WO2017115637A1

WO2017115637A1 - Particulate laminated material for forming charges on substrate surface and film shaping liquid for forming charges on substrate surface

Info

Publication number: WO2017115637A1
Application number: PCT/JP2016/086757
Authority: WO
Inventors: 緒方　四郎; 義光松井
Original assignee: サスティナブル・テクノロジー株式会社
Priority date: 2015-12-28
Filing date: 2016-12-09
Publication date: 2017-07-06
Also published as: TW201736273A; JPWO2017115637A1

Abstract

The present invention is characterized in that: a particulate laminated material is formed on a substrate surface or in a substrate surface layer to positively and/or negatively charge the substrate surface or the substrate surface layer, in order to cause a contaminating substance from the outside to be electrostatically repelled or adsorbed; and titanium oxide and/or silicon oxide (including a compound of titanium oxide and/or silicon oxide) is interposed as a dielectric material or a semiconductor material in a substance having positive charges and/or a substance having negative charges, in order to efficiently and stably form charges in the particulate laminated material without the charges being distributed unevenly.

Description

Substrate surface charge forming particulate laminate and substrate surface charge forming film forming liquid

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.

Various pollutants are floating in the atmosphere, and these pollutants affect the function and environment of the substrate surface and the vicinity of the substrate surface. As a typical technique for protecting the substrate from contaminants that affect the substrate from the outside in this way, a photocatalytic technique can be cited.

On the other hand, the applicant, in 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. In addition, in the patent document 2, 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. In this technique, 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.

In 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.

On the other hand, in order to effectively exert the function of electrostatically repelling or adsorbing contaminants from outside by charging the substrate surface or the substrate surface layer, a positively charged substance or a negatively charged substance is simply disposed. In addition, it is required to form the substrate surface or the substrate surface layer efficiently and stably without uneven distribution of charges.

Here, in order to avoid uneven distribution of charges formed on the substrate surface or substrate surface layer, a dielectric or semiconductor for stably forming charges is appropriately interposed between the conductive materials. Is one of the solutions. In addition, as 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. And 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.

International Publication WO2005 / 108056 International Publication No. WO2008 / 013148

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.

In another aspect of the particulate laminate, 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.

In addition, 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).

Furthermore, 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 In the case of using 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. When using a compound of silicon), 1: 0.03 to 1: 2.7, and when using titanium oxide and silicon oxide (including these compounds), 1: 0.01 to 1: 0. A ratio of 3 is preferable.

In the above-described particulate laminate for forming a substrate surface charge or a film forming solution for forming a substrate surface charge,
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.

According to the present invention, 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. 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. .
In the present invention, 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.

Further, according to the present invention, not only can 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 | substrate is metal, it becomes possible to reduce generation | occurrence | production of rust from the same process.
Furthermore, according to the present invention, it is possible to remove carbonized contaminants fixed to the substrate surface by heating by positively or positively and negatively charging the substrate surface.

It is a figure which shows typically the example of the film-forming cross section of the particulate-form laminated body for base surface charge formation by this invention. It is a figure which shows typically the cross section of the aspect which formed the particulate-form laminated body for base-material surface charge formation by this invention on the base-material surface layer. It is a figure which shows an example of the preparation methods of the dispersion liquid of a metal dope titanium oxide. It is a figure which shows an example of the preparation methods of the dispersion liquid of a metal dope silicon oxide. It is the figure which showed typically the principle which provides an electric charge to a base-material surface or a base-material surface layer. It is the figure which showed typically the principle which provides an electric charge to a base-material surface or a base-material surface layer.

Embodiments according to the present invention will be described below with reference to the drawings.
Outline 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. 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.

Furthermore, 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.

