WO2000068330A1 - Inorganic-organic film and starting liquid composition therefor and method for preparation thereof, and applications and method for preparing them - Google Patents

Abstract

A coating and a coating type adhesive having ceramic fine particles as a film-forming component, specifically, a coating and a coating type adhesive which contain a varnish having an inorganic material as a main component or a modified acrylic resin and superfine ceramic particles such as silica and alumina particles having a particle diameter of the order of nm, as main film-forming components, and a solvent and an additive which are appropriately selected based on the application method employed, in a mixing ratio which is also dependent on the application method. The coating and the coating type adhesive are advantageous in that, as the bonding between the components thereof proceeds, superfine ceramic particles being dispersed homogeneously in a liquid phase enter into the space between the molecules of the components thereof in the liquid phase, which markedly enhances the strength of the bonding between the molecules, resulting in the modification of a cured resin to a resin having a structure capable of preventing the entry of oxygen or moisture, and thus are compositions which can be suitably used in a variety of applications such as a rust-inhibiting resin, a hydrophilic resin, a hydrophobic resin and an ultraviolet rays-screening resin. The coating and the adhesive have a simple composition and structure, and also exhibit excellent adhesion to any adherent, and further it is possible with ease to impart an additional function with selectivity to them.

Description

 Specification

 Inorganic organic film and its starting liquid composition and its production method,

 And applicable products and their manufacturing methods

 Technical field

 The present invention provides an inorganic film or an inorganic organic film containing an inorganic substance such as ceramics or an organic substance (hereinafter, both are collectively referred to as an inorganic / organic film) by a simple method called painting.

 Background art

 As a general property, paints must adhere firmly to the surface of the workpiece, assuming that they provide the desired function, and form a film that is difficult to transmit water, various ions, oxygen, etc. To protect the surface of the object to be coated, and that the film has appropriate hardness, ductility, and elasticity so that it does not peel off, and its color, gloss, and strength are affected by extraneous substances such as light, water, and oil. It is said that it is necessary that adhesion and the like do not deteriorate easily.

 The components and raw materials that make up the paint are extremely diverse, and all can be said to be used. The constituent components of the paint include a coating film forming element and a coating film forming auxiliary element. The coating film-forming elements include the main elements that are generally called polymers and oligomers, which are the main components of the coating film, and sub-elements such as plasticizers and modifiers added to complement or modify the main elements. It consists of a film-forming aid consisting of a solvent to provide the necessary fluidity and disperse soot.The addition of a pigment to these elements is called enamel, and the parts of the enamel other than the pigment other than the vehicle are called vehicles. , Bindemittal).

For the paint, one or more polymer or oligomer main elements are selected according to the use, type, material, etc. of the object to be coated, and according to the intended function, and the plasticizer is modified. Select the sub-elements such as the agent, select the required pigment, A certain paint is completed by adding a film-forming auxiliary element consisting of a solvent and disperse soot selected in response.

 For example, antifouling antifouling paints for the purpose of preventing fouling organisms from adhering to the bottom of ships, such as Fujibo and Cerbra, fall under the category of so-called biologically active paints. It has only a single function.

 In addition, the bottom paint is required as a bottom paint to provide the protection function and to provide the protection performance and high bonding strength to metal materials such as iron and aluminum. A plurality of different paints are selected according to various functions, and these paints are blended so as to function mutually.

 Bottom paint for the purpose of preventing the adhesion of organisms attached to the bottom of the ship is often configured to dissolve toxic substances that do not like organisms, and is naturally consumed over time. Is essential.

 However, from the viewpoint of preventing pollution of the global environment, the use of such bottom paint, in which such toxic substances dissolve, has been banned from being used since 2000 due to self-restraint in recent years.

 On the other hand, as for inorganic materials, especially ceramic films, the method of vapor phase growth is mainly used at present, and it is possible to form an extremely high-purity thin film. However, for example, a special device in which a vacuum atmosphere is indispensable is required. is there. Simple processes such as coating in the air cannot be adopted.

Although the content in the solvent is low, various methods for forming ceramics as a coating film have been proposed. Both proposals use polymer resins called polymers and oligomers, which have been developed in recent years and have excellent properties, in order to provide these resins with properties such as heat resistance, flame resistance, and durability. The goal was to achieve this by adding inorganic substances with the desired properties to high-performance organic paints. As described above, means for obtaining a target multifunctional paint depending on the properties of organic substances such as polymer resins have been developed. However, in order to add another function to a resin or a resin film which was useful in a certain function, the above-mentioned inorganic substance-containing coating is used. The application of a coating material may erode the film or cause other unexpected problems. Therefore, a method of forming another resin layer for preventing erosion of the inorganic-containing paint and forming a multilayer is adopted.

 The inventors have found that a paint having a simpler composition and structure can exhibit excellent adhesive strength regardless of a coating target, and a paint that can easily achieve various functions selectively can be achieved. I realize that it is necessary. Disclosure of the invention

 The inventors of the present invention have not proposed a single type of paint that has both hull protection and hull antifouling properties. did. Focusing on the fact that if the cured film does not allow oxygen or moisture to permeate, it can provide a protective function.If the intermolecular distance of the paint components constituting the film is reduced, the impermeability of oxygen and moisture will be reduced. I thought I could get it.

 In addition, the inventors of the present invention have conducted various studies on the composition of a coating material capable of producing a coating film having a small intermolecular distance between the coating components constituting the above-described coating film. As a result, along with the polymer and oligomer as main components of the coating material, We thought that by using ceramic particles as small as this, it would be possible to penetrate between the polymer and oligomer molecules of the paint component and minimize the intermolecular distance.

 The inventors of the present invention aimed at producing a coating having excellent adhesion strength to metals such as iron and aluminum on ships, creating a coating with a small intermolecular distance between the coating components constituting the above-mentioned coating, Various studies were made on the composition of the paint having a high degree of odor.

For example, the inventors use a varnish mainly composed of an acrylic resin or an inorganic substance as a liquid phase and a ceramic ultrafine particle powder such as alumina or silica having a particle diameter of nm class as a main coating film constituting component, and appropriately adjust the coating method according to the coating method. It was prepared with the selected solvent and additive type and the appropriately selected quantitative ratio. When this paint is applied to ordinary steel, stainless steel, aluminum, etc., after the film is cured, the transparent film can be removed with a knife. It was also found that it was not attacked by acid, was not damaged by the burner flame, did not produce metal mackerel in salt spray tests and salt water immersion tests, and had little marine organisms in the sea.

 The inventors of the present invention have found that, while the bonding of the coating components is progressing, nm-class alumina and silica ultrafine particles of ceramics enter between the molecules of the coating components, and as a result, a certain kind of We speculate that the bonding force between the molecules will be very strong, as in the case of crystallization, and that it will also be strong against thermal contraction. In addition, the cured resin is free of oxygen and moisture, which cause the burning of the base metal and the resin, so that it has significantly improved protection and flame resistance, and is impervious to oxygen and moisture. It is estimated that an inorganic-organic film that satisfies all the properties of (anti-fouling property), stain resistance (fouling resistance), chemical resistance, heat resistance, flame resistance, abrasion resistance and specularity was obtained. .

 In addition, the inventors have found that the paint having the above-mentioned composition has particularly excellent adhesion strength to aluminum and stainless steel. This is because the polymer is densely polymerized as if the film is crystallized, It is speculated that the fine particles exert an anchoring effect on the aluminum surface, resulting in strong adhesion and adhesion.

 The paint of the present invention has a particularly strong attractive force due to nm-class silica and alumina particles, which acts as a penetrating power to the counterpart material, and has a remarkable penetrating and impregnating power into glass, ceramic materials, and wood. In addition, it has been confirmed that it has a strong anchoring and sticking power, as it has an anchoring effect and penetrating power on all material surfaces such as various metals and resins, various glasses, ceramic materials, paper, wood, and inorganic materials.

In addition, the present inventors have found that titanium oxide for photocatalyst is formed into fine particles of several nm to several tens of nm in the same manner as alumina and mixed, whereby titanium oxide is present on the surface of the film, and the so-called photocatalytic effect by UV irradiation is exhibited. It was found that photocatalyst-specific functions such as antifouling property, antibacterial property and hydrophilicity were added. It is well known that, when titanium oxide for photocatalyst is mixed into a paint to exhibit a photocatalytic effect, the coating itself is rapidly deteriorated due to the photocatalytic effect. It has been confirmed that even if the coating is densely polymerized as if it is crystallized, even if the coating is mainly composed of organic components, it is hardly deteriorated. The photocatalytic effect can be imparted to any material and place.

 In the beginning, while the bonding between the paint component and the curing agent used as needed progressed, the ultrafine particles of ceramics of nm-class alumina and silica entered between the molecules of the paint component and caused some polymerization. Thought that it would advance. This can be explained when the amount of ultrafine powder relative to the paint component is small.

 However, during the experiment with increasing amounts of ceramic ultra-fine particles added to various organic paint components, when using organic flammable materials, it was flammable after blending with alumina ceramic ultra-fine particles. It was found that it did not ignite even at about 300 ° C during the subsequent semi-curing, and exhibited fire resistance of 600 ° C after several days and 800 ° C or more after one week.

 In other words, this is a film in which the organic components occupy a large amount as described above, but the bonding degree is increased by the ultra-fine powder, and after being modified and stabilized, there is almost no deterioration, and the ceramic ultra-fine particles With the increase in the amount of cerium, ceramics did not change.

 More specifically, the inventors have found out the extremely unique properties of ceramic ultrafine particles, and by making effective use of them, they can be carried out extremely easily as compared with, for example, vapor phase growth. It was found that almost perfect inorganic / ceramic film can be formed by the coating method.

In the present invention, an organic resin, an inorganic resin, or a resin mixture thereof having a relatively simple structure is called a carrier. It is characterized in that it is used as an entity like The ultra-fine particles in the liquid phase after being applied to the liquid phase, the mutual attractive force between the ultra-fine particles, the penetrating power to other material surfaces, the function of decomposing the liquid phase itself, or further breaking the bonding of the liquid phase It is considered to have a catalytic function to promote the function.

 More specifically, a liquid phase is prepared for arranging the ultrafine particles close to or in contact with each other, and the ultrafine powder and the liquid phase material are uniformly dispersed and mixed from 1: 5 to almost the same volume in the power lake. This liquid composition is mixed with a so-called thinner selected according to the application means, and is used as a form of a paint or an adhesive which is arbitrarily diluted. In other words, ultrafine particles suitable for the intended function are selected, and a coating method selected according to the adherend, and a liquid phase material and a thinner suitable for the method are used to obtain the required paint and adhesive composition. Make up and apply this.

 Any known coating means can be used.Apply using the coating method selected according to the properties of the selected ultrafine particles, liquid phase, thinner, etc., and apply the coating film to the object by natural drying or forced drying. When formed, the coating film formed by evaporating the thinner and the like formed a uniform dispersion of ultrafine particles in a composition with a large amount of liquid phase, and the ultrafine particles were arranged in contact with each other as the number of ultrafine particles increased A state in which a small gap can reduce the liquid phase force has been realized almost from the beginning. This is because there is almost no decrease in the thickness of the coating film from the time of application, it exhibits high hardness from the time of initial curing, the hardness increases further over time, and there is no reduction in thickness at that time. From the point of view, it is inferred from the beginning that this is the organization mentioned above.

 Ultra-fine particles are arranged close to each other and in contact with each other, and even if it is a liquid phase that fills the gaps between these ultra-fine particles, or if it is a modified product that has been decomposed or divided, strong adhesion occurs between the ultra-fine particles Therefore, it is considered that these are firmly integrated.

 The most important point here is to disperse the ultrafine particles homogeneously in the liquid phase, and the above-mentioned effects can be obtained even when the amount of the ultrafine particles is small.

As described above, when a combustible material of an organic resin such as a general acrylic resin mainly composed of MMA is used for a liquid phase, ceramic ultrafine particles such as silica and alumina are used. Is flammable after blending. However, it did not ignite at about 200 ° C during semi-curing after application, and exhibited fire resistance of 400 ° C after curing for more than 10 hours, 600 ° C or more after several days, and complete curing. Since the same tendency is observed when a resin that requires time is used, it is inferred that the above-described structure has a small gap between the ultrafine particles. In the case of the silicone-modified acrylic resin, the above-described curing was extremely fast, and immediately the high hardness and the fire resistance of 800 ° C or more were immediately exhibited.

 In particular, after the ultrafine particles are close to each other and arranged in contact with each other by the liquid composition in which the ultrafine particles and the liquid phase material are mixed in substantially equal volumes, the completed thin film is mixed with the ultrafine particles and the liquid phase material. Not only when the volume of the liquid phase material is about the same, but also as the liquid phase material is divided and decomposed by the catalytic function of the ultrafine particles, and the weight is reduced, the proportion of the ultrafine particles increases, and the purity of the ultrafine inorganic particles This means that a film is formed, and there is no decrease in the film thickness at this time. Even if the amount of the liquid phase is large in the initial composition, if the volume becomes equal to or less than the applied volume, an ultrafine inorganic film is similarly formed.

 In the above-mentioned composition, it is considered that the closer to the state of the solidified inorganic / organic film, the closer the ultrafine particles and the arrangement of the ultrafine particles are progressing, and moreover, the more the ultrafine particles are in the liquid phase body after being applied. Once the aggregation of fine particles has started, it cannot be returned like an irreversible reaction. Therefore, the complete contact arrangement of the ultrafine particles is completed, and the thin film having the function of the ultrafine inorganic material regardless of the presence or absence of the solidified liquid material or the denatured solidified material between the ultrafine particles. Become. In other words, if the ultrafine particles are alumina, they will have the properties and functions of alumina, for example, a highly insulating thin film, regardless of the type of liquid phase.

