repelled or adsorbed to effectively protect the substrate.
  • the surface of the substrate or the surface of the substrate can be obtained by interposing titanium oxide and / or silicon oxide (including these compounds) as a dielectric or semiconductor in a substance having a positive charge and / or a substance having a negative charge.
  • a thin and highly transparent film with a particulate laminate can be formed on the surface layer of the substrate without using a binder.
  • the substrate surface be protected by electrostatically adsorbing or repelling contaminants from the outside by charging the substrate surface positively and / or negatively, but also a substrate by electromagnetic waves. It is also possible to reduce the oxidative degradation. That is, the oxidative degradation of the substrate is caused by the generation of radicals such as 1 O 2 , .OH, etc. on the substrate surface or in the substrate to cause an oxidative decomposition reaction. Let these radicals be stable molecules. Therefore, it is considered that the oxidative deterioration of the substrate is prevented or reduced. In addition, when a base
  • the inventor of the present application electrostatically repels or adsorbs contaminants from the outside by placing and charging a positively charged substance and / or a negatively charged substance on the substrate surface or substrate surface layer.
  • a positively charged substance and / or a negative charge In the process of developing a substrate protection or environmental improvement method, in order to efficiently and stably form a charge on the surface or surface layer of the substrate without uneven distribution, a positively charged substance and / or a negative charge
  • the present inventors have found that it is important to form a particulate laminate in the surface or surface layer of a substrate, with a dielectric or semiconductor appropriately interposed between materials having sinter.
  • the particulate laminate refers to a film or layer formed of particulate substances arranged in layers and formed on the surface of the substrate or the surface layer.
  • the inventor of the present application is an excellent dielectric material in that it is a material that is relatively low in cost and easy to handle as a dielectric or semiconductor interposed between substances for charging the substrate surface or the substrate surface layer in the particulate laminate.
  • Titanium oxide and / or silicon oxide (including titanium oxide and / or silicon oxide compounds) from the point of having excellent characteristics such as characteristics and semiconductor characteristics and capable of forming a no-binder film I found that I can choose.
  • titanium oxide and / or silicon oxide including a titanium oxide and / or silicon oxide compound
  • a dielectric or semiconductor excluding titanium oxide and / or silicon oxide including titanium oxide and / or silicon oxide compound
  • the surface of the substrate or the surface layer of the substrate is positively or negatively charged both positively and negatively depending on the type of dielectric or semiconductor.
  • a substance that positively charges the substrate surface or the substrate surface layer is referred to as a “substance having a positive charge”, and a substance that negatively charges the substrate surface or the substrate surface layer is referred to as a “substance having a negative charge”.
  • the substance having a positive charge and the substance having a negative charge are defined as “a dielectric or semiconductor excluding titanium oxide and / or silicon oxide (including a compound of titanium oxide and / or silicon oxide)”. Shall also be included. These dielectrics or semiconductors have excellent electrostatic polarization and electrostatic induction properties, and have the property that the charge dipoles in these materials fluctuate due to the irradiation of electromagnetic waves, heat or light energy. desirable.
  • the particulate laminate is applied to the substrate surface or surface.
  • the dried and solidified particles are regularly taken in and a uniform and uniform charge is formed.
  • preferred examples of such a particulate laminate include the following (a) to (c).
  • the particle size of the particulate laminate formed in is preferably 0.1 nm to 100 nm.
  • the layer thickness of the laminate is not particularly limited, but is preferably in the range of 10 nm to 1 ⁇ m, and more preferably in the range of 10 nm to 100 nm.
  • the principle of charge formation will be described below mainly by the particulate laminate formed on the substrate surface or the substrate surface layer described in (a) above.
  • the substrate surface or the substrate surface layer is positively charged, negatively charged, or positively charged.
  • the principle of charge formation for applying a negative charge will be described with reference to FIGS.
  • FIG. 5 (1), FIG. 5 (2), and FIG. 5 (3) show a substance having a positive charge and / or a substance having a negative charge, and titanium oxide or silicon oxide as a dielectric or semiconductor (these compounds are combined).
  • a particle BB of titanium oxide or silicon oxide (including these compounds) as a dielectric or semiconductor is adjacent to a conductive particle AP having a positive charge.
  • the dielectric or semiconductor adjacent to the conductor is dielectrically polarized due to the influence of the surface charge state of the conductor, and the negative charge is present on the side adjacent to the positively charged conductor and the side adjacent to the negatively charged conductor. Has a positive charge state, and a reverse charge state is generated on the counter electrode side. Therefore, uniform and uniform charges are formed on the surface of the formed particulate laminate.
  • FIG. 6 (1), FIG. 6 (2), and FIG. 6 (3) show a dielectric or semiconductor excluding titanium oxide and silicon oxide (including these compounds), and titanium oxide or oxidation as a dielectric or semiconductor. It is the figure which showed typically the principle which provides a positive charge, a negative charge, a positive charge, and a negative charge, respectively, to a substrate surface or a substrate surface layer using silicon (including these compounds). 6 (1) to (3), dielectric or semiconductor particles CC excluding titanium oxide and silicon oxide (including these compounds), and titanium oxide or silicon oxide (these compounds) as a dielectric or semiconductor. In the state where the particles BB of the substrate surface are adjacent to each other, a film or a layer is formed on the substrate surface or the substrate surface layer, respectively.
  • the electrical dipole that forms the material is adjacent to the material (ie, titanium oxide or silicon oxide (including these compounds). )) Reacts quickly to the dielectric-polarized surface charge, and if the dipole moves with a charge opposite to the dielectric-polarized charge, it is considered that a uniform positive or negative charge is generated on the substrate surface or surface layer. .
  • a uniform positive charge is generated.
  • a uniform negative charge is generated.
  • a uniform positive charge and a negative charge are generated.
  • FIG. 1 (1) is a diagram schematically showing a film formation cross section on the substrate S1 according to the embodiment (a).
  • colored circles are particles of a substance having a positive charge and / or a substance having a negative charge
  • non-colored circles are titanium oxide and / or silicon oxide (a compound of these compounds as a dielectric or semiconductor). Particle).
  • single particles formed of a substance having a positive charge and / or a substance having a negative charge are uniformly dispersed during bonding of single particles formed of titanium oxide and / or silicon oxide. It is a form that has been.
