JP2017196874A - Surface protection structure for substrate and surface protection method for substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide means to protect a substrate surface, especially a highly precise display surface, against scratches, stains or the like, to maintain or improve optical functions of the substrate, and further to maintain or improve operability with the finger.SOLUTION: A surface protection structure of a substrate is a fine uneven structure formed directly on a substrate surface or on a surface layer of the substrate, or is a fine uneven structure formed on a film formed on the substrate surface or on the surface layer of the substrate, in which a height and a pitch of the uneven structure are 50-900 nm.SELECTED DRAWING: Figure 1

Description

  The present invention maintains the antifouling property of the substrate surface by forming a fine structure on the substrate surface or the substrate surface layer, or makes it possible to easily remove the stain even when the stain adheres to it. The present invention also relates to an excellent substrate surface protection technique.

  The inventors of the present application have proposed various methods for protecting (antifouling) the substrate surface. For example, Patent Literature 1, Patent Literature 2, and Patent Literature 3 relate to photocatalytic technology.

  On the other hand, the applicant, in Patent Document 4, 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 surface layer of the substrate. A technique for protecting a substrate surface by electrostatically attracting or repelling is disclosed. In addition, in the patent document 5, the applicant arranges a positively charged substance and a negatively charged substance on the substrate surface or the substrate surface layer, charges the substrate surface positively and negatively, and introduces external contaminants on the substrate surface. A technique for protecting a substrate surface by electrostatically attracting or repelling is disclosed.

  Furthermore, in the patent document 6, the applicant has a substrate provided with a photosemiconductor-containing layer and a positively charged substance or a negatively charged substance-containing layer, or a single layer containing a photosemiconductor / positively charged substance and a negatively charged substance on the surface. Discloses a technique for protecting the substrate surface by irradiating the substrate with light and changing the conductive properties of the substrate surface.

  The technology disclosed in Patent Documents 1 to 6 described above is a general-purpose base material such as a painted surface, a metal surface, stone, concrete, and the like that protects the surface of various devices and structures used indoors and outdoors. It was intended to be applied regardless of the type of substrate, such as a surface, a glass surface, or a polymer resin surface.

  On the other hand, high-definition display screens such as smartphones, tablet terminals, and small electronic devices require optical functions such as anti-scratch and anti-stain properties, anti-glare properties, and anti-reflection properties that suppress reflection of external light. It is done. In addition, since these devices operate the screen with a finger, there is a problem that fingerprints adhere to the screen surface and the visibility of the image is easily impaired. Then, the film which provides the optical function for solving the above problems by sticking a film on a display screen is proposed (for example, patent documents 7 and patent documents 8).

  However, there is a problem in that the manufacturing cost is increased by providing the above-described film on the display screen at the manufacturing stage. In these devices, since the screen is operated with a finger, it is desirable not to impair operability by applying a protective film or hard coat on the display screen.

Japanese Patent Laid-Open No. 9-262481 JP-A-10-235201 JP 11-333303 A International Publication WO2005 / 108056 International Publication No. WO2008 / 013148 International Publication WO2012 / 093632 JP 2009-025734 A JP 2014-235235 A

  The present invention provides means for protecting the surface of a substrate, particularly a high-definition display screen, from scratches and dirt, maintaining or improving the optical function of the substrate, and further maintaining or improving the operability with a finger. With the goal.

  The structure for protecting the surface of the substrate according to the present invention is formed on the surface of the substrate or the surface layer of the substrate, or formed on the surface of the substrate or the surface layer of the substrate. A fine concavo-convex structure formed on a film, wherein the concavo-convex structure has a height and pitch of 50 nm to 900 nm.

Preferred components for forming the concavo-convex structure are particles or crystals of silicon oxide, particles or crystals of titanium oxide, particles or crystals of inorganic compounds (excluding metals) compounds excluding silicon oxide, and metal compounds excluding titanium oxide Particles or crystals of silicon, ions, metal particles or crystals doped silicon particles or crystals, metal particles or crystals doped silicon compound particles or crystals, metal compounds particles or crystals doped Silicon compound particles or crystals, ion-doped silicon particles or crystals, ion-doped silicon compound particles or crystals, inorganic (except metal) particles or crystal-doped silicon particles or Crystalline, inorganic (excluding metals) particles, or silicon compound particles or crystals doped with crystalline substances, inorganic (excluding metals) compound particles Is doped silicon particles or crystals doped with crystals, particles or crystals of inorganic compounds (excluding metals) or silicon compounds doped with crystals, or particles or crystals of metals (except titanium) Particles or crystals of titanium, particles or crystals of titanium compounds doped with metal (except titanium) particles or crystals, particles or crystals of titanium doped with particles or crystals of metal (except titanium) compounds Particles or crystals of titanium compounds doped with particles or crystals of metal (excluding titanium), particles or crystals of titanium doped with ions, particles or crystals of titanium compounds doped with ions, inorganic substances (metals) Particles or crystals of titanium doped with particles or crystals, and titanium compounds doped with inorganic particles (excluding metals) or crystals Particles or crystals of titanium or doped with particles or crystals of inorganic substances (excluding metals), and particles or crystals of titanium compounds doped with particles or crystals of inorganic (except metals) compounds Including at least one of the following.
Moreover, the component which forms the said uneven structure body can contain organic substance further.

  The substrate surface protection method according to the present invention is a substrate surface protection method for directly forming a fine concavo-convex structure having a height and pitch of 50 nm to 900 nm on the surface of the substrate or the surface layer of the substrate, A liquid containing a component that forms a concavo-convex structure is dropped on the surface or surface layer of the substrate, and then the solvent in the liquid is volatilized by heating or drying, or the surface is melted with an acid or alkali solution. The concavo-convex structure is formed on the surface or surface layer by a construction method.

  In another aspect of the substrate surface protection method according to the present invention, there is provided a substrate surface protection method in which a fine concavo-convex structure having a height and pitch of 50 nm to 900 nm is directly formed on the surface of the substrate or the surface layer of the substrate. The concavo-convex structure is formed by ionizing a component forming the concavo-convex structure by a dry method including sputtering / ion plating and spraying the ion onto the surface or surface layer of the substrate, or polishing the substrate surface. Form.

  In still another aspect of the method for protecting a surface of a substrate according to the present invention, a fine concavo-convex structure having a height and a pitch of 50 nm to 900 nm is formed on the surface of the substrate or a film formed on the surface layer of the substrate. A method for protecting a surface of a substrate, wherein a liquid containing a component forming an uneven structure and an organic substance is applied on the surface or surface layer of the substrate to form a film, and then heated at a high temperature or irradiated with ultraviolet rays or plasma. The concavo-convex structure is formed on the film by burning organic matter.

  In the above-described substrate surface protecting method, the component forming the concavo-convex structure preferably includes at least one of the components forming the concavo-convex structure listed above. Moreover, the component which forms the said uneven structure body can contain an organic substance further.

  According to the present invention, the surface of a substrate, particularly a high-definition display screen, is protected from scratches and dirt, and the optical functions of the substrate such as antiglare properties (glossiness), visible light transmission, and reflectance are maintained or improved. In addition, the antifouling property against fingerprint adhesion is excellent, and the operability (slidability) of the surface of the substrate by the finger can be improved.

It is a figure which shows typically the example of the base | substrate cross section in which the structure for the surface protection of the base | substrate by this invention was formed. It is a figure which shows typically the relationship between the structure for surface protection of the base | substrate by this invention, and a contact thing. It is a figure which shows typically the relationship between the height and pitch in the structure for surface protection of the base | substrate by this invention. It is a figure which shows an example of the preparation methods of the dispersion liquid of a metal (inorganic substance) dope titanium oxide. It is a figure which shows an example of the preparation methods of the dispersion liquid of a metal (inorganic substance) dope silicon oxide.

