TW201332654A - Composite material and coating composition - Google Patents

Abstract

Disclosed is a composite material whereby: said composite material exhibits sufficient self-cleaning performance when a large amount of water (rainwater) has come into contact therewith; but even if the amount of water (rainwater) is low, lines of dirt comprising accumulated dust or the like do not form on the surface of the composite material. This composite material, which comprises a substrate and a surface layer formed on the surface of said substrate, is characterized in that said surface layer comprises the following: a compound (A) that contains oxygen and at least one metal selected from the group consisting of silicon, aluminum, titanium, tin, and tungsten; and one or more compounds (B) selected from the group consisting of oxides, inorganic salts, and organic salts and containing at least one metal selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, gallium, zirconium, yttrium, indium, and hafnium. This composite material is further characterized in that the oxide-equivalent mass of the aforementioned compound(s) (B) is at least 30% but less than 99% of the sum of said oxide-equivalent mass and the mass of the other compound (A).

Description

Composite material and coating composition

This invention relates to composite materials having improved self-cleaning properties and coating compositions for making the composite materials.

The hydrophilic surface has a property of being readily soluble in water. Therefore, even if dirt such as dust adheres to the surface, water will seep between the dirt and the surface when it is drenched, and the dirt will be removed together with the water to purify the surface. Such properties are known to be self-cleaning. Next, various building materials such as wall materials or inner wall materials which impart self-cleaning properties to the surface are proposed.

As for the component dirt of such a self-cleaning property, the following points are pointed out. That is, it is pointed out that when a large amount of water (rainwater) flows to the surface of the member, the dirt on the surface is sufficiently removed by self-cleaning, but when the water (rain) is a small amount, the dust accumulated on the surface The dirt is not sufficiently removed, and as a result of drying after the water droplets flow, a linear trace remains, which deteriorates the appearance.

WO03/028996 (Patent Document 1) indicates that such an appearance is poor and aims to solve the problem. Further, in WO03/028996 (Patent Document 1), a hydrophilic film composed of a photocatalyst, an organic zirconium, and a polyoxyxylene resin material is disclosed. The addition amount of the zirconia contained in the film to be disclosed is 10 parts by mass or less, and the effect of maintaining the contact angle with water can be improved. According to the publication, the surface of the member formed by the film has antifouling properties, and the dirt can be prevented from being along when the amount of water is small. The flow of rain is linear.

For example, Japanese Laid-Open Patent Publication No. 2009-213954 (Patent Document 2) or JP-A-2009-270040 (Patent Document 3).

Japanese Laid-Open Patent Publication No. 2009-213954 (Patent Document 2) discloses a film comprising zirconia or cerium oxide and titanium oxide, and the amount of zirconia contained in the film is such that Zr:Ti is 100: Two examples of 1 and 1:1 are described in the examples. According to this publication, the film forms water droplets when water adheres due to water repellency. Further, according to the publication, the film is provided with a property that water droplets are easily slipped off and removed.

In Japanese Patent Laid-Open Publication No. 2009-270040 (Patent Document 3), it is disclosed that zirconia is used as a binder in the photocontact medium coating liquid in order to improve the adhesion to the substrate. In the examples described in the publication, TiO ₂ :ZrO ₂ is the largest example of 50:50, and only the photocatalytic decomposition properties of the film obtained as a coating liquid and the coating liquid are applied. Evaluation.

Further, in WO2000/53689 (Patent Document 4), a hydrophilic film having an antifogging agent and antifouling properties, which comprises ceria, alumina and zirconia, is disclosed. In the examples described in the publication, the maximum value of the amount of zirconia of ceria and alumina is [SiO ₂ ]: [Al ₂ O ₃ ]: [ZrO ₂ ] described in Example A2. = 0.75 (43 wt%): 0.5 (29 wt%): 0.5 (29 wt%).

The surface system described in Patent Document 1 has a contact angle with water of 5 to 30°, and since it has high hydrophilicity, it can be self-cleaning, but prevents water droplets. The effect of running down is weak, and practically, it is not sufficient to prevent linear traces. Further, the surface described in Patent Document 2 cannot be expected to be self-cleaning due to water repellency. Furthermore, since the water droplets are liable to slip, the linear traces generated by the water droplets still occur. The film structure described in Patent Document 3 is similar to the film described in Patent Document 2, and thus is considered to have the same problem. The surface of the film system described in Patent Document 4 exhibits high hydrophilicity. That is, for a member having a self-cleaning property, a member that does not cause the above-described linear trace is still sought.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] WO03/028996

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-213954

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-270040

[Patent Document 4] WO2000/53689

The inventors of the present invention have found that by providing a surface layer having a specific component on a substrate, it is possible to achieve sufficient self-cleaning performance when in contact with a large amount of water (rainwater), and on the other hand, in water (rainwater) When it is a small amount, a member which does not generate linear dirt generated by the accumulated dust or the like on the surface does not occur. In detail, the present inventors have found that water can be sufficiently enlarged on the surface of the member when it comes into contact with a large amount of water (rain water). When the water (rain water) is a small amount, the water droplets are prevented from slipping off and remain on the surface of the member, whereby a member that does not allow the occurrence of linear dirt can be realized, because the linear dirt is considered to be When the water droplets slide down, sand and dust accumulated on the traction surface are generated. The present invention is an invention based on this finding.

Accordingly, it is an object of the present invention to provide a composite material which exhibits sufficient self-cleaning performance when contacted with a large amount of water (rain water), and which does not generate on the surface when water (rain water) is small. Linear dirt formed by accumulated dust and the like.

Further, the composite material of the present invention comprises a composite material having a base material and a surface layer formed on the surface of the base material, wherein the surface layer comprises the compound (A) and the compound (B). In addition, the compound (B) is blended in an amount of 30% by mass or more and less than 99% by mass in terms of the mass of the compound (B) and the mass of the compound (B). The compound (A) contains at least one metal selected from the group consisting of Si, Al, Ti, Sn, and W, and oxygen, and the compound (B) is composed of Cr, Mn, Fe, Co, At least one selected from the group consisting of oxides of at least one metal, inorganic salts, and organic salts selected from the group consisting of Ni, Cu, Ga, Zr, Y, In, and Hf.

definition

In the present specification, when the amount of water (rainwater) flowing to the member is small, the dirt such as dust deposited on the surface is not sufficiently removed, and the linear trace remains, and the dirt which is a cause of poor appearance is called "line". Shaped dirt."

Composite material

The composite material of the present invention basically comprises a surface layer having a substrate and a surface formed on the substrate. On the other hand, the composite material exhibits sufficient self-cleaning performance when it comes into contact with a large amount of water (rain water), and on the other hand, when water (rain water) is small, no linear dirt is generated. It is considered that when the water droplets adhering to the surface of the member slide down, the dust deposited on the surface is pulled by the water droplets, and then the water required to sufficiently remove the dust remaining on the surface is not supplied ( Rain water) and the producer. Further, in the present invention, the surface of the surface layer of the composition described later does not immediately expand on the surface when the water adheres, but remains in the form of water droplets and resists external forces such as gravity and does not slide to the surface (hereinafter, This is referred to as "water drop retention performance" in the specification. However, when water is further supplied and a plurality of water droplets are collected, the form of the water droplets collapses, and the water is wetted and spread on the surface of the surface layer, and flows downward by an external force such as gravity. At this time, the water removes the dirt from the surface and cleans the surface (hereinafter, referred to as "water film formation performance" in the present specification).

Further, the composite material of the present invention is characterized in that the surface layer provided on the substrate contains the compound (A) and (B), the compound (B) is formulated in an amount of 30% by mass or more based on the mass of the compound (A) and the mass of the compound (B). And not more than 99% by mass, wherein the compound (A) contains at least one metal selected from the group consisting of Si, Al, Ti, Sn, and W, and oxygen, and the compound (B) is contained by Cr And at least one selected from the group consisting of at least one metal oxide, an inorganic salt, and an organic salt selected from the group consisting of Mn, Fe, Co, Ni, Cu, Ga, Zr, Y, In, and Hf.

In accordance with the present invention, three preferred embodiments of the composite materials described below are provided.

The first form of the invention Surface layer

In the first aspect of the invention, the surface layer of the composite material comprises the material (I-1) as the compound (A) and the material (I-2) as the compound (B).

Material (I-1)

In the first form of the invention, the material (I-1) is at least one compound selected from the group consisting of ceria, alkali silicate, alumina, and amorphous titanium oxide. In the first form of the present invention, sodium citrate, potassium citrate or lithium niobate may be used singly or in combination as the alkali citrate.

In the first form of the invention, the material (I-1) is a hydrophilic compound. In the first form of the present invention, the material (I-2) to be described later is a metal compound which is less hydrophilic than the material (I-1). According to the present invention, the reason for preventing the linear dirt is not clear, but it can be estimated as follows. On the surface of the member resulting from the present invention, the portion in which the material (I-1) exists is formed with a hydrophilic region. On the surface of the member to which the present invention is applied, a portion where the material (I-2) exists is formed with a region having a weaker affinity with the material (I-1) than water. The hydrophilicity and the causative material (I-) due to the material (I-1) achieved by the presence of the material (I-1) and the material (I-2) specified in the first form of the present invention 2) The two properties which are caused by the weak hydrophilicity of water exhibit water droplet retention performance and water film formation property, so that linear dirt can be effectively prevented. In other words, on the surface, the force which is formed by the hydrophilic portion is absorbed by the water to form a water film, and the force due to the formation of the water droplet due to the weak affinity with water is balanced. When a small amount of water of the raindrop adheres, the movement of the three-phase line of the water droplet (the interface of the gas, the liquid, and the solid, that is, the contour of the surface portion contacting the water droplet) is suppressed, and the water droplet is retained by the external force such as gravity. surface. As a result, linear dirt can be prevented. Thereafter, it is presumed that when a large amount of water is supplied, the water droplets are collected, and the water is enlarged on the surface to form a water film, that is, the so-called self-cleaning performance is exerted, and the surface is cleaned. However, the above description is assumed after all, and the present invention is not limited to this assumption.

In the first form of the invention, the material (I-1) is preferably a particle. A suitable particle size is 10 nm or more and 100 nm calculated by using a scanning electron microscope to measure a 100,000-fold field of view of any 100 particle lengths. The average number of particles below. The shape of the particles is preferably spherical, but may be a different shape such as an ellipse. The particle length at this time is roughly calculated by dividing the sum of the longest diameter and the shortest diameter of the particle shape observed by the scanning electron microscope by two. The material (I-1) is formed into a surface layer together with the material (I-2) as a particle shape, whereby the material (I-1) and the material (I-2) can be dispersed on the surface of the surface layer. Thereby, the desired wetting characteristics (water drop retention performance and water film formation performance) can be exhibited more effectively. Furthermore, it is also advantageous from the viewpoint of obtaining a transparent surface layer.

In the first form of the present invention, the material (I-1) is added in an amount determined in relation to the material (I-2) to be described later.

Material (I-2)

In the first aspect of the invention, the material (I-2) is at least one metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Ga, Zr, Y, In, and Hf. The at least one compound selected from the group consisting of oxides, inorganic salts and organic salts is preferably at least one compound selected from the group consisting of oxides of Zr or Hf, inorganic salts and organic salts.

The material (I-2) exhibits a metal compound which is weaker in affinity with water than the material (I-1). As described above, the surface layer of the composite material according to the present invention is obtained by blending the material (I-2) together with the material (I-1), thereby effectively preventing linear dirt and imparting self-cleaning properties. Wetting characteristics (water droplet retention performance and water film formation properties).

In the first aspect of the present invention, the oxide containing the above metal is, for example, Cr ₂ O ₃ , MnO ₂ , Fe ₂ O ₃ , CoO, NiO, CuO, Ga ₂ O ₃ , ZrO ₂ , Y _{2 .} O ₃ , In ₂ O ₃ , HfO ₂ and the like. Further, examples of the inorganic salt include oxychlorides, hydroxychlorides, nitrates, sulfates, acetates, oxynitrates, carbonates, ammonium carbonates, sodium carbonates, potassium carbonates, and sodium phosphates of the above metals. Salt and so on. Further, examples of the organic salt include oxalates, propionates, metal alkoxides, hydrolyzates of metal alkoxides, chelating compounds, and the like of the above metals. The metal alkoxide is a compound in which an alkoxy group having about 1 to 8 carbon atoms is bonded to a metal atom. For example, when the metal atom is Zr, zirconium tetramethoxide, zirconium tetraethoxy oxide, zirconium tetra is exemplified. N-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, and the like. Further, as the chelating compound, for example, a β-ketoester complex, a β-diketone complex, an ethanolamine complex, a diethylene glycol complex, or the like can be used.

According to a preferred embodiment of the present invention, the material (I-2) is an amorphous oxide or an oxide particle or an inorganic salt having an average crystal diameter of less than 10 nm. The surface layer obtained by applying these compounds is excellent in water droplet retention performance and water film formation property. Here, the average crystallite diameter is calculated from the product of the strongest ray peak of XRD and calculated by the Scherrer equation.

In the first aspect of the present invention, when the material (I-2) is a particle, it is 5 nm or more and 100 nm or less calculated by measuring the length of an arbitrary 100 particles of a field of view of 200,000 times by a scanning electron microscope. Particles having an average number of particle diameters are preferred. The material (I-2) is formed into a surface layer together with the material (I-1) as a particle shape, whereby the material (I-1) and the material (I-2) can be dispersed on the surface of the surface layer. Thereby, it can be more effective Demonstrates the desired wetting characteristics (water droplet retention properties and water film formation properties). Furthermore, it is also advantageous from the viewpoint of obtaining a transparent surface layer. Further, the material (I-2) can also be expected to function as a binder of the fixing material (I-1).