In the prior art disclosed by the applicant, as a substance for charging the substrate surface or the substrate surface layer, if positively charged, a cation, a positively charged conductor, a positively charged conductor and a dielectric A composite of a positively charged conductor and a semiconductor; if negatively charged, a negative ion, a negatively charged conductor, a negatively charged conductor and a dielectric, It is disclosed to use a composite of a negatively charged conductor and a semiconductor, or a substance having a photocatalytic function (Patent Document 1, Patent Document 2, and the like described above). Applicants have further found that when two or more dielectrics or semiconductors are combined, they are positively or negatively charged depending on the type of dielectric or semiconductor used.

On the other hand, when titanium oxide and / or silicon oxide (including a titanium oxide and / or silicon oxide compound) is used as a dielectric or semiconductor interposed between substances for charging the substrate surface or the substrate surface layer, the above-mentioned When a dielectric or semiconductor excluding titanium oxide and / or silicon oxide (including titanium oxide and / or silicon oxide compound) is used in place of the positively charged substance and / or the negatively charged substance, these The inventor of the present application has newly found that 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.

Therefore, hereinafter, in the present specification, 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.

In order for the film or layer formed on the substrate surface or the substrate surface layer to more effectively exhibit the function of electrostatically repelling or adsorbing contaminants from the outside, the particulate laminate is applied to the substrate surface or surface. In the particulate laminate, it is desirable that the dried and solidified particles are regularly taken in and a uniform and uniform charge is formed. For example, preferred examples of such a particulate laminate include the following (a) to (c).

(A) A substrate surface film or surface layer in which 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 each particle-bonded by single particles (b) A) substrate surface film or surface layer in which a positively charged substance and / or a negatively charged substance is particle-bonded by colloidal particles encapsulated in titanium oxide or silicon oxide; and (c) a positively charged substance and / or Substrate surface film or surface layer in which substance having negative charge and titanium oxide and / or silicon oxide are particle-bonded as perovskite type or perovskite type pseudo crystal particles as a complex at molecular level 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 μm, 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.

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). Is a diagram schematically showing the principle of imparting a positive charge, a negative charge, a positive charge, and a negative charge to a substrate surface or a substrate surface layer. In FIG. 5 (1), 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. Then, in the state where the particle BB of titanium oxide or silicon oxide (including these compounds) as a dielectric or semiconductor is adjacent to the particle AN of the conductor having a negative charge, in FIG. In the state where the conductive particle AN and the conductive particle AP having a positive charge are alternately adjacent to the particle BB of titanium oxide or silicon oxide (including these compounds) as a dielectric or semiconductor, Alternatively, a film or layer is formed on the substrate surface layer. A conductor has a high concentration of free electrons that can move freely inside, and positive or negative charges are formed by the concentration of holes or negative electrons on the surface of the film forming or forming layer by excitation. Will have a state. 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.

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. In dielectrics or semiconductors excluding titanium oxide and silicon oxide (including these compounds), 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. . In FIG. 6 (1), a uniform positive charge is generated. In FIG. 6 (2), a uniform negative charge is generated. In FIG. 6 (3), a uniform positive charge and a negative charge are generated. Each of the embodiments is shown.

Substrate Surface Film Formation Method Next, the charge surface formation method and film formation method for each substrate surface (a) to (c) described in paragraph 0025 will be described in the following (A) to (C). .
(A) Film Formation Method Using Single Particles FIG. 1 (1) is a diagram schematically showing a film formation cross section on the substrate S1 according to the embodiment (a). In the figure, colored circles are particles of a substance having a positive charge and / or a substance having a negative charge, and non-colored circles are titanium oxide and / or silicon oxide (a compound of these compounds as a dielectric or semiconductor). Particle). That is, in the embodiment (a), 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.

As described with reference to FIGS. 5 and 6, theoretically, 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 (these compounds). 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 | coats the film forming liquid to a base | substrate, and forms a film can be used. In addition, a film-forming method can be used in which the above-described film-forming solution is used and a fine powder or ionic fine particles contained in the film-forming solution is formed on a substrate by a dry method such as ion plating or sputtering. . A more detailed description of the substrate film forming method and a detailed manufacturing method of the film forming solution will be given later.