Embodiments according to the present invention will be described below with reference to the drawings.
Outline Protection of the surface of a substrate according to the present invention can be achieved by forming a fine concavo-convex structure directly on the surface of the substrate or the surface layer of the substrate, or by forming a film on the surface of the substrate or the surface layer of the substrate. Is formed in a fine concavo-convex structure.
As a method for forming the fine concavo-convex structure, several methods such as a wet method and a dry method can be selected.

In addition, the component that forms the fine concavo-convex structure includes at least one of the substances listed below, and further includes other components to protect the surface of the substrate. Various functions can be provided.
-Particles or crystals of silicon oxide-Particles or crystals of titanium oxide-Particles or crystals of inorganic compounds (excluding metals) other than silicon oxide-Particles or crystals of metal compounds excluding titanium oxide-Ions-Metals Particles or crystals of silicon doped with particles or crystals-Particles or crystals of silicon compounds doped with metal particles or crystals-Particles or crystals of silicon compounds doped with metal compounds or crystals-Ions Particles or crystals of silicon doped with ions-Particles or crystals of silicon compounds doped with ions-Inorganic particles (excluding metals) or silicon particles or crystals doped with crystals-Inorganic materials (excluding metals) Particles or crystals of silicon compound doped with particles or crystals ・ Inorganic (except metal) compound particles or crystals of silicon doped Particles or crystals of inorganic compounds (excluding metals) compounds or silicon compounds doped with crystals • Particles or crystals of titanium doped with metals (except titanium) or crystals • Metals Particles or crystals of titanium compounds doped with particles or crystals (excluding titanium)-Particles or crystals of titanium doped with particles or crystals of metals (excluding titanium)-Metals (excluding titanium) compounds Particles or crystals of titanium compounds doped with particles or crystals of: ・ Ion-doped titanium particles or crystals ・ Ions-doped titanium compounds of particles or crystals ・ Inorganic (excluding metals) particles or crystals Particles or Crystals of Titanium Doped with Inorganic Particles or Crystals of Titanium Compounds Doped with Inorganic (except Metal) Particles or Crystals Titanium particles or crystals doped with compound particles or crystals) Except for the genus) Titanium compound particles or crystals doped with inorganic (except metal) compound particles or crystals It is a substance mainly for providing various functions for protecting the surface of the substrate. In addition to the above-mentioned substances, to form and maintain the irregular shape at a low temperature, or to process the irregular shape at a low temperature. In addition, a resin component may be included as a component of the concavo-convex structure.

  Hereinafter, the details of the fine concavo-convex structure, its formation method, and its components will be described in order.

<Structure of uneven structure>
The structure for protecting the surface of the substrate according to the present invention is formed on the surface of the substrate or the surface layer of the substrate, or formed on the surface of the substrate or the surface layer of the substrate. It is a fine concavo-convex structure formed in a film. Rather than providing a protective film on the surface of the substrate, the surface of the substrate or the surface layer, or a film formed on the surface or surface layer of the substrate, is directly formed to protect the surface of the substrate. By doing so, the manufacturing cost can be reduced.

  Hereinafter, with reference to FIG. 1, the aspect and shape of the surface protecting structure for a substrate according to the present invention will be described. FIG. 1 is a diagram schematically showing a surface protecting structure formed on a surface of a substrate or a surface layer of the substrate. The structure for protecting the surface of a substrate according to the present invention is an uneven structure formed on the surface of the substrate as shown in FIGS. 1 (a) and 1 (c), or as shown in FIGS. 1 (b) and (d). In addition, a concavo-convex structure formed on a functional film formed on the surface of the substrate and combined with the characteristics of the lower layer, such as processing the surface of the substrate itself as shown in FIG. The concavo-convex structure formed by the above.

  As for the concavo-convex structure (hereinafter referred to as “concavo-convex structure”) formed on the surface of the substrate or the surface layer of the substrate, the convex portions may be in contact with each other as shown in FIG. The substrate surface may be exposed between the portion and the convex portion. In addition, as shown in FIG. 1B, the convex portions are formed on the substrate and the surface layer of the substrate with a space therebetween, so that the characteristics of the functional film formed in the lower layer are combined. It may be. Furthermore, in the embodiment shown in FIGS. 1C and 1D, fine irregularities may be formed on the surface of the layer by the components of the irregular structure. In particular, in the embodiment shown in FIG. 1 (d), when the component of the concavo-convex layer formed on the surface is formed of ultrafine particles, the characteristics of the underlying functional film may be expressed and the functions may be combined. It becomes possible.

  The concavo-convex structure is formed by a single body or a laminate of particles or crystals, and the cross-sectional shape thereof may be any shape such as a trapezoidal shape, a triangular shape, a square shape, a circular shape, and a semicircular shape. However, the triangular shape has been improved by reducing the contact area with contaminants, improving the smoothness by reducing the contact area with fingers and solid contaminants, and the regularity of reflected light. A circular shape, semicircular shape, etc. are desirable.

  The height and pitch of the concavo-convex structure are 50 nm to 900 nm, desirably 70 nm to 600 nm, and more desirably 80 nm to 400 nm. As shown in FIG. 2, the pitch basically refers to the interval between the tops of adjacent convex portions or the interval between the bottom portions of adjacent concave portions. However, as shown in FIG. 3, when fine irregularities are further formed on each of the formed irregularities (it is considered that there are many cases in fact), the pitch is 1 pitch. In addition, the pitch 2 (the interval between the tops of adjacent convex portions or the interval between the bottom portions of adjacent concave portions) is also included. In addition, the height refers to the distance between the bottom of the recess and the top of the projection, but when fine irregularities are formed on each of the formed irregularities, not only the height 1 but also the height 2 (the distance between the bottom of the concave portion and the top of the convex portion in the fine unevenness) is also included. The reason for the above-mentioned desirable numerical values is as follows.

  Considering the sliding property when the contaminant is placed on the surface of the concavo-convex structure, when the size of the contaminant is 1 μm, the two-point support dimension of about 500 nm or less that does not allow the contaminant to be buried in the concave portion is the height and pitch. It can be said that it is the maximum optimum dimension. Incidentally, the environmental pollutant PM2.5 has an average particle size of 2.5 μm.

  In addition, in order to give “smoothness” when manipulating the surface of a substrate with a finger or the like (performance that allows smooth operation with little friction when manipulating the surface with a finger) When the height and pitch are 40 nm or less, or 600 to 800 nm or more, the contact area increases and the contact resistance value increases, and the effect of the uneven surface, so-called “slip” property, decreases. It is desirable that the value is between these values.

  Furthermore, since the amount of transmission with a visible light wavelength of 400 to 700 nm increases, the above-described desirable height and pitch values of the concavo-convex structure are selected.

<Method for forming uneven structure>
Examples of the method for forming the concavo-convex structure on the surface of the substrate or the surface layer of the substrate include the methods <1> to <4> described below.

<1> Wet construction method After dripping a liquid containing a component for forming the concavo-convex structure onto the surface or surface layer of the substrate, the surface of the concavo-convex structure is obtained by a wet construction method in which the solvent in the liquid is volatilized by heating or drying. Or it can form on a surface layer.

  Further, the substrate is dipped in a liquid containing a component that forms a concavo-convex structure, or dip coating is performed, or the liquid is applied to the surface or surface layer of the substrate with a spray, roll, brush, sponge, or the like and then dried. It can be formed by performing the process of volatilizing the solvent at least once.

  In order to form a concavo-convex structure with a desired height and pitch, for example, when using a sol solution such as water, an alcohol solvent or a volatile organic solvent and setting the mist diameter to 100 μm by a spray method, the extrusion pressure And the distance between the substrate and the substrate is determined, and then a 1% solution of the concavo-convex component concentration in the sol solution is dropped to make the mist diameter spread on the substrate about 200 μm and the height about 50 μm. A concavo-convex structure having a pitch and height of about 500 nm is formed, and the pitch and height dimensions can be combined with the assumed concavo-convex pitch dimension by dropping movement speed or overcoating.