In the first aspect of the present invention, the material (I-2) is blended in the oxide conversion ratio with respect to the mass of the material (I-1) and the mass of the material (I-2). 30% by mass or more and 70% by mass or less, preferably 30% by mass or more and 50% by mass or less.

Further, according to another preferred embodiment of the present invention, the material (I-2) is formulated in the surface layer in an amount of 30% by mass or more and 70% by mass or less, preferably 30% by mass in terms of the oxide. The above and 50% by mass or less are preferred. Further, the quality of the surface layer is actually a value equal to the amount (mass) of the film forming component to be described later.

Other optional ingredients

The surface layer of the composite material according to the first aspect of the present invention may contain any of the components other than the components of the above materials (I-1) and (I-2) as needed. Examples of the optional component include pigments, fillers, photosensitizers, dyes, and the like, and can be selected and combined for various purposes without impeding the desired wetting characteristics (water droplet retention performance and water film formation performance). .

Further, in the surface layer of the composite material resulting from the first form of the present invention, it is preferred that the photocatalytic material is not actually present. In fact, it does not exist, which means the hydrophilicity in the surface layer of the composite material caused by the present invention. Sexuality is not caused by the action of photocatalyst, and thus means that a photocatalyst exhibiting an amount of hydrophilicity is not formulated.

Physical properties of the surface layer

The water droplet retaining property and the water film forming property of the composite material having the first form of the present invention are those which exhibit self-cleaning performance while preventing linear dirt, but as a method for specifically evaluating such properties, The following two methods.

First, as a method of evaluating the water droplet retention performance, the following methods can be mentioned. The method-based composite material of the surface layer is inclined 80 °, respectively measured 15 μ L of water droplets adhered thereto after the movement distance of the water droplet surface portion 5, based on the following criteria given a score corresponding to the moving distance.

0 points: the drop of water drops is less than 2cm

1 point: Water droplets slipped more than 2cm

2 points: Water droplets slipped more than 4cm

3 points: Water droplets slipped more than 6cm

4 points: Water droplets slipped more than 8cm

5 points: Water droplets slipped more than 10cm

The composite material of the present invention preferably has a total score of 20 points or less, more preferably 5 or less, and still more preferably 0.

Further, as a method of evaluating the water film formation performance, the following methods can be mentioned. In this method, the surface layer of the composite material is kept in a vertical state, and 15 g of ion-exchanged water is sprayed from a distance of 10 cm from the surface. 100mm × 200mm surface. The composite material according to the present invention may be formed with a water film in its entirety, or may be a state in which water is poured on a part of the surface and a water film is formed on the other surface.

According to one aspect of the present invention, the surface layer of the composite material according to the first aspect of the present invention is preferably one having the following surface characteristics.

The composite material resulting from the present invention is preferably a forward contact angle of 30 or more, more preferably 35 or more, still more preferably 40 or more.

Further, the back contact angle is preferably 20 or less, preferably 16 or less, more preferably 13 or less, and most preferably 10 or less.

Further, the difference between the advancing contact angle and the receding contact angle, that is, the hysteresis is preferably 20° or more and 80° or less, more preferably a lower limit of 35°, and a more preferable lower limit of 40°. A better upper limit is 75°, and a better upper limit is 70°.

The surface layer of the composite material resulting from the present invention is preferably a forward contact angle, a receding contact angle, and a hysteresis satisfying the above range. When it is in this range, the water droplet retainability at the time of water droplet formation and the water film formation property at the time of a large amount of water droplets become more excellent.

The above surface characteristics, that is, the dynamic contact angle (advancing contact angle and receding contact angle) and the slip angle, are measured by conventional or established measurement methods, but are preferably measured by the following methods. That is, an automatic contact angle measuring device (for example, OCA20 manufactured by Hidehiro Seiki Co., Ltd.) is used to measure the dynamic contact angle (advancing contact angle and receding contact angle) with respect to water. More specifically, after the dropping of the water droplets 50 μ L on the surface layer, while the speed of the surface layer is 1.6 deg./s inclined, water droplets were observed from the side of the contact angle measuring device attached camera, respectively, for the water droplets fall The contact angle (advancing contact angle) of the slip side of the instantaneous water drop and the contact angle (reverse contact angle) on the side opposite to the slip side of the water drop were measured.

Further, the surface layer of the composite material caused by a first type of the present invention, water-based roll-off angle to 30 μ L of 40 ° or more is preferred. It can be said that the larger the slip angle, the higher the water droplet retention.

The above-described slip angle is measured by a conventional or established measurement method, but it is preferably measured by the following method. That is, the slip angle is measured by the slip method. More specifically, after the dropping of 30 μ L water droplet on the surface layer, while the speed of the surface layer is 1.6 deg./s inclined, water droplets were observed from the side of the camera, the water droplets fall to the instantaneous angle of inclination of: slip angle measuring.

According to a preferred embodiment of the present invention, the surface layer of the composite material according to the first aspect of the present invention is preferably a static contact angle with water at an average value of 5 or more points at any measurement point of 20 or more. Preferably, the temperature is less than 90°, the lower limit is 30°, the lower limit is 35°, the upper limit is 80°, and the optimum upper limit is 75°. If it is in this range, the water droplet retainability at the time of water droplet formation becomes more excellent. After the static contact angle with water-based contact angle measurement device (e.g., manufactured by Kyowa Interface Science Co., product name CA-X150 type), 5 μ L of water droplets dropwise at room temperature, by θ / 2 method to measure Static contact angle after 5 seconds.

The surface layer of the composite material according to the first aspect of the present invention is preferably a film thickness of 300 nm or less. A better lower limit is 10 nm, which is even better. The lower limit is 15 nm. The upper limit is more preferably 200 nm, still more preferably 150 nm. By setting it as this range, since the 1st component and the 2nd component exist in the surface layer more homogeneous, the desired wetting characteristics (water droplet retention performance and water film formation performance) can be acquired reliably. Further, it is also advantageous from the viewpoint of obtaining a transparent surface layer by setting it as the range.

According to a preferred embodiment of the present invention, the surface layer of the composite material resulting from the present invention is a laser microscope having a wavelength of 405 nm and an arithmetic mean measured in a field of 20 times in accordance with JIS B 0601-1982. The roughness Ra is preferably an average value of 3 points or more at any measurement point of more than 5 nm and 50 nm or less. A preferred lower limit is 5 nm, and a more preferred lower limit is 10 nm. Further, a preferred upper limit is 50 nm, and a more preferred upper limit is 30 nm. In the first aspect of the present invention, when the surface roughness is within this range, the water is attracted by the fine unevenness to hinder the movement of water, and the water contacting the surface does not infiltrate and expand, and the so-called water is not strengthened. The role of contraction.

Substrate

The base material which forms the composite material of the first form of the present invention is a material which can achieve self-cleaning properties and is desired to prevent linear dirt. The substrate may be a flat or curved material, and the material thereof may also be, for example, metal, ceramic, glass, plastic, rubber, stone, cement, concrete, fiber, cloth, tree, paper, a combination of these, such a laminate. The surface is applied to the painter. Specifically, a building material of an exterior material or an interior material of a building is mentioned as a preferable example. In particular, it is preferable to use a building material applied to a facade. When the composite material of the present invention is used as an exterior material, it is in contact It is used in the rainy environment. According to the present invention, since it is possible to prevent linear dirt, it can be suitably used in places where it is difficult to sufficiently contact the rain, such as under the rain cover or under the eaves. The interior material can be applied to areas where condensation water will condense on the surface.

The building materials to be used for the façade of the present invention are, for example, wall materials and window materials, and more particularly, such as wall materials such as outer walls and sound insulating walls, and window materials such as window glass. In particular, the transparent sound insulating wall and the window glass have a base material which is transparent, and since the dust and dirt such as linear dirt are conspicuous, the substrate of the present invention can be suitably used.

According to a preferred embodiment of the present invention, the surface of the substrate preferably has an arithmetic mean roughness Ra of 100 nm or less. In the case of such a smooth surface, it is easy to set the surface roughness of the surface layer to the aforementioned range.

Coating composition

According to the present invention, a coating composition for producing the composite material of the first aspect of the present invention described above can be provided. The coating composition of the first aspect of the present invention basically comprises the above materials (I-1) and (I-2) and a solvent.

The material (I-1) and the material (I-2) contained in the coating composition resulting from the first form of the present invention may also mean the material (I-1) and the material (I-) previously described. 2) Same.

Therefore, the material (I-1) is at least one compound selected from the group consisting of ceria, alkali silicate, alumina, and amorphous titanium oxide. Yu Benfa In the present invention, as the alkali citrate, sodium citrate, potassium citrate or lithium niobate may be used singly or in combination.

Further, the material (I-1) is preferably a particle. A suitable particle diameter is a number average particle diameter of 10 nm or more and 100 nm or less calculated by a scanning electron microscope to measure the length of any 100 particles of 200,000-fold field of view. The shape of the particles is preferably spherical, but may be a different shape such as an ellipse. The particle length at this time is roughly calculated by dividing the sum of the longest diameter and the shortest diameter of the particle shape observed by the scanning electron microscope by two. The material (I-1) is formed into a surface layer together with the material (I-2) as a particle shape, whereby the material (I-1) and the material (I-2) can be dispersed on the surface of the surface layer. Thereby, the desired wetting characteristics (water drop retention performance and water film formation performance) can be exhibited more effectively. Further, it is also advantageous from the viewpoint of obtaining a transparent surface layer.

Further, the material (I-2) contains at least one metal oxide, inorganic salt and organic salt selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Ga, Zr, Y, In and Hf. The at least one compound selected from the group formed is preferably at least one compound selected from the group consisting of oxides of Zr or Hf, inorganic salts and organic salts.

In the first aspect of the present invention, the oxide containing the above metal means, for example, Cr ₂ O ₃ , MnO ₂ , Fe ₂ O ₃ , CoO, NiO, CuO, Ga ₂ O ₃ , ZrO ₂ , Y. ₂ O ₃ , In ₂ O ₃ , HfO ₂ and the like. Further, examples of the inorganic salt include oxychlorides, hydroxychlorides, nitrates, sulfates, acetates, oxynitrates, carbonates, ammonium carbonates, sodium carbonates, potassium carbonates, phosphoric acid of the above metals. Sodium salt, etc. Further, examples of the organic salt include oxalates, propionates, metal alkoxides, hydrolyzates of metal alkoxides, chelating compounds, and the like of the above metals. The metal alkoxide is a compound in which an alkoxy group having about 1 to 8 carbon atoms is bonded to a metal atom. For example, when the metal atom is Zr, zirconium tetramethoxide, zirconium tetraethoxy oxide, zirconium tetra - propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butyl oxide, and the like. Further, as the chelating compound, for example, a β-ketoester complex, a β-diketone complex, an ethanolamine complex, a diethylene glycol complex, or the like can be used.

According to a preferred embodiment of the present invention, the material (I-2) is an amorphous oxide or an oxide particle or an inorganic salt having an average crystal diameter of less than 10 nm.

In the first aspect of the present invention, when the material (I-2) is a particle, it is 5 nm or more and 100 nm or less calculated by measuring the length of an arbitrary 100 particles of a field of view of 200,000 times by a scanning electron microscope. Particles having an average number of particle diameters are preferred. The material (I-2) is formed into a surface layer together with the material (I-1) as a particle shape, whereby the material (I-1) and the material (I-2) can be dispersed on the surface of the surface layer. Thereby, the desired wetting characteristics (water drop retention performance and water film formation performance) can be exhibited more effectively. Further, it is also advantageous from the viewpoint of obtaining a transparent surface layer. Further, the material (I-2) can also be expected to function as a binder of the fixing material (I-1).

The blending amount of the material (I-1) and the material (I-2) in the coating composition of the first aspect of the present invention is required to achieve the above-mentioned invention. The composition of the surface layer of the composite. Therefore, in the coating composition of the first form of the present invention, the mass of the material (I-1) and the mass of the material (I-2) are converted, and the material (I-2) The amount of the oxide is also 30% by mass or more and 70% by mass or less, preferably 30% by mass or more and 50% by mass or less.

Further, according to another preferred embodiment of the present invention, the material (I-2) is formulated in an amount of 30% by mass or more and 70% by mass or less, preferably 30% by mass based on the oxide-forming component. % or more and 50% by mass or less. Here, the film forming component refers to a component obtained by removing a volatile component such as a solvent and a water-soluble additive such as a surfactant from the coating composition, and the amount of the film forming component is substantially equal to that of the coating composition. The value of the value of the amount of the water-soluble additive is excluded from the evaporation residue.

According to a preferred form of the invention, the material (I-1) can also be added to the precursor of the material (I-1) in the manufacturing step. Therefore, the material (I-1) and the precursor which are contained in the coating composition of the present invention are exemplified by cerium oxide, alkyl cerate, alkali cerate, alumina, At least one selected from the group consisting of amorphous titanium oxide, titanium peroxide, aluminum hydroxide, and gibbsite. Among these, alkyl citrate is a precursor of cerium oxide, a precursor of titanium oxide-based amorphous titanium oxide, and a precursor of aluminum hydroxide and gibbsite-based alumina. These precursors are changed to cerium oxide, alkali cerate, alumina or amorphous titanium oxide after the film is formed.