 In the starting composition of the present invention, the fact that ultrafine inorganic substances and the like are homogeneously mixed or kneaded in or mixed with the liquid phase material and dispersed as homogeneously as possible results in the formation of an organic-organic film. Becomes the most important thing.

The ultrafine powder may be the same substance alone or a mixture of different substances.Even if the same substance is used, the average particle diameter is different. It is considered preferable because the penetrating power to the coating material works effectively, but it is easy to disperse uniformly in a liquid phase having the same average particle size.

 The most important thing in the present invention is that the ultrafine particles are uniformly dispersed in the liquid phase as described above, and the combination and mixing method of the ultrafine particles are appropriately determined so as not to cause primary or secondary aggregation. It needs to be considered.

 The inventors have found that as a method for easily realizing a state in which ultrafine powder is uniformly dispersed in a liquid phase, a method of mechanically kneading with a ball minole (bead mill) is preferable.

 The peculiar phenomena and functions of such ultrafine particle powder vary depending on the material, but the above-mentioned ability depends on the particle outer diameter. Therefore, the average particle size of the ultrafine powder is preferably 200 nm or less, 150 nm or less, 100 nm or less, 50 nm or less, 30 nm or less, 20 nm or less, and lOnm or less, in that order, the effect is larger. It is also considered preferable to appropriately mix several types of ultrafine particles having different particle sizes.

 Therefore, if ultra-fine particles of the nanometer class, such as inorganic substances, metals, alloys, and organic substances, can be formed, the use of a liquid phase material enables the formation of thin films of any substance, and enables application and adhesion to any substance. It is considered to be.

 In addition, the inventors of the present invention have found that, in addition to the one-pack type starting composition in which the ultrafine powder and the liquid phase substance are mixed in almost the same volume or in various ratios, the coating component, which is the main element selected according to the purpose, is used. A two-component or multi-component composition of a base material consisting of ceramic fine particles and a solvent with a particle size of nm and a curing agent consisting of a solvent and a solvent selected according to the above-mentioned paint components. -We found that organic films can be formed.

In other words, for the paint, it is possible to select the necessary sub-elements according to the function, to select the solvent and its amount as auxiliary elements, and to select the quantitative ratio of the main agent and the curing agent as appropriate. It can be used as a paint for various purposes and functions. Furthermore, the present inventors have proposed that, besides coloring pigments such as titanium oxide, carbon black, and red bengal, paint pigments such as talc, kaolin, calcium carbonate, etc .; The inventors found that flake pigments (Micaceous iron oxide or glass flakes) could be used, and added various functional inorganic powders such as ferrite powders, metal powders, and ceramic powders such as oxides as pigments. As a result, they found that it can be effectively used as an inorganic / organic film having the function of the added inorganic fine particle powder. Here, the average particle size of the ultra-fine particle powder and the various inorganic powders to be added may be appropriately varied, the average particle size of the added powder, particularly the metal or the inorganic powder may be set to the nm class, and the average particle size may be appropriately varied to provide uniformity. By dispersing and mixing the film, the coating film can be formed into a dense and strong thin film with a coherent appearance.

 In addition, the inventors have found that the above-mentioned paint composition is extremely effective as an adhesive as it is, and all kinds of materials such as ordinary steel, stainless steel, aluminum foil and resin film, paper and resin, and inorganic material and resin are different or different. It has been found that it is suitable for manufacturing a laminated material that is capable of bonding various materials and has various functions.

 The inventors have found that the above-mentioned paints and adhesives may be used in combination, for example, as steel and stainless steel, as an adhesive for laminating aluminum foil and a resin film, and as a paint as a protective film on the surface. Was found to be possible.

It will be apparent from the foregoing knowledge that the paints and adhesives of the present invention are applicable to almost any application. Furthermore, the inventors have found a new use. For example, a coating film made of a silica-based paint with an average particle size of run class, for example, should be able to completely block ultraviolet rays, and should have excellent transmittance and scattering effect for visible light transmitted through the coating film. It has an extremely low frictional resistance, and can provide excellent hydrophilicity by forcibly drying and heating at the time of painting, and this hydrophilicity is achieved by polishing the surface of the coating film with an abrasive pad (such as zirconia, diamond, etc.). Can also be applied by polishing with a pad that has been coated and solidified), and a coating film made of a paint using alumina with an average particle size of nm class functions as a highly insulating film with impermeability to oxygen and water. And so on. BEST MODE FOR CARRYING OUT THE INVENTION

 The inorganic eco-friendly film according to the present invention is formed as a film from a liquid phase body containing at least one kind of inorganic or organic or inorganic and organic liquid containing at least one kind of inorganic or organic or inorganic and organic ultrafine particles. It is an inorganic / organic film composed of ultrafine particles arranged adjacent to each other without aggregation or dispersion in the solidified film, and a liquid phase solidified between the ultrafine particles. Here, the liquid composition may contain, in addition to the required one or more kinds of ultrafine particles, other kinds of fine particles having a larger particle diameter than the ultrafine particles.

 As described above, the inventors have found that if the coating film itself is dense, the adhesion of marine organisms is small, and if the adhesion to metal is strong, the performance can be maintained for a long time until the next repainting, and It was developed considering that it is most suitable for stain paint. This inorganic or organic film is not only self-contained easily mirror-finished by the ceramic fine particle powder as a component of the coating film, but also becomes dense as if the coating film itself was crystallized, resulting in oxygen and moisture. It does not allow light to pass through, so it does not attract anyone from outside.

 In addition, the inventors have found that the ceramic ultrafine powder has a strong suction force and a penetrating force to the resin for the coating film and the substrate to be coated, thereby significantly improving the anchoring effect on the substrate. In addition to being applicable to almost all functions and applications as a paint, this paint component can be bonded as it is in an extremely thin film regardless of the mating material, for example, as an adhesive for lamination of various materials I was surprised to find that it was optimal, and that it would be infinitely widespread.

The paint according to the present invention has a coating film that is self-contained, dense and strong, has an extremely high adhesion strength to metal and the other party for the first time, and is similar to pigments added to conventional paints. Since functional material powder can be added, not only post-coating and pre-coating with the purpose of classical protection and beautification, but also special functions such as thermal bioresistance function, electrical function, mechanical function, Applicable to optical functions and environmental protection functions.

 Thermal bioresistance functions include heat-resistant paints, fire-retardant paints, non-striking (anti-sticking) paints, anti-fouling paints for ship bottoms, anti-mold paints, and insecticide paints.

 Electrical functions include electrical insulating coatings, coatings for semiconductors, antistatic coatings, conductive coatings, radio wave absorbing coatings, coatings for electrode wave shielding, electric field relaxation coatings, secondary electron emission coatings, magnetic coatings, and electronic scribing coatings Paints, printed circuit IC paints, lithography paints, etc.

 Mechanical functions include anti-hydrogen embrittlement paints, anti-rupture materials, high-elastic paints, lubricating paints, low-friction coefficient paints, paint protectants, and thick-film paints.

 Optical functions include photocatalytic paints, luminescent and fluorescent paints, self-luminous paints, retroreflective paints, heat-ray absorbing paints, UV blocking paints, photoconductive paints, photoelastic paints, leather light paints, liquid crystal display paints, lenses and glass Paints and the like.

 Environmental protection functions include anti-icing, snow-prevention paint, anti-condensation paint, super-weather-resistant paint, anti-slip paint, soundproofing, anti-vibration paint, heavy-duty anticorrosion paint with chelate polymer, radiation shielding paint, leak detection paint, and anti-sticking paint , Self-cleaning paint, superhydrophobic paint, hydrophilic paint, etc.

In the present invention, the inorganic / ceramic ultrafine particle powder has the same function and effect regardless of any metal, alloy, or nonmetallic inorganic material. According to the findings of the inventors, the effect obtained depends on the particle size, and the smaller the particle size, the more effective.The average particle size of the powder is desirably 100 nm or less, preferably 50 nm or less, 30 nm or less, 20 nm or less, 10 nm or less. Particle size of several nm. In industry, for example, is used as a polishing agent _{A1 2 0 3, Si0 2,} MgO, Zr0 2, preferred for diamond powder various particle sizes of several nm ~ several hundred nm is obtained relatively easily . In addition, for example, In Si0 _2, if not enhance its purity, in order to mix the A1 ₂ 0 _3, MgO, Zr0 _{because 2} and was contained, the plurality of ultrafine powder, apply a different Si0 ₂ purity and an average particle size It is also preferable to mix them appropriately. Such as amorphous Si0 _2, the form of such crystals is also available different as shall.

In the present invention, the unique properties of the ultrafine particle powder are provided by ultrafine particles having a size of 100 nm or less, preferably 50 nm or less. In addition to this, the specific properties of the ultrafine particles are desirably 、 μπι or less, preferably 500 nm or less, 100 nm or less. Use of the fine particle powder as a mixed powder as appropriate is extremely effective in improving the bonding strength and the compactness. For example, A1 and ₂ 0 _3, Si0 ₂ 50nm following ultrafine powder such as may be provided an average particle size suitably greater than lOOnm differences various fine powder added as a pigment for paint, or Ya metal as Pigment By reducing the average particle size of the inorganic powder to a few 100 nm class and appropriately providing a difference in particle size from that of the ultrafine particle powder, the coating film can be formed into a dense and strong thin film like pigment plating.

Ceramics have various compositions having the following various functions. In order to impart each function, the following ceramic powder is added in the same manner as the pigment described below, and the effect of the present invention, that is, the effect of modifying the paint, the ceramic fine particles to obtain a penetration effect can mainly adopted formulation method using a A1 ₂ 0 _3, Si0 _2.

 In the present invention, there are no restrictions on the functions that can be added by the ceramic ultrafine particle powder or the like, but the main functions include the following.

 High adhesion strength, durability, sea protection, seaworthiness, impermeability (water, air, oxygen), antibacterial, odor prevention, volatilization prevention, odor sealing, oil resistance, dirt resistance, mirror finish, smoothness , Low friction coefficient, designability, coloring, abrasion resistance, high hardness, surface strength, scratch resistance, fire resistance, flame resistance, heat resistance, high insulation, hydrophilicity, hydrophobicity.

 A detailed example of the function of ceramics is as follows.

Highly insulating (A1 ₂ 0 _3), high capacitance (BaTi0 _3), piezoelectric (? 2?, 8 ₂ 110), Semiconductive (LaCrO ₃ , SiC, iron group oxide, BaTi0 ₃ , vanadium oxide

_{Things, ZnOBi 2 0 3, Sn0 2} ), superconducting _{(Ba2YCu 3 0 7, PbMo 6} S 8),

Ion conductivity _{(P-Al 2 0 3,} Zr0 2), thermionic emission property (LaB6),

Secondary electron emission property (BaTi0 _3), soft (Zn-Mn ferrite, _Y -Fe ₂ 0 _3, YIG), the hard magnetic (SrO6Fe ₂ 0 _3), translucency (A1 ₂ 0 ₃ sintered body), guide light resistance (Si0 ₂ fibers, ZnO thin), reflective _{(Sn0 2, In 2 0 3} , TiN), X -ray-ultraviolet excitation (CaW0 _4),

Infrared excitation (LaF ₃ (including Yb, Er)), electron excitation (Y ₂ 0 ₂ S (including Eu), ZnS (including Ag, Cl)), light emitting Daio one de (GaAs (including Si)), electroluminescent ( ZnS (including Cu, Al)),

Electro-optical effect _{(Bi 4 (Ge0 4) 3} , PLZT), magneto-optical effect (YIG),

Acousto-optic effect (LiTa0 _3, LiNb0 _3), heat resistance (Th0 _2, Zr0 _2),

Thermal insulation _{(K 2 O'nTiO 2, CaO'nSi0 2} ),

Hard function _{(Al 2 0 3, WC,} TiC, B 4 C, SiC, diamond),

Strength function (Si ₃ N ₄ , SiC, tempered glass, crystallized glass),

Catalyst Kiyarya one _{(Al 2 0 3, Ti02)} , catalytic _{(Κ 2 0, ηΑ1 2 0} 3, Fuweraito),

Bactericidal (Ti0 _2), antifouling properties (Ti0 _2).

 In the present invention, a case will be described in which a classic coating material comprises a coating film component and a volatile component. The components of the coating film include pigments, resins, and additives, and volatile components are solvents. In the classification based on the film-forming elements described above, the main element is resin, the sub-element is additives, and the film-forming auxiliary element is volatile.

Pigments have the effect of increasing the strength by giving color and hiding power to the coating film to give it a thickness, but usually, depending on the characteristics of the pigment itself, anti-corrosion, magnetism, heat resistance, anti-fouling, temperature display, fluorescence, electromagnetic Adds shielding and radio wave absorption. Along with the ceramic ultrafine particle powder of the present invention, pigments comprising the ceramic powder and the fine particle powder for imparting the above-mentioned functionality can be added. Inorganic materials include carbon, titanium oxide, strong oxide (including trans-oyaroid Elo and red), zinc, navy blue, ultramarine, aluminum powder, brass powder pigment, pearl pigment, etc.

 Examples of organic compounds include azo pigments (monoazo, disazo, chelateazo, benbu midagaron, chelateazo) and polycyclics (phthalocyanine, quinacridone, dioxazine, anthraquinone, theoingo'berlen, isoindolinone).