  • a method for forming a particulate laminate according to this embodiment will be described below.
  • a substance having a positive charge and / or a substance having a negative charge and titanium oxide and / or silicon oxide as a dielectric or semiconductor are preferably combined at a ratio of 1: 1 for film formation.
  • Various methods can be considered as a method of forming such a composite film or layer on the surface of the substrate or the surface layer, and the method is not particularly limited.
  • One example is a method using a film-forming solution. Specifically, after preparing particles of titanium oxide and / or silicon oxide (including these compounds) and particles of a substance having a positive charge and / or a substance having a negative charge, these particles are , Dispersed in water or an organic medium to form a film-forming solution. And the film forming method by the wet system which apply
  • a film-forming solution in which particles of titanium oxide and / or silicon oxide (including these compounds) and particles of a substance having a positive charge and / or a substance having a negative charge are dispersed in water, an organic medium, or the like.
  • the ratio of these particles is theoretically preferably 1: 1 as described above, but the stability of the film-forming solution is stable.
  • titanium oxide and / or silicon oxide (including these compounds) when used, it is preferably 1: 0.01 to 1: 0.3, and when silicon oxide (including a compound of silicon oxide) is used, preferably 1: 0. .03 to 1: 2.7, titanium oxide and silicon oxide When using (containing these compounds) is preferably 1: 0.01 to 1: 0.3, a ratio of.
  • FIG. 1 (2) is a schematic cross-sectional view of the film formed on the substrate S1 according to the embodiment (b). It is the figure shown in.
  • a colored circle is a substance having a positive charge and / or a substance having a negative charge
  • a non-colored circle is titanium oxide and / or silicon oxide (including these compounds) as a dielectric or semiconductor.
  • a film is formed by joining colloidal particles in which titanium oxide and / or silicon oxide (including these compounds) contain a positively charged substance and / or a negatively charged substance. ing.
  • titanium oxide or silicon oxide (including these compounds) has a positive charge in a step of mixing or combining with a substance having a positive charge and / or a substance having a negative charge.
  • titanium oxide and / or silicon oxide (including these compounds) has a positive charge and / or a negative charge.
  • the colloidal particles are formed by encapsulating a substance having a charge. That is, when titanium oxide and / or silicon oxide (including these compounds) and a positively charged substance and / or a negatively charged substance are solidified by drying, ions are integrated as colloidal particles. Can be laminated.
  • the composite ratio of titanium oxide and / or silicon oxide (including titanium oxide and / or silicon oxide compound) in the above-described film-forming solution to a positively charged substance and / or a negatively charged substance is a solid type.
  • titanium oxide (including titanium oxide compound) preferably 1: 0.01 to 1: 0.3
  • silicon oxide (including silicon oxide compound) Is preferably a ratio of 1: 0.03 to 1: 2.7, preferably 1: 0.01 to 1: 0.3 when titanium oxide and silicon oxide (including these compounds) are used. It is.
  • film formation to the substrate, the peroxo group and a methyl group is a self-pinning modifications of titanium oxide or silicon oxide, or H 2 O, such Shiranmonima or polysiloxane polymer which is an organic silicon compound, by separation of CO 2 No-binder fixing by a condensation polymerization reaction is preferable.
  • FIG. 1 (3) is a view schematically showing a cross section of the film formed on the substrate S1 according to the embodiment (c).
  • a colored circle is a substance having a positive charge and / or a substance having a negative charge
  • a non-colored circle is titanium oxide and / or silicon oxide (including these compounds) as a dielectric or semiconductor.
  • the circles displayed on the outside indicate that the particles at the molecular level have a crystal structure or pseudo-crystal structure in which ions are incorporated.
  • the composite ratio of titanium oxide and / or silicon oxide to be reacted (including a compound of titanium oxide and / or silicon oxide) and a substance having a positive charge and / or a substance having a negative charge is expressed as a solid molar ratio.
  • titanium oxide including a titanium oxide compound
  • silicon oxide including a silicon oxide compound
  • the ratio is preferably 1: 0.01 to 1: 0.3.
  • the above-mentioned composite crystal has a perovskite type crystal structure or pseudo crystal structure in which a composite molecule is incorporated as an ion in a generally known inside, and Ti or Si is contained from the composite crystal particle.
  • a positive charge O 2 functions as a negative charge. Therefore, the composite crystal particle can selectively exhibit an amphoteric, positive> negative, or negative> positive charge depending on the included ions.
  • a film in which a substance having a positive charge and / or a substance having a negative charge is interposed with titanium oxide and / or silicon oxide (including these compounds) as a dielectric or semiconductor is used. An example of a method for forming a film was described. When the film forming method using FIG.
  • FIG. 1 film formation is possible with any type of substrate.
  • 1 (1), (2) and (3) in FIG. 1 show an example in which the particle layer of the particulate laminate formed on the surface of the substrate has one or two layers. In order to exhibit the function, it is desirable that the particulate laminate is formed of a plurality of layers.
  • FIG. 2 shows a substance having a positive charge in a surface layer of a substrate containing titanium oxide and silicon oxide (including these compounds) as dielectrics or semiconductors.
  • (1), (2), and (3) of FIG. 2 are drawings schematically showing a cross section of the substrate according to these embodiments.
  • colored circles are particles of a substance having a positive charge and / or a substance having a negative charge
  • non-colored circles are titanium oxide and / or silicon oxide (a compound of these compounds as a dielectric or semiconductor). Particle).
  • particles of a substance having a positive charge and / or a substance having a negative charge are formed, and a layer of these particles is formed as titanium oxide and / or silicon oxide as a dielectric or semiconductor. It is formed on the surface layer of the substrate S2 made of (including these compounds).
  • a method of forming such a surface layer on the substrate S2 there is a method in which particles of a positively charged substance and / or a negatively charged substance are pressed against the surface of the substrate S2 by pressing or the like.
  • particles of titanium oxide and / or silicon oxide are formed, and these particles, a substance having a positive charge and / or a substance having a negative charge.
  • the surface layer as shown in the figure can be produced by pressure-bonding to the substrate S3 by press working or by molding at the time of producing the substrate S3.
  • particles of titanium oxide and silicon oxide (including these compounds) as a dielectric or semiconductor are interposed between particles having a positive charge and / or a substance having a negative charge.