<2> Dry Construction Method The components forming the concavo-convex structure can be ionized by a dry construction method including sputtering / ion plating and sprayed onto the surface or surface layer of the substrate to form the concavo-convex structure. In order to adjust the concavo-convex structure to a desired pitch and height, the particle size can be selected based on the assumed height and pitch dimension, and ionized substances having different particle sizes can be laminated a plurality of times.

<3> Method by Film Formation After forming a film by applying a liquid containing a component that forms a concavo-convex structure and an organic substance (for example, sugars or carbon compounds) onto the surface or surface layer of a substrate, heating at a high temperature or The concavo-convex structure can be formed by burning organic substances by irradiation with ultraviolet rays or plasma. In order to adjust the concavo-convex structure to a desired height or pitch, it can be determined by the film thickness to be formed and the molecular weight of the component to be baked out. For example, the height and pitch can be 100 nm by using saccharides.

<4> Method of processing the surface of the substrate The surface of the substrate itself is made uneven by finely colliding fine particles with the surface of the substrate or by polishing the surface of the substrate by selecting the hardness and particle size of the abrasive. It can be formed as a body. In addition, an acid or alkaline solution that dissolves the surface of the substrate is combined with a substance that is suitable for the uneven pitch and has a different melting time in acid or alkali, and the solution is applied to the surface of the substrate while adjusting the time, or the substrate is made into a solution. By dipping, the surface of the substrate itself can be formed as an uneven structure.

<Ingredients that form an uneven structure>
The concavo-convex structure for protecting the surface of the substrate according to the present invention can exhibit effects such as an improvement in the stain-proofing effect on the surface of the substrate, an improvement in smoothness, and an increase in the amount of permeation due to its shape and size. On the other hand, various functions can be given to the concavo-convex structure by selecting a substance contained as a component for forming the concavo-convex structure, and by compounding other components with these substances. The substances that can be selected as the components of the concavo-convex structure are already listed in the summary column. However, when the concavo-convex structure is formed by the method <3> described above, it is necessary to include an organic substance. Furthermore, by combining other components, not only antifouling and optical functions but also functions such as hydrophilicity, hydrophobicity, water repellency and oil repellency can be imparted to the substrate.

  In the following <A> to <SA>, materials preferable as components of the concavo-convex structure will be described mainly in detail mainly by function. Note that, even if not specifically mentioned in the following description, the concavo-convex structure is formed of a single substance or a laminate of particles or crystals of a substance that forms the concavo-convex structure.

<A> Silicon oxide and titanium oxide Silicon oxide is a material that can be supplied inexpensively and stably as a component for forming an uneven structure, has a relatively small refractive index, and is electrically neutral as a semiconductor. It is easy to process and has excellent fixability.

  Titanium oxide is a component that forms a concavo-convex structure, has a relatively high refractive index, easily forms electrical characteristics as a dielectric (semiconductor) or composite metal, has excellent UV absorption, and achieves high transparency. can do. Titanium oxide can control the hydrophilicity and water repellency of the substrate surface by coexistence with other components and complexing. Moreover, it is suitable for forming a film not containing each binder.

  Silicon oxide and titanium oxide, when a positively charged substance and a negatively charged substance, which will be described later, are included as components for forming a concavo-convex structure, respectively, are dielectrics or semiconductors interposed between these positively charged substances and negatively charged substances Function as. In this case, titanium oxide and silicon oxide may be used alone or in combination, and various oxides and peroxides of titanium oxide and silicon oxide, and these compounds can be used. In addition to these metals, these compounds such as Group 4 zirconium and hafnium may be combined or coexisted with dielectrics or semiconductors other than conductive metals.

<I> Titanium oxide doped with particles of metal, metal compound, inorganic substance (excluding metal), other inorganic substance (excluding metal) metal, metal compound, inorganic substance (excluding metal), other inorganic substance (excluding metal) ) Titanium oxide doped with compound particles functions as a substance that charges the surface of the substrate to a positive charge and / or a negative charge when used as a component of the concavo-convex structure. Any substance having a positive charge or a negative charge can be combined with titanium oxide as long as it can impart a positive charge and / or a negative charge to the surface of the substrate, but enables a stable charge formation on the surface of the substrate. In this respect, it is preferable to use a metal or a part of an inorganic substance other than the metal. Titanium oxide complexed with a positively charged and / or negatively charged substance functions as a dielectric or semiconductor, and functions as a substance for forming a uniform and uniform charge on the surface of these complexed substances.

  Metals to be combined with titanium oxide include transition metals such as gold, silver, platinum, copper, manganese, nickel, cobalt, iron, zirconium, hafnium, typical metals such as zinc and tin, alkali metals, alkaline earths The metal element is preferably at least one metal element selected from the group of metals, and more preferably two metal elements are combined. In addition, silver and copper are particularly preferable as the metal elements to be combined. Silicon is preferable as the inorganic substance other than the metal combined with titanium oxide.

Titanium oxide (including a titanium oxide compound) that is combined with a metal (including some inorganic substances other than metals) will be described. Examples of titanium oxide (including titanium oxide compounds) to be combined with metal (including some inorganic substances other than metals) include various oxides such as TiO ₂ , TiO ₃ , TiO, TiO ₃ / nH ₂ O, and the like. 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.

  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 titanium oxide does 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. Amorphous titanium oxide is converted to anatase titanium oxide over time by heating with sunlight, etc., but when combined with copper, manganese, nickel, cobalt, iron or zinc, anatase titanium oxide has a photocatalytic function. descend. 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. In addition, 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.

<C> Manufacturing Method of Metal or Other Inorganic Particle Doped Titanium Oxide Next, a manufacturing method of metal or other inorganic particle doped titanium oxide will be described. The above-mentioned metal or other inorganic particle-doped titanium oxide may adopt a production method based on a hydrochloric acid method or a sulfuric acid method, which is a general method for producing titanium dioxide powder, and various liquid-dispersed titania solutions. A manufacturing method may be adopted. 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 a metal or other inorganic-doped titanium oxide will be described with reference to FIG. First, an inorganic compound and a metal compound (compound having crystal water) illustrated on the left side of FIG. 4 are mixed at a molar ratio of 1:50 in a solution obtained by diluting 50% titanium tetrachloride (commercially available product) with pure water 80 to 100 times. Mix at a ratio of 0.05.

  A plurality of types of inorganic compounds and metal compounds can be mixed. The mixing ratio of titanium tetrachloride and 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, 2.5% ammonia water prepared by diluting 25% ammonia water (commercially available product) 10 times with pure water is added dropwise to adjust the pH to around 7 to precipitate titanium and inorganic or metal hydroxides. . The precipitated hydroxide is washed with pure water until the supernatant has a conductivity of 0.9 mS / m or less. 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 amorphous material is 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 particles or crystals are dispersed is obtained.

  The concentration of titanium peroxide in the aqueous dispersion obtained by the above-described production method (total amount including coexisting metals such as gold, silver, platinum, copper, manganese, nickel, cobalt, iron, and zinc) was 0.00. 05-15 wt% is preferable and 0.1-5 wt% is more preferable.

  Gold mixed to obtain inorganic materials and metals (including alkali metals and alkaline earth metals) combined with titanium oxide (including its compounds) in the manufacturing process of the above metal or other inorganic-doped titanium oxide Examples of the compounds of silver, platinum, 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 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 , ZnSO 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, etc. Hf compound: HfCl ₂ , Hf (OH) _2, etc. The metal or other inorganic-doped titanium oxide described with reference to FIG. 4 In addition to the dispersion manufacturing method, there are many methods for compounding inorganic substances and metals with titanium oxide. For example, titanium oxide particles and inorganic substances and metal particles to be compounded are prepared separately in advance. , Each may be mixed. 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.