 Resins are important components that determine the performance of the coating film.They have the function of adhering to the object to be coated as a pigment binder.Resins are selected from solvent evaporation type or reaction type. There are many pre-bolimers designed for paints, and the reactive paints become more polymerized at the same time as the coatings are formed. In the present invention, a low molecular weight acrylic resin is particularly preferred.

 Available oils and fats include linseed oil, soybean oil, china paulownia oil, safflower oil, coconut oil, castor oil, and dehydrated castor oil. Natural and processed resins include rosin, damma-copanil, shellac, lime rosin, ester gum, maleated ester gum and the like. Cellulose derivatives include nitrocellulose, cellulose butyrate, benzylcellulose and ethylcellulose. Examples of synthetic resins include alkyd, vinyl acryl, various acryl, epoxy (thermoplastic and thermosetting), phenol, butyral, urethane, polyester (unsaturated and oil-free), silicone, and fluorine resin. And etherified amino resin, polyisocyanate-based propolymer, butadiene prepolymer and the like.

Additives are added in small amounts to improve coating film formation, storage stability, physical properties of the coating film, weather resistance, coating workability, etc., and include pigment dispersants, wetting agents, color separation inhibitors, Anti-settling agent, anti-skinning agent, leveling agent, antifoaming agent, slipping agent, abrasion resistance improver, plasticizer, antistatic agent, titanium or silane coupling agent (secondary physical property Upper agent), antifungal agent, ultraviolet absorber, metal stone gen desiccant, Leo mouth G Modifier.

 The volatile solvents are those that dissolve the above-mentioned resins to make them usable liquids, and that are employed according to the selected coating method. Esters such as ethyl acetate, butyl, isobutyl and ethylene glycol monoether acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone and isophorone; alcohols such as methyl, ethyl, butyl and isobutyl alcohol; toluene, xylene And aromatic hydrocarbons such as sorbesso.

 Various types of coatings are produced by selecting the above-mentioned coating components and volatile components. The coatings according to the present invention are prepared by appropriately adding inorganic / ceramic ultrafine particles as coating components. It is characterized in that its constituent components are modified to become impermeable to oxygen and moisture, and that it exhibits extremely high adhesion.Other than this, conventional functions and features according to the selected composition are used. Paint. Therefore, paints of the following classification can be obtained.

Oil-based paint, alkyd resin paint, amino, alkyd resin paint, acrylic resin paint, epoxy resin paint, urethane resin paint, unsaturated polyester resin paint, chlorinated rubber paint, inorganic paint, fluorine Resin paints, silicone resin paints, emulsions and water-based paints, nitrocellulose paints, vinyl resin paints, etc. are classified according to the state of the paint.Emulsion paints, multi-component paints, etc. None, multi-colored patterns, etc., according to the coating method.Steel paint, light metal paint, woodwork paint, leather paint, plastic paint, etc. Classification according to the drying method, such as electropaints, electrodeposition paints, etc. Line curable coating material, as any known coating such as moisture curable coating material is available. W 00/68330

 16

Thermoplastic paints and thermosetting paints are classified as thermal classifications, and the curing processes of the coating films are different from each other. However, it can be assumed that the paints of the present invention bond more strongly in the behavior of the thermosetting paints.

 In the case of thermosetting paints, the distance between the molecules decreases as the solvent evaporates during the drying process after the application, and the reactive groups present in the coexisting pre-polymers collide to form chemical bonds. It is thought that the cross-linking between the molecules progresses, and a strong three-dimensional chemical bond is formed to form a strong coating film.

 That is, the above-mentioned components are selected so as to form a strong three-dimensional chemical bond in the coating film under the conditions given at the time of paint design.For example, two or more functional groups that react under specific conditions In the presence, evaporation and drying progress under specific conditions such as temperature, light rays, and electron beams, shortening the intermolecular distance of the components, facilitating the reaction of the functional groups, and cross-linking between the molecules. Form a strong three-dimensional chemical bond.

The liquid phase within a few to several tens nm in particle size A1 ₂ 0 _3, Si0 _2, when the ceramic ultrafine particles, such as diamond powder is present uniformly dispersed, can be to bridge the gap between the liquid phase molecule next, also ceramic ultrafine particles is strong penetration force pole Umate acts attraction itself, the irreversible reaction at the time of solidification is completed, no longer 0 to about ₂ or H ₂ 0 is no gap through, dense as crystals Daiamondo I guess. The behavior when the amount of rnn-class ultrafine powder relative to the resin component during solidification is large is as described above. In particular, when an acrylic or silicon-modified acryl-based EB-cured resin that solidifies with an electron beam in the liquid phase is used, the gaps between the resin molecules that are bonded by the electron beam can be filled with ceramic ultrafine particles, resulting in higher hardness. It is usually thought that it can no longer be disassembled.

Further, on the surface of the object to be coated, the attractive force of the ceramic ultra-fine particles itself acts together with the above-mentioned reaction, and the ultra-fine particles enter into the fine dents on the surface. It is. It should be noted that the strong penetrating power of the paint of the present invention may be excessively penetrated depending on the material to be coated. Therefore, the paint of the present invention may be applied after separately performing a known base treatment and painting. using a strong penetration force by Ti0 ₂ ultrafine powder nm class and how to stop when cut need this will be described later as a machine configuration of a strong adhesion.

 It can also be used as a laminated coating film with other paints if necessary. A known coating film can be laminated as a base layer, or another known coating film can be interposed between the coating films of the present invention. Various coating configurations can be adopted, such as a configuration in which the coating of the present invention is disposed between other known coatings.

 In the present invention, the synergistic effect of the above-described modification of the coating film itself and the penetrating force and the anchor effect is exhibited even in an extremely thin coating film because the ceramic ultrafine particles have a size of the nm class. It can be easily understood that this is useful as it is as an adhesive. In the experiments conducted by the inventors, strong adhesion is exhibited by strong penetration force in the bonding of various materials such as metals, resins, glass, ceramics, paper, wood, inorganic materials, and other materials. Make sure you do.

 Since the adhesive according to the present invention basically performs the adhesive function as it is with the composition that is basically established as the above-mentioned various paints, there is a part different from the concept of the conventional adhesive, but the adhesive force as the paint is extremely high. For example, after coating as a coating on material A, when material B is laminated during semi-curing, strong adhesion is exhibited.

On the other hand, in the case of thermoplastic paints, the polymer resin for the coating material is applied to the required material with fluidity imparted by a solvent, and then dried and dried. A film is formed while maintaining physical properties by the intermolecular attractive force of the resin.However, the fact that heat is applied to the coated film weakens the intermolecular attractive force due to the thermal motion of the resin and makes it flowable Characterize. The presence of ultrafine ceramic particles having a particle size of several to several tens of nm in this thermoplastic coating will modify the coating film during curing, as in the case of the above-mentioned thermosetting coating, and will provide a strong penetration force and The synergistic effect of the anchor effect appears, and extremely strong adhesive force is generated.

 In addition, it is also possible to use the strong adhesive force as a binder for kneading materials such as ceramics and oxide powders of various functions. For example, while using as a binder for kneading and molding oxides for radio wave absorption, It can be applied as a protective film on the molded body, used for bonding the molded bodies to each other or to other objects, and a paint or adhesive having the same composition can be used for various purposes.

 The paint and adhesive according to the present invention are basically synonymous because they are basically the same substance as described above, but they are used synonymously. In some cases, it is preferable to appropriately change the curing component even if the components are the same. Therefore, known air-cured resins, UV-irradiated curable resins, and UV-irradiated curable resins can be appropriately used for the liquid phase.

 Furthermore, the unique properties of the paints and adhesives according to the present invention, that is, the use of ultrafine ceramic powders, have the effect of modifying coatings, adhesive layers, strong penetration-impregnation, and anchoring effects. Therefore, as shown in the examples, any coating film components can be applied, and new uses and functions as paints and adhesives can be created.

 In particular, coatings and adhesives that use low molecular weight resin as the main component of the coating film, use an appropriate hardening agent as necessary, and mix ultrafine ceramic powders, exhibit strong penetration and impregnation power. When a coating film or a resin film is laminated, these can be cured together, and the effect is that a plurality of layers are cured as a single layer to form an integrally polymerized resin film.

Further, since the paint and the adhesive according to the present invention exhibit a strong permeation / impregnation force and an anchor effect, as shown in Examples, glass, ceramics, inorganic materials Strength that simplifies the basic processing such as various cleaning treatments and neutralization treatments that were previously indispensable such as alkali cleaning, aluminum, stainless steel sheet, pickling and degreasing cleaning of steel sheets, or strong This makes it possible to form or adhere to a coating film and greatly simplifies the conventional coating process.

 In the above description, the ceramic ultra-fine particle powder has been mainly described. In short, the present invention provides a liquid phase that allows the ultra-fine particles to be finally brought into contact with each other and arranged. A liquid composition in which powder and a liquid phase substance are homogeneously mixed at a required ratio or almost the same volume, and a thinner selected in accordance with the means of application mixed with so-called thinner to arbitrarily dilute paints and adhesives The present invention provides a high-performance and high-performance inorganic / organic film by using it as a form.

 In addition, in the starting liquid composition for forming an inorganic / organic film according to the present invention, ultrafine inorganic particles or the like are homogeneously mixed and kneaded in or with the liquid phase substance and dispersed as uniformly as possible. Is most important.

 Therefore, various kinds of stirring and kneading devices such as a known ball mill and mixer are appropriately used to appropriately knead to prepare a uniformly dispersed starting solution composition, which is diluted or kneaded with other resins. It is necessary to. In particular, it is important to use a ball (bead) mill to produce a liquid composition in which ultrafine particles in a liquid phase are dispersed so that they cannot be centrifuged.

 In the present invention, in order to uniformly disperse the ultrafine particles in the liquid phase, in addition to mechanical kneading and dispersing methods using a ball (bead) mill, the average molecular size of the liquid phase substance and the ultrafine particles, It is also important to adopt a method that approximates the average molecular weight (formula weight) as much as possible.

The average molecular size of the liquid phase in the starting liquid composition is desirably close to the range of the average particle diameter of the ultrafine particles ± 100%, and more preferably the average molecular size of the liquid phase is the average of the ultrafine particles. It is preferable that the particle size is approximated within a range of ± 50%. The average particle size of the ultrafine particles is preferably 30 nm or less, and 20 nm or less. Further, the average molecular weight (formula weight) of the liquid phase body is preferably equal to or less than + 200%, + 150%, and more preferably + 100% of the average molecular weight (formula weight) of the ultrafine particles. The average molecular weight (formula weight) of the entire liquid phase body excluding the solvent of the liquid composition, or the main liquid phase substance occupying 50 vol% or more of the liquid phase body, is preferably 250 or less, more preferably 150 or less.

 As a method for forming an inorganic or organic film, any known coating method can be employed. In detail, first, brush coating, flow coating, dip coating, electrodeposition coating, etc. can be adopted, and coating with a plate coater or curtain flow coater, which is advantageous for plate-shaped objects to be coated, can be performed. Can be adopted.

 Furthermore, there are various types of spray coating, such as cold, hot, airless, and airless, as well as various types of electrostatic coating, such as air, airless, and ultrasonic, and electrostatic powder coating. Conventionally known devices and methods can be employed.

 In electrostatic powder spray, powder paint is electrostatically adsorbed to the object to be coated as powder, and while negative (-) charged powder paint is electrically adsorbed, It is used to form a heated coating film in a heating furnace at a temperature around the powder melting temperature. However, since the state of the liquid phase does not exist, it cannot be used as it is in the present invention. According to the coating method using a powder coating, the powder is melted before film formation, but here, the powder is not uniformly dispersed, but immediately secondary aggregates to increase the average particle size of the powder coating. It is impossible to reveal the state of a liquid composition containing a liquid phase body and ultrafine particles, and the effects of the present invention cannot be obtained. Further, it is not practically possible to electrostatically adsorb the ultrafine particle powder to the object to be coated as it is, because the ultrafine particle powder immediately diffuses into the gas phase. The inventors have confirmed and confirmed that.

In particular, as a unique method of the present invention, a liquid phase body (which may have a solvent or may be solventless) is first applied, and then the ultrafine powder is uniformly dispersed and kneaded. Spraying or electrostatic atomization can be adopted. The coating method can be selected according to the desired function and film thickness.

 It is also possible to adopt a lining method, and it is possible to provide an inorganic / organic film corresponding to the general concept of a hollow lining or a glass lining. For example, a known thermal spraying method, a fluidized immersion method, a powder spray method, and a discharge purge method can be employed.

 In the thermal spraying method, a plastic powder is passed through a high-temperature flame at high speed to a semi-molten state, and a resin mixed with ultra-fine powder is blown to the preheated material side with compressed air. In the powder spray method, the adherend preheated in a heating furnace is sprayed, and the powder is melted and lined using an electrostatic coating machine. In the present invention, the resin is made into a molten state, and this is used as a carrier, and a resin prepared by uniformly dispersing and kneading ultrafine particle powder prepared separately is sprayed. In the dispersion method, ultrafine powder and resin powder are homogeneously suspended in a solvent or water to make a dispersion, which is then spray-coated, evaporated to dryness, and then heated in a heating furnace to dissolve the resin powder.

 An application method using a sheet material can also be adopted. The force of premixing the ultrafine powder uniformly into the thermoplastic resin sheet is preferably applied together with other resin, the sheet is adhered to the adherend, melted, and then dried.

 In essence, the present invention provides an inorganic / organic film only by allowing the ultrafine powder to be uniformly kneaded and arranged in a mixed liquid phase so that it cannot be centrifugally separated in various processes of coating in a broad sense. Can be provided.