The alkyl phthalate which can be blended in the coating composition of the first form of the present invention may be exemplified by hydrolysis of decane oxides and decane oxides. The solution, the chelating compound, and the like. In the above, the decane oxide is a compound in which an alkoxy group having about 1 to 4 carbon atoms is bonded to a ruthenium atom, and examples thereof include ruthenium tetramethoxide, ruthenium tetraethoxylate, and ruthenium tetra-n- Propoxide, cesium tetraisopropoxide, ruthenium tetra-n-butyl oxide, ruthenium tetra-t-butyl oxide, and the like. Further, examples of the chelate compound include a β-ketoester complex, a β-diketone complex, an ethanolamine complex, and a dialkylethylene glycol complex.

The solvent contained in the coating composition of the first aspect of the present invention is a substance which can disperse or dissolve the material (I-1) and the material (I-2) and is liquid at normal temperature. Examples of the examples include alcohols such as water, ethylene glycol, butyl sarbuta, isopropanol, n-butanol, ethanol, and methanol, aromatic hydrocarbons such as toluene or xylene, and hexane and cyclohexane. An aliphatic hydrocarbon such as an alkane or a heptane; an ester such as ethyl acetate or n-butyl acetate; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone; tetrahydrofuran or dioxane; An amine such as an ether, dimethylacetamide or dimethylformamide; a halogen compound such as chloroform, dichloromethane or carbon tetrachloride; dimethyl hydrazine or nitrobenzene. These solvents may be used singly or in combination.

Further, the coating composition of the first form of the present invention is preferably one containing a leveling agent, and examples thereof include diacetone alcohol, ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether. , 4-hydroxy-4-methyl-2-pentanone, dipropylene glycol, tripropylene glycol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, propylene glycol monomethyl ether, 1 - propoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, acetylene alcohol, and the like.

The coating composition according to the first form of the present invention may be formulated and combined according to different conditions and materials (I-1) and materials according to various purposes. Other pigments other than (I-2), hardening catalyst, crosslinking agent, filler, dispersant, light stabilizer, wetting agent, tackifier, rheology control agent, defoamer, filming aid, whole Additives such as flat agents, rust inhibitors, dyes, preservatives, and the like. In particular, when water is used in a solvent, various surfactants may be added as an additive in order to improve the wettability of the coating composition.

The coating composition of the first aspect of the present invention can be obtained by dissolving or dispersing the material (I-1) and the material (I-2) and other optional components in a solvent. Each material can be combined and formulated into various coating materials such as a dispersion of a powder, a solution, or a sol to form a coating composition.

The solid content concentration in the coating composition is preferably from 0.05% by mass to 20% by mass, more preferably from 0.05% by mass to 10% by mass. The solid content concentration is actually equal to the concentration of the above-mentioned film-forming component. Specifically, the coating composition can be dried at 105 ° C to 110 ° C to divide the difference between the obtained evaporation residue and the amount of the water-soluble additive. It is obtained by coating the amount of the composition.

Composite material manufacturing method

The composite material of the first form of the present invention can be favorably produced by using the above-described coating composition. Specifically, after the coating composition of the first form described above is applied onto the surface of the substrate, (a) the surface of the substrate is heated at 300 ° C or lower, and (b) dried at room temperature. Or (c) forming the surface of the substrate well by heating at a temperature of more than 300 and less than 1000 ° C for 2 to 60 seconds. In any of the manufacturing methods, it is set to a heating condition of no heating or lower temperature or a short time. By heating conditions, a surface layer which sufficiently exhibits desired wetting characteristics (water drop retention property and water film formation property) can be obtained.

The coating of the substrate can be carried out by means of bristles, rolls, or coating, shower coating, dip coating, screen printing, gravure printing or the like by spraying.

The second form of the invention Surface layer

In the second aspect of the invention, the surface layer of the composite material comprises the material (II-1), the material (II-2), and the material (II-3).

Material (II-1)

In the second aspect of the invention, the material (II-1) is composed of anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, zinc oxide, tin oxide, crystalline tungsten oxide and non- At least one photocatalyst material selected from the group consisting of crystalline tungsten oxide. These photocatalyst materials are composed of a photocatalyst excited by light having a wavelength of 350 to 500 nm. According to a preferred embodiment of the present invention, anatase-type titanium oxide, rutile-type titanium oxide, and brookite-type titanium oxide can be suitably used among the photocatalyst materials. These titanium oxides are non-toxic and have excellent chemical stability.

In the second aspect of the present invention, the photocatalyst as the material (II-1) exhibits a property of highly hydrophilicizing itself and decomposing the organic substance by light irradiation. Further, the material (II-3) described later is also a hydrophilic compound. In the second aspect of the present invention, the material (II-2) described later is less hydrophilic than the photocatalytic material of the material (II-1), and is not easily used. a metal compound that decomposes by decomposition. According to the present invention, the reason for preventing the linear dirt is not clear, but it can be estimated as follows. In the surface of the member resulting from the present invention, a portion of the material (I-1) is formed by photoexcitation to form a highly hydrophilic region, and a portion present in the material (II-3) is also formed with a hydrophilic portion. region. The material (II-2) that is in contact with the material (II-1) forms a clean surface by photocatalytic action and maintains a weaker affinity with the material (II-1) than water, in the material (II- 2) The portion present is formed with a region having weak affinity with water. The material (II-1) and the material (II) are realized according to the existence ratio of the material (II-1), the material (II-2) and the material (II-3) specified in the second form of the present invention. The hydrophilicity caused by -3) and the weak affinity with water due to the material (II-2) exhibit water droplet retention performance and water film formation properties, so that linear dirt can be effectively prevented. In other words, on the surface, the water formed by the hydrophilic portion is attracted to form a water film, and the force due to the water-bead affinity is balanced. When a small amount of water of the raindrops adheres, the movement of the three-phase line of the water droplets (the interface of the gas, the liquid, and the solid, that is, the contour of the portion contacting the surface of the water droplet) is suppressed, and the water droplets are retained against external forces such as gravity. on the surface. As a result, linear dirt can be prevented. Thereafter, it is presumed that when a large amount of water is supplied, the water droplets are collected, and the water is enlarged on the surface to form a water film, that is, the so-called self-cleaning performance is exerted, and the surface is cleaned. However, the above description is assumed after all, and the present invention is not limited to this assumption.

In the second aspect of the invention, the material (II-1) is preferably a particle. Suitable particle size, using a scanning electron microscope to measure 200,000 The number average particle diameter of 10 nm or more and 100 nm or less calculated by arbitrary 100 particle lengths. The shape of the particles is preferably spherical, but may be a different shape such as an ellipse. The particle length at this time is roughly calculated by dividing the sum of the longest diameter and the shortest diameter of the particle shape observed by the scanning electron microscope by two. The material (II-1) is formed into a surface layer together with the material (II-2) as a particle shape, whereby the material (II-1) and the material (II-2) can be dispersed on the surface of the surface layer. Thereby, the desired wetting characteristics (water drop retention performance and water film formation performance) can be exhibited more effectively. Further, it is also advantageous from the viewpoint of obtaining a transparent surface layer.

According to a preferred embodiment of the present invention, as the photocatalyst particles, a metal such as Pt, Pd, Rh, Ru, Nb, Ag, Cu, Sn, Ni, Fe, or the like may be added to the photocatalyst material. And/or such oxides or immobilized particles, or photocatalysts coated with porous calcium phosphate.

In the second aspect of the present invention, the mass of the material (II-1), the amount of the oxide of the material (II-2), the amount of the oxide of the material (II-3), and the optional component described later. The mass of the alumina and the amount of the material (II-1) are more than 0% by mass and less than 20% by mass, a preferred lower limit is 0.1% by mass or more, and a preferred upper limit is less than 20% by mass. Jiawei is less than 10% by mass.

Further, according to another preferred embodiment of the present invention, the material (II-1) is more than 0% by mass and less than 20% by mass with respect to the surface layer, and a preferred lower limit is 0.1% by mass or more. Ideal and better The upper limit is less than 20% by mass, and more preferably less than 10% by mass. Further, the mass of the surface layer is actually a value equal to the amount (mass) of the film forming component to be described later.

Material (II-2)

In the second aspect of the present invention, the material (II-2) is at least one metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Ga, Zr, Y, In, and Hf. The at least one compound selected from the group consisting of oxides, inorganic salts and organic salts is preferably at least one compound selected from the group consisting of oxides of Zr or Hf, inorganic salts and organic salts.

The material (II-2) exhibits a metal compound which is weaker than the material (II-1) and which does not decompose due to the material (II-1). As described above, the surface layer of the composite material obtained by the present invention is formed by blending the material (II-2) together with the material (II-1), thereby effectively preventing the linear dirt and imparting self-cleaning properties. Wetting characteristics (water droplet retention performance and water film formation properties).

In the second aspect of the present invention, the oxide containing the above metal is, for example, Cr ₂ O ₃ , MnO ₂ , Fe ₂ O ₃ , CoO, NiO, CuO, Ga ₂ O ₃ , ZrO ₂ , Y _{2 .} O ₃ , In ₂ O ₃ , HfO ₂ and the like. Further, examples of the inorganic salt include oxychlorides, hydroxychlorides, nitrates, sulfates, acetates, oxynitrates, carbonates, ammonium carbonates, sodium carbonates, potassium carbonates, phosphoric acid of the above metals. Sodium salt, etc. Further, examples of the organic salt include oxalates, propionates, metal alkoxides, hydrolyzates of metal alkoxides, chelating compounds, and the like of the above metals. The metal alkoxide is a compound in which an alkoxy group having about 1 to 8 carbon atoms is bonded to a metal atom. For example, when the metal atom is Zr, zirconium tetramethoxide, zirconium tetraethoxy oxide, zirconium tetra - propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butyl oxide, and the like. Further, as the chelating compound, for example, a β-ketoester complex, a β-diketone complex, an ethanolamine complex, a diethylene glycol complex, or the like can be used.

According to a preferred embodiment of the present invention, the material (II-2) is an amorphous oxide or an oxide particle or an inorganic salt having an average crystal diameter of less than 10 nm. The surface layer obtained by applying these compounds is excellent in water droplet retention performance and water film formation property. Here, the average crystallite diameter is calculated from the product of the strongest ray peak of XRD and calculated by the Scherrer equation.

In the second aspect of the present invention, when the material (II-2) is a particle, it is 5 nm or more and 100 nm or less calculated by measuring the length of an arbitrary 100 particles of a field of view of 200,000 times by a scanning electron microscope. Particles having an average number of particle diameters are preferred. The material (II-2) is formed into a surface layer together with the material (II-1) as a particle shape, whereby the material (II-1) and the material (II-2) can be dispersed on the surface of the surface layer. Thereby, the desired wetting characteristics (water drop retention performance and water film formation performance) can be exhibited more effectively. Further, it is also advantageous from the viewpoint of obtaining a transparent surface layer. Further, the material (II-2) can also be expected to function as a binder for fixing a photocatalyst.

In the second form of the invention, the amount of the material (II-1), the amount of the oxide of the material (II-2), and the oxidation of the material (II-3) The amount of the material to be converted and the mass of the alumina of the optional component described later and the amount of the material (II-2) are more than 35% by mass and not more than 60% by mass in terms of the oxide-converted concentration, and a preferred lower limit is more than 35% by mass. Further, the upper limit is preferably 50% by mass or less.

Further, according to another preferred embodiment of the present invention, the material (II-2) is formulated in an amount of more than 35% by mass and not more than 60% by mass, preferably 35, in terms of the oxide with respect to the surface layer. It is preferred that the mass is not less than 50% by mass. Further, the quality of the surface layer is actually a value equal to the amount (mass) of the film forming component to be described later.

Material (II-3)

The surface layer of the composite material according to the second aspect of the present invention may contain the material (II-3) in addition to the material (II-1) and the material (II-2). Here, the material (II-3) means at least one selected from the group consisting of cerium oxide, alkali cerate, and amorphous titanium oxide. This material (II-3) is a hydrophilic material. Therefore, when the light for exciting the photocatalyst as the material (II-1) is small (for example, when the sunlight is on a cloudy day or when the sunlight of the applicable portion is short or when it is applied to the interior material), the function of assisting hydrophilicity is provided. . In addition, since these materials are weaker than the photocatalyst material as the material (II-1) and more hydrophilic than the material (II-2), the amount of the material (II-2) can be suppressed to low. Further, these materials (II-3) also have a function of fixing the photocatalyst material as the material (II-1) to the surface of the substrate. These materials (II-3) do not impede the desired wetting characteristics (water droplet retention properties and water film formation properties), but enhance the so-called surface layer The properties of the substrate are excellent in adhesion, strength, durability, and weather resistance.

In the second embodiment of the present invention, as the alkali citrate, sodium citrate, potassium citrate or lithium silicate may be used singly or in combination.

In the second aspect of the invention, the material (II-3) is formulated in an amount determined relative to the first and the above materials (II-2), that is, the remaining portion. Therefore, the mass of the material (II-1), the amount of the oxide of the material (II-2), the amount of the oxide of the material (II-3), and the mass of the alumina of any of the components described later, the material ( The blending amount of II-3) is more than 10% by mass and less than 65% by mass in terms of the concentration in terms of the oxide.