<D> Silicon oxide doped with particles of metal, metal compound, inorganic substance (excluding metal), other inorganic substance (excluding metal) metal, metal compound, inorganic substance (excluding metal), other inorganic substance (excluding metal) ) Silicon oxide doped with compound particles is a component of a concavo-convex structure, similar to titanium oxide doped with particles of the above-mentioned metals, metal compounds, inorganics (excluding metals), and other inorganic (excluding metals) compounds. In this case, it functions as a substance that charges the surface of the substrate to a positive charge and / or a negative charge. Any substance having a positive or negative charge can be combined with silicon oxide as long as it can impart a positive charge and / or a negative charge to the surface of the substrate, but enables stable charge formation on the surface of the substrate. In this respect, it is preferable to use a metal or a part of an inorganic substance other than the metal. Silicon oxide that is compounded with a positively or negatively charged substance functions as a dielectric or a semiconductor, and functions as a substance for forming a uniform and uniform charge on the surface of the compounded substance.

Examples of silicon oxides (including silicon oxide compounds) to be combined with metals (including some inorganic substances other than metals) include various oxides such as SiO ₂ , SiO ₃ , SiO, SiO ₃ / nH ₂ O, 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

<E> Manufacturing method of metal or other inorganic particle-doped silicon oxide Using the above-described material containing silicon oxide, a film-forming solution of metal or other inorganic particle-doped silicon oxide can be produced. Hereinafter, with reference to FIG. 5, a metal or other inorganic-doped silicon oxide when the composite is a typical metal such as gold, silver, platinum, copper, manganese, nickel, cobalt, iron, zinc, and a transition metal An example of a method for producing the dispersion liquid will be described. First, alcohol, pure water and a predetermined amount of catalyst are mixed with methyl silicate and hydrolyzed. When stirred until it is transparent, a silica sol is produced. This silica sol is diluted with pure water. 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 with crystal water) are preferably in a molar concentration ratio with respect to silica, preferably 1: 0.03 to 1: 2.7, more preferably 1 : Mix in a ratio of 0.03 to 1: 0.27.

  Next, an example of a method for producing a dispersion of inorganic / metal-doped silicon oxide in the case where the composite is an alkali metal such as potassium or sodium will be described. First, alcohol, pure water and a predetermined amount of catalyst are mixed with methyl silicate and hydrolyzed. When stirred until it is transparent, 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 an alkali metal such as Na adjusted to 1% concentration are preferably in a molar concentration ratio to silica of 1: 0.03 to 1: 2.7, more preferably 1: 0.03. Mix at ˜1: 0.27.

  In addition, as shown in FIG. 5, 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.

<F> Manufacturing Method for Metal or Other Inorganic Particle Doped Titanium Oxide and Silicon Oxide Finally, a method for preparing a solution in which a metal or other inorganic substance is combined with titanium oxide and silicon oxide will be described. First, titanium tetrachloride and silica sol are mixed with pure water at a molar ratio of 1: 0.5, and an inorganic compound and a metal compound (compound having crystal water) are further mixed. A plurality of kinds of inorganic compounds and metal compounds can be mixed. The mixing ratio of titanium tetrachloride and 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. 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 amorphous material of titanium is 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.

<G> 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 Charging the substrate surface or substrate surface layer 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 to be formed, titanium oxide and / or silicon oxide (titanium oxide and / or When one or more kinds of dielectrics and semiconductors excluding (including silicon oxide compounds) are combined, the surface of the substrate is charged with a positive charge, a negative charge and an amphoteric charge. The film forming method for forming the film according to this embodiment on the surface of the substrate can be carried out in the same manner as the metal doped titanium oxide.

  Dielectrics and semiconductors excluding titanium oxide and / or silicon oxide (including titanium oxide and / or silicon oxide compound) combined with titanium oxide and / or silicon oxide (including titanium oxide and / or silicon oxide compound) For example, the following can be used.

That is, as a dielectric that is a composite for forming an electric charge, so-called SBT, BLT, SBTN—SrBi ₂ (Ta, Nb) ₂ O ₉ , LSCO— (La, Sr) CoO ₃ , which are ferroelectrics, are used. , Etc. can be used. Various low dielectric materials such as organic polymer insulating film arylene ether-based polymer, benzocyclobutene, fluorine-based polymer parylene N or F, and fluorinated amorphous carbon can also be used.

Examples of the semiconductor include C, Ge, Sn, GaAs, Inp, GeN, ZnSe, and PbSnTe. A semiconductor metal oxide, an optical semiconductor metal, and an optical semiconductor metal oxide can also be used. Preferably, ZnO, CdS, CdO, CaP, InP, In ₂ O ₃ , CaAs, K ₂ NbO ₃ , Fe ₂ O ₃ , Ta ₂ O ₃ , WO ₃ , NiO, Cu ² O, MoS ₃ , InSb, RuO ₂ , CeO ₂ or the like is used.

<K> Positive and negative charge substances as components forming the concavo-convex structure body In the present invention, among the components forming the concavo-convex structure body, as positive and negative charge substances that charge the substrate surface, metals, metals Silicon oxide doped with particles of compound, inorganic substance (excluding metal), inorganic substance (excluding metal) compound, and oxidation doped with metal, metal compound, inorganic substance (excluding metal), inorganic substance (excluding metal) compound Titanium has been described as a preferred example. However, since other substances can be used as the positively charged substance and the negatively charged substance for charging the substrate surface, in the following, a positively charged substance and a negatively charged substance that can be used as components for forming the concavo-convex structure in the present invention will be described. The charged substance in general will be described in detail.

  The positively charged substance is a substance having one or more positive charges selected from the group consisting of the following (1) and (2).

(1) a cation (2) a positively charged conductor, a composite of a positively charged conductor and a dielectric or semiconductor, a composite of two or more kinds of positively charged dielectrics or semiconductors, and The negatively charged substance is a substance having one or more negative charges selected from the group consisting of the following (3) to (5).
(3) Anion (4) Conductor having negative charge, composite of conductor having negative charge and dielectric or semiconductor, composite made of two or more kinds of dielectric or semiconductor having negative charge (5) Substance having a photocatalytic function The cation used as the positively charged substance is not particularly limited, but alkali metal ions such as sodium and potassium; alkaline earth metal ions such as calcium; aluminum, tin, cesium, Ions of other metal elements such as indium, cerium, selenium, chromium, cobalt, nickel, antimony, iron, copper, manganese, tungsten, zirconium, and zinc are preferable, and copper ions are particularly preferable. Furthermore, cationic molecules such as methyl violet, bismarck brown, methylene blue and malachite green, and organic molecules having a cationic group such as silicone modified with a quaternary nitrogen atom-containing group can also be used. The valence of ions is not particularly limited, and for example, a cation having 1 to 4 valences can be used.

  It is also possible to use a metal salt as a source of the metal ion as the cation described above. Specifically, aluminum chloride, first and second tin chloride, chromium chloride, nickel chloride, first and second antimony chloride, first and second iron chloride, cesium chloride, indium trichloride, first cerium chloride, Examples include various metal salts such as selenium tetrachloride, cupric chloride, manganese chloride, tungsten tetrachloride, tungsten oxychloride, potassium tungstate, zirconium oxychloride, zinc chloride, and barium carbonate. Furthermore, metal hydroxides such as aluminum hydroxide, iron hydroxide, chromium hydroxide, and indium hydroxide, hydroxides such as silicotungstic acid, and oxides such as oil and fat oxides can be used.

  Examples of the positively charged conductor include conductors in which a positive charge other than the above-mentioned cation is generated. For example, a positive electrode of a battery made of various conductors described later, and positively by friction. Examples thereof include dielectric materials such as charged wool and nylon.