  • the layer is formed in advance on a sheet-like or block-like substrate S4 (which may contain an inorganic component inside) using an organic polymer resin or the like before curing, and the substrate S4 is irradiated with ultraviolet electromagnetic waves.
  • a layer in which particles of titanium oxide and silicon oxide (including these compounds) as a dielectric or semiconductor are interposed in particles of a substance having a positive charge and / or a substance having a negative charge is formed on the substrate S4.
  • particles of a substance having a positive charge and / or a substance having a negative charge and a dielectric or semiconductor as shown in FIG. It is not an embodiment in which particles of titanium oxide and / or silicon oxide (including these compounds) are adjacently bonded, but from titanium oxide and / or silicon oxide (including these compounds) as a dielectric or semiconductor.
  • Titanium oxide and / or silicon oxide as a dielectric or a semiconductor Titanium oxide and / or silicon oxide as a dielectric or semiconductor interposed in a substance having a positive charge and / or a substance having a negative charge has dielectric properties and semiconductor characteristics.
  • An excellent thin film having high hardness and high transparency can be formed without using a binder. Further, it can be used at a relatively low cost from the viewpoint of cost.
  • Various oxides and peroxides of titanium oxide and silicon oxide, and compounds thereof can be used as a dielectric or semiconductor interposed in a substance having a positive charge and / or a substance having a negative charge.
  • metals alkaline earth metals, group 3 scandium and yttrium, and lanthanoids such as lanthanum and cerium, group 4 zirconium and hafnium, and other compounds such as dielectrics and semiconductors other than conductive metals Or coexist.
  • Substance having positive charge and / or substance having negative charge As substance having positive charge and / or substance having negative charge combined with titanium oxide and / or silicon oxide (including these compounds) as dielectric or semiconductor Any substance having any positive or negative charge can be used as long as it can impart a positive charge or a negative charge to the surface of the substrate, but it is selected from the group consisting of the following (1) to (6): It is preferable that the substance has at least one positive charge and / or a negative charge.
  • Cation (2) Conductor having positive charge, composite of conductor having positive charge and dielectric, composite of conductor having positive charge and semiconductor, two or more kinds having positive charge A dielectric or / and a composite made of a semiconductor, a positively charged conductor or a composite (3) an anion (4) a negatively charged conductor, a negatively charged conductor and a dielectric Conductor or composite having negative charge of composite, composite of conductor having negative charge and semiconductor, composite of two or more kinds of dielectric having negative charge or / and semiconductor (5) ) Substance having photocatalytic function (6) Dielectric or semiconductor excluding titanium oxide and / or silicon oxide (including compounds of titanium oxide and / or silicon oxide)
  • (1) to (6) cations, anions, negatively charged or positively charged conductors, substances that function as photocatalysts, dielectrics or semiconductors include organic substances, inorganic substances, and composites of organic and inorganic substances. Regardless of the type of substance such as the body, a stable charge can be formed on the surface of the substrate, and in order to protect the substrate by electrostatically adsorbing or repelling contaminants, It is particularly preferable to use a metal or a part of an inorganic substance other than a metal from the viewpoint that a charge can be formed in accordance with the use conditions of a substrate to which energy is irradiated.
  • a substance having a positive charge and / or a substance having a negative charge to be combined with titanium oxide and / or silicon oxide (including these compounds) as a dielectric or a semiconductor is mainly a metal
  • a composite of a metal or a part of an inorganic substance other than metal and titanium oxide (including a titanium oxide compound) as a dielectric or semiconductor is hereinafter referred to as metal-doped titanium oxide.
  • metal-doped titanium oxide A composite of a part of the inorganic substance and silicon oxide (including a silicon oxide compound) as a dielectric or semiconductor is referred to as metal-doped silicon oxide.
  • Metals to be combined with titanium oxide and / or silicon oxide (including these compounds) as a dielectric or semiconductor include gold, silver, platinum, copper, manganese, nickel, cobalt, iron, zirconium, hafnium and the like It is preferably at least one metal element or inorganic element selected from transition metals, typical metals such as zinc and tin, alkali metals, alkaline earth metals, lanthanides such as lanthanum and cerium, and metal elements More preferably, two of these are combined.
  • the metal element to be combined silver and copper are particularly preferable.
  • silicon is preferable as the inorganic substance other than the metal to be combined with titanium oxide and / or silicon oxide (including these compounds) as a dielectric or semiconductor.
  • titanium oxide As for the metal-doped titanium oxide , a metal (including some inorganic substances other than the metal) and a titanium oxide as a dielectric or semiconductor, which are preferable as a material for composing the particulate laminated film for surface charge formation according to the present invention.
  • a combination with (including a titanium oxide compound) will be described.
  • Titanium oxide (including a titanium oxide compound) as a dielectric or semiconductor compounded with a metal (including some inorganic substances other than metals) includes TiO 2 , TiO 3 , TiO, TiO 3 / nH 2 O, etc.
  • Various oxides and peroxides can be used. In particular, titanium peroxide having a peroxo group is preferable.
  • the titanium oxide may be any of amorphous type, anatase type, brookite type, and rutile type, and these may be mixed, but amorphous type titanium oxide is preferred. However, the titanium oxide after the titanium oxide is combined with a metal to form a solid content exhibits anatase type crystals or anatase type crystal precursors.
  • titanium oxide exhibits a photocatalytic function on the surface of the substrate, the substrate itself may be decomposed and deteriorated by the photocatalytic action depending on the type of the substrate.
  • titanium oxides amorphous type titanium oxide and anatase type crystal precursor titanium oxide do not have a photocatalytic function.
  • anatase-type, brookite-type and rutile-type titanium oxides have a photocatalytic function.
  • titanium oxides when copper, manganese, nickel, cobalt, iron, or zinc is combined with these titanium oxides above a certain concentration, the photocatalytic function is reduced or lost To do.
  • amorphous type titanium oxide and anatase type crystal precursor titanium oxide are converted to anatase type titanium oxide over time by heating with sunlight, etc., but when combined with copper, manganese, nickel, cobalt, iron or zinc Anatase-type titanium oxide has a reduced photocatalytic function. Therefore, regardless of the type of titanium oxide, the titanium oxide doped with copper, manganese, nickel, cobalt, iron or zinc does not have to take into account the adverse effects of photocatalysis.