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. When the film is formed on the substrate surface, the ratio of these particles is theoretically preferably 1: 1 as described above, but the stability of the film-forming solution is stable. In consideration of the property, when the ratio of titanium oxide and / or silicon oxide (including these compounds) to a positively charged substance and / or a negatively charged substance is expressed as a solid molar ratio, When titanium oxide (including a titanium oxide compound) is 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.

(B) Method of forming a film with colloidal particles containing a positively charged substance and / or a negatively charged substance 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. In the figure, a colored circle is a substance having a positive charge and / or a substance having a negative charge, and 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. In forming a film according to this form, 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. Incorporating titanium oxide and / or silicon oxide (including these compounds) as a dielectric or semiconductor in an ionic complex solution prepared by reacting a substance and / or a negatively charged substance with an alkaline agent or an acidic agent. When the film forming solution is used and is fixed to the substrate surface by film formation by a wet method or a dry method, 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. In terms of molar ratio, when using titanium oxide (including titanium oxide compound), preferably 1: 0.01 to 1: 0.3, when using 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.

Note that 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.

(C) A film in which a substance having a positive charge and / or a substance having a negative charge and titanium oxide and / or silicon oxide are particle-bonded as a perovskite-type or perovskite-type pseudo-crystal particle as a molecular-level complex Film Forming Method FIG. 1 (3) is a view schematically showing a cross section of the film formed on the substrate S1 according to the embodiment (c). In the figure, a colored circle is a substance having a positive charge and / or a substance having a negative charge, and 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.

A substance having a positive charge in a state in which a Ti molecule and an O ₂ molecule or an O ₃ molecule, or a Si molecule and an O ₂ molecule or an O ₃ molecule forming titanium oxide or / and silicon oxide are dissociated in a solution, and / or A compound having a negative charge is reacted in a molecular ion state and solidified by an acid agent / alkaline agent or electromagnetic wave irradiation to form a composite crystal. 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. When titanium oxide (including a titanium oxide compound) is used, preferably 1: 0.01 to 1: 0.3, and when using silicon oxide (including a silicon oxide compound), preferably 1 : 0.03 to 1: 2.7, and when titanium oxide and silicon oxide (including these compounds) are used, 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. As 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.
As described above, referring to FIG. 1, 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. 1 is used, 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.

Formation of a particulate laminate on a surface layer of a substrate On the other hand, 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. In addition, an example of an aspect in which, by interposing in a substance having a negative charge, an electric charge can be efficiently and stably formed in the substrate surface layer without being unevenly distributed. (1), (2), and (3) of FIG. 2 are drawings schematically showing a cross section of the substrate according to these embodiments. In the figure, colored circles are particles of a substance having a positive charge and / or a substance having a negative charge, and non-colored circles are titanium oxide and / or silicon oxide (a compound of these compounds as a dielectric or semiconductor). Particle).

In the embodiment shown in FIG. 2 (1), 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). As 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. There is a method of molding a layer made of particles of a substance having a charge and / or a substance having a negative charge on the surface of the substrate S2.

In the embodiment shown in FIG. 2 (2), particles of titanium oxide and / or silicon oxide (including these compounds) 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.

In the embodiment shown in FIG. 2 (3), 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. Alternatively, 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. By molding, a surface layer as shown can be produced.

In the embodiment shown in FIGS. 2 (1) and 2 (2), 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. By bonding particles of a substance having a positive charge and / or a substance having a negative charge to the surface side of the substrate S2, or on the surface side of the substrate S3 of a substance having a positive charge and / or a substance having a negative charge By bonding particles of titanium oxide and / or silicon oxide (including these compounds), a uniform and uniform charge can be similarly formed on the substrate surface.
2 (1), (2), and (3) show an example in which the layer of particles formed in the surface layer of the substrate is one or two layers, the function according to the present invention is exhibited. In order to achieve this, it is desirable that the particle layer formed in the surface layer of the substrate is formed of a plurality of layers.