  The anion used as the negatively charged substance is not particularly limited, but halide ions such as fluoride ion, chloride ion and iodide ion; hydroxide ion, sulfate ion, nitrate ion, carbonate ion, etc. Inorganic ions; organic ions such as acetate ions. The valence of ions is not particularly limited, and for example, a 1 to 4 valent anion can be used.

  Examples of the conductor having a negative charge include conductors having a negative charge other than the above anions, such as metals such as gold, silver and platinum; metal oxides; graphite, sulfur, selenium, Elements such as tellurium; sulfides such as arsenic sulfide, antimony sulfide, mercury sulfide; clay, glass powder, quartz powder, asbestos, starch, cotton, silk, wool, etc .; conger, indigo, aniline blue, eosin, naphthol yellow Examples include dye colloids. Of these, colloids of metals such as gold, silver and platinum and metal oxides are preferred, and silver colloids are more preferred. In addition, the negative electrode of the battery which consists of the various conductors mentioned later, dielectric materials, such as negatively charged halogen, a fluororesin, vinyl chloride, polyethylene, polyester, and these compounds and composites are mentioned. .

As a substance having a photocatalytic function used as a negatively charged substance, a substance containing a specific metal compound and having a function of oxidizing and decomposing organic and / or inorganic compounds on the surface of the layer by photoexcitation can be used. The principle of photocatalyst by photoexcitation specific metal compounds, from the water or oxygen in the air OH ^- or O ₂ ^- radical species is generated in, that the radical species oxidize reductive decomposition of organic and / or inorganic compound It is generally understood that there is.

Examples of the metal compound as the substance having a photocatalytic function include ZnO, SrTiOP ₃ , CdS, CdO, CaP, InP, In ₂ O ₃ , CaAs, BaTiO ₃ , K, in addition to typical titanium oxide (TiO ₂ ). ₂ NbO ₃ , Fe ₂ O ₃ , Ta ₂ O ₅ , WO ₃ , NiO, Cu ₂ O, SiC, SiO ₂ , MoS ₃ , InSb, RuO ₂ , CeO _{2 and the} like are known.

  The substance having a photocatalytic function may contain a metal (Ag, Pt) that improves the photocatalytic performance. Moreover, various substances, such as a metal salt, can be included in a range that does not deactivate the photocatalytic function. Examples of the metal salt include metal salts such as aluminum, tin, chromium, nickel, antimony, iron, silver, cesium, indium, cerium, selenium, copper, manganese, calcium, platinum, tungsten, zirconium, and zinc. In addition, hydroxides or oxides can be used for some metals or nonmetals. Specifically, aluminum chloride, stannous chloride and stannic chloride, chromium chloride, nickel chloride, primary and secondary antimony chloride, ferrous chloride, silver nitrate, cesium chloride, indium trichloride, selenium tetrachloride And various metal salts such as cupric chloride, manganese chloride, calcium chloride, platinum chloride, tungsten tetrachloride, tungsten oxychloride, potassium tungstate, cupric chloride, zirconium oxychloride, and zinc chloride. Examples of compounds other than metal salts include indium hydroxide, silicotungstic acid, silica sol, potassium hydroxide, calcium hydroxide and the like.

  The conductor used in the present invention is preferably a metal from the viewpoint of durability, and is a metal such as aluminum, tin, indium, cerium, selenium, chromium, nickel, antimony, iron, silver, copper, manganese, platinum, tungsten, or zinc. Is mentioned. Also, oxides, composites or alloys of these metals can be used. The shape of the conductor is not particularly limited, and may be any shape such as a particle shape, a flake shape, or a fiber shape.

  As the above-described conductor, a metal salt of a part of metal can also be used. Specifically, aluminum chloride, 1st and 2nd tin chloride, chromium chloride, nickel chloride, 1st and 2nd antimony chloride, 1st and 2nd iron chloride, silver nitrate, cesium chloride, indium trichloride, selenium tetrachloride And various metal salts such as cupric chloride, manganese chloride, second platinum chloride, tungsten tetrachloride, tungsten oxydichloride, potassium tungstate, second gold chloride, and zinc chloride. Also, hydroxides or oxides such as indium hydroxide and silicotungstic acid can be used.

  Furthermore, the above conductors include polyaniline, polypyrrole, polythiophene, polythiophene vinylon, polyisothianaphthene, polyacetylene, polyalkylpyrrole, polyalkylthiophene, poly-p-phenylene, polyphenylene vinylon, polymethoxyphenylene, polyphenylene sulfide, Conductive polymers such as polyphenylene oxide, polyanthracene, polynaphthalene, polypyrene, and polyazulene can also be used.

Examples of the semiconductor constituting the composite with the conductor used in the present invention include C, Si, Ge, Sn, GaAs, Inp, GeN, ZnSe, PbSnTe, and the like. An optical semiconductor metal oxide can also be used. Preferably, besides titanium oxide (TiO ₂ ), ZnO, SrTiOP ₃ , CdS, CdO, CaP, InP, In ₂ O ₃ , CaAs, BaTiO ₃ , K ₂ NbO ₃ , Fe ₂ O ₃ , Ta ₂ O ₃ , WO ₃ , NiO, Cu ² O, SiC, SiO ₂ , MoS ₃ , InSb, RuO ₂ , CeO _2, etc. are used. When used as a semiconductor, the photocatalytic ability is deactivated with Na or the like. Is preferred.

Examples of the dielectric constituting the composite with the conductor used in the present invention include ferroelectric barium titanate (PZT), so-called SBT, BLT and the following PZT, PLZT- (Pb, La) (Zr). , Ti) O ₃ , SBT, SBTN-SrBi ₂ (Ta, Nb) ₂ O ₉ , BST- (Ba, Sr) TiO ₃ , LSCO- (La, Sr) CoO ₃ , BLT, BIT- (Bi, La) ₄ Ti ₃ O ₁₂ , BSO—Bi ₂ SiO _{5 and} other composite metals can be used. Also, silane compounds, silicone compounds, so-called organic modified silica compounds, which are organosilicon compounds, organic polymer insulating films, arylene ether-based polymers, benzocyclobutene, fluorine-based polymer parylene N, or F, fluorinated amorphous carbon, etc. Various low dielectric materials can also be used.

  The dielectrics and semiconductors excluding titanium oxide and / or silicon oxide (including titanium oxide and / or silicon oxide compounds) used as positively charged substances and / or negatively charged substances in the present invention are described above. In addition, a semiconductor or a dielectric (except for titanium oxide, silicon oxide, and these compounds) constituting a composite with a conductor can be used.

<G> Substance that periodically varies the electrical resistance of the substrate surface between a conductive surface state and an insulating surface state (1)
As a component of the concavo-convex structure, an oxygen deficient substance particle (or crystal) of an optical semiconductor doped with a metal, a metal compound, an inorganic substance (excluding a metal) or an inorganic substance (excluding a metal) compound particle, It functions as a substance that varies periodically between a conductive surface state and an insulating surface state.

Substances that can be used as the above optical semiconductor include titanium dioxide (TiO ₂ ), ZnO, SrTiOP ₃ , CdS, CdO, CaP, InP, In ₂ O ₃ , CaAs, BaTiO ₃ , K ₂ NbO ₃ , Fe ₂ O. ₃ , Ta ₂ O ₅ , WO ₃ , NiO, Cu ₂ O, SiC, SiO ₂ , MoS ₃ , InSb, RuO ₂ , CeO _2, and TiO ₂ and the periodic table 4th period and 5th period metal or non-metal doped material Etc. can be used. In the present invention, one type of these optical semiconductor materials may be used, or two or more types may be used in combination.