In order to effectively utilize the functions and properties of the inorganic / organic substances used as the ultrafine powder, the functions to be added and the optimal film forming method are appropriately selected according to the film formation target. Whether it is a paint or an adhesive is only a variation of what form it takes in the chosen film-forming method. It becomes important how to realize. An example will be described below. If you want to apply antifouling treatment to window glass, you can first apply a paint with antifouling function directly to the glass or attach it as an antifouling film.

Therefore, by selecting a known coating which is suitable for application to the glass, the coating material as a liquid phase body, selects the _{A1 2 0 3, Si0 2,} Zr0 2 ultrafine powders as eg translucent ceramics, the paint of volatile components and their amounts in consideration of a mixing ratio of the constant Tokoro by these alone or combined, after applying it to the glass, homogeneously kneaded Ti0 ₂ ultrafine powder of a photocatalyst at the time of the semi-cured, mix by applying a resin, antifouling coating film is completed most of the Ti0 ₂ particles are exposed fixed after curing.

 In addition, a paint that does not corrode the PET film is selected, and the paint is used as a liquid phase. Similarly, ultrafine powder is mixed and applied to the film, and then the titanium oxide ultrafine particles are dispersed and kneaded. Apply similarly.

 For example, the antifouling coating is preferably applied to a glass surface of a solar cell, and may be applied to ceramics, porcelain, metal, and the like. In this case, it is possible to improve the adhesion by selecting the type and particle size of the ultrafine particles or the pigment which has been made into ultrafine particles according to the material of the application partner.

Do Put Ti0 ₂ ultrafine particles of a photocatalyst in the above examples, the coating itself is hardly hardcoat smudges in dense and high hardness, glass or a resin material, ceramics, porcelain, functions as a protective film of a metal. Further, it is also suitable as a protective film for glass and plastic optical lenses. That is, the coating film by coating the average particle diameter had use of Si0 _2, Zr0 ₂ of run class, ultraviolet can be completely cut off, also you re excellent in scattering effect visible light transmittance passing through the same coating It has excellent hydrophilicity by forcibly drying and heating at the time of painting.

Next, when it is desired to provide moisture proofing, waterproofing, water resistance, gas proofing, or electrical insulation, it can be assumed that the film is directly applied or the film is provided with the function. Since the above function requires a dense membrane through which water molecules and gas molecules do not pass, Capable coating Kirill A1 ₂ 0 _3, Si0 ₂ has to desired to be formed only by ultrafine particles, such as. Therefore, although selected paint according to the application destination or film material, such as volatile, as a liquid phase body so choose that has excellent curability, the average particle different A1 ₂ 0 _3, Si0 ₂ and predetermined By mixing and applying at a ratio of, a coating film having the above-mentioned function is completed with an extremely thin film.

The coating film of the present invention has a moisture-proof and water-proof function and can be applied to various metal materials such as iron and aluminum for the purpose of corrosion resistance and protection. Therefore, it can be applied to large structures, various products, and parts made of these metals to improve the corrosion resistance of the material and to provide a protection function. Bosaba Simultaneously A1 ₂ 0 _3, Si0 able to provide other functions that Yusuke of ultrafine particles, such as _2, of course.

Of course, materials other than metals can be applied, and for example, the present invention is also suitable for an extremely easy-to-react Fe-BR-based sintered magnet and a heat-resistant film of a bonded magnet. In the case of a magnet for a motor, it can be used as an adhesive for a magnet to a rotor or the like, and can also be used as a waterproof film. Furthermore, since it functions not only as a protective film for the magnet but also as an adhesive, a small magnet can be bonded to form a large block. Here, to have a non-conductive in A1 ₂ 0 ₃ in the coating, when a large block magnet by adhering a small or thin magnet, to grant the ability to prevent the occurrence of eddy currents in the block magnet It becomes possible. For example, the best example is to apply it to Fe-BR permanent magnets used in MRI equipment, ESR equipment, etc.

 Aircraft and ships are constantly in contact with air or water, so there is a need to protect the fuselage and reduce friction with the fluid. As an example, a hard coat with properties such as corrosion resistance, high hardness, seaworthiness, heat resistance, and a low coefficient of friction has been long-awaited. The coating must be dense and have a low coefficient of friction.

For adhesion to metals such as, in the present invention, utilizing the erosion force with Ti0 ₂ ultrafine particles of a photocatalyst, Si0 ₂ ultrafine particles in order to stop the photocatalytic function It is used, considering the use of A1 ₂ 0 ₃ ultrafine particles for realizing a low friction coefficient.

The inventors have obtained the following findings in various experiments. More small things to Si0 ₂ ultrafine particles as ultrafine particles nm classes, it selects the A1 ₂ 0 ₃ ultrafine particles photocatalytic Ti0 ₂ ultrafine particles, the more larger the larger than suitable Yibin these mixing amount ratio When selected and mixed into various paints that became liquid phase bodies, extremely strong adhesion to metals was obtained for all compositions. Not only that, Ti0 ₂ ultrafine particles of a photocatalyst function is stopped without eroding the metals and liquid phase material itself, the film itself provides high hardness and and surface layer (a low coefficient of friction IAL ₂ 0 ₃ I was

The mechanism by which the above functions are obtained is described in detail. In the process of curing the paint applied to the metal surface, that is, the paint component of the liquid phase containing three types of ultrafine powder, the adhesion to the metal surface shall apply in the most erosion force strong Ti0 ₂ ultrafine particles act to cause erosion by the Ti0 ₂ ultrafine particles will be followed and each is where the ultraviolet in the case of this single exists little. As rearrangement of ultrafine particles with a force liquid phase body progresses place, to stop the function of the Ti0 ₂ ultrafine particles surrounds the outer surface of the large Ti0 ₂ ultrafine particles even the smallest Si0 ₂ ultrafine particles than of the three and then close a large A1 ₂ 0 ₃ ultrafine particles further, by going arranged, abutting sequences of the three super-fine particles are assumed to continue to completion.

That is, in the liquid phase material originates forces such as thinner is solidified, there is Ti0 ₂ ultrafine particles to first contact as erosion liquid phase body to decompose vital metal surface, which is then to encirclement Si0 ₂ greater fine particles are gathered, gather further A1 ₂ 0 ₃ ultrafine particles. These layers are assembled and abutted and arranged to form a layer of ultrafine powder, and there is a solidified liquid phase in the gaps between the ultrafine particles. A dense ceramic layer is formed by three types of ultrafine powder.

The correctness of this inference can be supported by other phenomena and functions brought about by the above paints. Liquid phase composed of acryl resin containing the above three types of ultrafine powder The paint component of the body was colorless and transparent, which was applied to paper that easily changed color with ultraviolet light, and left outdoors. Also, most small, Ti0 ₂ ultrafine particles of the three kinds of particle size, case, by coating having composition excluding the three Si0 ₂ ultrafine particles of the paper was left outdoors Similarly . Further, it was applied to the paper, brought into close contact with the aluminum foil, and similarly left outdoors.

The paper, which was not coated with anything, was weak to ultraviolet light and turned yellow in two days, and began to collapse when touched after two weeks. Ti0 ₂ ultrafine particles are most small V, if the immediately yellowing direct sunlight, similarly immediately yellowing Excluding Si0 ₂ ultrafine particles, it has been found that the photocatalytic function is progress. However, in the case of an acrylic resin having three types of ultrafine powder having the above-described particle size difference, no yellowing was observed on the paper even after 3 months, either for the paper alone or for the lamination with the metal. Did not change. That is, in the coating film, ultraviolet rays not transmitted, by Ti0 ₂ ultrafine particles of a photocatalyst is not functioning clarified, in particular lamination of the metal, paper is adhered strongly to the metal, high degree of adhesion, Demonstrated high strength and UV resistance.

In the coating composition of the three kinds of ultrafine particles and the acrylic resin having different particle diameters different from each other and predetermined, the volume ratio of the solidified ultrafine particles to the acrylic resin is set to 1: 1 and the resin side is reduced. then, the finished coating film forces the surface layer comprising a dense ceramic layer by three ultrafine powder as described above is mainly sequence A1 ₂ 0 ₃ ultra fine particles, ultrafine particles nm class for this film The extremely remarkable hydrophilic function provided by the above is exerted. The hydrophilic feature is not one obtained by Ti0 ₂ ultrafine particles of a so-called photocatalyst, it is apparent from the foregoing description of the ultraviolet-opaque. Further, the inventors inorganic and only modified Akuri Le resin Si0 ₂ ultrafine particles - in the case of the organic film was found that exhibits a function of hydrophilic. On the other hand, Si0 ₂ so as not to surround the ultrafine particles Ti0 ₂ particles, when Ru Sagaa the particle size of both, Ti0 ₂ particles Si0 ₂ ultrafine particles are uniformly dispersed in the liquid phase body is without UV light transmitting It is thought to stop the catalytic function of. As a method of imparting hydrophilic (oil) properties, excellent hydrophilicity can be imparted by forcibly drying and heating at the time of painting, as described above, and a polishing pad (zirconia, diamond) It is also possible to employ a method in which the resin layer is polished by UV irradiation or EB irradiation, in addition to the method of polishing with a pad that has been applied and solidified with an ultra-fine powder paste. In other words, EB-curing glue or UV-curing glue is used alone or in combination with another resin in the liquid phase, and the amount of this liquid phase is slightly larger than that of the ultrafine powder, so that a resin layer is formed on the surface during application and solidification. and so, after semi-curing, by 0 ₂ flow during EB or UV radiation, only the surface layer of the resin layer

0 ₂ Asshingu to the surface can be hydrophilized. Since the ceramic layer has adhesiveness and weather resistance, hydrophilicity can be added to the surface layer while preventing the oxygen from moving to the lower layer. Incidentally, it is also possible to provide 0 ₂ Atsushingu later the surface layer of the resin separately.

 When UV-curable glue or EB-cured glue is used for the liquid phase, the effect of the UV- or EB-irradiated resin curing and the ultrafine particle layer of nm-class ultrafine particles are combined, resulting in a denser and higher hardness. Since a coating film can be obtained and its curing can be controlled, it is also useful as an adhesive.

Further, the paint of the present invention can be considered as an ink for printing. It goes without saying that a known printing technique can be adopted in the coating. The difference from conventional inks is that if ceramics are used as the ultrafine particles, ceramic inks will be used, and if metal ultrafine particles are used, then metal inks will be used. These inks can be used as inks with new functions. For example, the insulating property and the conductive ink is present prior art, A1 ₂ 0 ₃ and insulating ink by ultrafine particles, can provide a conductive I link by A1 and Cu ultrafine particles, electrically since the integrated circuits and electric circuits It is possible to greatly improve the characteristics.

Today, the formation of fine patterns by applying printing technology is indispensable for fabricating integrated circuits and electric circuits. In addition, in order to improve the integration, The vapor phase growth method such as puttering is adopted. The present invention can be applied not only to these integrated circuits but also to the field of micromachining. For example, the ink jet printing method, which has been put to practical use to form a required pattern by skipping fine ink with a micropump using a piezoelectric element or the like, is used, and the paint of the present invention is applied to the insulating ink or the conductive ink. Thus, integrated circuits and electric circuits can be formed. In this case, it is extremely effective to use it as emulsion and water-based paint. The method of using the UV curing glue to simultaneously cure the resin by UV irradiation is also extremely convenient for forming a circuit. Needless to say, it is also possible to form a required pattern in a vacuum atmosphere.

Finally, the best embodiment of the present invention will be described. It uses a Akuriru modified resin or a silicon § acrylic modified resin in paint and liquid phase material component of the adhesive for film deposition, at least Si0 as ceramic ultrafine particles powder component _2, A1 ₂ 0 _3,

_{Zr0 2, SiC, SiN, A1N} , a liquid composition using ZrN, one of TiN. What further best uses a curable Akuriru modified resin or sheet Rikonakuriru modified resin with EB irradiation in liquid phase cell components, using a Si0 ₂及beauty / or (IAL ₂ 0 ₃ as the ceramic ultrafine particle powder component liquid The composition.

 The most preferred combination is a silicone acrylic modified resin and at least

Si0 _2, A1 ₂ 0 _3, Zr0 to the one combination of the _two may be at least + 100% of the molecular weight type weight for ceramic ultrafine particles in the liquid phase material, silicon § acrylic transformed into further The first main factor is that the solidified bond becomes extremely strong because the gap created between the bond between the resin molecules can be filled with ceramic ultrafine particles to obtain a strong bond.

In addition, the modified silicone acrylic resin has the best physical properties among the currently known resins, and the effect of dispersing ceramic ultra-fine particles in the resin can improve the physical property value much more. In addition, all properties required for the adhesive can be improved. In particular, when bonding between acrylic-modified resin molecules is obtained by EB irradiation, it is almost impossible to decompose the resin bonds, because the gaps between the bonding between the resin molecules can be filled with ultrafine ceramic particles. Have confirmed.