Next, a positively charged substance and / or a negatively charged substance constituting the particulate laminated film for surface charge formation according to the present invention, titanium oxide and / or silicon oxide as a dielectric or semiconductor (these materials) What kind of substance is preferable as the compound (including the compound) will be described in detail.

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. Including 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.
(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 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. Note that, since 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, here, For convenience, 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. 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. As the metal element to be combined, silver and copper are particularly preferable.
In addition, 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.

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.

Here, the relationship between the photocatalytic function of titanium oxide and the metal-doped titanium oxide will be described. This is because if the 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. Among titanium oxides, amorphous type titanium oxide and anatase type crystal precursor titanium oxide do not have a photocatalytic function. On the other hand, anatase-type, brookite-type and rutile-type titanium oxides have a photocatalytic function. However, 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. In addition, 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 However, when a positively charged substance coexists with a certain concentration or more, 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. However, when 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.

Next, a method for producing the above metal-doped titanium oxide will be described. 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.

Hereinafter, an example of a method for producing a dispersion of metal-doped titanium oxide will be described with reference to FIG. First, an inorganic compound or a metal compound (compound having crystal water) exemplified on the left side of FIG. Mix in proportions.

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. To this, 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. Mixing the washed hydroxide with hydrogen peroxide solution with a concentration of 35%, reacting for several hours and performing ultrafiltration, the composite inorganic substance and the modified amorphous titanium peroxide modified with metal A solution in which fine particles are dispersed is obtained. In addition, after mixing and reacting hydrogen peroxide with the above-mentioned hydroxide, heating and ultrafiltration, the fine structure of anatase-type titanium peroxide modified with complex inorganic substances and metals is achieved. A solution in which the particles are dispersed is obtained.

The concentration of titanium peroxide in the aqueous dispersion obtained by the above-described production method (total amount including metals and inorganic substances such as coexisting gold, silver, platinum, copper, manganese, nickel, cobalt, iron, and zinc) 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. Li compound: LiOH, Li ₂ CO ₃ , LiCl 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. In addition to the method for producing the metal-doped titanium oxide dispersion described with reference, there are many methods for combining inorganic substances and metals with titanium oxide. For example, titanium oxide particles and inorganic substances to be combined Metal particles may be prepared separately and mixed together. In the present invention, in order to produce metal-doped titanium oxide, in addition to the above production method, there are various methods of producing fine particles of titanium oxide and dispersions thereof, any of which may be used.

As for 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. Examples of 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.

Many types of products are commercially available as materials containing silicon oxide. For example, the following can be cited as 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

Using the above-mentioned material containing silicon oxide, a film-forming solution for forming a surface charge film in which a metal is combined can be produced. Hereinafter, with reference to FIG. 4, 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 (compound having crystal water) 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 same applies to the combination of silicon oxide with an alkali metal, an alkaline earth metal, or the like.

In addition, as shown in FIG. 4, 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.

About metal doped titanium oxide and silicon oxide Finally, the preparation method of the solution which made the metal complex with respect to titanium oxide and silicon oxide is demonstrated. First, 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 plurality of kinds of metal compounds can be mixed. In addition, 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 (total amount including metals and inorganic substances such as coexisting gold, silver, platinum, copper, manganese, nickel, cobalt, iron, and zinc) is 0.05 to 15 wt% is preferable, and 0.1 to 5 wt% is more preferable.

As described above for the combination of titanium oxide and / or silicon oxide (including these compounds) as a dielectric or semiconductor and dielectric and / or semiconductor excluding titanium oxide and silicon oxide , 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. 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 . A particle having a positive charge and / or a substance having a negative charge, and particles of titanium oxide and / or silicon oxide as a dielectric or semiconductor However, FIG. 1 (2) and FIG. 1 (3) show a substance having a positive charge and / or a substance having a negative charge. In addition, 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 μm, 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. In addition, 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. Or 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.