Further, according to a preferred embodiment of the present invention, the material (II-3) is preferably contained in an amount of more than 10% by mass and less than 65% by mass in terms of the oxide in terms of the surface layer. Further, the quality of the surface layer is actually a value equal to the amount (mass) of the film forming component to be described later.

Alumina

The surface layer of the composite material according to the second form of the present invention may contain alumina as a material of one of the compounds (A) and as an optional component thereof. It is preferable that the alumina is not contained, and the amount of the material (II-1), the amount of the oxide of the material (II-2), the amount of the oxide of the material (II-3), and the oxidation amount are preferably contained. The mass of the aluminum itself and the blending amount thereof are 0% by mass or more and 10% by mass or less. According to one of the forms of the present invention, it is preferred that the alumina is formulated to be smaller than the third component.

In addition, in the preferred embodiment of the present invention, it is preferred that the alumina is blended in an amount of 0% by mass or more and 10% by mass or less based on the oxide in terms of the surface layer. Further, the quality of the surface layer is actually a value equal to the amount (mass) of the film forming component to be described later.

Other optional ingredients

The surface layer of the composite material according to the second aspect of the present invention may include any other components other than the components of the above materials (II-1), (II-2), and (II-3) as needed. . Examples of the optional component include pigments, fillers, photosensitizers, dyes, and the like, and can be selected and combined for various purposes without impeding the desired wetting characteristics (water drop retention property and water film formation property). Provisioning.

Physical properties of the surface layer

The water droplet retaining property and the water film forming property of the composite material according to the second aspect of the present invention can also be evaluated by the same method as the first type of the present invention described above.

According to one aspect of the present invention, the surface layer of the composite material of the second aspect of the present invention preferably has the surface characteristics described below.

The composite material of the second aspect of the present invention preferably has an advancing contact angle of 30 or more, preferably 35 or more, more preferably 40 or more.

Further, the back contact angle is preferably 20 or less, preferably 16 or less, more preferably 13 or less, and most preferably 10 or less.

Further, the difference between the advancing contact angle and the receding contact angle, that is, hysteresis is preferably 20° or more and 80° or less, and a more preferable lower limit value is 35°, and a more preferable lower limit value is 40°. A better upper limit is 75° and a better upper limit is 70°.

The surface layer of the composite material according to the second aspect of the present invention is preferably the same as the advancing contact angle, the receding contact angle, and the hysteresis satisfying the above range. When it is in this range, the water droplet retainability at the time of water droplet formation and the water film formation property at the time of a large amount of water droplets become more excellent.

The above surface characteristics, that is, the dynamic contact angle (advancing contact angle and receding contact angle) and the slip angle are measured by conventional or established measurement methods, but are preferably measured by the following method. That is, an automatic contact angle measuring device (for example, OCA20 manufactured by Hidehiro Seiki Co., Ltd.) is used to measure the dynamic contact angle (advancing contact angle and receding contact angle) with respect to water. More specifically, after the dropping of the water droplets 50 μ L on the surface layer, while the speed of the surface layer is 1.6 deg./s inclined, water droplets were observed from the side of the contact angle measuring device attached camera, respectively, for the water droplets fall The contact angle (advancing contact angle) of the sliding side of the instantaneous water droplet and the contact angle (reverse contact angle) on the side opposite to the sliding side of the water droplet were measured.

Further, due to the surface layer of the composite material of the present invention a second type, water-based roll-off angle to 30 μ L of 40 ° or more is preferred. It can be said that the larger the slip angle, the higher the water droplet retention.

The above-described slip angle is measured by a conventional or established measurement method, but it is preferably measured by the following method. That is, the slip angle is measured by the slip method. After More specifically, dropping of water droplets 30 μ L on the surface layer, while the speed of the surface layer is 1.6 deg./s inclined, water droplets were observed from the side of the camera, the water droplets fall to the instantaneous angle of inclination: slip angle measurement .

According to a preferred embodiment of the present invention, the surface layer of the composite material obtained by the present invention is preferably a static contact angle with water at an average value of 5 or more points at any measurement point of 20° or more and less than 90°. Preferably, the lower limit is 30°, the lower limit is 35°, the upper limit is 80°, and the optimum upper limit is 75°. If it is in this range, the water droplet retention property at the time of water droplet formation becomes more excellent. After the static contact angle with water-based contact angle measurement device (e.g., manufactured by Kyowa Interface Science Co., product name CA-X150 type), 5 μ L of water droplets dropwise at room temperature, by θ / 2 method to measure Static contact angle after 5 seconds.

The surface layer of the composite material according to the second aspect of the present invention is preferably a film thickness of 300 nm or less. A more preferred lower limit is 10 nm, and a more preferred lower limit is 15 nm. The upper limit is more preferably 200 nm, still more preferably 150 nm. By setting this range, the first component and the second component are more uniformly present in the surface layer, so that desired wetting characteristics (water drop retention performance and water film formation performance) can be surely obtained. Further, it is also advantageous from the viewpoint of obtaining a transparent surface layer by setting it as the range.

According to a preferred embodiment of the present invention, the surface layer of the composite material resulting from the present invention is a laser microscope having a wavelength of 405 nm and an arithmetic mean measured in a field of 20 times in accordance with JIS B 0601-1982. The roughness Ra is an average value of more than 3 points of any measurement point, and is more than 5 nm and 50 nm. The following are preferred. A preferred lower limit is 5 nm, and a more preferred lower limit is 10 nm. Further, a preferred upper limit is 50 nm, and a more preferred upper limit is 30 nm. In the second aspect of the present invention, if the surface roughness is within this range, the water is attracted by the fine unevenness to hinder the movement of water, and the water contacting the surface does not infiltrate and expand, and the so-called water is not strengthened. The role of contraction.

Substrate

The substrate forming the composite material of the second form of the present invention may be the same as the substrate of the first type described above.

Coating composition

According to the present invention, a coating composition for producing the composite material of the second aspect of the present invention described above can be provided. The coating composition according to the second aspect of the present invention basically comprises any of the components (II-1) and (II-2), the material (II-3), and the like, and the solvent. to make.

The coating composition according to the second aspect of the present invention contains the material (II-1) and the material (II-2), and may also mean the material (II-1) and the material (II- described previously). 2) Same.

Therefore, the material (II-1) is a group of anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide, zinc oxide, tin oxide, crystalline tungsten oxide, and amorphous tungsten oxide. At least one photocatalyst material selected. These photocatalyst materials are composed of a photocatalyst excited by light having a wavelength of 350 to 500 nm. If according to a preferred form of the invention, such light touches Among the media, anatase type titanium oxide, rutile type titanium oxide, and brookite type titanium oxide can be suitably used.

Further, the material (II-1) is preferably a particle. A suitable particle diameter is a number average particle diameter of 10 nm or more and 100 nm or less calculated by a scanning electron microscope to measure the length of any 100 particles of 200,000-fold field of view. The shape of the particles is preferably spherical, but may be a different shape such as an ellipse. The particle length at this time is roughly calculated by dividing the sum of the longest diameter and the shortest diameter of the particle shape observed by the scanning electron microscope by two. The material (II-1) is formed into a surface layer together with the material (II-2) as a particle shape, whereby the material (II-1) and the material (II-2) can be dispersed on the surface of the surface layer. Thereby, the desired wetting characteristics (water drop retention performance and water film formation performance) can be exhibited more effectively. Further, it is also advantageous from the viewpoint of obtaining a transparent surface layer.

According to a preferred embodiment of the present invention, as the photocatalyst particles, a metal such as Pt, Pd, Rh, Ru, Nb, Ag, Cu, Sn, Ni, Fe, or the like may be added to the photocatalyst material. / or such oxides are either immobilized particles or photocatalysts coated with porous calcium phosphate.

Further, the material (II-2) is an oxide or inorganic salt of at least one metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Ga, Zr, Y, In, and Hf. The at least one compound selected from the group consisting of organic salts is preferably at least one compound selected from the group consisting of oxides of Zr or Hf, inorganic salts and organic salts.

In the second aspect of the present invention, the oxide containing the above metal is, for example, Cr ₂ O ₃ , MnO ₂ , Fe ₂ O ₃ , CoO, NiO, CuO, Ga ₂ O ₃ , ZrO ₂ , Y _{2 .} O ₃ , In ₂ O ₃ , HfO ₂ and the like. Further, examples of the inorganic salt include oxychlorides, hydroxychlorides, nitrates, sulfates, acetates, oxynitrates, carbonates, ammonium carbonates, sodium carbonates, potassium carbonates, and sodium phosphates of the above metals. Salt and so on. Further, examples of the organic salt include oxalates, propionates, metal alkoxides, hydrolyzates of metal alkoxides, and chelate compounds of the above metals. The metal alkoxide is a compound in which an alkoxy group having about 1 to 8 carbon atoms is bonded to a metal atom. For example, when the metal atom is Zr, zirconium tetramethoxide, zirconium tetraethoxy oxide, zirconium tetra is exemplified. N-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, and the like. Further, as the chelating compound, for example, a β-ketoester complex, a β-diketone complex, an ethanolamine complex, a dialkylethene complex, or the like can be used.

According to a preferred embodiment of the present invention, the material (II-2) is an amorphous oxide or an oxide particle or an inorganic salt having an average crystal diameter of less than 10 nm.

In the second aspect of the present invention, when the material (II-2) is a particle, it is 5 nm or more and 100 nm or less calculated by measuring the length of an arbitrary 100 particles of a field of view of 200,000 times by a scanning electron microscope. Particles having an average number of particle diameters are preferred. The material (II-2) is formed into a surface layer together with the material (II-1) as a particle shape, whereby the material (II-1) and the material (II-2) can be dispersed on the surface of the surface layer. Thereby, the desired wetting characteristics can be exhibited more effectively (water drop retention performance and water film shape) Into performance). Further, it is also advantageous from the viewpoint of obtaining a transparent surface layer. Further, the material (II-2) can also be expected to function as a binder for fixing a photocatalyst.

The amount of the material (II-1) and the material (II-2) in the coating composition of the second aspect of the present invention and the material (II-3) as an optional component are required to achieve the above-mentioned The composition of the surface layer of the composite material resulting from the second form of the invention.

Further, according to a preferred embodiment of the present invention, the material (II-2) is blended in an amount of more than 35% by mass and not more than 60% by mass, preferably more than 35, in terms of the oxide-forming component. % by mass and 50% by mass or less. Here, the film forming component refers to a component obtained by removing a volatile component such as a solvent and a water-soluble additive such as a surfactant from the coating composition, and the amount of the film forming component is substantially equal to the coating composition. The value of the value of the water-soluble additive is excluded from the evaporation residue.

The coating composition of the second aspect of the present invention contains the material (II-3), but may be added to the precursor of the material (II-3) in the production step. Therefore, the material (II-3) which can be contained in the coating composition of the second aspect of the present invention and the change thereof are precursors, and examples thereof include cerium oxide, alkyl cerate, and alkali citric acid. At least one selected from the group consisting of salt, amorphous titanium oxide, and titanium peroxide. Among these, alkyl citrate is a precursor of cerium oxide, and a precursor of titanium oxide-based amorphous titanium oxide. These precursors are changed to cerium oxide, alkali cerate or amorphous titanium oxide after the film is formed.

An alkyl group which can be formulated in the coating composition of the second form of the present invention Examples of the citrate include decane oxides, hydrolyzed decomposition products of decane oxides, ruthenium chelating compounds, and the like. In the above, the decane oxide is a compound in which an alkoxy group having about 1 to 4 carbon atoms is bonded to a ruthenium atom, and examples thereof include ruthenium tetraoxide, ruthenium tetraethoxylate, and ruthenium tetra-n-propane oxidation. And tetraisopropoxide, ruthenium tetra-n-butoxide, ruthenium tetra-t-butoxide and the like. Further, examples of the chelate compound include a β-ketoester complex, a β-diketone complex, an ethanolamine complex, a dialkylethene complex, and the like.

The coating composition resulting from the second form of the present invention may also be added with alumina or its precursor. Examples of the precursors thereof include aluminum hydroxide and gibbsite.

The solvent contained in the coating composition of the second aspect of the present invention may be obtained by dispersing or dissolving the material (II-1), the material (II-2) and the material (II-3), and A substance that is liquid at normal temperature. Examples of the examples include alcohols such as water, ethylene glycol, butyl sarbuta, isopropanol, n-butanol, ethanol, and methanol, aromatic hydrocarbons such as toluene or xylene, and hexane and cyclohexane. An aliphatic hydrocarbon such as an alkane or a heptane; an ester such as ethyl acetate or n-butyl acetate; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone; tetrahydrofuran or dioxane; An amine such as an ether, dimethylacetamide or dimethylformamide; a halogen compound such as chloroform, dichloromethane or carbon tetrachloride; dimethyl hydrazine or nitrobenzene. These solvents may be used singly or in combination.

Further, the coating composition of the second aspect of the present invention is preferably one containing a leveling agent, and examples thereof include diacetone alcohol, ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether. , 4-hydroxy-4-methyl-2-pentanone, dipropylene glycol, tripropylene glycol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, C Glycol monomethyl ether, 1-propoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, acetylene alcohol, and the like.

The coating composition according to the second aspect of the present invention may be formulated according to different conditions and selected and combined for each purpose to prepare materials (II-1), materials (II-2) and materials (II-3). Other pigments, hardening catalysts, crosslinking agents, fillers, dispersants, light stabilizers, wetting agents, tackifiers, rheology control agents, defoamers, filming aids, leveling agents, rust prevention Additives such as agents, dyes, and preservatives. In particular, when water is used in a solvent, various surfactants may be added as an additive in order to improve the wettability of the coating composition.