  In addition to the above optical semiconductor, a metal (Ag, Pt, etc.) may be included. Moreover, various substances, such as a metal salt, can also be included. Examples of the metal salt include metal salts such as aluminum, tin, chromium, nickel, antimony, iron, cesium, indium, cerium, selenium, copper, manganese, calcium, platinum, tungsten, zirconium, zinc, and the like. In addition, some metals or non-metals may contain a hydroxide or an oxide. Specifically, aluminum chloride, stannous chloride, stannic chloride, chromium chloride, nickel chloride, primary and secondary antimony chloride, ferrous chloride, silver nitrate, cesium chloride, indium trichloride, primary chloride Various metals such as cerium, selenium tetrachloride, cupric chloride, manganese chloride, calcium chloride, platinum chloride, tungsten tetrachloride, tungsten oxychloride, potassium tungstate, ferric chloride, zirconium oxychloride, zinc chloride A salt can be illustrated. Examples of compounds other than metal salts include indium hydroxide, silicotungstic acid, silica sol, and calcium hydroxide.

  It is desirable that the inorganic substance or metal to be doped in these is a substance in which the substance is charged with a positive charge or a negative charge by compounding. These doping substances may be organic substances.

  In addition, among inorganic substances and metals doped into optical semiconductors, fifth periodic metal species such as Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, In, Sn, Si, P, S, etc. A composite with an inorganic substance is desirable.

<K> Substance that periodically varies the electrical resistance of the substrate surface between a conductive surface state and an insulating surface state (2)
As a component of the concavo-convex structure, alkali metal or / and alkaline earth metal doped silicon oxide compound particles (crystals), or composite material particles of conductive metal particle doped silicon compounds and positively charged substances and / or negatively charged substances (crystals) ) Functions as a substance that periodically varies the electric resistance of the substrate surface between a conductive surface state and an insulating surface state.

  The positively charged substance and the negatively charged substance that are combined with the conductive metal particle-doped silicon compound described above are the same as those described in the above section <K>.

<Function> Combining functions in intermediate layer or base substrate and concavo-convex structure An intermediate layer can be provided between the concavo-convex structure and the substrate. For the intermediate layer and the base substrate, for example, various organic or inorganic substances that can impart hydrophilicity or hydrophobicity or water repellency or oil repellency to the substrate can be used. In addition, as a component included in the substrate when the surface of the substrate itself is processed to form the concavo-convex structure and the concavo-convex structure formed on the substrate, the substrate is similarly hydrophilic or hydrophobic or water-repellent or water-repellent. Various organic or inorganic substances that can impart oiliness can be used.

  Among organic or inorganic substances that can be used for intermediate layers, substrates and concavo-convex structures for functional compounding, hydrophilic organic substances include polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol block copolymers, etc. Ether; 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 (alkali metal salts) Copolymers, including salts such as ammonium salts); polyacrylamide; polyvinylpyrrolidone; hydrophilic celluloses such as carboxymethylcellulose (CMC) and methylcellulose (MC); and natural hydrophilic polymer compounds such as polysaccharides. . 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 an intermediate layer, a substrate, and a concavo-convex structure for functional compounding, examples of hydrophilic inorganic materials include silane coupling agents, SiO _{2, and} other silicon compounds.

  Among organic or inorganic materials that can be used for intermediate layers, substrates and uneven structures for functional compounding, water-repellent organic materials include polyolefins such as polyethylene, polypropylene and polystyrene; polyacrylates, acrylonitrile / styrene copolymers (AS), acrylic resins such as acrylonitrile / butadiene / styrene copolymer (ABS); polyacrylonitrile; polyvinyl halides such as polyvinyl chloride and polyvinylidene chloride; polytetrafluoroethylene, fluoroethylene / propylene copolymers, Fluorine resins such as polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), and vinylidene fluoride / trifluoroethylene copolymer; polyesters such as polyethylene terephthalate and polycarbonate; pheno Le resins; urea resins; melamine resins; polyimide resin; polyamide resins such as nylon, epoxy resins, polyurethanes, and the like.

  Of the above water-repellent organic substances, fluororesins are preferable, and in particular, vinylidene fluoride / trifluoroethylene copolymer having ferroelectricity and water repellency, β-type crystals of polyvinylidene fluoride and the like are contained. Those that do are preferred. A commercially available fluororesin can be used, and examples of the commercially available product include HIREC 1550 manufactured by NTT-AT Corporation.

  Furthermore, a copolymer comprising two or more kinds of olefins containing fluorine atoms, a copolymer of an olefin containing fluorine atoms and a hydrocarbon monomer, and a copolymer comprising two or more kinds of olefins containing fluorine atoms And a fluororesin emulsion comprising a surfactant and at least one fluororesin selected from the group consisting of a mixture of an acrylic resin and a thermoplastic acrylic resin, and a curing agent (JP-A-5-124880, JP-A-5-117578) JP-A-5-179191) and / or a composition comprising the above-mentioned silicone resin water repellent (see JP2000-121543A and JP2003-26461A) can also be used. As this fluororesin emulsion, what is marketed can be used, and it can be purchased as a zaffle series from Daikin Industries, Ltd. and as a Lumiflon series from Asahi Glass Co., Ltd. As the curing agent, a melamine curing agent, an amine curing agent, a polyvalent isocyanate curing agent, and a block polyvalent isocyanate curing agent are preferably used.

  Among organic or inorganic substances that can be used for an intermediate layer, a substrate or a concavo-convex structure for functional compounding, examples of water-repellent inorganic materials include silane-based, siliconate-based, silicone-based and silane-complexed systems, or Examples thereof include a fluorine-based water repellent and a water absorption inhibitor. 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 a fluorine-containing compound having high adsorptivity to the substrate surface is included in the intermediate layer or the uneven structure, the chemical component of the water repellent or water absorption inhibitor of the intermediate layer or uneven structure reacts with the substrate. It is not always necessary that a chemical bond is generated or that chemical components of the intermediate layer or the concavo-convex structure and the substrate are 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, and specifically, perfluorosulfonic acid. Salt, perfluorosulfonic acid ammonium salt, perfluorocarboxylate, perfluoroalkyl betaine, perfluoroalkylethylene oxide adduct, perfluoroalkylamine oxide, perfluoroalkyl phosphate ester, perfluoroalkyltrimethylammonium salt, etc. Is mentioned. Especially, since it is excellent in the adsorptivity to the base-material surface, perfluoroalkyl phosphate ester and perfluoroalkyl trimethyl ammonium salt are preferable. As such a material, Surflon S-112 and Surflon S-121 (both trade names, manufactured by Seimi Chemical Co., Ltd.) are commercially available.

  In the case of a water-absorbing substrate, an intermediate layer containing a silane compound is provided under the concavo-convex structure made of the positively charged substance and / or the negatively charged substance and titanium oxide and / or silicon oxide as a dielectric or semiconductor. It is preferable to form it on the substrate in advance. Since this intermediate layer functions as a water absorption preventing layer and contains a large amount of Si-O bonds, the strength of the layer made of a positively charged substance and / or a negatively charged substance and titanium oxide and / or silicon oxide as a dielectric or semiconductor can be increased. It becomes possible to improve the adhesion to the substrate. In addition, the intermediate layer also has a function of preventing moisture from entering the substrate.

  Examples of the silane compound include hydrolyzable silanes, hydrolysates thereof, and mixtures thereof. Various alkoxysilanes can be used as the hydrolyzable silane, and specific examples include tetraalkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane, and trialkylalkoxysilane. Among these, one type of hydrolyzable silane may be used alone, or two or more types of hydrolyzable silanes may be confused and used as necessary. Moreover, you may mix | blend various organopolysiloxane with these silane compounds. As a constituent material of the water absorption preventing layer containing such a silane compound, for example, there is Dry Seal S (manufactured by Toray Dow Corning Co., Ltd.).

  In addition, room temperature curable silicone resins such as methyl silicone resin and methyl phenyl silicone resin may be used as a constituent material used for the intermediate layer, the base body, and the concavo-convex structure for functional compounding. Examples of such room temperature curable silicone resins include AY42-170, SR2510, SR2406, SR2410, SR2405, SR2411 (manufactured by Toray Dow Corning Co., Ltd.).