Specifically, for example, a metal-doped amorphous titanium oxide dispersion, a metal-doped silicon oxide dispersion, and a dispersion thereof, in which metals such as gold, silver, platinum, copper, manganese, nickel, cobalt, and iron are combined. 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.

In the above-mentioned particulate laminate, in order to uniformly promote 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.

As the surfactant or dispersant described above, various organosilicon compounds can be used as fine powder / fine particle fixing agent for forming a uniform film. As the 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.

About an intermediate | middle layer and a coating layer , an intermediate | middle layer can be provided between the above-mentioned particulate laminated body and a base | substrate, or a coating layer can be provided in the surface of an above-mentioned particulate laminated body. As 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.

Among organic or inorganic materials that can be used for the intermediate layer and the coating layer, 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.

Among organic or inorganic substances that can be used for the intermediate layer and the coating layer, examples of hydrophilic inorganic materials include silane coupling agents, SiO _{2, and} other silicon compounds.

Among organic or inorganic substances that can be used for the intermediate layer and the coating layer, 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. In particular, fluorine-based water repellents are preferable, and examples include fluorine-containing compounds such as perfluoroalkyl group-containing compounds or fluorine-containing compound-containing compositions. In addition, when the intermediate layer contains a fluorine-containing compound having high adsorptivity to the substrate surface, 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.

In the case of a water-absorbing substrate, 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. In addition, the intermediate layer also has a function of preventing moisture from entering the substrate.

Examples of the silane compound described above include hydrolyzable silanes, hydrolysates thereof, and mixtures thereof. Moreover, you may mix | blend various organopolysiloxane with these silane compounds.

Also, as the constituent material of the intermediate layer, 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. Is included, 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. .

Regarding the substrate, 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. .

Examples of the inorganic substrate 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. Examples of the organic base 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.

INDUSTRIAL APPLICABILITY The present invention can be used in various fields where various design properties and high waterproof / dye-proof performance are required. Glass, metal, ceramics, concrete, wood, stone, polymer resin cover, polymer resin sheet Building materials, air-conditioning outdoor units, kitchen equipment top plates and cabinets, sanitary equipment, lighting equipment, automobiles, bicycles, motorcycles, aircraft, trains, etc., consisting of textiles (clothing, curtains, etc.), sealing materials, etc. 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.
In Examples of the present invention, 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.

Reference Example 1 Titanium oxide (dielectric: amorphous titanium peroxide),
Composite dispersion of positively charged substance (conductor: Cu) and titanium tetrachloride (Osaka Titanium Technologies Co., Ltd.) dilution and 97% CuCl ₂ · 2H ₂ O (cupric chloride) (Nippon Chemical Industry) Aqueous ammonia was added dropwise to a solution in which the product was completely dissolved 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 type titanium peroxide solution modified with copper was obtained.

Reference Example 2 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. 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.

Reference Example 4 Titanium oxide (dielectric: amorphous titanium peroxide),
Complex dispersion of dielectrics other than titanium oxide (Ce: dielectric) (film formation by this combination exhibits negative charge)
Of titanium tetrachloride (manufactured by OSAKA Titanium Technologies) dilutions CeCl 3 · _7H 2 O _(chloride cerous) (Mitsuwa Chemicals Co., Ltd.) and completely dissolved solution was dropped aqueous ammonia Adjust to pH around 7 to precipitate the hydroxide. The precipitated hydroxide is washed with pure water until the supernatant has a conductivity of 0.9 mS / m or less. Next, when this hydrogen peroxide was mixed with hydrogen peroxide and allowed to react for several hours, an amorphous titanium peroxide solution modified with cerium was produced.

Reference Example 5 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.

Reference Example 6 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. .

Examples 2 to 9
Substrates produced using the dispersions of Reference Example 2 to Reference Example 9 in the same process as Example 1 were designated as Examples 2 to 9, respectively.
Comparative 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 μw / 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.