  • Titanium oxide doped with gold, silver and platinum has photocatalytic performance, including the case where amorphous titanium oxide is converted to anatase titanium oxide, but titanium oxide doped with gold, silver and platinum
  • photocatalytic performance is not exhibited. Therefore, metal-doped titanium oxide combined with gold, silver, platinum, copper, manganese, nickel, cobalt, iron, or zinc can eventually lose or reduce the photocatalytic performance. It is not necessary.
  • a photocatalytic substance is used as the negatively charged substance, a surface negative charge or a negatively charged substance generated by the photocatalytic function can be used effectively.
  • the above metal-doped titanium oxide may employ a production method based on a hydrochloric acid method or a sulfuric acid method, which is a common production method of titanium dioxide powder, or may employ various liquid dispersion titania solution production methods. May be.
  • the metal to be combined with titanium oxide and some inorganic substances other than the metal can be combined with titanium oxide regardless of the manufacturing stage.
  • Inorganic compounds and metal compounds can be mixed in multiple types.
  • the mixing ratio of titanium tetrachloride to the inorganic compound or metal compound is preferably 1: 0.01 to 1: 0.3, more preferably 1: 0.02 to 1: 0.1 in terms of molar ratio.
  • 25% aqueous ammonia (commercially available) is dropped to adjust the pH to around 7, and titanium, inorganic and metal hydroxides are precipitated, and the supernatant is washed until the conductivity becomes 0.9 mS / m or less. To do.
  • the concentration of titanium peroxide in the aqueous dispersion obtained by the above-described production method is as follows: 0.05 to 15 wt% is preferable, and 0.1 to 5 wt% is more preferable.
  • Gold, silver, platinum mixed to obtain inorganic materials and metals (including alkali metals and alkaline earth metals) combined with titanium oxide (including its compounds) in the above-described metal-doped titanium oxide manufacturing process examples of the compounds of nickel, cobalt, copper, manganese, iron, zinc, lithium, sodium, silicon, potassium, zirconium, cerium, and hafnium are as follows.
  • Au compound AuCl, AuCl 3 , AuOH, Au (OH) 4 , Au 2 O, Au 2 O 3, etc.
  • Ag compound AgNO 3 , AgF, AgClO 3 , AgOH, Ag (NH 3 ) OH, Ag 2 SO 4, etc.
  • Pt compound PtCl 2 , PtO, Pt (NH 3 ) Cl 2 , PtO 2 , PtCl 4 , [Pt (OH) 6 ] 2 ⁇ etc.
  • Ni compound Ni (OH) 2 , NiCl 2 etc.
  • Co compound Co (OH ) NO 3 , Co (OH) 2 , CoSO 4 , CoCl 2, etc.
  • Cu compound Cu (OH) 2 , Cu (NO 3 ) 2 , CuSO 4 , CuCl 2 , Cu (CH 3 COO) 2, etc.
  • Mn compound MnNO 4 , MnSO 4 , MnCl 2, etc.
  • Fe compound Fe (OH) 2 , Fe (OH) 3 , FeCl 3 etc.
  • Zn compound Zn (NO 3 ) 2 , Zn SO 4 , ZnCl 2 etc.
  • Na compound NaOH, NaCl, Na 2 CO 2 etc.
  • Si compound SiO 2 , SiH 4 , SiCl 4 etc.
  • K compound KOH, K 2 O , KCl, etc.
  • Zr compound Zr 2 O, Zr (OH) 2 , ZrCl, etc.
  • Ce compound CeO 2 , CeCl 2 , Ce (OH) 3 etc.
  • Hf compound HfCl 2 , Hf (OH) 3 etc.
  • the metal-doped silicon oxide a metal (including some inorganic substances other than the metal) and a silicon oxide as a dielectric or semiconductor, which are preferable as a material for forming a particulate laminated film for forming a surface charge according to the present invention.
  • a combination with (including a silicon oxide compound) will be described.
  • silicon oxide (including silicon oxide compounds) as a dielectric or semiconductor compounded with metal (including some inorganic substances other than metals) include SiO 2 , SiO 3 , SiO, SiO 3 / nH 2 O, and the like.
  • Various oxides and peroxides can be used.
  • a binding material (composite material) of an organic material and an inorganic material.
  • -A water-soluble coating agent having a methoxy group or an ethoxy group in terms of hydrolyzability in a silane coupling agent that improves the mechanical strength, bondability, and surface hydrophilicity of the composite material.
  • -Silicone oligomers that are used as resin-modified or functional coating agents by combining various substances as oligomer-type coupling agents that have organic functional groups and alkoxy groups in the molecule.
  • -Alkoxylanes and alkoxylazanes having a methyl group, a long-chain alkyl group, and a phenyl group which are used as a water repellency-imparting functional material for the substrate described later.
  • Silylating agents that have an origanosilyl group that protects active hydrogen of organic and inorganic materials, and that can be used to make organic synthetic members by controlling the reaction position of alkyl groups
  • a film-forming solution for forming a surface charge film in which a metal is combined can be produced.
  • the dispersion of the metal-doped silicon oxide in the case where the composite is a typical metal such as gold, silver, platinum, copper, manganese, nickel, cobalt, iron, zinc, or a transition metal An example of a manufacturing method will be described. First, when methyl silicate is mixed with alcohol, pure water and a predetermined amount of catalyst and hydrolyzed, a silica sol is produced. The silica sol is pure and diluted.
  • the solid content concentration in the silica sol dilution is preferably 10% to 0.2%, more preferably 4% to 0.85%.
  • This silica sol diluted solution and a metal compound adjusted to 1% concentration are preferably in a molar concentration ratio to silica of 1: 0.03 to 1: 2.7, more preferably 1 : Mix in a ratio of 0.03 to 1: 0.27.
  • the metal compound and the inorganic compound that can be complexed with silicon oxide in the preparation of the dispersion liquid described above are the same as the metal compound and the inorganic compound used when preparing the metal-doped titanium oxide. Is possible.
  • titanium tetrachloride and silica sol are mixed with pure water at a molar ratio of 1: 0.5, and a metal compound (compound having crystal water) is further mixed.