In addition, this liquid composition is applicable to all the above-mentioned applications. In particular, when the acryl-modified resin molecules are bonded to each other by EB irradiation, the liquid having the composition is charged into a required mold and EB irradiation is performed. Irradiation makes it possible to produce molded articles of any form. In particular, the insulating film in a liquid composition using the A1 ₂ 0 _3, since the sheet can be easily produced, any electronic device, the electronic circuit sheet can be produced. Example

 Example 1

 Commercially available shellac varnish (shellac / industrial alcohol / oxalic acid = 20 / 79.9 / 0.1), commercially available acrylic resin paint (resin is mainly composed of MMA, HEMA, CHMA, solvent is

MIBK, xylene is the main component), the average particle diameter as the ceramic ultrafine particles powder was kneaded in varying proportions of 1% to 30% Si0 ₂ with respect to shellac and Akuriru resin 10 nm, Fushitome wood, Metome In the case of any of the resin coatings, the penetration force increases in proportion to the amount of the ceramic ultra-fine particles added. The surface became transparent vitreous. Further, the paint of the present invention using the above-mentioned acrylic resin as a liquid phase is spray-coated on a commercially available untreated or conversion-treated aluminum plate or ordinary steel plate, and dried at 200 ° C. for 20 minutes. -The results of measuring the physical properties of the organic film are shown below.

Incidentally, the coating of the invention was analyzed by gas chromatography, the volatile matter 51%, resin content 39%, were Si0 ₂ min 10%. Further, Si0 ₂ minutes was impossible even liquid by re separated by centrifugation. Further, Si0 molecular weight of ₂ (formula weight) is 60, the molecular weight of MMA (formula weight) of approximately 100, HEMA is 130, CHMA is about 168, in the entire resin was about 120.

Example 2

Commercially available woodworking sealer one-component (nitrocellulose 'Poribinirupuchira Ichiru based paints), mean particle size and Si0 ₂ having an average particle steroids 7nm as ceramic ultrafine particles powder and 20 ~ 100nmAl ₂ O ₃ sintered body A 1: 3 mixture of ceramic ultrafine powder mixed in a ratio of 1% to 50 <¾ in a sealer was used. Of course, the penetration power increased in proportion to the amount of ceramic ultrafine powder added, and penetrated from the back surface to the front surface at the thickness of the veneer plate. Incidentally, in the above ceramic ultrafine particles powder contain minor amounts of other types of ceramics in addition to Si0 ₂ and A1 ₂ 0 _3, but exhibit the same functions and the like Si0 ₂ not particularly show this. The same applies to the following.

 Example 3

Dhamma one varnish (Danmarugomu / turpentine / mineral spirits / = 55/15/30), the ceramic average particle diameter as ultrafine powder of 7 ~ 100 nm Si0 ₂ and the A1 ₂ 0 ₃ 1: ultrafine particles mixed with 1 Powder was used, kneaded at various ratios of 1% to 30% with respect to dammar rubber, and applied to wood and iron plates.

 Compared to the coating with the dammer varnish, the coating with the dunner varnish to which the ultrafine ceramic powder was added was hard and hard to damage, did not burn with the gas lighter flame, and could not be easily peeled off with a knife .

Furthermore, in the case of a dammer-varnish in which the volume ratio of the mixed ultrafine particles is 1: 1 with respect to the dammar rubber, when applied to wood or iron plate and solidified, the transparent coating film has hardness, heat resistance, and coefficient of friction. shows the A1 ₂ 0 ₃ equivalent properties or the like, can not peel the knife, Do peeled be beaten by a hammer, the degree of adhesion was obtained.

 Example 4

Commercially available stress one Ta acrylic lacquer for concrete coating, and kneaded in various proportions such that the mean particle diameter as the ceramic powdery particles is 1% ~ 60 <¾ the Si0 ₂ of 7nm in Akuriru, concrete and mortar Applied. Adhesion and penetration increased in proportion to the amount of ceramic ultrafine powder added.

 When only straight acryl lacquer is used, it can be damaged or peeled off with a knife or metal spatula. In the case of acrylic lacquer to which the ceramic ultrafine powder of the present invention is added, peeling does not occur in proportion to the amount added. Was.

Example 5 In Example 4, a Si0 ₂ and A1 ₂ 0 ₃ having an average particle diameter of 7 ~ 100 nm as a ceramic ultrafine particles powder 1: 9 to 9: 1 was used various ceramic ultrafine particles powder in a mixing ratio of. The tendency for the adhesive force and the penetrating power to increase in proportion to the amount of the added ceramic ultrafine powder was the same, and there was no significant difference in the adhesive power and the penetrating power between the single powder and the composite powder of Example 4. However, penetration and adhesion and Si0 ₂ of 7nm in ultrafine powder decreases significantly tended to decrease.

 Example 6

Commercial concrete, the vinyl chloride paint for mortar coating (paint chloride / vinyl acetate copolymer and the plasticizer was a binder I), ceramic average particle diameter as ultrafine powder is less lOOnm A1 ₂ 0 ₃ sintered body Was kneaded at various ratios so as to be 1% to 10% in the paint, and applied to concrete and mortar.

 In contrast to the base vinyl chloride paint film, the vinyl chloride paint film to which the ceramic ultrafine powder was added became hard and hard to scratch, and it became difficult to remove it with a knife.

 Example 7

The commercial household paint (synthetic resin Emaru Deployment paint based on colloidal dispersion Chillon), average particle diameter as the ceramic ultrafine powder 7Nm～: a Si0 ₂ and A1 ₂ 0 ₃ sintered body of LOOnm 1: 2 at a rate The mixed ceramic ultrafine powder was kneaded at various ratios so as to be 1% to 60% in the paint, and applied to a mortar and an iron plate. In the case of a commercially available paint alone, it can be damaged or peeled off with a knife or metal spatula.However, the paint containing the ceramic fine powder of the present invention is hard and not easily damaged, and it becomes difficult to peel it off with a knife. Was.

 Example 8

Commercially available can inner coating paint - in (polyvinyl butyral phenolic resin), an average particle diameter of the ceramic ultrafine particles powder of 7 nm ~ 100 nm Si02 and A1 ₂ 0 ₃ Ultrafine ceramic powder mixed with the sintered body at a ratio of 1: 2 was kneaded at various ratios so as to be 1% to 60% in the paint, and applied to an aluminum plate and an iron plate.

 In the case of a commercially available paint alone, it can be damaged or peeled off with a knife or a metal spatula. However, the paint to which the ceramic fine particle powder of the present invention has been added is hard to be easily damaged and cannot be peeled off with a knife.

 Example 9

Commercially available household paints for wood (alkyd resin varnish), ceramic average particle diameter as ultrafine powder 7Nm～: a Si0 ₂ and A1 ₂ 0 ₃ sintered body of ΙΟΟηιη 1: mixed ceramics in a ratio of 2 The ultrafine powder was kneaded at various ratios so as to be 1% to 60% in the paint, and applied to wood, aluminum plate, and iron plate.

 In the case of commercially available paints only, they are easily peeled off even when applied to an aluminum plate or an iron plate, and the wooden coating film can be damaged or peeled off with a knife or metal spatula. The powder-added paint adhered to any of the wood, aluminum plate and iron plate, making it difficult for fingerprints and scratches to be removed, and could not be peeled off with a knife.

 Example 10

 Commercially available thermosetting acryl resin paint clear (acryl resin: amino resin: epoxy resin = 70:20:10) has an average particle size of ceramic ultrafine particles.

Of 7 nm ~ 100 nm S> 2 and the A1 ₂ 0 ₃ sintered body 1: 2 ceramic ultrafine particles powder in a mixing ratio of kneaded in various proportions such that 1% to 60% in the paint, aluminum Plated on stainless steel plate.

 When using only commercially available paints, the coatings can be damaged or peeled off with a knife or metal spatula.However, the paints containing the ceramic ultrafine powder of the present invention can be applied to either aluminum plates or stainless steel plates. However, it was hard to be scratched and could not be peeled off with a knife.

Example 11 Commercially available moisture curing type polyurethane resin coating, ceramic average particle diameter as ultrafine powder of Si0 ₂ and A1 ₂ 0 ₃ sintered body of 7 nm ~ 100 nm 1: ceramics were mixed at a ratio of 2 ultrafine powder in the paint And kneaded at various ratios so as to be 1% to 10%, and applied to a wooden floor plate, an aluminum plate, and a stainless steel plate.

 In the case of a commercially available paint alone, it can be easily peeled off even when applied to an aluminum plate or iron plate, and the wooden coating film can be damaged or peeled off with a knife or metal spatula. The powder-added paint adhered to any of the wood, aluminum plate and iron plate, became hard and hard to scratch, and could not be peeled off with a knife.

 Example 12

A commercially available metal for 2-part polyurethane resin coating (polyol / poly I Société § sulfonate), average particle steroids 7nm~ as ceramic ultrafine particles powder: a Si0 ₂ and A1 ₂ 0 ₃ sintered body of LOOnm 1: 2 at a rate The mixed ceramic ultrafine powder was kneaded at various ratios so as to be 1% to 10% in the paint, and applied to a wooden floor plate, an aluminum plate, and a stainless plate.

 When using only commercially available paints, the coatings can be damaged or peeled off with a knife or metal spatula, but the paints containing the ceramic ultrafine powder of the present invention can be used for wooden floor boards, aluminum boards, and stainless steel boards. It adhered to any of them, and it was hard and hard to scratch, and could not be peeled off with a knife.

 Example 13

Commercially available heat-resistant, electrically insulating epoxy resin coating - the (epoxy-silicone-modified epoxy resin coating material), the Si0 ₂ and A1 ₂ 0 ₃ sintered average grain steroids 7 nm ~ 100 nm as a ceramic ultrafine particles powder 1: 2 at a rate The mixed ceramic ultrafine powder was kneaded at various ratios so as to be 1% to 60% in the paint, and applied to a wooden floor plate, an aluminum plate, and a stainless steel plate. When using only commercially available paints, the coatings can be damaged or peeled off with a knife or metal spatula, but the paints containing the ceramic ultrafine powder of the present invention can be used for wooden floor boards, aluminum boards, and stainless steel boards. It adhered to any of them, became hard and not easily scratched, and could not be peeled off with a knife.

 Example 14

Commercially available phenolic resin varnish, as ceramic fine powder, average particle diameter 7ηπ! 1 Si0 ₂ and A1 ₂ 0 ₃ sintered body of ~ lOOnm: 2 of the mixed ceramic ultrafine particles powder in a proportion kneaded in various proportions such that 1% to 60% in paint, wood floorboards, Coated on aluminum plate and stainless steel plate.

 In the case of a commercially available paint only, it can be easily peeled off even when applied to an aluminum plate or a stainless steel plate, and the wood coating can be damaged or peeled off with a knife or metal spatula. The paint to which the fine-particle powder was added adhered to any of the wooden floor boards, the aluminum plates, and the stainless steel plates, and could not be peeled off with a hard and hardly damaged knife.

 Example 15

Commercially available oil paint (oil-based varnishes), ceramic average particle size force as ultrafine powder ^ nm to 100 nm Si0 ₂ and the A1 ₂ 0 ₃ sintered body 1: mixed ceramic ultrafine particles powder in the paint in a ratio of 2 The mixture was kneaded at various ratios so as to be 1% to 60%, and applied to a glass, a gay plate, a wooden floor plate, an aluminum plate, and a stainless plate.

 In the case of only commercially available paint, it can be easily peeled off even when applied to glass, aluminum plate, or stainless steel plate, and the wood coating can be damaged or peeled off with a knife or metal spatula. The paint containing the ultrafine ceramic powder adhered to the glass, the car board, the wooden floor board, the aluminum board, and the stainless steel board, and could not be peeled off with a knife that was hard and hard to damage.

Example 16 Commercially available uv curing resin paint (epoxy § chestnut rate system), ceramic average particle diameter as ultrafine child powder of Si0 ₂ and A1 ₂ 0 ₃ sintered body of 7 nm ~ 100 nm 1: mixed combined ceramics in a ratio of 2 The ultrafine powder was kneaded at various ratios so as to be 1% to 60% in the paint, and applied to a plastic tile, a glass, a gaical board, a wooden floor board, an aluminum board, and a stainless steel board.

 When using only commercially available paints, good adhesion is obtained on plastic tiles, gaical boards, and wooden floor boards, and the coating films on glass, aluminum plates, and stainless steel plates are easily peeled off. The powdered paint adheres to any of the plastic tile, glass, gayal board, wooden floor board, aluminum board and stainless steel board, and has a hard layer that is hard to be scratched and cannot be peeled off with a knife. Was.

 Example 17

Commercially available purified lacquer, ceramic average particle diameter as ultrafine powder of Si0 ₂ and A1 ₂ 0 ₃ sintered body of 7nm ~ 100nm 1: 1% ~ 60 2 of the mixed ceramic ultrafine particles powder in a proportion in the paint % And kneaded at various ratios, and applied to plastic tiles, glass, gay cal boards, wooden floor boards, aluminum boards, and stainless steel boards. The paint to which the ceramic ultrafine powder of the present invention is added adheres to any of plastic tile, glass, gaical board, wooden floor board, aluminum board, and stainless steel board. It could not be peeled off with a knife.

 Example 18

Commercially available amino alkyd resin paint (Amino: Alkyd = 30 70), ceramics Si0 ₂ having an average particle steroids 7 nm ~ 100 nm as ultrafine powder and A1 ₂ 0 ₃ to 1: 2 ceramic ultrafine particles flour combined mixed in a ratio of Is kneaded as a main ingredient, and a commercially available polysocyanate compound for a curing agent and a thinner are used as a curing agent. 36

A two-component paint was prepared in which the components were as follows: 36% of powder content, 3% of additives, 51% of solvent (in the main agent), 6% of hardener, and 4% of solvent (in the hardener).

 After mixing the main agent and the curing agent, they were applied to various materials by a spray coating method.

 Paints to which the ceramic ultrafine powder of the present invention is added include plastic films such as Nippon roof tiles, porcelain tiles, plastic tiles, PET, plastic molded bodies such as ABS, resin tubes, soda glass, plate glass, glass fiber, FRP , Mortar, concrete, gayal board, MDF, wooden floor board, aluminum board, stainless steel board, steel plate, steel pipe, and harder than ordinary aminoalkyd resin paint. I couldn't let it.