The coating composition of the second aspect of the present invention can dissolve or disperse the material (II-1), the material (II-2), the material (II-3), and other optional components of the alumina in the solvent. And get it. Each material can be combined and formulated into various coating materials such as a dispersion of a powder, a solution, or a sol to form a coating composition.

The solid content concentration in the coating composition is preferably from 0.05% by mass to 20% by mass, more preferably from 0.05% by mass to 10% by mass. The solid content concentration is actually equal to the concentration of the above-mentioned film-forming component. Specifically, the coating composition can be dried at 105 ° C to 110 ° C to obtain the difference between the obtained evaporation residue and the amount of the water-soluble additive. It is obtained by dividing the amount of the coating composition.

Composite material manufacturing method

The composite material of the second form of the present invention can be used as described above. The composition was applied and was produced satisfactorily. Specifically, after the coating composition of the second form is applied to the surface of the substrate, (a) the surface of the substrate is heated at 300 ° C or lower, and (b) dried at room temperature. Or (c) forming the surface of the substrate well by heating at a temperature of more than 300 and less than 1000 ° C for 2 to 60 seconds. In any of the manufacturing methods, the heating conditions of no heating or lower temperature or the heating conditions of a short time are employed, whereby a surface which sufficiently exhibits desired wetting characteristics (water drop retention property and water film formation property) can be obtained. Floor.

The coating of the substrate can be carried out by means of bristles, rolls, or coating, shower coating, dip coating, screen printing, gravure printing or the like by spraying.

The third type of the invention Surface layer

In the third aspect of the present invention, the surface layer of the composite material further comprises a material (III-1) as the compound (A) and a material (III-2) as the compound (B), and further depending on the case. It is composed of a material (III-3) which is one of the aforementioned compounds (A).

Material (III-1)

In the third aspect of the present invention, the material (III-1) is composed of anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, zinc oxide, tin oxide, crystalline tungsten oxide, and non- At least one photocatalyst material selected from the group consisting of crystalline tungsten oxide. These photocatalyst materials are composed of a photocatalyst excited by light having a wavelength of 350 to 500 nm. If preferred in accordance with the present invention In the form of such photocatalyst materials, anatase type titanium oxide, rutile type titanium oxide, and brookite type titanium oxide can be suitably used. These titanium oxides are non-toxic and have excellent chemical stability.

In the third aspect of the present invention, the photocatalyst as the material (III-1) exhibits a property of self-hydrophilization by light irradiation and decomposition of an organic substance. In the third aspect of the present invention, the material (III-2) to be described later is a metal compound which is less hydrophilic than the photocatalyst material of the material (III-1) and which is not easily decomposed by the decomposition action thereof. According to the present invention, the reason for preventing the linear dirt is not clear, but it can be estimated as follows. On the surface of the member resulting from the present invention, the portion of the material (III-1) is formed by photoexcitation to form a highly hydrophilic region. The material (III-2) that is in contact with the material (III-1) forms a clean surface by photocatalytic action and maintains a weaker affinity with the material (III-1) than water. -2) The part that exists is formed with a weak affinity with water. According to the third aspect of the present invention, the presence of the material (III-1) and the material (III-2) is stronger than that of the material (III-1) due to the material (III-1). The weak affinity with water caused by III-2) exhibits water droplet retention properties and water film formation properties, so that linear dirt can be effectively prevented. In other words, on the surface, the water formed by the hydrophilic portion is attracted to form a water film, and the force formed by the water droplet due to the weak affinity with water is balanced. When the water of a small amount of raindrops adheres, the movement of the three-phase line of the water droplets (the interface of the gas, the liquid, and the solid, that is, the contour of the portion that contacts the surface of the water droplet) is suppressed, and the water droplets are retained by the external force such as gravity. surface. The result can be Prevent linear dirt. Thereafter, it is presumed that when a large amount of water is supplied, the water droplets are collected, and the water is enlarged on the surface to form a water film, that is, the so-called self-cleaning performance is exerted, and the surface is cleaned. However, the above description is assumed after all, and the present invention is not limited to this assumption.

In the third aspect of the invention, the material (III-1) is preferably a particle. A suitable particle diameter is a number average particle diameter of 10 nm or more and 100 nm or less calculated by measuring 100,000 times of the field of view of any 100 particle lengths by a scanning electron microscope. The shape of the particles is preferably spherical, but may be a different shape such as an ellipse. The particle length at this time is roughly calculated by dividing the sum of the longest diameter and the shortest diameter of the particle shape observed by the scanning electron microscope by two. The material (III-1) is formed into a surface layer together with the material (III-2) as a particle shape, whereby the material (III-1) and the material (III-2) can be dispersed on the surface of the surface layer. Thereby, the desired wetting characteristics (water drop retention performance and water film formation performance) can be exhibited more effectively. Further, it is also advantageous from the viewpoint of obtaining a transparent surface layer.

According to a preferred embodiment of the present invention, as the photocatalyst particles, a metal such as Pt, Pd, Rh, Ru, Nb, Ag, Cu, Sn, Ni, Fe, or the like may be added to the photocatalyst material. / or such oxides or immobilized particles, or photocatalysts coated with porous calcium phosphate.

In the third aspect of the present invention, the material (III-1) is added in an amount determined in relation to the material (III-2) to be described later and the material (III-3) to be further added as the case may be.

Material (III-2)

In the third aspect of the present invention, the material (III-2) is at least one metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Ga, Zr, Y, In, and Hf. The at least one compound selected from the group consisting of oxides and inorganic salts is preferably at least one compound selected from the group consisting of oxides of Zr or Hf and inorganic salts.

The material (III-2) exhibits a metal compound which is weaker than the material (III-1) and which does not decompose due to the material (III-1). As described above, the surface layer of the composite material obtained by the present invention is formed by blending the material (III-2) together with the material (III-1), thereby effectively preventing the linear dirt and imparting self-cleaning properties. Wetting characteristics (water droplet retention performance and water film formation properties).

In the third aspect of the present invention, the oxide containing the above metal is, for example, Cr ₂ O ₃ , MnO ₂ , Fe ₂ O ₃ , CoO, NiO, CuO, Ga ₂ O ₃ , ZrO ₂ , Y _{2 .} O ₃ , In ₂ O ₃ , HfO ₂ and the like. Further, examples of the inorganic salt include oxychlorides, hydroxychlorides, nitrates, sulfates, acetates, oxynitrates, carbonates, ammonium carbonates, sodium carbonates, potassium carbonates, and sodium phosphates of the above metals. Salt and so on.

According to a preferred embodiment of the present invention, the material (III-2) is an amorphous oxide or an oxide particle or an inorganic salt having an average crystal diameter of less than 10 nm. The surface layer obtained by applying these compounds is excellent in water droplet retention performance and water film formation property. Here, the average crystallite diameter is calculated from the product of the strongest ray peak of XRD and calculated by the Scherrer equation.

In the third aspect of the present invention, when the material (III-2) is a particle, the number of 5 nm or more and 100 nm or less calculated by measuring the length of any 100 particles of the field of view of 200,000 times with a scanning electron microscope is used. Particles having an average particle size are preferred. The material (III-2) is formed into a surface layer together with the material (III-1) as a particle shape, whereby the material (III-1) and the material (III-2) can be dispersed on the surface of the surface layer. Thereby, the desired wetting characteristics (water drop retention performance and water film formation performance) can be exhibited more effectively. Further, it is also advantageous from the viewpoint of obtaining a transparent surface layer. Further, the material (III-2) can also be expected to function as a binder for fixing a photocatalyst.

In the third aspect of the present invention, the material (III-2) is blended in the oxide conversion ratio with respect to the mass of the material (III-1) and the mass of the material (III-2). It is more than 50% by mass and not more than 99% by mass, preferably 56% by mass or more and 90% by mass or less. As described later, when the surface layer contains the material (III-3), the mass of the material (III-1), the amount of the oxide of the material (III-2), and the mass of the material (III-3) Further, the material (III-2) is formulated in an amount of more than 50% by mass and not more than 99% by mass in terms of an oxide conversion, and a preferred lower limit value is 56% by mass or more, and a preferred upper limit value is 90% by mass or less. More preferably, it is 80 mass% or less, and a more preferable range is 56 mass% or more and 90 mass% or less.

Further, according to another preferred embodiment of the present invention, the material (III-2) is formulated in the surface layer in an amount of more than 50% by mass and not more than 99% by mass in terms of the oxide. It is preferably 56% by mass or more and 90% by mass or less. As will be described later, the surface layer contains the material (III- 3), in terms of the mass of the material (III-1), the amount of the oxide of the material (III-2), and the mass of the material (III-3), the material (III-2) is converted into oxide. The blending ratio is more than 50% by mass and less than 99% by mass, and the preferred lower limit value is 56% by mass or more, and the preferred upper limit value is 90% by mass or less, more preferably 80% by mass or less, and more preferably The content is 56% by mass or more and 90% by mass or less. Further, the quality of the surface layer is actually a value equal to the amount (mass) of the film forming component to be described later. By formulating the material (III-1), the material (III-2), and the material (III-3) according to the situation in such a range, it is possible to exhibit more effective water drop retention performance and water film formation. performance.

Material (III-3)

The surface layer of the composite material resulting from the present invention may contain the material (III-3) in addition to the material (III-1) and the material (III-2). Here, the material (III-3) means at least one selected from the group consisting of cerium oxide, alkali silicate, alumina, and amorphous titanium oxide. The material (III-3) is a hydrophilic material having an auxiliary hydrophilicity when the amount of light for exciting the photocatalyst is small (for example, when the sunlight is on a cloudy day or when the sunlight of the applicable portion is short or when it is applied to the interior material). The function. Further, since the material (III-3) is weaker than the material (III-1) and more hydrophilic than the material (III-2), the amount of the material (III-2) can be suppressed to be low. Further, these materials (III-3) also have a function of fixing a photocatalyst material as the material (III-1) to the surface of the substrate. This material (III-3) does not interfere with the desired wetting characteristics (water droplet retention properties and water film formation properties), but The properties of the substrate of the surface layer, such as adhesion, strength, durability, and weather resistance, contribute.

In the third aspect of the present invention, as the alkali citrate, sodium citrate, potassium citrate or lithium silicate may be used singly or in combination.

In the third aspect of the invention, the material (III-3) is added in an amount determined in relation to the first material and the material (III-2). Therefore, the material (III-3) is formulated to be 0% by mass based on the mass of the material (III-1), the amount of the oxide of the material (III-2), and the mass of the material (III-3). The above lower limit is 49% by mass or less, and a preferred lower limit value is 1% by mass, and more preferably 3% by mass. A preferred upper limit is 45% by mass or less, and more preferably 40% by mass or less.

Other optional ingredients

The surface layer of the composite material according to the third aspect of the present invention may contain any other components other than the components of the above materials (III-1), (III-2) and (III-3) as needed. By. Examples of the optional component include pigments, fillers, photosensitizers, dyes, and the like, and can be selected and combined for various purposes without impeding the desired wetting characteristics (water drop retention property and water film formation property). Provisioning.

Physical properties of the surface layer

The water droplet retaining property and the water film forming property of the composite material according to the third aspect of the present invention can also be evaluated by the same method as the first type of the present invention described above.

According to one aspect of the present invention, the surface layer of the composite material according to the third aspect of the present invention is preferably one having the surface characteristics described below.

The composite material according to the third aspect of the present invention preferably has an advancing contact angle of 30 or more, preferably 35 or more, more preferably 40 or more.

Further, the back contact angle is preferably 20 or less, preferably 16 or less, more preferably 13 or less, and most preferably 10 or less.

Further, the difference between the advancing contact angle and the receding contact angle, that is, the hysteresis is preferably 20° or more and 80° or less, more preferably a lower limit of 35°, and a more preferable lower limit of 40°. A better upper limit is 75°, and a better upper limit is 70°.

The surface layer of the composite material according to the third aspect of the present invention is preferably an advancing contact angle, a receding contact angle, and a hysteresis satisfying the above range. When it is in this range, the water droplet retainability at the time of water droplet formation and the water film formation property at the time of a large amount of water droplets become more excellent.

The above surface characteristics, that is, the dynamic contact angle (advancing contact angle and receding contact angle) and the slip angle are measured by conventional or established measurement methods, but are preferably measured by the following method. That is, an automatic contact angle measuring device (for example, OCA20 manufactured by Hidehiro Seiki Co., Ltd.) is used to measure the dynamic contact angle (advancing contact angle and receding contact angle) with respect to water. More specifically, after the dropping of the water droplets 50 μ L on the surface layer, while the speed of the surface layer is 1.6 deg./s inclined, water droplets were observed from the side of the contact angle measuring device attached camera, respectively, for the water droplets fall The contact angle (advancing contact angle) of the sliding side of the instantaneous water droplet and the contact angle (reverse contact angle) on the side opposite to the sliding side of the water droplet were measured.

Further, the surface layer of the composite material due to a third type of the present invention, water-based roll-off angle to 30 μ L of 40 ° or more is preferred. It can be said that the larger the slip angle, the higher the water droplet retention.

The above-described slip angle is measured by a conventional or established measurement method, but it is preferably measured by the following method. That is, the slip angle is measured by the slip method. More specifically, after the dropping of 30 μ L water droplet on the surface layer, while the speed of the surface layer is 1.6 deg./s inclined, water droplets were observed from the side of the camera, the water droplets fall to the instantaneous angle of inclination of: slip angle measuring.