<Result 1>
In Table 1 (negative dye: indigo red), the decoloration rate is high due to electrostatic repulsion in the elapsed time (5.8 days) in Examples 4 to 6 having negative charge surface characteristics. On the contrary, the decolorization rate is low in Examples 1 to 3 having positive 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. In addition, the non-formed film of Comparative Example 1 shows negative charge characteristics due to surface glaze.

In Table 2 (positive pigment: methylene blue), 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.

Evaluation 2
The dust adsorption and antifouling evaluation of Examples 11 to 19 and Comparative Example 2 was performed using three types of Kanto loam layer dust, Middle East Dubai desert dust, and Kyushu volcanic ash. On the surface of the substrates of Examples 11 to 19 and Comparative Example 2, Kanto loam layer dust, Middle East Dubai desert dust, and Kyushu volcanic ash were dropped one teaspoon each to make an evaluation substrate, and these evaluation substrates were set up lightly twice. The gloss was measured using a gloss meter IG-331 (manufactured by Horiba, Ltd.) by hitting the top of the table. And the result of evaluating the antifouling performance by the dust adsorption prevention by the diffuse reflectance of light due to the adhesion residue by calculating the difference between the gloss rate of the substrate of each Example and Comparative Example measured before dropping dust and volcanic ash (Measurement average of three locations) is shown in Table 3 below (numerical value: gloss before powder evaluation-gloss after powder evaluation).

<Result 2>
Table 3 shows the following results.
When 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 Dubai desert dust powder is the same.

When the Kyushu volcanic ash powder was used, 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. On the other hand, 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
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.

<Result 3>
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.

From these, 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.

Claims

In the surface of the substrate or the surface layer of the substrate, 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). A particulate laminate for forming a surface charge on a substrate, characterized in that
The particulate laminate includes particles made of a positively charged substance and / or a negatively charged substance, and titanium oxide and / or silicon oxide (a compound of titanium oxide and / or silicon oxide as a dielectric or semiconductor). 2. The particulate laminate for forming a substrate surface charge according to claim 1, which is formed by adjoining particles composed of
In the particulate laminate, a substance having a positive charge and / or a substance having a negative charge is included in titanium oxide and / or silicon oxide (including a compound of titanium oxide and / or silicon oxide) as a dielectric or semiconductor. The charged particle-like laminate for forming a substrate surface according to claim 1, wherein the colloidal particles are bonded together.
In the particulate laminate, a substance having a positive charge and / or a substance having a negative charge and titanium oxide and / or silicon oxide (including a compound of titanium oxide and / or silicon oxide) as a dielectric or semiconductor are molecules. The particulate laminate for forming a substrate surface charge according to claim 1, which is bonded as particles of a level composite.
Substrate surface charge formation comprising a positively charged substance and / or a negatively charged substance and titanium oxide and / or silicon oxide (including titanium oxide and / or silicon oxide compounds) as a dielectric or semiconductor Film-forming fluid.
The ratio of titanium oxide and / or silicon oxide (including a compound of titanium oxide and / or silicon oxide) as the dielectric or semiconductor to the substance having a positive charge and / or the substance having a negative charge is a solid ratio. When using titanium oxide (including a titanium oxide compound), the molar ratio of the mold is 1: 0.01 to 1: 0.3, and 1: 0 when using silicon oxide (including a silicon oxide compound). The substrate according to claim 5, which has a ratio of 0.03 to 1: 2.7, and a ratio of 1: 0.01 to 1: 0.3 when titanium oxide and silicon oxide (including these compounds) are used. Surface charge forming film forming liquid.
The substance having a positive charge and / or the substance having a negative charge are
(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 Beauty / or a substance having a negative charge, according to claim 1 to the substrate surface charge forming particulate laminate of claim 4.
The substance having a positive charge and / or the substance having a negative charge are
(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 Beauty / or a substance having a negative charge, according to claim 5 or substrate surface charge film-forming solution for according to claim 6.