 Example 19

Commercially available inorganic-organic composite varnish, ceramic average particle diameter as ultrafine powder of 7rnn ~ 100nm Si0 ₂ and A1 ₂ 0 ₃ to 1: kneading a base resin 2 in a mixed ceramic ultrafine particles powder in a proportion in various proportions A commercially available polyisocyanate compound for a curing agent and thinner are used as a curing agent, resin and ceramic ultrafine particles 66%, additives 5%, solvent (in the main agent) 9%, curing agent 13%, solvent (In the curing agent) A two-pack type paint was prepared so as to have a 7% component.

 In a state where the main agent and the curing agent were mixed, the mixture was uniform without lumps. The solidification was dried at room temperature and required 2-3 words. The appearance of the colorless and transparent coating film was good, and no cracks or cracks were generated even when a weight of 15 mm in outer diameter and 500 g was dropped from a height of 30 cm.

 In addition, the curing agent was removed from the two-pack type paint, and the one-part paint composition in which the inorganic-organic composite varnish and the ceramics ultrafine powder were mixed at a ratio of 1: 1 was diluted with a solvent, and brush-coated and spray-coated. It was applied to the surface of various materials in the same manner as in Example 18. In this case, a hardening material was not required, and it exhibited better permeability and adhesion than the two-pack type paint, and was hardened quickly.

Example 20 5ηπ as ceramic ultrafine particles! Si0 ₂ having a ~ 500 nm and a variety of average particle diameter, A1 ₂ 0 _3, using a photocatalyst for Ti0 _2, average particle diameter and mixing amount ratio variously changed to prepare a ceramic ultrafine particles powder, a commercially available paint base compound which It was kneaded with a modified acryl resin for use in various proportions to obtain a starting composition.

 Numerous starting compositions were prepared in which the average particle diameter and the mixing ratio of the three kinds of ultrafine particles were variously changed, and the mixing ratio with the modified acryl resin was also variously changed. At the time of use, it is diluted with acryl resin solvent, and if necessary, isocyanate is appropriately added as a hardener, applied by brush coating or spray coating on the surface of various materials in the same manner as in Example 18, and applied to the painted surface, respectively. The properties such as permeability, adhesion, and hardness of the coating film were observed. In addition, it was applied to paper that easily deteriorates due to ultraviolet light and left outdoors, and changes over time were observed.

In order to improve properties such as permeability to the painted surface, adhesion, and hardness of the coating film, the smaller the average particle size of the ultrafine particles is, the better it is when viewed as a whole powder. law from A1 ₂ 0 _3, it was confirmed that shall be reduced to the order of the photocatalytic Ti0 _2, Si0 _2. For example, if the average particle size is smaller for photocatalytic Ti0 ₂ to about Si0 _2, although further great adhesion and penetration resistance of the coating film, the finished coating film strength over time altered and the material of the coated surface This causes a problem of deterioration. Moreover, Do mixing Si0 _2, or, less is Si0 _2, the paper coated with coating material began to discolor immediately sunlight.

Thus, the smallest Si0 ₂ surrounds the Ti0 _2, and block UV believed to stop the photocatalyst, the amount added to the average particle diameter of Si0 _2, in response to the added amount and the average particle size of Ti0 ₂ it is necessary to select appropriate Te, also confirm that there needs to be determined in consideration Ti0 and ₂ and Si0 ₂ to by coated surface material permeability and adhesion, the balance between the temporal stability of the coating did.

Incidentally, it considered if the small A1 ₂ 0 ₃ obtained about Si0 _2, it is possible to place the Si0 ₂ for Function surrounding the Ti0 _2. Ceramic ultrafine particle powder with the average particle diameter decreasing in the order of Al ₂ O ₃ (100 to 500 nm), TiO ₂ for photocatalyst (20 to 30 nm), SiO2 (7 to 10 nm), and the mixing ratio is appropriately selected. After confirming that it is advisable to use a modified acrylic resin, the mixing ratio with the modified acrylic resin was examined.If the amount of resin was large during application, the coating film became dense and hard with the increase in ultrafine powder. Conversely, it was confirmed that when the amount of resin was small, application became difficult or the coating film was not homogeneous. Microscopic observation of the above various coatings confirmed that the ultrafine particles and their aggregates were in excellent contact and alignment. Therefore, in the completed coating film, the target was set so that the volume ratio of the ultrafine particle powder and the resin component was around 1: 1 and various experiments were conducted on the amount of both and the amount of solvent within a range where the paintability was good. The coatings were observed under a microscope and tested for flame resistance.

 A coating film in which the ratio of ultrafine powder to the resin component is considered to be a little higher from 1: 1 by volume ratio of resin will burn when the fire is applied after semi-curing, but then the fire will be extinguished and then the coating will be cured. Both the film and the film whose surface resin was wiped off with a solvent after semi-curing showed excellent flame resistance. In addition, coatings in which the ratio of ultrafine powder to resin is 1: 1 by volume or the resin is seen to have further decreased due to volatilization or decomposition have already exhibited excellent flame resistance when semi-cured after application. Was.

Further, in place of the photocatalytic Ti0 _2, it was used ultrafine particles Ti0 ₂ for the pigment, but adhesion and penetration resistance of the coating was reduced compared to the case of photocatalytic Ti0 _2, a conventional Akuriru resin Has an incomparable adhesiveness and permeability, and it was confirmed that the properties of the coating film were not much different from those of the above Examples.

 Example 21

Si0 ₂ and (average particle size 7 nm) of ceramic ultrafine particles powder and modified Akuriru resin in a volume ratio of the coating film 1: 5 determining the mixing ratio to the target and the adjusted coating composition, for their respective spray one painting And applied to steel plates with various surfaces. The steel sheet was applied to three types of cold-rolled as follows: (1) non-coated surface, with washing, (2) mackerel surface, non-washing, (3) non-coated surface, no washing. In each case, in the impact test of Example 19, no cracks or cracks occurred, and the knife could not be removed with a knife.

 The coating film is not polished, but it is mirror-finished and it is difficult to get fingerprints.It can be removed by simply wiping it off when left outdoors.Boiled for 5 hours. Although it was immersed in seawater for a month, there was no occurrence of cracks.

 After 3 months of spraying with 5% salt water at 30 ° C, no cracking occurred. Example 22

 The coating composition prepared in Example 21 was further diluted for spray coating and applied to stainless steel plates having various surfaces.

 The stainless steel sheet was applied to two types: (1) degreasing and cleaning, and (2) no cleaning (water only). In each case, no cracks or cracks were generated in the impact test of Example 19, and the impact test with the knife could not be performed.

 The chemical resistance test was performed by dropping approximately 0.2 ml of reagent on the surface, covering with a watch glass, leaving it at room temperature for 24 hours, cleaning it with a dry cloth, and observing the surface condition. Hydrochloric acid

 (5%, 10%), sulfuric acid (5%, 10%), glacial acetic acid (98%), sodium hydroxide (5%, 10%), acetone, hydrogen peroxide (31%), (99%), there was no change for any of the ethanol.

 Example 23

The coating compositions prepared in Examples 20 and 21 were diluted for spray coating and applied to aluminum plates having various surfaces. There were four types of aluminum plates, with or without surface treatment and with or without degreasing, and were applied to these. In each case, in the impact test of Example 19, there were no cracks or cracks in the coating film, and the coating film could not be removed with a knife. In the case of the coating composition of Example 21, the coating film did not ignite even at 400 ° C., and the surface turned slightly brown after being exposed to a flame with an alcohol lamp for 30 seconds. There was no scar, no peeling, no deformation.

 In the case of the coating composition of Example 20, the coating film did not ignite even at 600 ° C., there was no ignition even after applying a flame with an alcohol lamp for 1 minute, there was no burn mark, and no peeling or deformation occurred.

 Example 24

 The coating compositions prepared in Examples 20 and 21 were diluted for spray coating and applied to glass plates which had been washed to ensure transparency. The coating on the glass plate surface was colorless and transparent and could not be removed with a knife.

An antibacterial test was performed by the dropping method of Escherichia coli. The bacterial solution preparation solution was a 1 / 500NB medium, and the viable cell count per cell was 3.4 to 3.7 × 10 ⁵ immediately after inoculation, and was 10 or less after 24 hours at 35 ° C.

 Example 25

 The coating compositions prepared in Examples 20 and 21 were diluted for spray coating, and applied to ABS resin plates having various surfaces.

 The ABS resin plate was applied to four types, with or without surface treatment and with or without degreasing. In each case, in the impact test of Example 19, there were no cracks or cracks in the coating film, and the coating film could not be removed with a knife.

 Example 26

 The coating compositions prepared in Examples 20 and 21 were diluted for spray coating and respectively applied to a cement-based board for building exterior.

 Cement-based boards were applied with and without alkali cleaning. In each case, in the impact test of Example 19, there was no cracking or cracking of the coating film, and the knife could not be removed with a knife.

Example 27 0 /

 41

The coating compositions prepared in Examples 20 and 21 were diluted for roll coating and applied to an inorganic plate (a gay plate).

 In the coating film formed on the inorganic plate with fine pores, not only a uniform surface but also many places penetrating to a depth of several mm were observed.

 Example 28

 The coating compositions prepared in Examples 20 and 21 were diluted for roll coating and applied to natural wood boards, respectively.

 In the coating film formed on the natural wood board with conduits and fibrous material, not only a uniform surface but also many places penetrating to a depth of several mm were observed.

 Example 29

 After mixing the coating compositions and the inorganic pigments prepared in Examples 20 and 21, they were further diluted for roll coating and applied to MDF, respectively.

 The coating film formed on the MDF had flatness and a uniform color tone like a mirror-finished coating, and could not be removed with a knife.

 Example 30

 After mixing the coating compositions and the inorganic pigments prepared in Examples 20 and 21, they were further diluted for roll coating and applied to natural veneers.

 When the veneer was applied to a 0.3 mm, 0.5 mm, lnrni material, the penetration of the coating film was remarkable. It is hardly scratched, scratched or scratched, and its wear resistance is remarkably improved, and its moisture resistance and water resistance are remarkably improved.

 Example 31

The coating compositions prepared in Examples 20 and 21 were diluted for spray coating, applied to an iron shaft of a caster used for a luggage trolley, and used after solidification. Frequent wear and replacement required fell sharply to 1/10. Example 32

 The coating compositions prepared in Examples 20 and 21 were further diluted for spray coating, applied to corrugated paper and cured.

 The paint of the present invention, which penetrated the paper, was modified as if the paper was made into plastic, hardly scratched and damaged, markedly improved in abrasion resistance, and significantly improved in moisture resistance and water resistance.

 In addition, extremely thin coated and cured untreated wrapping paper could be modified into moisture-resistant paper and water-resistant paper that retain the original flexibility of paper. It was also confirmed that the fabric can be modified similarly.

 Example 33

 After mixing the coating compositions prepared in Examples 20 and 21 and various pigments, they were further diluted for roll coating and applied as ship bottom paint.

 Inorganic pigments for coloring, aluminum powder, and copper powder were mixed alone and applied.After solidification for one week, they were berthed at a port for four months and observed for dirt and marine organisms. . There was no change in the coating film itself except for the oxidation of the aluminum powder and copper powder exposed on the coating film surface, and a small barnacle adhered, but all were removed to the extent that they could be removed during voyage along with dirt.

 In addition, when a paint containing an aluminum powder pigment was applied and then a paint without a pigment was applied as a coat film, it was a steel plate ship, but the texture was similar to that of aluminum.

 Example 34

 The coating compositions prepared in Examples 20 and 21 were further diluted for spray coating, and applied to a so-called bilge pool and a transparent resin drain pipe in a ship. After one week of solidification, it was put into service for two months. Oil and dirt were removed only by spraying low-pressure water, and the original painted surface appeared.

Example 35 After mixing the paint compositions prepared in Examples 20 and 21 with the aluminum powder pigment, the mixture was further diluted for spray coating and applied to low-pressure and forged aluminum alloy tire wheels.

 Aluminum alloy tire wheels are usually degreased, washed, polished, washed again, and then painted.However, with the paint of the present invention, it can be applied immediately after mere washing, and the cured coating contains aluminum powder pigment. The mirror-like surface of an aluminum substrate was polished, that is, the effect was as if it had been polished. This eliminates the need for repeated steps of degreasing, cleaning, and polishing.

 Example 36

 After mixing the base agent and the hardener with the alcohol-based solvent in the one-pack type paint prepared in Example 21, it was applied over the entire surface of the integrated circuit board by spray coating and solidified.

 After painting, the integrated circuit board became a complete moisture-proof and water-resistant board, and the electrical insulation was improved.

 Example 37

Various mixed in a ratio of Example 20, the coating composition was adjusted at 21, and in the commercial two coating compositions of the Ti0 ₂ particles powder anatase prepared in Example 19 for the photocatalyst 0.1% to 0.5% Each of the prepared coating compositions was further diluted for spray coating or for roll or brush coating.

 The obtained photocatalytic paint was applied to a porcelain tile, a plastic tile, a resin mat, a steel plate, and a stainless steel plate.

 The treatment of the object to be coated was performed only by washing with water and drying, without any degreasing or cleaning with a special chemical solution. The resin mat was applied after coating and solidifying a commercially available sealant.

Porcelain tile, plastic tile, resin mat, steel plate, stainless steel plate are specifications commonly used in hospitals. It was used for normal use for a month. At night when not in use, irradiation with black light was performed.