According to a preferred embodiment of the present invention, the surface layer of the composite material obtained by the present invention is desirably a static contact angle with water of 20° or more and an average value of 5 points or more at any measurement point. Preferably, the 90° is better, the lower limit is 30°, the lower limit is 35°, the upper limit is 80°, and the optimum upper limit is 75°. If it is within this range, the water droplet retention property at the time of formation of a water droplet becomes more excellent. After the static contact angle with water-based contact angle measurement device (e.g., manufactured by Kyowa Interface Science Co., product name CA-X150 type), 5 μ L of water droplets dropwise at room temperature, by θ / 2 method to measure Static contact angle after 5 seconds.

The surface layer of the composite material according to the third aspect of the present invention is preferably a film thickness of 300 nm or less. A more preferred lower limit is 10 nm, and a more preferred lower limit is 15 nm. The upper limit is more preferably 200 nm, still more preferably 150 nm. By setting this range, the first component and the second component are more homogeneously present in the surface layer, so that the desired infiltration can be surely obtained. Characteristics (water droplet retention performance and water film formation properties). Further, it is also advantageous from the viewpoint of obtaining a transparent surface layer by setting it as the range.

According to a preferred embodiment of the present invention, the surface layer of the composite material resulting from the present invention is a laser microscope having a wavelength of 405 nm and an arithmetic mean measured in a field of 20 times in accordance with JIS B 0601-1982. The roughness Ra is preferably more than 5 nm and 50 nm or less in terms of an average value of three or more arbitrary measurement points. A preferred lower limit is 5 nm, and a more preferred lower limit is 10 nm. Further, a preferred upper limit is 50 nm, and a more preferred upper limit is 30 nm. In the present invention, when the surface roughness is within this range, the water is attracted by the fine unevenness to hinder the movement of water, and the water contacting the surface does not infiltrate and expand, and the so-called water does not shrink.

Substrate

The substrate forming the composite material of the third form of the present invention may be the same as the substrate of the first type described above.

Coating composition

According to the present invention, a coating composition for producing the composite material of the third aspect of the present invention described above can be provided. The coating composition of the third aspect of the present invention basically comprises the above material (III-1) and material (III-2), the material (III-3) of any component, and a solvent.

The material (III-1) and the material (III-2) contained in the coating composition of the third aspect of the present invention may also mean the material (III-1) and the material (III) previously described. -2) Same.

Therefore, the material (III-1) is a group of anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide, zinc oxide, tin oxide, crystalline tungsten oxide, and amorphous tungsten oxide. At least one photocatalyst material selected. These photocatalyst materials are composed of a photocatalyst excited by light having a wavelength of 350 to 500 nm. According to a preferred embodiment of the present invention, anatase-type titanium oxide, rutile-type titanium oxide, and brookite-type titanium oxide can be suitably used among the photocatalysts.

Further, the material (III-1) is preferably a particle. A suitable particle diameter is a number average particle diameter of 10 nm or more and 100 nm or less calculated by a scanning electron microscope to measure the length of any 100 particles of 200,000-fold field of view. The shape of the particles is preferably spherical, but may be a different shape such as an ellipse. The particle length at this time is roughly calculated by dividing the sum of the longest diameter and the shortest diameter of the particle shape observed by the scanning electron microscope by two. The material (III-1) is formed into a surface layer together with the material (III-2) as a particle shape, whereby the material (III-1) and the material (III-2) can be dispersed on the surface of the surface layer. Thereby, the desired wetting characteristics (water drop retention performance and water film formation performance) can be exhibited more effectively. Further, it is also advantageous from the viewpoint of obtaining a transparent surface layer.

According to a preferred embodiment of the present invention, as the photocatalyst particles, a metal such as Pt, Pd, Rh, Ru, Nb, Ag, Cu, Sn, Ni, Fe, or the like may be added to the photocatalyst material. / or such oxides or immobilized particles, or photocatalysts coated with porous calcium phosphate.

In addition, the material (III-2) is composed of Cr, Mn, Fe, Co, At least one compound selected from the group consisting of oxides and inorganic salts of at least one metal selected from the group consisting of Ni, Cu, Ga, Zr, Y, In, and Hf is preferably an oxide containing Zr or Hf and At least one compound selected from the group consisting of inorganic salts.

In the third aspect of the present invention, the oxide containing the above metal is, for example, Cr ₂ O ₃ , MnO ₂ , Fe ₂ O ₃ , CoO, NiO, CuO, Ga ₂ O ₃ , ZrO ₂ , Y _{2 .} O ₃ , In ₂ O ₃ , HfO ₂ and the like. Further, examples of the inorganic salt include oxychlorides, hydroxychlorides, nitrates, sulfates, acetates, oxynitrates, carbonates, ammonium carbonates, sodium carbonates, potassium carbonates, phosphoric acid of the above metals. Sodium salt, etc.

According to a preferred embodiment of the present invention, the material (III-2) is an amorphous oxide or an oxide particle or an inorganic salt having an average crystal diameter of less than 10 nm.

In the third aspect of the present invention, when the material (III-2) is a particle, it is 5 nm or more and 100 nm or less calculated by measuring the length of an arbitrary 100 particles of a field of view of 200,000 times by a scanning electron microscope. Particles having an average number of particle diameters are preferred. The material (III-2) is formed into a surface layer together with the material (III-1) as a particle shape, whereby the material (III-1) and the material (III-2) can be dispersed on the surface of the surface layer. Thereby, the desired wetting characteristics (water drop retention performance and water film formation performance) can be exhibited more effectively. Further, it is also advantageous from the viewpoint of obtaining a transparent surface layer. Further, the material (III-2) can also be expected to function as a binder for fixing a photocatalyst.

The material in the coating composition resulting from the third form of the invention (III- 1) and the material (III-2) and the material (III-3) as an optional component are required to be able to realize the composition of the surface layer of the composite material according to the third aspect of the present invention described above. Therefore, even in the composition of the third form of the present invention, the material (III-2) is based on the mass of the material (III-1) and the mass of the material (III-2). The oxide conversion is also adjusted to be more than 50% by mass and not more than 99% by mass, preferably 56% by mass or more and 90% by mass or less. When the surface layer contains the material (III-3), the mass of the material (III-1), the amount of the oxide of the material (III-2), and the mass of the material (III-3), the material ( III-2) The ratio of the oxide conversion is more than 50% by mass and not more than 99% by mass, and the preferred lower limit is 56% by mass or more, and the preferred upper limit is 90% by mass or less, more preferably 80% by mass. The mass% or less is more preferably 56% by mass or more and 90% by mass or less.

Further, according to a preferred embodiment of the present invention, the material (III-2) is blended in an amount of more than 50% by mass to less than 99% by mass, preferably more than 56% by mass based on the oxide-forming component. % and 90% by mass or less. As described later, when the surface layer contains the material (III-3), the mass of the material (III-1), the amount of the oxide of the material (III-2), and the mass of the material (III-3) Further, the material (III-2) is formulated in an amount of more than 50% by mass and not more than 99% by mass in terms of an oxide conversion, and a preferred lower limit value is 56% by mass or more, and a preferred upper limit value is 90% by mass or less. More preferably, it is 80 mass% or less, and a more preferable range is 56 mass% or more and 90 mass% or less. Here, the film forming component means a water-soluble additive such as a volatile component such as a solvent and a surfactant removed from the coating composition. The component after the addition, the amount of the film-forming component, is substantially equal to the value of the amount of the water-soluble additive excluding the evaporation residue of the coating composition.

The coating composition of the third aspect of the present invention contains the material (III-3) as an optional component, but may be added to the precursor of the material (III-3) in the production step. Therefore, the material (III-1) contained in the coating composition of the third aspect of the present invention and the change thereof are precursors, and examples thereof include cerium oxide, alkyl cerate, and alkali citric acid. At least one selected from the group consisting of salt, alumina, amorphous titanium oxide, titanium peroxide, aluminum hydroxide, and gibbsite. Among these, alkyl citrate is a precursor of cerium oxide, a precursor of titanium oxide-based amorphous titanium oxide, and a precursor of aluminum hydroxide and gibbsite-based alumina. These precursors are changed to cerium oxide, alkali cerate, alumina or amorphous titanium oxide after the film is formed.

The alkyl phthalate to be added to the coating composition of the third aspect of the present invention may, for example, be a decane oxide, a hydrolyzed decomposition product of a decane oxide, or a ruthenium chelate compound. In the above, the decane oxide is a compound in which an alkoxy group having about 1 to 4 carbon atoms is bonded to a ruthenium atom, and examples thereof include ruthenium tetraoxide, ruthenium tetraoxide, and ruthenium tetra-n-propyl. Oxide, ruthenium tetraisopropoxide, ruthenium tetra-n-butyl oxide, ruthenium tetra-t-butyl oxide, and the like. Further, examples of the chelate compound include a β-ketoester complex, a β-diketone complex, an ethanolamine complex, a dialkylethene complex, and the like.

The solvent contained in the coating composition of the third aspect of the present invention may be obtained by dispersing or dissolving the material (III-1), the material (III-2) and the material (III-3), and A substance that is liquid at normal temperature. This example can be enumerated Alcohols such as water, ethylene glycol, butyl sarbuta, isopropanol, n-butanol, ethanol, methanol, aromatic hydrocarbons such as toluene or xylene, hexane, cyclohexane, heptane, etc. An aliphatic hydrocarbon, an ester such as ethyl acetate or n-butyl acetate; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone; an ether such as tetrahydrofuran or dioxane; An amine such as methyl acetamide or dimethylformamide; a halogen compound such as chloroform, dichloromethane or carbon tetrachloride; dimethyl hydrazine or nitrobenzene. These solvents may be used singly or in combination.

Further, the coating composition of the third aspect of the present invention is preferably one containing a leveling agent, and examples thereof include diacetone alcohol, ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether. , 4-hydroxy-4-methyl-2-pentanone, dipropylene glycol, tripropylene glycol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, propylene glycol monomethyl ether, 1 - propoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, acetylene alcohol, and the like.

The coating composition of the third aspect of the present invention may be formulated and combined according to the circumstances and selected and combined for each purpose to prepare the material (III-1), the material (III-2) and the material (III-3). Other pigments, hardening catalysts, crosslinking agents, fillers, dispersants, light stabilizers, wetting agents, tackifiers, rheology control agents, defoamers, filming aids, leveling agents, rust prevention Additives such as agents, dyes, preservatives, and the like. In particular, when water is used in a solvent, various surfactants may be added as an additive in order to improve the wettability of the coating composition.

The coating composition of the third aspect of the present invention can dissolve or disperse the material (III-1), the material (III-2), and further the optional component material (III-3) and other optional components. Obtained in a solvent. Various materials In the case of a material, various substances such as a dispersion of a powder, a solution, and a sol can be combined and formulated to form a coating composition.

The solid content concentration in the coating composition is preferably from 0.05% by mass to 20% by mass, more preferably from 0.05% by mass to 10% by mass. The solid content concentration is actually equal to the concentration of the above-mentioned film-forming component. Specifically, the coating composition can be dried at 105 ° C to 110 ° C to obtain the difference between the obtained evaporation residue and the amount of the water-soluble additive. It is obtained by dividing the amount of the coating composition.

Composite material manufacturing method

The composite material of the third aspect of the present invention can be favorably produced by using the above-described coating composition. Specifically, after the coating composition of the third form is applied onto the surface of the substrate, (a) the surface of the substrate is heated at 300 ° C or lower, and (b) dried at room temperature. Or (c) forming the surface of the substrate well by heating at a temperature of more than 300 and less than 1000 ° C for 2 to 60 seconds. In any of the manufacturing methods, the heating conditions of no heating or lower temperature or the heating conditions of a short time are employed, whereby a surface which sufficiently exhibits desired wetting characteristics (water drop retention property and water film formation property) can be obtained. Floor.

The coating of the substrate can be carried out by means of bristles, rolls, or coating, shower coating, dip coating, screen printing, gravure printing or the like by spraying.

[Examples] The first form of the invention Modulation of coating composition

The following materials were prepared as raw materials for the coating composition.

Material (I-1)

‧ cerium oxide (aqueous colloidal cerium oxide): average particle size 10nm solid content rate 30%

Material (I-2)

‧ Zirconia (aqueous amorphous zirconia sol): solid content rate 7.2%

Surfactant

‧矽 surfactants

The solid content concentration in the following examples and comparative examples indicates the concentration of the total solid content of the material (I-1) and the material (I-2) contained in the coating composition.

Example I1

The aqueous amorphous zirconia, the aqueous colloidal cerium oxide sol, and the lanthanoid surfactant were mixed in water as a solvent, and the solid content concentration was adjusted to 0.3% by mass to obtain a coating composition. Here, the mass ratio of ZrO ₂ to SiO ₂ is set to 40:60.

Comparative Example I1

The aqueous amorphous zirconia, the aqueous colloidal cerium oxide sol, and the lanthanoid surfactant were mixed in water as a solvent, and the solid content concentration was adjusted to 0.3% by mass to obtain a coating composition. Here, the mass ratio of ZrO ₂ to SiO ₂ is set to 80:20.