  • a metal compound compound having crystal water
  • a plurality of kinds of metal compounds can be mixed.
  • the metal compound which can be mixed can use the metal compound shown, for example in FIG. 3 used when producing metal dope titanium oxide.
  • the mixing ratio of titanium tetrachloride / silica sol and the metal compound is preferably 1: 0.01 to 1: 0.3, more preferably 1: 0.02 to 1: 0.1 in terms of molar ratio.
  • Ammonia water adjusted to 25% is added dropwise thereto to adjust the pH to around pH 7, thereby precipitating titanium, silicon, and a composite inorganic substance or metal hydroxide.
  • the precipitated hydroxide is washed with pure water until the supernatant has a conductivity of 0.9 mS / m or less.
  • Amorphous peroxidation in which metals and inorganic substances combined with silica are modified by mixing the washed hydroxide with hydrogen peroxide solution with a concentration of 35%, reacting for several hours and performing ultrafiltration. A solution in which fine particles of titanium are dispersed is obtained.
  • the concentration of titanium peroxide in the aqueous dispersion obtained by the above-described production method is 0.05 to 15 wt% is preferable, and 0.1 to 5 wt% is more preferable.
  • the substrate surface or substrate surface When titanium oxide and / or silicon oxide (including a compound of titanium oxide and / or silicon oxide) is used as a dielectric or semiconductor interposed between substances that charge the layer, titanium oxide and / or silicon oxide (oxidized) When one or more kinds of dielectrics and semiconductors excluding (including titanium and / or silicon oxide compounds) are combined, the surface of the substrate is charged with a positive charge, a negative charge and an amphoteric charge.
  • titanium oxide In order to form a film according to this embodiment on the surface of the substrate, in the same manner as the metal-doped titanium oxide, titanium oxide and / or silicon oxide (including a titanium oxide and / or silicon oxide compound), titanium oxide, in addition, a dispersion liquid in which a dielectric and a semiconductor excluding silicon oxide (including titanium oxide and / or silicon oxide compounds) are combined can be used. The method for producing this dispersion is the same as the method shown in FIGS. Next, a method for forming a particulate laminate for charging the substrate surface on the substrate surface or the substrate surface layer will be described in more detail.
  • FIG. 1 (1) shows a method for forming a charge on a surface of a substrate .
  • FIG. 1 (2) and FIG. 1 (3) show a substance having a positive charge and / or a substance having a negative charge.
  • a particulate laminated film composed of particles in which titanium oxide and / or silicon oxide as a dielectric or semiconductor is combined is formed on the substrate surface.
  • the layer thickness of these particulate laminates is not particularly limited, but is preferably in the range of 10 nm to 1 ⁇ m, and more preferably in the range of 10 nm to 100 nm.
  • the above-mentioned particulate laminate can be formed by, for example, sputtering, thermal spraying, ion plating (cathode arc discharge type), CVD coating, or electrodeposition coating.
  • the substrate is dipped in a solution / suspension or emulsion containing a positively charged substance and / or a negatively charged substance and titanium oxide and / or silicon oxide as a dielectric or semiconductor.
  • a solution / suspension or emulsion containing a positively charged substance and / or a negatively charged substance and titanium oxide and / or silicon oxide as a dielectric or semiconductor.
  • a spray, roll, brush, sponge, etc. after applying the solution / suspension or emulsion on a substrate with a spray, roll, brush, sponge, etc., and then drying and evaporating the solvent or medium at least once. I can do it.
  • the film mixture shown in FIG. 1 can be formed on the substrate through a step of drying the mixed solution after coating on the substrate.
  • the dispersion of a solid content including a positively charged substance, a negatively charged substance, and titanium oxide and / or silicon oxide as a dielectric or semiconductor in the layer it is preferable that various surfactants or dispersants coexist with a positively charged substance and / or a negatively charged substance.
  • the compounding amount of the surfactant or dispersant is in the range of 0.001 to 1.0% by weight, preferably 0.1 to 1.0% by weight, based on the total amount of the positively charged substance and / or the negatively charged substance. It can be.
  • organosilicon compounds can be used as fine powder / fine particle fixing agent for forming a uniform film.
  • organosilicon compound various silane compounds and various silicone oils, silicone rubbers and silicone resins can be used, but those having an alkyl silicate structure or a polyether structure in the molecule, or having an alkyl silicate structure and a polyether structure. Those having both are preferred.
  • middle layer can be provided between the above-mentioned particulate laminated body and a base
  • the intermediate layer or the coating layer for example, various organic or inorganic substances capable of imparting hydrophilicity or hydrophobicity or water repellency or oil repellency to the substrate can be used.
  • hydrophilic organic materials include polyether; polyvinyl alcohol; polyacrylic acid (including salts such as alkali metal salts and ammonium salts), polymethacrylic acid ( (Including salts such as alkali metal salts and ammonium salts), polyacrylic acid-polymethacrylic acid (including salts such as alkali metal salts and ammonium salts) copolymers; polyacrylamide; polyvinylpyrrolidone; hydrophilic celluloses; polysaccharides And natural hydrophilic polymer compounds such as It is also possible to use a composite material obtained by blending these polymer materials with an inorganic dielectric such as glass fiber, carbon fiber or silica. It is also possible to use a paint as the polymer material.
  • hydrophilic inorganic materials include silane coupling agents, SiO 2, and other silicon compounds.
  • examples of water-repellent inorganic materials include silane-based, siliconate-based, silicone-based and silane composite-based, or fluorine-based water repellent or water absorption prevention. Agents and the like.
  • fluorine-based water repellents are preferable, and examples include fluorine-containing compounds such as perfluoroalkyl group-containing compounds or fluorine-containing compound-containing compositions.
  • the chemical component of the intermediate layer water repellent or water absorption inhibitor reacts with the substrate to form a chemical bond, or It is not always necessary for the chemical components of the intermediate layer and the substrate to be cross-linked.
  • the fluorine-containing compound that can be used as such a fluorine-based water repellent preferably has a molecular weight of 1,000 to 20,000 containing a perfluoroalkyl group in the molecule.
  • Perfluoroalkyl phosphate ester and perfluoroalkyltrimethylammonium salt are preferable.