 Due to the irradiation of black light, the antibacterial function, which is a function of the photocatalyst, self-cleaning ability to decompose adhering substances, hydrophilicity, etc. are effectively exerted, it is hard to get dirt, and it easily gets dirty with water etc. Had fallen.

 After use, there was no choking of the photocatalytic coating itself, the coating itself did not decompose to the material to be coated as a barrier, and the coating could not be peeled off with a knife.

 Example 38

 For the photocatalytic paint obtained in Example 37, aluminum plate, aluminum window frame, glass, roof steel plate, building exterior, without degreasing or washing with any special chemicals, etc., only with water washing and drying It was applied to the inorganic plate, the bottom of the ship, the outer surface of the marine outboard engine, and the PET film. After solidification for 3 days to 1 week, it was used by leaving it outdoors or berthing at sea for 2 months.

 Aluminum window frames and roof steel plates were coated with a protective film by the manufacturer.However, they penetrate into the protective film and exert an anchoring effect on the substrate, providing the same adhesion as that applied to solid aluminum plates. Yes, a strong film was formed on the inorganic plate without alkali washing.

The glass was not a quartz glass with few impurities, but a normal window glass plate.The coating film itself was considered to be the barrier, and the photocatalytic function due to the floating of the impurities did not decrease or decrease at all. . Incidentally, the use of Si0 ₂ to ceramics fine powder as glass is further advantageously for work in terms of transparency and impurities.

Both the hull bottom and marine outboard engines have strong adhesion of the coating film, exhibiting excellent self-cleaning and hydrophilic properties as a photocatalytic coating film, and are effective in removing dirt, oil, and marine life. There was little adhesion, and in places where light near the draft was well irradiated, only the waves hit and the soil was removed.

 Example 39

The ceramic ultrafine particles powder, only an average particle steroids rnn of Si0 ₂ (molecular weight (formula weight) 60), the average A1 ₂ 0 ₃ of particle size and Si0 ₂ of 7 nm ~ 100 nm (molecular weight (formula weight) 102) 1 : A mixture of mixed powder mixed at a ratio of 1: 1, SiO ₂ (5 to 30 nm), TiO ₂ for photocatalyst (20 to 50 nm, molecular weight (formula weight) 79.90), and Al ₂ O ₃ (100 to 500 nm) Using three types of powders, each using silicon-modified acrylic resin as the liquid phase body, kneading with a solvent so that the mixing ratio of ultrafine powder: resin is 0.1: 0.9 to 1: 1 A two-pack type paint was prepared, consisting of a one-pack type paint obtained by mixing a solvent and an isocyanate-based curing agent, and a main solution mixed with a solvent and a hardener.

 Liquid modified silicone modified acryl resin is based on 100 parts by weight of isopropyl alcohol maintained at 80 ° C, 42.5 parts by weight of methyl methacrylate (average molecular weight: 100), 18.0 parts by weight of 2-hydroxyethyl methacrylate (130 parts by weight) ), 27.5 parts by weight of n-butyl methacrylate (142.2), 5.0 parts by weight of n-butyl acrylate (128), 5.0 parts by weight of 3-methacryloxypropyltrimethoxysilane, methacryloxydimethylpolysiloxane at one end (Mw = 5000) ) 1.0 part by weight, 1.0 part by weight of methacrylic acid (86) and 1.0 part by weight of benzoyl peroxide, and a monomer mixture for polymerization was added dropwise and reacted, and then 0.5 part by weight of benzoyl peroxide was further added. The resulting mixture was reacted at 80 ° C. to obtain a silicon-modified acryl resin solution (molecular weight: about 70,000) having a resin (average molecular weight of about 140) and a concentration of 50% by weight. This solution was adjusted by adding a mixed solvent of isopropyl alcohol and ethyl acetate (weight ratio: 3/1).

The above-mentioned liquid-modified silicone modified acrylic resin can be applied to a film or the like with a knife coater, but cannot be brushed or sprayed. However, the one-pack type paint and the two-pack type paint prepared at various mixing ratios with the above resin can be used in any of the mixing ratios by brushing, spraying, or dipping. Even if it is, Japanese tile, porcelain tile, plastic tile, plastic film such as PET, plastic molded body such as ABS, resin tube, soda glass, plate glass, glass fiber, FRP, mortar, concrete, gayal plate,

It could be applied uniformly to MDF, wooden floor, aluminum, stainless, steel, and steel pipe.

 Further, it solidified faster than any of the paints and adhesive compositions of the above-mentioned examples, and obtained a hardness of 4 to 5H 3 to 4 hours after application and a hardness of 7 or more after 7 to 8 hours. In addition, the flame resistance did not show any change in odor, discoloration, and peeling even when the coating film was exposed to the coating film after 24 hours with an alcohol lamp for several minutes.

The liquid-modified silicone-modified acrylic resin, when applied to a film or the like with a knife coater, showed super-hydrophobicity, so that the splashed water splashed and was never wetted with water. However, only the Si0 ₂ ultrafine particles, the coating film of the invention using the A1 ₂ 0 ₃ and Si0 ₂ in Seramitsu box ultrafine powder, the relatively high composition amount of the resin, after the initial curing frictional resistance is extremely Although it is low and shows the hydrophobicity found in general resins, it became hydrophilic when the cured coating was activated by polishing or the like. Although it is expected that a large amount of resin is present in the surface layer, it is mysterious that the surface layer changes to hydrophilic upon activation. In particular, those of only Si0 ₂ ultra-fine powder, while you are hitting the sunlight was filed wonder is that he had to demonstrate a hydrophilic.

Conversely, a composition in which the amount of ceramic ultrafine particles was relatively large had extremely low frictional resistance and had superior hydrophilicity from the beginning. In the coating film using the powder of three kinds including a photocatalyst for Ti0 ₂ The ceramic ultrafine particles powder had originally it has excellent hydrophilic Li. Inorganic and organic films obtained from liquid compositions using silicone-modified acrylic resins have high adhesion, high hardness, low coefficient of friction, excellent fire resistance, hydrophilicity, or superhydrophobicity. Ideal as a protective film for metals, resins, and glass that make up vehicles and aircraft.

 Example 40

Using the liquid composition using only Si02 as the ceramic ultrafine particle powder of Example 39, there are _two types, a hydrophobic type based on a liquid composition using a silicon-modified acrylol resin and a hydrophilic type based on a liquid composition using a modified acrylyl resin. Was prepared and applied to the skiing surface (P-tex) of the competition ski. The hydrophobic type repelled too much water, and the sliding was alienated depending on the snow quality. The hydrophilic type has improved gliding properties compared to the skis with today's best racing wax.

 Until now, there was no resin that could be applied and fixed on P-Tex, but this is now possible. However, if the base material on which the coating film of the present invention can be applied to an appropriate thickness is used as the sliding surface, no P-tex is required for skiing, and no polymer polymer wax, which is an environmental problem, is required.

 In addition, when making the hydrophilic type, even better hydrophilicity could be imparted by forcibly drying at the time of coating and heating at 150 ° C for 5 minutes. The hydrophobic type also changed to a hydrophilic type.

 When the surface of the coating film was polished with a polishing pad (a pad hardened by applying a zirconia ultra-fine powder paste, a glass cleaning pad manufactured by NCA), the polished surface became hydrophilic. .

 Example 41

In the same manner as in Example 40, two types of inorganic-organic films of a hydrophobic type and a hydrophilic type are applied to a roll that is used in a roll forming machine and that generates a roll mark without being driven. After molding, no roll mark was generated. Of course, stable operation for a long period of time has been made possible without attaching a coating film to the molding material.

 Example 42

Commercially available Aminoalkyd resin paint (Amino: Alkyd = 30: 70), Ceramic powder with average particle diameter of 7nrr! The Si0 ₂ and A1 ₂ 0 ₃ sintered body of ~ lOOnm 1: kneading the mixed ceramic ultrafine particles powder in a ratio of 2 to a base material, a commercially available curing agents for poly Isoshianeto compound and thinner and curing agent and without, A two-part adhesive was prepared in which the components were 35% resin, 35% ceramic fine powder, 10% solvent (in the main agent), 12% hardener, and 8% solvent (in the hardener).

 After mixing the main agent and the curing agent, the mixture was further diluted with a commercially available thinner to facilitate application to a thin film, and applied to a plastic tile, glass, gaical plate, wooden plate, aluminum plate, and stainless plate.

 After semi-curing to the extent that the surface was not sticky, the same materials were laminated and bonded. At this time, the same adhesive was applied and semi-cured to the mating material, and two types were used without applying anything. Two days were allowed for curing.

 The laminate could not be peeled under any of the conditions and materials. Example 43

Commercially available inorganic-organic composite varnish, the Si0 ₂ and A1 ₂ 0 ₃ sintered having an average particle diameter of 7 nm ~ 100 nm as the ceramic powdery particles 1: kneaded in various proportions mixed ceramic ultrafine particles powder in a ratio of 2 The main agent is a commercially available polyisocyanate compound for the hardener and thinner, and the hardener is not used.Resin and ceramic ultrafine powder content 66%, ceramic fine powder additive 5%, solvent (in the main material) 9 %, A hardener 13%, and a solvent (within the hardener) 7% were prepared to prepare a two-part adhesive.

 This is the same component as the paint of Example 19, and the film properties of the thin film are completely the same.

Example 44 SiO ₂ (5 to 30 nm), mixed powder obtained by mixing SiO ₂ (5 to 30 nm) and Α1 ₂ Ο ₃ (100 to 250ηιη), and SiO2 (5 to 30 nm), TiO2 for pigments (0.2 to 0.3 m), Al _Using three types of ceramic ultrafine particles mixed with ₂ O3 (100 to 200 nm), each of the liquid phases was mixed with a silicon-modified acryl resin at a ratio of 1: 4 to form a starting liquid composition, and a solvent and A two-part adhesive was prepared, consisting of a one-part adhesive mixed with an isocyanate-based curing agent, and a main liquid and a curing agent mixed with a solvent.

 Example 45

 After mixing the main component and the curing agent of the two-part adhesive of Examples 43 and 44, the mixture was applied to an aluminum thin plate and an aluminum foil, and a polyethylene film was laminated and bonded.

 Two types of polyethylene film were used, with no treatment and corona discharge treatment. In both cases, they adhered irremovably.

 By bonding a polyethylene film to an aluminum thin plate or foil, it is possible to easily laminate materials having other functions on aluminum to achieve multi-functionality.

 Example 46

 After mixing the main component of the two-part adhesive and the curing agent of Examples 43 and 44, the mixture was applied to an aluminum foil, and paper was laminated and adhered.

 The paper used was printed with various patterns and grain. In the event of misalignment, penetrate the entire paper and adhere to the aluminum foil as a single piece.The paper becomes plastic and ceramic, so put a lit cigarette on the paper side of the resulting laminated foil. In addition, even when the lighter was lit, the example of Example 41 was slightly browned, while the example of Example 42 was not changed at all, and a reforming effect such as remarkable improvement in fire resistance was obtained. Example 47

 After mixing the main component of the two-part adhesives of Examples 43 and 44 and the curing agent, they were applied to a piece of wood and combined to produce a lumbar core.

Example 48 After mixing the main component and the curing agent of the two-component adhesive of Examples 43 and 44, the mixture was applied to a veneer plate and an MDF plate, and a natural veneer was laminated and bonded to produce a floor material.

 The adhesive according to the present invention, after solidifying for 4 days, penetrates a natural wood veneer of 0.1 to 0.3 mm and has a mirror-like finish on the floor material surface. It was seen as plastic and ceramic.

 The adhesion of the veneer also served as the coating, and it was confirmed that the floor material surface was not easily scratched and the abrasion resistance was significantly improved.

 Example 49

 After mixing the main component of the two-part adhesive and the curing agent of Examples 43 and 44, the mixture was applied to bricks, concrete blocks, and glass blocks, and the bricks, concrete blocks, and glass blocks were respectively laminated. It could be used as a so-called mortar, and the adhesion was extremely strong.

 In addition, a resin bar could be firmly bonded as a spacer between bricks and glass blocks.

 Example 50

 Single-layer and laminated transfer resin films, which are often used to enhance the design of woodwork products, were bonded to each of the materials of carpet, veneer, and aluminum.

 After mixing the main component of the two-component adhesive and the curing agent of Examples 43 and 44, the mixture was applied to each material of a car board, a veneer board, and an aluminum board, and various transfer resin films were laminated and bonded. That is, the transfer resin film was bonded without using the transfer glue.

The transfer resin film was not only firmly bonded to each of the materials such as the gaical plate, veneer plate, and aluminum plate, but also the transfer resin film itself was extremely strong, had excellent surface smoothness, and improved design. After mixing the main component of the two-part adhesive and the hardener of Examples 43 and 44, brazing aluminum and stainless steel side bars and corrugated fins constituting the plate fin type heat exchanger to the same plate. The adhesive was applied to a predetermined surface, and after semi-hardening, a plate was placed and pressed to adhere.

 After solidification and curing, heat exchange with heated gas at 200 ° C or boiling water was performed.This is equivalent to a plate-fin type heat exchanger using a brazing material for ordinary aluminum or stainless steel, and is expensive. Since no brazing material was used and a heating process for brazing was not required, it became an economical plate-fin heat exchanger.

 Example 52

 In Example 51, on both sides of the side bar, corrugation fin, and plate exposed in the fluid passage of the blade fin type heat exchanger after normal assembly, the base material of the two-component paint prepared in Example 39 and curing were applied. After mixing with the agent, it was slightly diluted for spray coating and applied, and after semi-curing, these were assembled and pressed to adhere.