Comparative Example I2

The aqueous amorphous zirconia, the aqueous colloidal cerium oxide sol, and the lanthanoid surfactant were mixed in water as a solvent, and the solid content concentration was adjusted to 0.3% by mass to obtain a coating composition. Here, the mass ratio of ZrO ₂ to SiO ₂ is set to 20:80.

Composite material production

The floating glass substrate of 100 mm × 200 mm was ground with an abrasive for the glass substrate, and the abrasive was completely washed with ion-exchanged water. Thereafter, the substrate was dried with a dryer at 40 ° C for 30 minutes. The coating compositions of the above-described Example 1 and Comparative Examples 1 and 2 were roll-coated on the washed floating glass substrate, and dried at a temperature of 25 ° C and a humidity of 50% RH for one day. Then, the substrate was immersed in ion-exchanged water for 2 hours to elute the surfactant, and dried by a dryer at 40 ° C for 30 minutes to obtain a composite material. The composite material was produced so that the coating amount of the coating composition with respect to the substrate was 8 to 10 g/m ² and the film thickness of the coating film was 20 to 40 nm.

Evaluation I1: Water film formation test

The coating composition of Example I1 and Comparative Examples I1 to I2 obtained in the above manner was used for a BLB lamp (manufactured by Sankyo Electric Co., Ltd., product name FL20SBL, peak wavelength 352 nm) having an irradiation intensity of 1 mW/m ² . The composite material having the surface layer formed thereon was subjected to light irradiation for 3 days. The surface of the member was vertically inclined to the ground, and 15 g of ion-exchanged water was sprayed on the entire substrate of 100 mm × 200 mm by an accumulator sprayer (manufactured by Maruyama Sangyo Co., Ltd.) from a distance of 10 cm from the surface of the member. The evaluation indicators are as follows. The results are as shown in Table 1 below.

A: A water film is formed on the entire surface of the component surface.

B: part of the surface of the component is the one that bounces the water

C: The entire surface of the component is used to bounce the water.

Evaluation I2: Water Drop Sliding Test

The coating composition of Example I1 and Comparative Examples I1 to I2 obtained in the above manner was used for a BLB lamp (manufactured by Sankyo Electric Co., Ltd., product name FL20SBL, peak wavelength 352 nm) having an irradiation intensity of 1 mW/m ² . The composite material having the surface layer formed thereon was subjected to light irradiation for 3 days. The member as shown in Figure 1 from camel ground was 80 ° inclined stand, respectively, 5 parts of the member surface using a micro-syringe so that the water droplets are 15 μ L, based on the total score was evaluated for each 5 parts of water droplet roll-off properties. The evaluation indicators are as follows, and the total score is obtained. The results are as shown in Table 1 below.

0 points: The drop of water drops is less than 2 cm.

1 point: The water droplets slide down more than 2cm.

2 points: The water droplets slipped more than 4 cm.

3 points: The water droplets slipped more than 6cm.

4 points: The water droplets slipped more than 8cm.

5 points: The water droplets slipped 10 cm.

The second form of the invention Modulation of coating composition

The following materials were prepared as raw materials for the coating composition.

Material (II-1)

‧ Photocatalytic titanium oxide (aqueous anatase titanium oxide sol): average particle size 22nm solid content rate 0.3%

Material (II-2)

‧ Zirconia (aqueous amorphous zirconia sol): solid content rate 7.2%

Material (II-3)

‧ cerium oxide (aqueous colloidal cerium oxide): average particle size 10nm solid Ingredient content rate of 30%

Surfactant

‧矽 surfactants

The solid content concentration in the following examples and comparative examples indicates the concentration of the total solid content of the material (II-1), the material (II-2), and the material (II-3) contained in the coating composition. .

Example II1

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia, the aqueous colloidal cerium oxide sol, and the lanthanide-based surfactant are mixed in water as a solvent to prepare a solid content concentration of 0.3% by mass. And a coating composition was obtained. Here, the mass ratio of TiO ₂ to ZrO ₂ to SiO ₂ is set to 0.5:49:50.5.

Example II2

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia, the aqueous colloidal cerium oxide sol, and the lanthanide-based surfactant are mixed in water as a solvent to prepare a solid content concentration of 0.3% by mass. And a coating composition was obtained. Here, the mass ratio of TiO ₂ to ZrO ₂ to SiO ₂ is set to 1:49:50.

Example II3

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia, the aqueous colloidal cerium oxide sol, and the lanthanide-based surfactant are mixed in water as a solvent to prepare a solid content concentration of 0.3% by mass. And a coating composition was obtained. Here, the mass ratio of TiO ₂ to ZrO ₂ to SiO ₂ is set to 5:49:46.

Example II4

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia, the aqueous colloidal cerium oxide sol, and the lanthanide-based surfactant are mixed in water as a solvent to prepare a solid content concentration of 0.3% by mass. And a coating composition was obtained. Here, the mass ratio of TiO ₂ to ZrO ₂ to SiO ₂ is set to 5:60:35.

Example II5

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia, the aqueous colloidal cerium oxide sol, and the lanthanide-based surfactant are mixed in water as a solvent to prepare a solid content concentration of 0.3% by mass. And a coating composition was obtained. Here, the mass ratio of TiO ₂ to ZrO ₂ to SiO ₂ is set to 10:60:30.

Example II6

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia, the aqueous colloidal cerium oxide sol, and the lanthanide-based surfactant are mixed in water as a solvent to prepare a solid content concentration of 0.3% by mass. And a coating composition was obtained. Here, the mass ratio of TiO ₂ to ZrO ₂ to SiO ₂ is set to 15:60:25.

Comparative Example II1

The aqueous amorphous zirconia, the aqueous colloidal cerium oxide sol, and the lanthanoid surfactant were mixed in water as a solvent, and the solid content concentration was adjusted to 0.3% by mass to obtain a coating composition. Here, the mass ratio of ZrO ₂ to SiO ₂ is set to 80:20.

Composite material production

The floating glass substrate of 100 mm × 200 mm was ground with an abrasive for the glass substrate, and the abrasive was completely washed with ion-exchanged water. Thereafter, the substrate was dried by a dryer at 40 ° C for 30 minutes. The coating compositions of the above Examples II1 to II14 and Comparative Examples II1 to II5 were roll-coated on the washed floating glass substrate, and dried at a temperature of 25 ° C and a humidity of 50% RH for one day. Then, the substrate was immersed in ion-exchanged water for 2 hours to elute the surfactant, and dried by a dryer at 40 ° C for 30 minutes to obtain a composite material. The composite material was produced so that the coating amount of the coating composition with respect to the substrate was 8 to 10 g/m ² and the film thickness of the coating film was 20 to 40 nm.

Assessment II1: Water film formation test

The coating composition of Examples II1 to II6 and Comparative Example II1 obtained in the above manner was used for a BLB lamp (manufactured by Sankyo Electric Co., Ltd., product name FL20SBL, peak wavelength 352 nm) having an irradiation intensity of 1 mW/m ² . The composite material having the surface layer formed thereon was subjected to light irradiation for 3 days. The surface of the member was vertically inclined to the ground, and 15 g of ion-exchanged water was sprayed on the entire substrate of 100 mm × 200 mm by an accumulator sprayer (manufactured by Maruyama Sangyo Co., Ltd.) from a distance of 10 cm from the surface of the member. The evaluation indicators are as follows. The results are as shown in Table 2 below.

A: A water film is formed on the entire surface of the component surface.

B: part of the surface of the component is the one that bounces the water

C: The entire surface of the component is used to bounce the water.

Assessment II2: Water Drop Sliding Test

The coating composition of Examples II1 to II6 and Comparative Example II1 obtained in the above manner was used for a BLB lamp (manufactured by Sankyo Electric Co., Ltd., product name FL20SBL, peak wavelength 352 nm) having an irradiation intensity of 1 mW/m ² . The composite material having the surface layer formed thereon was subjected to light irradiation for 3 days. The members were placed at an inclination of 80° from the ground as shown in Fig. 1, and 15 μL of water droplets were attached to the surface of the member 5 by using a micro syringe, and the water drop slip property was evaluated based on the total score of each of the five parts. The evaluation indicators are as follows, and the total score is obtained. The results are as shown in Table 2 below.

0 points: The drop of water drops is less than 2 cm.

1 point: The water droplets slide down more than 2cm.

2 points: The water droplets slipped more than 4 cm.

3 points: The water droplets slipped more than 6cm.

4 points: The water droplets slipped more than 8cm.

5 points: The water droplets slipped 10 cm.

Assessment II3: Measurement of static contact angles for water

The coating composition of Examples II1 to II6 and Comparative Example II1 obtained in the above manner was used for a BLB lamp (manufactured by Sankyo Electric Co., Ltd., product name FL20SBL, peak wavelength 352 nm) having an irradiation intensity of 1 mW/m ² . The composite material having the surface layer formed thereon was subjected to light irradiation for 3 days. For the surface of the members of Examples 1 to 6 and Comparative Example 1, a contact angle measuring device (for example, a product name CA-X150 manufactured by Kyowa Interface Science Co., Ltd.) was used for the static contact angle of water, and it was dropped at room temperature. After a water droplet of μ L , the static contact angle after 5 seconds was measured by the θ/2 method. The results are as shown in Table 2 below.

The third type of the invention Photocatalyst coating composition modulation

The following materials were prepared as raw materials for the coating composition.

Material (III-1)

‧ Photocatalytic titanium oxide (aqueous anatase titanium oxide sol): average particle size 22nm solid content rate 0.3%

Material (III-2)

‧ Zirconia (aqueous amorphous zirconia sol): solid content rate 7.2%

‧ Zirconia (aqueous tetragonal zirconia sol): average particle size 63nm solid content rate 30%

‧ ammonium zirconium carbonate (ammonium zirconium carbonate aqueous solution): solid content (ZrO ₂ conversion) content rate 13%

‧ carbon black (hydrophobic carbon black water dispersion): solid content rate 1%

Material (III-3)

‧ cerium oxide (aqueous colloidal cerium oxide): average particle size 10nm solid content rate 30%

‧ Alumina (neutral / high dispersion sol): average particle size 7nm solid content rate 7%

‧Over-titanium oxide (titanium titanate acid solution): pH 6~8 solid content (TiO ₂ conversion) content rate 0.85%

Surfactant

‧矽 surfactants

The concentration of the solid component in the following examples and comparative examples refers to When the total solid content of the material (III-1) and the material (III-2) further includes the material (III-3), it means the material (III-1), the material (III-2), and the material (III-3). The concentration in the coating composition of the total solid content.

Example III1

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia sol, and the lanthanide-based surfactant are mixed in water as a solvent, and the solid content concentration is adjusted to 0.3% by mass to obtain a coating composition. Things. Here, the mass ratio of TiO ₂ to ZrO ₂ was set to 44:56.

Example III2

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia sol, and the lanthanide-based surfactant are mixed in water as a solvent, and the solid content concentration is adjusted to 0.3% by mass to obtain a coating composition. Things. Here, the mass ratio of TiO ₂ to ZrO ₂ is set to 40:60.

Example III3

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia sol, and the lanthanide-based surfactant are mixed in water as a solvent, and the solid content concentration is adjusted to 0.3% by mass to obtain a coating composition. Things. Here, the mass ratio of TiO ₂ to ZrO ₂ is set to 30:70.

Example III4

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia sol, and the lanthanide-based surfactant are mixed in water as a solvent, and the solid content concentration is adjusted to 0.3% by mass to obtain a coating composition. Things. Here, the mass ratio of TiO ₂ to ZrO ₂ is set to 10:90.

Example III5

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia, the aqueous colloidal cerium oxide sol, and the lanthanide-based surfactant are mixed in water as a solvent to prepare a solid content concentration of 0.3% by mass. And a coating composition was obtained. Here, the mass ratio of TiO ₂ to ZrO ₂ to SiO ₂ is set to 5:60:35.

Example III6

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia, the aqueous colloidal cerium oxide sol, and the lanthanide-based surfactant are mixed in water as a solvent to prepare a solid content concentration of 0.3% by mass. And a coating composition was obtained. Here, the mass ratio of TiO ₂ to ZrO ₂ to SiO ₂ is set to 15:60:25.

Example III7

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia, the aqueous colloidal cerium oxide sol, and the lanthanide-based surfactant are mixed in water as a solvent to prepare a solid content concentration of 0.3% by mass. And a coating composition was obtained. Here, the mass ratio of TiO ₂ to ZrO ₂ to SiO ₂ is set to 30:60:10.

Example III8

The aqueous anatase-type titanium oxide sol, the aqueous tetragonal zirconia sol, the aqueous colloidal cerium oxide sol, and the lanthanide-based surfactant are mixed in water as a solvent, and the solid content concentration is 0.3% by mass. Modulation was carried out to obtain a coating composition. Here, the mass ratio of TiO ₂ to ZrO ₂ to SiO ₂ is set to 20:60:20.

Example III9

The aqueous anatase-type titanium oxide sol, the aqueous ammonium zirconium carbonate solution, the aqueous colloidal cerium oxide sol, and the cerium-based surfactant are mixed in water as a solvent, and the solid content concentration is adjusted to 0.3% by mass. A coating composition was obtained. Here, the mass ratio of TiO ₂ to ammonium zirconium carbonate (ZrO ₂ equivalent value) to SiO ₂ is set to 20:60:20.

Example III10

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia sol, the neutral/high-dispersion alumina sol, and the ruthenium-based surfactant are mixed in water as a solvent so that the solid content concentration is 0.3% by mass. The method was prepared to obtain a coating composition. Here, the mass ratio of TiO ₂ to ZrO ₂ to Al ₂ O ₃ is set to 20:60:20.