  • an intermediate layer containing a silane compound under a particulate laminate of the positively charged substance and / or negatively charged substance and titanium oxide and / or silicon oxide as a dielectric or semiconductor is preferably formed in advance on the substrate. Since this intermediate layer contains a large amount of Si—O bonds, the strength of the layer and the adhesion between the positively charged substance and / or the negatively charged substance and titanium oxide and / or silicon oxide as a dielectric or semiconductor are improved. It becomes possible to improve.
  • the intermediate layer also has a function of preventing moisture from entering the substrate.
  • silane compound described above examples include hydrolyzable silanes, hydrolysates thereof, and mixtures thereof. Moreover, you may mix
  • room temperature curable silicone resins such as methyl silicone resin and methyl phenyl silicone resin may be used.
  • the above-mentioned particulate laminate component composed of a positively charged substance and / or a negatively charged substance and titanium oxide and / or silicon oxide as a dielectric or semiconductor includes an intermediate layer and a coating layer of a silane compound or a silicone resin.
  • the mixing ratio (weight ratio) with these silane compounds or silicone resins is preferably in the range of 1: 2 to 1: 0.05, more preferably in the range of 1: 1 to 1: 0.1. .
  • the material of the substrate which is the subject of the present invention is not particularly limited, and various hydrophilic or hydrophobic inorganic substrates and organic substrates, or combinations thereof can be used. .
  • the inorganic substrate examples include substrates made of a material such as transparent or opaque glass such as soda lime glass, metal oxide such as zirconia, ceramics, concrete, mortar, stone, and metal.
  • the organic base examples include a base made of a substance such as an organic resin, wood, paper, and cloth. More specific examples of the organic resin include, for example, polyethylene, polypropylene, polycarbonate, acrylic resin, polyester such as PET, polyamide, polyurethane, ABS resin, polyvinyl chloride, silicone, melamine resin, urea resin, silicone resin, and fluorine resin. , Cellulose, epoxy-modified resin and the like.
  • the shape of the substrate that is the subject of the present invention is not particularly limited, and can be any shape such as a cube, a rectangular parallelepiped, a sphere, a sheet, and a fiber.
  • the substrate may be porous.
  • the surface of the substrate may be made hydrophilic by corona discharge treatment or ultraviolet irradiation treatment.
  • the substrate is preferably used for a construction / civil engineering substrate or a sealing material, a device, a body for conveying an apparatus, a display screen, or the like.
  • the present invention can be used in various fields where various design properties and high waterproof / dye-proof performance are required.
  • It is suitably used for articles used indoors and outdoors, such as ships, and face panels such as various machines, electronic devices, and televisions.
  • the present invention is particularly suitable for building materials, and buildings such as houses, buildings, roads, and tunnels that are built using building materials to which the present invention is applied exhibit a high waterproofing and dyeing effect over time. I can do it.
  • the present invention can also be applied to air purification devices (including air conditioners) and water purification devices (including pitchers, pots, etc.). An effect can be exhibited in preventing or reducing contamination of the surface of a substrate exposed to air or water, such as a light emitting element. Furthermore, it is also effective in preventing carbonized sticking adhesion in pans, pans, cooking utensils and the like.
  • Examples of the present invention will be described below, but the present invention is not limited to these examples.
  • substrates of Examples 1 to 9, Examples 11 to 19, and Examples 20 to 23 were prepared using the dispersions described in Reference Examples 1 to 9 below. Evaluation with Comparative Examples 1, 2, and 3 was performed.
  • Titanium oxide (dielectric: amorphous titanium peroxide), A substance having a positive charge (a composite of conductor: Cu and dielectric: Zr), a composite dispersion of titanium tetrachloride (manufactured by Osaka Titanium Technologies Co., Ltd.) and 97% CuCl 2 .2H 2 O Ammonia water is dropped into a solution in which (cupric chloride) (manufactured by Nippon Kagaku Sangyo Co., Ltd.) and zirconium oxychloride are completely dissolved to adjust the pH to around 7 to precipitate hydroxide.
  • cupric chloride manufactured by Nippon Kagaku Sangyo Co., Ltd.
  • zirconium oxychloride are completely dissolved to adjust the pH to around 7 to precipitate hydroxide.
  • the precipitated hydroxide is washed with pure water until the supernatant has a conductivity of 0.9 mS / m or less. Next, when hydrogen peroxide was mixed with this hydroxide and allowed to react for several hours, an amorphous titanium peroxide solution modified with copper and zirconium was produced.
  • Reference Example 3 Silicon oxide (semiconductor: polysilicate), When a composite dispersion of a positively charged substance (conductor: Cu), methyl silicate 51 (manufactured by Mitsubishi Chemical Corporation), meta-modified alcohol, pure water, and 3% hydrochloric acid is mixed and stirred while heating. A polysilicate is produced. Further, the prepared polysilicate is adjusted to a solid content concentration of 4 wt% with pure water, and Cu powder, 35% hydrogen peroxide water and ammonia water are stirred and mixed to produce a composite dispersion of silicon oxide and copper. It was done.
  • Titanium oxide (dielectric: amorphous titanium peroxide), A substance having a negative charge (composite of conductor: Sn and dielectric: Ce), a composite dispersion of titanium tetrachloride (manufactured by Osaka Titanium Technologies Co., Ltd.) and SnCl 2 .2H 2 O (chloride) Stannous) (made by Kishida Chemical Co., Ltd.) and CeCl 3 ⁇ 7H 2 O (first cerium chloride) (made by Mitsuwa Chemicals Co., Ltd.) were added dropwise with ammonia water to a pH of around 7 To prepare a hydroxide.
  • the precipitated hydroxide is washed with pure water until the supernatant has a conductivity of 0.9 mS / m or less. Next, when hydrogen peroxide was mixed with this hydroxide and allowed to react for several hours, an amorphous titanium peroxide solution modified with tin and cerium was produced.
  • Silicon oxide (semiconductor: polysilicate), A composite dispersion of a negatively charged substance (conductor: K), methyl silicate 51 (manufactured by Mitsubishi Chemical Corporation), meta-modified alcohol, pure water and 3% hydrochloric acid are mixed and stirred while warming. A polysilicate is produced. Further, the prepared polysilicate was adjusted to a solid content concentration of 4 wt% with pure water and mixed with KOH (potassium hydroxide) to prepare a composite dispersion of silicon oxide and potassium.