  When the intermediate layer includes a silane compound or a silicone resin, the concavo-convex structure component of the positively charged substance and / or the negatively charged substance and titanium oxide and / or silicon oxide as a dielectric or semiconductor, these silane compounds Alternatively, the mixing ratio (weight ratio) with the silicone resin is preferably in the range of 1: 2 to 1: 0.05, and more preferably in the range of 1: 1 to 1: 0.1.

<About the substrate>
The structure for protecting the surface of a substrate and the method for protecting the surface of the substrate according to the present invention are not limited to models such as smartphones, tablet terminals, small electronic devices, and other devices that provide various functions. Regardless of whether or not a finger or the like is in direct contact, the present invention is effective when applied to a high-definition display screen. However, the material of the substrate that is the subject of the present invention is not particularly limited to these, and various hydrophilic or hydrophobic inorganic substrates and organic substrates, or combinations thereof, should be used. Can do.

  Examples of the inorganic substrate include a substrate 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, 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.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

[Convex / Uneven Surface Substrate Production Example 1]
Transparent soda lime glass Polysilicate (manufactured by Sustainable Technology: MS-AAAL) was adjusted to 4 wt% with pure water on the substrate surface with a thickness of 3 mm. The substrate was dried at the surface and heated at 200 ° C. for 15 minutes to prepare an uneven film-forming substrate. The average value (Ra value) of the surface roughness of the film-forming substrate was measured with a laser microscope (surface shape measuring microscope: VF-7500, manufactured by Keyence Corporation). The numerical value was 660 nm (concave / convex pitch 450 nm).

[Concavity and convexity surface substrate production example 2]
A transparent soda-lime glass substrate surface is adjusted to 0.84 wt% of a copper-doped amorphous type titanium peroxide solution (Z18-1600A manufactured by Sustainable Technology Co., Ltd.) as a positively charged surface-forming film solution on a substrate surface with a thickness of 3 mm. The same apparatus and spray method as those used in Production Example 1 were applied, and the surface was dried and heated at 200 ° C. for 15 minutes to produce an uneven film-forming substrate. The measured unevenness of the film-forming substrate was Ra value: 82 nm, uneven pitch 150 nm).

[Concavity and convexity surface substrate production example 3]
A transparent soda-lime glass substrate surface having a thickness of 3 mm was adjusted to 0.84 wt% of an amphoteric charge surface-forming film forming liquid copper-tin doped amorphous titanium peroxide solution (SZ-1200A, manufactured by Sustainable Technology Co., Ltd.) Irregular surface substrate preparation The same apparatus and spray method as those used in Example 1 were applied, and the surface was dried and heated at 200 ° C. for 15 minutes to prepare an irregular surface-formed substrate. The measured unevenness of the film-forming substrate was Ra value: 200 nm, uneven pitch 380 nm).

[Example 4 of making uneven surface substrate]
Indium-doped anatase-type titanium peroxide dispersion (0.84 wt%) and copper-doped anatase-type titanium peroxide dispersion (0.84 wt%) = 1: 1 mixture on a substrate surface of transparent soda lime glass having a thickness of 3 mm, Applying “conductive and insulating” switching film composed of potassium-doped silica sol (polysilicate) at a ratio of 2: 8 using the same apparatus and spray method as used in Example 1 of the uneven surface substrate. A concavo-convex film-forming substrate was produced by heating at 200 ° C. for 15 minutes. On this lower layer, a flat film having the same thickness of 80 nm was formed, and an uneven shape was prepared. The measured unevenness of the film-forming substrate was Ra value: 310 nm, uneven pitch 190 nm).

[Embodiment Example 5 for Producing Uneven Surface Surface]
After forming a flat volume resistance (Ω / □) of 10 ³ to 10 ^{4 on} the surface of a transparent soda-lime glass substrate having a thickness of about 100 nm, the second layer is used to form irregularities. A tin-doped polysilicate silica sol (4.0 wt%) was prepared as a semiconductor film solution, applied by the same apparatus and spray method as used in Example 1 for producing the uneven surface substrate, and heated at 200 ° C. for 15 minutes after surface drying. Thus, a concavo-convex film-forming substrate was produced. The measured unevenness of the film-forming substrate was Ra value: 150 nm, uneven pitch 320 nm).

[Uneven surface substrate fabrication example 6]
A transparent soda lime glass having a thickness of about 100 nm as a first layer on a 3 mm thick substrate surface using a copper-doped amorphous titanium peroxide solution (Z18-1600A, made by Sustainable Technology Co., Ltd.) as a positively charged surface forming film solution. After forming a flat positive-charged surface film with a sponge squeegee method, an amorphous titanium peroxide solution (0.84 wt%) and PTFE dispersion liquid are used as a water- and oil-repellent titania film liquid for forming irregularities in the second layer. (Asahi Glass Co., Ltd .: AD915E) was mixed at a volume ratio of 1: 1, and then applied by the same apparatus and spray method as used in Example 1 for producing an uneven surface substrate. A water-repellent / oil-repellent / amphoteric charge surface uneven film-forming substrate was prepared by heating. The measured unevenness of the film-forming substrate was Ra value: 220 nm, uneven pitch 360 nm).

[Evaluation boards 1 to 6]
Irregular surface substrate preparation Examples 1 to 6 were designated as evaluation substrates 1 to 6, respectively.
[Comparative boards 1-6]
Preparation of uneven surface substrate Using the surface unevenness forming film liquid prepared for the spray method of Examples 1 to 6, a flat 80-100 nm film not forming unevenness was formed by the sponge squeegee method (SS method) (heating conditions) Were the same) and Comparative Examples 1 to 6 were obtained.

Evaluation 1
The reflectance of the evaluation substrates 1 to 6 and the comparative substrates 1 to 6, the surface shape and slipperiness of the non-film-formed substrate, and the transmittance of the optical characteristics are measured by the ultraviolet visible light altimeter (V-550 type) manufactured by JASCO Corporation. It measured with the spectrophotometer and the surface irregular reflection characteristic was evaluated with the gloss meter (1G-331: Horiba Ltd. make). The results are shown in Table 1.

[結果１]：表１の評価１結果から
凹凸を形成した評価基板１〜６は、凹凸構造により表面の指表面接触面積が減少し、表面摩擦抵抗が減少しスベリ性に優れていることが分かる。これに対し、比較例１〜６及び無造膜表面は、凹凸形状がだいたい１０〜３０ｎｍ程度であり、指表面と造膜表面及び無造膜ガラス表面との接触面積が凹凸基板に対して増大し、滑り性が悪い。また、評価基板１〜６では光沢度が比較例や無造膜基板に比べて低いが、光沢度が低い方が光反射性が低い。さらに、評価基板１〜６は、可視光透過、反射率も比較例及び無造膜基板に比べて優れていることが分かる。

[Result 1]: From the evaluation 1 results in Table 1, the evaluation substrates 1 to 6 formed with unevenness are such that the contact surface area of the surface is reduced due to the uneven structure, the surface friction resistance is reduced, and the smoothness is excellent. I understand. On the other hand, the comparative examples 1 to 6 and the non-formed film surface have an uneven shape of about 10 to 30 nm, and the contact area between the finger surface, the formed film surface, and the non-formed glass surface increases with respect to the uneven substrate And slipperiness is bad. Further, the evaluation substrates 1 to 6 have a lower gloss than the comparative example and the non-formed substrate, but the lower the gloss, the lower the light reflectivity. Furthermore, it can be seen that the evaluation substrates 1 to 6 are superior in visible light transmission and reflectance as compared with the comparative example and the non-formed substrate.