 After a certain degree of solidification and curing, heat exchange was performed to raise the temperature of the high-temperature wastewater into which foreign substances such as sand are mixed. In the case of aluminum, wear of corrugation fins and plates was significantly reduced.

 Example 53

 Aluminum materials for heat sinks, glass epoxy substrates, ceramic packaging materials, silicon substrates, semiconductor devices such as glass substrates, and electronic components, materials that are normally bonded and bonded, and bonding is not performed When the two materials were bonded using the two-component bonding method of Examples 43 and 44 for various types of bonding between the materials, bonding, bonding, and sealing were all possible.

Example 54 A commercially available resin film for preventing glass scattering was adhered to window glass using the various adhesives of Example 44. All the adhesives were not only transparent and could be stuck securely, but also provided a new UV-blocking function without the resin film. When the resin film was sandwiched between the glass plates and bonded with the adhesive of Example 44, it became possible to produce a safety laminated window glass plate capable of blocking ultraviolet rays. Example 55

 Using a commercially available aluminum panel plate and an angle material, a box-shaped or barrel-shaped container was prepared. The adhesive of Example 44 was subjected to forced drying using a drier, and then bonded and assembled. Conventionally, to manufacture an aluminum container, a brazing material and a heating furnace or a spot welding device are required. However, according to the present invention, a container having high rigidity can be easily manufactured.

 Further, a box-shaped container made of a commercially available tin plate was prepared using the conventional brazing material and the adhesive of Example 44, and the rigidity of the container was compared by the weight load. The one using the brazing agent withstood a load equal to or greater than that using the brazing filler metal. Industrial applicability

 The present invention relates to a coating material containing a ceramic ultrafine particle powder as a coating film component, for example, a resin having a relatively low molecular weight liquid phase such as a varnish or denatured acryl mainly composed of an inorganic material and a particle size. The main constituent components of the coating film are ultrafine ceramic powders such as nm-class alumina and silica, as well as curing agents and pigments that are used as necessary.The types and amounts of solvents and additives appropriately selected according to the application method The ratio can be determined and manufactured.

In the paint thus prepared, when the amount of the ceramic ultrafine particles is relatively small, as the hardening and bonding of the paint components progresses, the fine ceramic particles enter between the molecules of the paint components. It is characterized by the fact that the bonding strength between molecules is very strong, and as a result, the cured-bonded resin is modified to a structure that does not allow oxygen or moisture to enter.

 In addition, in the above-mentioned paint, when the ceramic ultra-fine particle power is relatively large, the ceramic ultra-fine particles are arranged, and the attractive force of the ceramic ultra-fine particles exerts a strong penetrating power, and after the curing-bonding, the base material is cured. An inorganic material that satisfies all of the properties of adhesive strength, non-permeability of oxygen and moisture (anti-smudge), stain resistance (stain resistance), chemical resistance, heat resistance, flame resistance, abrasion resistance, and mirror finish · An organic film is obtained.

The present invention also provides a paint-type adhesive containing a ceramic ultrafine particle powder as a coating film component, for example, a resin as a liquid phase and ceramic ultrafine particles such as alumina and silica having a particle size of rnn class. Powder-type adhesives with the same composition as the above-mentioned paints, with powder as the main coating film constituent and determined by the curing agent, solvent, and additive types appropriately selected according to the application method, and their ratios, are exactly the same Exhibits strong penetration into the coating resin and the mating material such as the coating base by the mechanism, and satisfies all the properties of adhesion strength, non-permeability of oxygen and moisture, chemical resistance, heat resistance, and flame resistance An adhesive function is obtained. Therefore, the paint and the adhesive according to the present invention can be applied to almost all functions and uses as paint as shown in the embodiment ^ J, and the paint component remains as it is, and is a very thin film regardless of the mating material. It can be applied and adhered, and when used as an adhesive for lamination of various materials, it is said that it is interposed and adhered. It integrates into the material on the side and exerts an anchor effect by penetrating into the material to be bonded, and can produce the effect of bonding and integration as if it were directly joined to the laminated material. For example, UV irradiation curing and UV irradiation curing methods are used to cure coatings, and they are used to produce dense coatings, but the coating according to the present invention is, of course, effective to use together. However, it can be considered that it has the ability to surpass these resins, and when used in combination with a low molecular weight resin, more penetrating effect and improvement function of curing can be obtained, and its potential as a paint for new applications have. In other words, the paints and adhesives according to the present invention have unique properties, that is, use of inorganic materials and ceramics ultrafine powders to improve coatings, adhesive layers, strong penetration, impregnation, and anchor effect. Therefore, any coating film component such as resin shown in the examples can be applied, and new uses and functions as paints and adhesives can be created.

 In addition, when the adhesive form is used, the adhesive strength to metal is particularly high, and it is possible to bond all materials and dissimilar materials and to produce laminated materials.For example, the bonding between metal foil and resin film The obtained laminated material can be used as a material that can be used for various applications or as an intermediate material for adding multiple functions.

 The present invention not only provides the above-mentioned multifunctional paint and adhesive, which exceeds the functions of conventional paints and adhesives, but also can easily impart the characteristics of inorganic substances to other substances as a thin film. It is a new technology that opens endless possibilities for all industrial products.

 The inorganic-organic film according to the present invention has extremely excellent permeability, adhesion strength, film strength and non-permeability of oxygen and moisture required for a coating material, regardless of the coating material. The functions of inorganic substances or modified organic substances can be added for any use. Furthermore, when the adhesive is used, the adhesive strength to metal is particularly excellent, and it becomes possible to bond various materials and dissimilar materials and to produce a laminated material. This invention not only exerts many functions beyond the functions of conventional paints and adhesives, but also can easily impart the characteristics of inorganic substances to other substances as a thin film. This is a new technology that opens up possibilities.

Claims

The scope of the claims 1. An inorganic / organic film formed from a liquid phase containing at least one inorganic or organic or inorganic and organic liquid, including at least one inorganic or organic or ultrafine particle of inorganic and organic.  2. The inorganic / organic organic material according to claim 1, wherein the ultrafine particles are dispersed or arranged adjacent to each other without agglomeration in the formed solidified film, and the liquid phase component is solidified between these particles. film.  3. The inorganic / organic film according to claim 1, wherein the film is formed from a liquid phase body in which ultrafine particles are non-centrifugably dispersed.  4. The inorganic / organic film according to claim 1, wherein the ultrafine particles have an average particle size of 30 nm or less.  5. The inorganic / organic film according to claim 1, wherein the average particle diameter of the ultrafine particles is 20ηπι or less. 6. ultrafine _{particles, Si0 2, A1 2 0 3} , Zr0 2, SiC, SiN, A1N, ZrN, inorganic or organic film according to claim 1 is at least one kind of TiN.  7. The inorganic / organic film according to claim 1, wherein the film-forming layer has an ultraviolet blocking property.  8. The inorganic or organic film according to claim 1, wherein the film formation layer has a light transmitting property and a light scattering property.  9. The inorganic or organic film according to claim 1, wherein the film forming layer has hydrophilicity.  10. The inorganic / organic film according to claim 1, wherein the film-forming layer has an electrical insulating property. 11. At least one inorganic or organic or at least one inorganic or organic that can be dispersed or arranged adjacently without aggregation in the solidified film (layer) in a liquid phase body containing an inorganic and organic liquidヽ is a starting liquid composition for forming an inorganic / organic film having ultrafine particles composed of inorganic and organic. 12. The starting liquid composition for forming an inorganic-organic film according to claim 11, comprising a liquid phase body in which ultrafine particles are dispersed so as to be unable to be centrifuged.  13. The starting liquid composition according to claim 11, wherein the average particle diameter of the ultrafine particles is 0 nm or less.  14. The starting liquid composition for forming an inorganic or organic film according to claim 11, wherein the average particle diameter of the ultrafine particles is 20 nm or less. 15. ultrafine particles _{Si0 2, A1 2 0 3,} Zr0 2, SiC, SiN, A1N, ZrN, starting solution composition for forming the inorganic-organic film according to claim 11 is at least one Chi sac TiN object.  16. The starting liquid composition for forming an inorganic / organic film according to claim 11, wherein the average molecular weight (formula weight) of the liquid phase occupying 50 vol% or more of the liquid phase body is 250 or less.  17. The starting liquid composition for forming an inorganic-organic film according to claim 11, wherein an average molecular weight (formula weight) of a liquid phase occupying 50 vol% or more of the liquid phase body is 150 or less.  18. The starting liquid composition for forming an inorganic / organic film according to claim 11, wherein the average molecular weight (formula weight) of the liquid phase body is equal to or less than + 150% of the average molecular weight (formula weight) of the ultrafine particles. object.  19. The starting liquid composition for forming an inorganic-organic film according to claim 11, wherein the average molecular weight (formula weight) of the liquid phase body is equal to or less than + 100% of the average molecular weight (formula weight) of the ultrafine particles. object.  20. The starting liquid composition for forming an inorganic-organic film according to claim 11, wherein the average molecular weight (formula weight) of the ultrafine particles is 150 or less. 21. The starting liquid composition for forming an inorganic / organic film according to claim 11, wherein the liquid phase body contains an acryl-modified resin. 22. The starting liquid composition for forming an inorganic-organic film according to claim 21, wherein the acryl-modified resin is an EB or UV curable resin.  23. At least one kind of inorganic or organic t is at least capable of being adjacently arranged without being aggregated or aggregated in a solidified film (layer) in a liquid phase containing inorganic and organic liquids. A paint or adhesive having one kind of inorganic or organic or ultrafine particles composed of inorganic and organic.  24. The paint or adhesive according to claim 23, wherein the paint or adhesive comprises a liquid phase in which ultrafine particles are dispersed so as to be non-centrifugable.  25. The paint or adhesive according to claim 23, wherein the average particle size of the ultrafine particles is 30 nm or less.  26. The paint or adhesive according to claim 23, wherein the average particle size of the ultrafine particles is 20 mn or less. 27. ultrafine particles _{Si0 2, A1 2 0 3,} Zr0 2, SiC, SiN, A1N, ZrN, paint or adhesive according to claim 23 is at least one Chi sac TiN.  28. The paint or adhesive according to claim 23, wherein the average molecular weight (formula weight) of the liquid phase occupying 50 vol% or more of the liquid phase body is 250 or less.  29. The paint or adhesive according to claim 23, wherein an average molecular weight (formula weight) of a liquid phase occupying 50 vol% or more of the liquid phase body is 150 or less.  30. The paint or adhesive according to claim 23, wherein the average molecular weight (formula weight) of the liquid phase body is equal to or less than + 150% of the average molecular weight (formula weight) of the ultrafine particles.  31. The paint or adhesive according to claim 23, wherein the average molecular weight (formula weight) of the liquid phase body is equal to or less than + 100% of the average molecular weight (formula weight) of the ultrafine particles. 32. The paint or adhesive according to claim 23, wherein the average molecular weight (formula weight) of the ultrafine particles is 150 or less. 33. The paint or adhesive according to claim 23, wherein the liquid phase body contains an acryl-modified resin.  34. The coating or adhesive according to claim 23, wherein the acryl-modified resin has a B or UV curable resin.  35. The paint or adhesive according to claim 23, wherein the paint or the adhesive is used as an insulating ink in printing means using ultrafine particles having electrical insulation or a liquid component having further electrical insulation.  36. The coating or adhesive according to claim 23, wherein the coating or adhesive is used as a conductive ink by using ultrafine particles having conductivity or a liquid phase component having further conductivity.  37. A liquid phase body containing at least one kind of inorganic or organic or inorganic and organic substance liquid and at least one kind of ultrafine particles of inorganic or organic or inorganic and organic matter are kneaded in a ball mill, and A method for producing a starting liquid composition for forming an inorganic / organic film in which ultrafine particles are dispersed so that they cannot be centrifuged.  38. A liquid phase body containing at least one inorganic or organic or inorganic-organic liquid, and at least one inorganic, organic or inorganic-organic ultrafine particle are kneaded in a ball mill, and A method for producing a paint or an adhesive in which ultrafine particles are dispersed so that they cannot be centrifuged. 39. After applying a coating or adhesive according to claim 23 as a base, a method of forming the antifouling coating film for coating the semi-cured resin mixed homogeneously Ti0 ₂ ultrafine powder of the photocatalyst at the time was. 40. The paint or adhesive according to claim 23, wherein a component that does not corrode the PET is blended with the liquid phase component, and applied as a base on the PET film. A method for forming a fouling coating film. 41. A method for forming a hydrophilic coating film for imparting hydrophilicity to a coating film by applying forced drying and heating when applying the paint or adhesive according to claim 23.  42. After applying the paint or adhesive according to claim 23, the surface of the coating film is polished with a polishing pad that has been coated with an ultra-fine ceramic paste and solidified to impart hydrophilicity to the coating film. Method of forming a functional coating film. 43. After application of the coating or adhesive according to claim 23, is semi-cured, EB or is 0 to ₂ flow during UV irradiation, hydrophilicity to only 0 ₂ Asshingu and coating the surface of the resin layer A method for forming a hydrophilic coating film to be applied.  44. An EB-curable resin is used as a liquid phase component of the starting liquid composition according to claim 11, and the starting liquid composition is filled in a mold having a required shape, and then irradiated with EB to form the desired shape. A molding method for obtaining molded articles. 45. In the liquid composition using the A1 ₂ 0 ₃ ultrafine particles, formed form a method of molding an insulating sheet material.