  • Reference Example 7 A composite dispersion obtained by mixing the dispersion of Reference Example 1 and the dispersion of Reference Example 4 at a volume ratio of 1: 1. Dispersion of Reference Example 1 (amorphous titanium peroxide doped with copper Solution) and the dispersion liquid of Reference Example 4 (amorphous titanium peroxide solution modified with cerium) were mixed at a volume ratio of 1: 1.
  • Reference Example 8 A composite dispersion in which the dispersion of Reference Example 2 and the dispersion of Reference Example 5 were mixed at a volume ratio of 1: 1. Dispersion of Reference Example 2 (amorphous type liquid modified with copper and zirconium) Titanium oxide solution) and the dispersion liquid of Reference Example 5 (amorphous titanium peroxide solution modified with tin and cerium) were mixed at a volume ratio of 1: 1 to prepare.
  • Reference Example 9 A composite dispersion obtained by mixing the dispersion of Reference Example 3 and the dispersion of Reference Example 5 at a volume ratio of 1: 1. Dispersion of Reference Example 3 (composite dispersion of silicon oxide and copper) And a dispersion of Reference Example 5 (amorphous titanium peroxide solution modified with tin and cerium) were mixed at a volume ratio of 1: 1.
  • Example 1 The dispersion liquid of Reference Example 1 was applied to the surface of a commercially available ceramic tile (100 mm ⁇ 100 mm) substrate with a spray gun at a rate of 10 g / m 2 (wet state) and heated at 200 ° C. for 10 minutes to give Example 1. .
  • Comparative Example 1 was a non-film-formed substrate that was not newly formed on the surface of a commercially available ceramic tile (100 mm ⁇ 100 mm) substrate.
  • Evaluation 1 0.007 g / 100 cm 2 of a solution obtained by diluting a commercial red ink (manufactured by Pilot Ink Co., Ltd.) containing negative dye Dye Inco red was applied to the tile surfaces of Examples 1 to 9 and Comparative Example 1, and dried at room temperature. Thus, an evaluation substrate was produced. Further, in the same procedure, a methylene blue reagent solution, which is a positively charged pigment, was applied to the tile surfaces of Examples 1 to 9 and Comparative Example 1 to prepare an evaluation substrate.
  • Each of the evaluation substrates prepared using these negatively charged dyes and positively charged pigments was irradiated with a 15 W black light fluorescent lamp (manufactured by Toshiba Corporation) from a position where the ultraviolet ray amount was 1300 ⁇ w / cm 2 , and each charge surface was decolored.
  • the rate was evaluated over time with a chromameter CR-200 (manufactured by Konica Minolta Co., Ltd.), and each surface charge state was evaluated from the decoloring rate of the evaluation substrate of each example.
  • the unit of time for evaluation over time is days.
  • the erasing rate of each evaluation substrate according to Examples 1 to 9 and Comparative Example 1 over time is shown in Table 1 for red ink and Table 2 for methylene blue reagent.
  • Examples 1 to 3 having positive charge surface characteristics have a high decoloration rate due to electrostatic repulsion in the elapsed time (5.8 days). On the contrary, the decolorization rate is low in Examples 4 to 6 having negative charge surface characteristics. It can be seen that Examples 7 to 9, which have a decolorization rate approximately halfway between the negatively charged surface and the positively charged surface, have amphoteric charge surface characteristics.
  • the non-formed film of Comparative Example 1 shows negative charge characteristics due to the surface glaze of the tile.
  • Examples 11 to 19 Apply the dispersions of Reference Example 1 to Reference Example 9 at a rate of 10 g / m 2 (wet state) on a normal float glass (100 mm ⁇ 100 mm thickness 3 mm) substrate surface with a spray gun, respectively, at 200 ° C. for 10 minutes. Heated to Examples 11-19.
  • Comparative Example 2 A non-formed glass substrate which was not newly formed on the ordinary float glass substrate used in Examples 11 to 19 was defined as Comparative Example 2.
  • Table 3 shows the following results.
  • Kanto Loam powder was used, the glosses before and after evaluation of Examples 11 to 13 which are positive charge surface characteristic film-forming substrates and Examples 17 to 19 which are amphoteric charge surface characteristic film formations
  • the rate change is low, indicating that a positive or amphoteric charge surface has an antifouling function for Kanto loam powder.
  • the antifouling function when using Caribbean desert dust powder is the same.
  • the negative charge surface characteristic film-forming substrate of Examples 14 to 16 had a low change in gloss rate before and after the evaluation. It shows that the surface has an antifouling function.
  • the non-film-formed blue float glass surface of Comparative Example 2 shows the gloss rate values due to the three types of powder adhesion.
  • Example 20 The dispersion liquid of Reference Example 1 was applied to a normal soda lime float glass (100 mm ⁇ 100 mm thickness 3 mm) substrate surface by a sponge squeegee method at a rate of 10 g / m 2 and heated at 300 ° C. for 10 minutes. It was.
  • Example 21 Example 21 was produced by the same production method as Example 20 using the dispersion liquid of Reference Example 4.
  • Example 22 Using the dispersion liquid of Reference Example 5, Example 22 was produced by the same production method as Example 20.
  • Example 23 Example 23 was produced by the same production method as Example 20 using the dispersion liquid of Reference Example 7. Comparative Example 3 Comparative Example 3 was an ordinary soda lime float glass (100 mm ⁇ 100 mm thickness 3 mm) substrate with no film formation.
  • Evaluation 3 On the upper surfaces of the evaluation substrates of Examples 20 to 23 and the substrate of Comparative Example 3, a liquid obtained by stirring chicken eggs and a commercially available olive oil liquid were applied to a width of about 20 mm and a length of about 60 mm, and then at 300 ° C. for 30 minutes. Each carbonized polymer is fixed by heating to make each evaluation board, and the ease of removal of these carbides by electrostatic repulsion is a method of absorbing a commercially available tissue paper and rubbing the surface of each evaluation board, and the softness of the kitchen sponge. Evaluation was performed by a method of wetting the side and rubbing the surface of each evaluation substrate. Further, the state of the surface film formed on the substrate of each example was visually evaluated for the presence or absence of scratches on the surface film after the carbonized polymer removal operation. The results are shown in Table 4 below.