Evaluation 2
The evaluation substrate 1-6 and the comparison substrate 1-6, and the antifouling property of the non-film-forming substrate are attached with fingerprints (finger pressure 1kg), and the visual evaluation is performed by forcibly attaching the fingerprints with difficulty in visibility and adhesion removal. Carried out. In addition, as for the adhesion characteristics of dust and other dirt, 1 teaspoon of 3 types of Kanto loam layer powder + cotton linter composite powder, Dubai desert dust, and volcanic ash was dropped on each substrate, and it was placed vertically and lightly placed twice. A visual assessment of the amount of deposit was performed. The results are shown in Table 2.

○：付着認知無、△：付着認知多少有、×：付着認知有

[結果２]：表２の評価２の結果から
指紋付着難視性及び除去性については、凹凸構造が平坦造膜である比較基板１〜６や無造膜表面では難視性及び除去性が悪いのに対し、８０ｎｍ〜６００ｎｍ、Ｒａ値やピッチを有する凹凸表面では指紋付着防汚性に対し優れていることが分かる。これには、合わせて表面の電荷及び水に対する親和度が関わることが分かる。

○: No adhesion recognition, △: Adhesion recognition somewhat, ×: Adhesion recognition

[Result 2]: From the result of evaluation 2 in Table 2, the fingerprint adhesion difficulty and removability are difficult to see and remove on the comparative substrates 1 to 6 where the uneven structure is a flat film or a non-film-formed surface. On the other hand, it can be seen that an uneven surface having an Ra value or pitch of 80 nm to 600 nm is excellent in antifouling property against fingerprints. It can be seen that this together involves the surface charge and the affinity for water.

  On the other hand, the comparative examples 1 to 6 having a large contact area between the contaminant and the film-forming surface (including the non-film-forming) and the surface of the non-film-forming substrate show a tendency to have poor fingerprint adhesion antifouling property. Moreover, in the evaluation of adhesion of powder such as dust, the evaluation substrates 1 to 6 having an uneven surface are excellent in antifouling properties while being slightly affected by the surface charge, but on the comparative substrates 1 to 6 and the non-formed surface It turns out that it is directly influenced by the surface charge, and it turns out that the comprehensive capability of dealing with dirt is excellent in fingerprint adhesion removal and antifouling properties having an uneven surface shape. In addition, it can be seen that the formation of the uneven surface, the electrical characteristics such as surface charge, and the affinity with water and oil on the surface are related to the antifouling property of the powder.

Claims (9)

A fine relief structure directly formed on the surface of the substrate or the surface layer of the substrate, or
A fine concavo-convex structure formed on a film formed on the surface of the substrate or the surface layer of the substrate,
A structure for protecting a surface of a substrate, wherein the uneven structure has a height and pitch of 50 nm to 900 nm. A method for protecting a surface of a substrate, which directly forms a fine concavo-convex structure having a height and pitch of 50 nm to 900 nm on the surface of the substrate or the surface layer of the substrate, comprising a component for forming the concavo-convex structure. After dripping the liquid onto the surface or surface layer of the substrate, the solvent in the liquid is volatilized by heating or drying, or the surface is melted by acid or alkali solution, or the concavo-convex structure is surfaced or surfaced by a wet method. A method for protecting a surface of a substrate, which is formed on a layer. A method for protecting a surface of a substrate, which directly forms a fine concavo-convex structure having a height and pitch of 50 nm to 900 nm on the surface of the substrate or the surface layer of the substrate, wherein the component for forming the concavo-convex structure is formed by sputtering. A method for protecting a surface of a substrate, wherein the concavo-convex structure is formed by ionizing by a dry method including ion plating and spraying on the surface or surface layer of the substrate or polishing the surface of the substrate. A method for protecting a surface of a substrate, comprising forming a fine concavo-convex structure having a height and pitch of 50 nm to 900 nm on a surface of the substrate or a film formed on the surface layer of the substrate, and forming the concavo-convex structure. A liquid containing components and organic matter is applied to the surface or surface layer of the substrate to form a film, and then the organic matter is burned by heating at a high temperature or by irradiation with ultraviolet rays or plasma to form the concavo-convex structure on the film. A method for protecting the surface of a substrate. 2. The structure for protecting a surface of a substrate according to claim 1, wherein the component forming the concavo-convex structure includes at least one of the substances listed below.
-Particles or crystals of silicon oxide-Particles or crystals of titanium oxide-Particles or crystals of inorganic compounds (excluding metals) other than silicon oxide-Particles or crystals of metal compounds excluding titanium oxide-Ions-Metals Particles or crystals of silicon doped with particles or crystals-Particles or crystals of silicon compounds doped with metal particles or crystals-Particles or crystals of silicon compounds doped with metal compounds or crystals-Ions Particles or crystals of silicon doped with ions-Particles or crystals of silicon compounds doped with ions-Inorganic particles (excluding metals) or silicon particles or crystals doped with crystals-Inorganic materials (excluding metals) Particles or crystals of silicon compound doped with particles or crystals ・ Inorganic (except metal) compound particles or crystals of silicon doped Particles or crystals of inorganic compounds (excluding metals) compounds or silicon compounds doped with crystals • Particles or crystals of titanium doped with metals (except titanium) or crystals • Metals Particles or crystals of titanium compounds doped with particles or crystals (excluding titanium)-Particles or crystals of titanium doped with particles or crystals of metals (excluding titanium)-Metals (excluding titanium) compounds Particles or crystals of titanium compounds doped with particles or crystals of: ・ Ion-doped titanium particles or crystals ・ Ions-doped titanium compounds of particles or crystals ・ Inorganic (excluding metals) particles or crystals Particles or Crystals of Titanium Doped with Inorganic Particles or Crystals of Titanium Compounds Doped with Inorganic (except Metal) Particles or Crystals Particles or crystals of the genus excluding) with the exception of particle or crystal-inorganic (metal titanium doped particles or crystals of the compound) titanium compound doped particles or crystals of the compound The structure for protecting a surface of a substrate according to claim 5, wherein the component forming the concavo-convex structure further contains an organic substance. The method for protecting a surface of a substrate according to claim 2, wherein the component forming the concavo-convex structure includes at least one of the substances listed below.
-Particles or crystals of silicon oxide-Particles or crystals of titanium oxide-Particles or crystals of inorganic compounds (excluding metals) other than silicon oxide-Particles or crystals of metal compounds excluding titanium oxide-Ions-Metals Particles or crystals of silicon doped with particles or crystals-Particles or crystals of silicon compounds doped with metal particles or crystals-Particles or crystals of silicon compounds doped with metal compounds or crystals-Ions Particles or crystals of silicon doped with ions-Particles or crystals of silicon compounds doped with ions-Inorganic particles (excluding metals) or silicon particles or crystals doped with crystals-Inorganic materials (excluding metals) Particles or crystals of silicon compound doped with particles or crystals ・ Inorganic (except metal) compound particles or crystals of silicon doped Particles or crystals of inorganic compounds (excluding metals) compounds or silicon compounds doped with crystals • Particles or crystals of titanium doped with metals (except titanium) or crystals • Metals Particles or crystals of titanium compounds doped with particles or crystals (excluding titanium)-Particles or crystals of titanium doped with particles or crystals of metals (excluding titanium)-Metals (excluding titanium) compounds Particles or crystals of titanium compounds doped with particles or crystals of: ・ Ion-doped titanium particles or crystals ・ Ions-doped titanium compounds of particles or crystals ・ Inorganic (excluding metals) particles or crystals Particles or Crystals of Titanium Doped with Inorganic Particles or Crystals of Titanium Compounds Doped with Inorganic (except Metal) Particles or Crystals Particles or crystals of the genus excluding) with the exception of particle or crystal-inorganic (metal titanium doped particles or crystals of the compound) titanium compound doped particles or crystals of the compound The method for protecting a surface of a substrate according to claim 7, wherein the component forming the concavo-convex structure further contains an organic substance. A substrate comprising the substrate surface protecting structure according to claim 1.

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