  • Table 4 shows the removal performance of the adhered contaminants due to electrostatic repulsion when the substrate is in an environment or usage conditions where the substrate is heated. From Table 4, it can be seen that the evaluation substrate on which the negative charge film was formed before heating according to Example 21 and Example 22 had no adsorption of carbonized contaminants and was excellent in removal performance. On the other hand, it is shown that the carbonized contaminant adhered cannot be removed with the evaluation substrate on which the positively charged film is formed before heating according to Example 20 and the non-formed substrate of Comparative Example 3. Further, the evaluation substrate on which the amphoteric charge film according to Example 23 is formed shows the removal performance of carbonized contaminants almost in the middle between Example 20 and Example 21. In addition, the state of the surface film of the substrate in each example indicates that there is no scratch even after the removal of the carbonized polymer, and that it is a hard film that can withstand such an environment and operation.
  • the application of antifouling technology by surface charge formation is based on the substance considering the antifouling object and the use environment or use condition of the film-forming substrate. It can be seen that the type of charge applied to the surface needs to be designed. Further, it is shown that not only a stable surface charge can be formed by using titanium oxide or silicon oxide as a dielectric and a semiconductor, but also a hard film can be formed.

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Abstract

La présente invention est caractérisée en ce que: un matériau stratifié particulaire est formé sur une surface de substrat ou dans une couche de surface de substrat pour charger positivement et/ou négativement la surface de substrat ou la couche de surface de substrat, afin de faire en sorte qu'une substance contaminante provenant de l'extérieur soit électrostatiquement repoussée ou adsorbée; et de l'oxyde de titane et/ou de l'oxyde de silicium (y compris un composé d'oxyde de titane et/ou d'oxyde de silicium) est interposé en tant que matériau diélectrique ou en tant que matériau semi-conducteur dans une substance dotée de charges positives et/ou une substance dotée de charges négatives, afin de former de manière efficiente et stable des charges dans le matériau stratifié particulaire sans que les charges soient réparties irrégulièrement.
PCT/JP2016/086757 2015-12-28 2016-12-09 Matériau stratifié particulaire pour former des charges sur une surface de substrat et liquide de mise en forme de film pour former des charges sur une surface de substrat WO2017115637A1 (fr)

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JP2019099693A (ja) * 2017-12-04 2019-06-24 星和電機株式会社 基体保護液、基体保護方法、および基体

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003160745A (ja) * 2001-08-21 2003-06-06 Sustainable Titania Technology Inc 導電性と光触媒性能を持つ被膜形成用水液、その製造方法及び該被膜を備える構造体
WO2003072661A1 (fr) * 2002-02-27 2003-09-04 Sustainable Titania Technology Incorporated Solution pour former un film photocatalyseur ultra-hydrophile, structure comportant ce film et procede de production de celui-ci
JP2005170057A (ja) * 2005-01-14 2005-06-30 Sumitomo Osaka Cement Co Ltd 防汚性及び易洗浄性の高い金属又は樹脂成形製品
JP2005319601A (ja) * 2004-05-06 2005-11-17 Sustainable Titania Technology Inc 撥水性基体の親水化防汚方法及びその人工物における使用
WO2008013148A1 (fr) * 2006-07-25 2008-01-31 Sustainable Titania Technology Inc. Procédé de protection d'un corps de base
JP2008184025A (ja) * 2007-01-30 2008-08-14 Toyota Motor Corp 自動車用ホイールの汚染防止方法および自動車用ホイール
JP2009096661A (ja) * 2007-10-16 2009-05-07 Jgc Catalysts & Chemicals Ltd 導電性シリカ粒子、その製造方法およびその用途
JP2009209319A (ja) * 2008-03-06 2009-09-17 Sustainable Titania Technology Inc 光透過性基体の透過可視光量増加剤及びそれを用いた高光透過性基体の製造方法
WO2009125847A1 (fr) * 2008-04-11 2009-10-15 株式会社エルブ Matériau minéral portant un métal précieux, procédé pour sa production, additif alimentaire et procédé de production d'aliment
JP2013060012A (ja) * 2012-10-15 2013-04-04 Sharp Corp 低反射性基体の製造方法及び基体の反射率低減方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003160745A (ja) * 2001-08-21 2003-06-06 Sustainable Titania Technology Inc 導電性と光触媒性能を持つ被膜形成用水液、その製造方法及び該被膜を備える構造体
WO2003072661A1 (fr) * 2002-02-27 2003-09-04 Sustainable Titania Technology Incorporated Solution pour former un film photocatalyseur ultra-hydrophile, structure comportant ce film et procede de production de celui-ci
JP2005319601A (ja) * 2004-05-06 2005-11-17 Sustainable Titania Technology Inc 撥水性基体の親水化防汚方法及びその人工物における使用
JP2005170057A (ja) * 2005-01-14 2005-06-30 Sumitomo Osaka Cement Co Ltd 防汚性及び易洗浄性の高い金属又は樹脂成形製品
WO2008013148A1 (fr) * 2006-07-25 2008-01-31 Sustainable Titania Technology Inc. Procédé de protection d'un corps de base
JP2008184025A (ja) * 2007-01-30 2008-08-14 Toyota Motor Corp 自動車用ホイールの汚染防止方法および自動車用ホイール
JP2009096661A (ja) * 2007-10-16 2009-05-07 Jgc Catalysts & Chemicals Ltd 導電性シリカ粒子、その製造方法およびその用途
JP2009209319A (ja) * 2008-03-06 2009-09-17 Sustainable Titania Technology Inc 光透過性基体の透過可視光量増加剤及びそれを用いた高光透過性基体の製造方法
WO2009125847A1 (fr) * 2008-04-11 2009-10-15 株式会社エルブ Matériau minéral portant un métal précieux, procédé pour sa production, additif alimentaire et procédé de production d'aliment
JP2013060012A (ja) * 2012-10-15 2013-04-04 Sharp Corp 低反射性基体の製造方法及び基体の反射率低減方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019099693A (ja) * 2017-12-04 2019-06-24 星和電機株式会社 基体保護液、基体保護方法、および基体
JP7101469B2 (ja) 2017-12-04 2022-07-15 星和電機株式会社 基体保護液、基体保護方法、および基体

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