Example III11

The aqueous anatase type titanium oxide sol, the aqueous amorphous zirconia sol, the aqueous colloidal cerium oxide sol, the titania acid solution, and the lanthanide surfactant are mixed in water as a solvent so that the solid content concentration becomes It was prepared in a manner of 0.3% by mass to obtain a coating composition. Here, the mass ratio of anatase type TiO ₂ to ZrO ₂ and SiO ₂ to perovskite acid (TiO ₂ equivalent value) is set to 20:60:10:10.

Example III12

The aqueous anatase type titanium oxide sol, the aqueous amorphous zirconia sol, the aqueous colloidal cerium oxide sol, the titania acid solution, and the lanthanide surfactant are mixed in water as a solvent so that the solid content concentration becomes It was prepared in a manner of 0.3% by mass to obtain a coating composition. Here, the mass ratio of anatase type TiO ₂ to ZrO ₂ and SiO ₂ to perovskite acid (TiO ₂ equivalent value) is set to 20:60:5:15.

Example III13

The aqueous anatase type titanium oxide sol, the aqueous amorphous zirconia sol, the aqueous colloidal cerium oxide sol, the titania acid (amorphous titanic acid solution), and the lanthanide surfactant are mixed in water as a solvent The coating composition was prepared so as to have a solid content concentration of 0.3% by mass. Here, the mass ratio of anatase type TiO ₂ to ZrO ₂ and SiO ₂ to titanic acid (TiO ₂ equivalent value) is set to 20:60:15:5.

Example III14

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia sol, the titaniactic acid (amorphous titanic acid solution), and the ruthenium-based surfactant are mixed in water as a solvent so that the solid content concentration becomes It was prepared in a manner of 0.3% by mass to obtain a coating composition. Here, the mass ratio of anatase type TiO ₂ to ZrO ₂ and perovskite acid (TiO ₂ equivalent value) is set to 20:60:20.

Comparative Example III1

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia sol, and the lanthanide-based surfactant are mixed in water as a solvent, and the solid content concentration is adjusted to 0.3% by mass to obtain a coating composition. Things. Here, the mass ratio of TiO ₂ to ZrO ₂ is set to 50:50.

Comparative Example III2

The aqueous anatase-type titanium oxide sol, the aqueous amorphous zirconia sol, and the lanthanide-based surfactant are mixed in water as a solvent, and the solid content concentration is adjusted to 0.3% by mass to obtain a coating composition. Things. Here, the mass ratio of TiO ₂ to ZrO ₂ is set to 1:99.

Comparative Example III3

The aqueous amorphous zirconia sol and the ruthenium-based surfactant were mixed in water as a solvent, and the solid content concentration was adjusted to 0.3% by mass to obtain a coating composition.

Comparative Example III4

The aqueous amorphous zirconia, the aqueous colloidal cerium oxide sol, and the lanthanoid surfactant were mixed in water as a solvent, and the solid content concentration was adjusted to 0.3% by mass to obtain a coating composition. Here, the mass ratio of ZrO ₂ to SiO ₂ is set to 60:40.

Comparative Example III5

The aqueous anatase-type titanium oxide sol, the hydrophobic carbon black aqueous dispersion, the aqueous colloidal cerium oxide sol, and the lanthanide-based surfactant are mixed in water as a solvent to have a solid content concentration of 0.3% by mass. Modulation was carried out to obtain a coating composition. Here, the mass ratio of TiO ₂ to carbon black to SiO ₂ is set to 20:60:20.

Composite material production

The floating glass substrate of 100 mm × 200 mm was ground with an abrasive for the glass substrate, and the abrasive was completely washed with ion-exchanged water. Thereafter, the substrate was dried by a dryer at 40 ° C for 30 minutes. The coating compositions of the above Examples III1 to III14 and Comparative Examples III1 to III5 were roll-coated on the washed floating glass substrate, and dried at a temperature of 25 ° C and a humidity of 50% RH for one day. Then, the substrate was immersed in ion-exchanged water for 2 hours to elute the surfactant, and dried by a dryer at 40 ° C for 30 minutes to obtain a composite material. The composite material was produced so that the coating amount of the coating composition with respect to the substrate was 8 to 10 g/m ² and the film thickness of the coating film was 20 to 40 nm.

Assessment III1: Water film formation test

By using a BLB lamp (manufactured by Sankyo Electric Co., Ltd., product name FL20SBL, peak wavelength 352 nm) having an irradiation intensity of 1 mW/m ² , the coatings of Examples III1 to III14 and Comparative Examples III1 to III5 obtained in the above manner were used. The composite material in which the surface layer was formed by the cloth composition was subjected to light irradiation for 3 days. The surface of the member was vertically inclined to the ground, and 15 g of ion-exchanged water was sprayed on the entire substrate of 100 mm × 200 mm by an accumulator sprayer (manufactured by Maruyama Sangyo Co., Ltd.) from a distance of 10 cm from the surface of the member. The evaluation indicators are as follows. The results are as shown in Table 3 below.

A: A water film is formed on the entire surface of the component surface.

B: part of the surface of the component is the one that bounces the water

C: The entire surface of the component is used to bounce the water.

Assessment III2: Water Drop Sliding Test

By using a BLB lamp (manufactured by Sankyo Electric Co., Ltd., product name FL20SBL, peak wavelength 352 nm) having an irradiation intensity of 1 mW/m ² , the coatings of Examples III1 to III14 and Comparative Examples III1 to III5 obtained in the above manner were used. The composite material in which the surface layer was formed by the cloth composition was subjected to light irradiation for 3 days. The member was placed at an inclination of 80° from the ground as shown in Fig. 1, and 0.15 μL of water droplets were adhered to the surface of the member 5 by using a micro syringe, and the water drop slip property was evaluated based on the total score of each of the five parts. The evaluation indicators are as follows, and the total score is obtained. The results are as shown in Table 3 below.

0 points: The drop of water drops is less than 2 cm.

1 point: The water droplets slide down more than 2cm.

2 points: The water droplets slipped more than 4 cm.

3 points: The water droplets slipped more than 6cm.

4 points: The water droplets slipped more than 8cm.

5 points: The water droplets slipped 10 cm.

[Fig. 1] is a view showing a setting condition of a member for testing the water droplet retaining property of the composite material of the present invention.

Claims (47)

A composite material comprising a base material and a surface layer formed on a surface of the base material, wherein the surface layer comprises a compound (A) and a compound (B), and is relatively The compound (B) is formulated in an amount of 30% by mass or more and less than 99% by mass in terms of the mass of the compound (A) and the mass of the oxide of the compound (B). The compound (A) contains at least one metal selected from the group consisting of Si, Al, Ti, Sn, and W, and oxygen, and the compound (B) is composed of Cr, Mn, Fe, Co, Ni, Cu. And at least one selected from the group consisting of at least one metal oxide, an inorganic salt, and an organic salt selected from the group consisting of Ga, Zr, Y, In, and Hf. The composite material according to the first aspect of the invention, wherein the surface layer comprises the material (I-1) as the compound (A) and the material (I-2) as the compound (B). The material (I-1) is at least one compound selected from the group consisting of ceria, alkali silicate, alumina, and amorphous titanium oxide, and the material (I-2) is composed of Cr, Mn, At least one compound selected from the group consisting of oxides, inorganic salts and organic salts of at least one metal selected from the group consisting of Fe, Co, Ni, Cu, Ga, Zr, Y, In, and Hf, and relative to the foregoing materials The quality of (I-1) and the aforementioned material (I-2) The material (I-2) is prepared in an amount of 30% by mass or more and 70% by mass or less based on the mass of the oxide. The composite material according to the second aspect of the invention, wherein the material (I-2) is the same as the mass of the material (I-1) and the oxide of the material (I-2). The oxide conversion is prepared by mixing 30% by mass or more and 50% by mass or less. The composite material according to the third aspect of the invention, wherein the material (I-2) is contained in the surface layer in an amount of 30% by mass or more and 70% by mass or less in terms of the oxide. The composite material according to the fourth aspect of the invention, wherein the material (I-2) is contained in the surface layer in an amount of 30% by mass or more and less than 50% by mass in terms of the oxide. The composite material according to any one of claims 2 to 5, wherein the material (I-1) is calculated by measuring a length of any 100 particles in a field of view of 200,000 times by a scanning electron microscope. Particles having a number average particle diameter of 10 nm or more and 100 nm or less. The composite material according to any one of claims 1 to 6, wherein the surface layer does not contain a photocatalyst material. The composite material according to the first aspect of the invention, wherein the surface layer comprises a material (II-1) which is one of the compounds (A), a material (II-2) which is the compound (B), and The material (II-3) which is one kind of the compound (A), the material (II-1) is a photocatalyst material, and the material (II-2) contains Cr, Mn, Fe, Co, At least one compound selected from the group consisting of oxides, inorganic salts and organic salts of at least one metal selected from the group consisting of Ni, Cu, Ga, Zr, Y, In, and Hf, the foregoing material (II-3) is composed of At least one compound selected from the group consisting of cerium oxide, an alkali ceric acid salt, and an amorphous titanium oxide, and the surface layer further contains a material which is one of the compounds (A) and is an alumina of an optional component. The above material (II- with respect to the mass of the above material (II-1), the mass of the oxide of the above material (II-2), the amount of the oxide of the above material (II-3), and the mass of the foregoing alumina. 1) The content of the material (II-2) is more than 35% by mass and not more than 20% by mass, and the material (II-2) is blended in an amount of more than 35% by mass and 60% by mass or less, and the material (II-3) is used as the material (II-3). The amount of the oxide is adjusted to be more than 10% by mass and not more than 65% by mass, and the alumina is formulated to be 0% by mass or more and 10% by mass or less. The composite material according to claim 8, wherein the photocatalyst material is anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, zinc oxide, tin oxide, crystalline tungsten oxide. And at least one photocatalyst material selected from the group consisting of amorphous tungsten oxide. The composite material according to the invention of claim 8 or 9, wherein the material (II-1) has a diameter of 10 nm calculated by measuring 100,000 times of the field of view by using a scanning electron microscope. Particles having an average number of particles of 100 nm or less. The composite material according to the first aspect of the invention, wherein the surface layer comprises the material (III-1) as the compound (A) and the material (III-2) as the compound (B). The material (III-1) is a photocatalyst material, and the material (III-2) is selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Ga, Zr, Y, In, and Hf. At least one compound selected from the group consisting of at least one metal oxide and an inorganic salt, and the mass of the mass of the material (III-1) and the oxide of the material (III-2) (III-2) is prepared by blending the oxide in an amount of more than 50% by mass and not more than 99% by mass. The composite material according to claim 11, wherein the photocatalyst material is anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, zinc oxide, tin oxide, crystalline tungsten oxide. And at least one photocatalyst material selected from the group consisting of amorphous tungsten oxide. The composite material according to claim 11 or 12, wherein the surface layer further comprises a material (III-3) which is one of the compounds (A), and the material (III-3) is At least one selected from the group consisting of cerium oxide, alkali cerate, alumina, and amorphous titanium oxide. The composite material according to claim 13, wherein the mass of the material (III-1), the oxide conversion mass of the material (III-2), and the mass of the material (III-3) are And before The material (III-2) is prepared in an amount of more than 50% by mass and not more than 99% by mass in terms of the oxide conversion system. The composite material according to claim 11 or 12, wherein the material (III-2) is the sum of the mass of the material (III-1) and the oxide converted mass of the material (III-2). In the oxide conversion system, the blending ratio is 56% by mass or more and 90% by mass or less. The composite material according to claim 13, wherein the mass of the material (III-1), the amount of the oxide of the material (III-2), and the mass of the material (III-3) are the same. The material (III-2) is blended in an amount of 56% by mass or more and 90% by mass or less in terms of the oxide conversion. The composite material according to any one of the preceding claims, wherein the material (III-2) is formulated in the surface layer in an amount of more than 50% by mass and not up to 99 in terms of the oxide. The quality is made. The composite material according to any one of the above aspects of the present invention, wherein the material (III-2) is blended in the surface layer in an amount of 56% by mass or more and 90% by mass in terms of the oxide. The following is made. The composite material according to any one of the items of the present invention, wherein the material (III-1) is calculated by measuring 100,000 times the field of view of an arbitrary 100 particle lengths by a scanning electron microscope. Particles having a number average particle diameter of 10 nm or more and 100 nm or less. The composite material according to any one of claims 1 to 19, wherein the compound (B) is at least one compound selected from the group consisting of an oxide of Zr or Hf and an inorganic salt. The composite material according to any one of claims 1 to 19, wherein the compound (B) contains Cr, Mn, Fe, Co, Ni, Cu, Ga, Zr, Y, In, and Hf. The amorphous oxide of at least one metal selected from the group formed is an oxide particle or an inorganic salt having an average crystal diameter of less than 10 nm. The composite material according to claim 21, wherein the compound (B) contains an amorphous oxide of Zr or Hf or an oxide particle or an inorganic salt having an average crystal diameter of less than 10 nm. The composite material according to any one of claims 1 to 22, wherein the substrate is a wall material or a window material. A coating composition comprising a compound (A), a compound (B), and a solvent, characterized by a mass of the mass of the compound (A) and an oxide converted to the mass of the compound (B) The compound (B) is contained in an amount of 30% by mass or more and less than 99% by mass in the oxide conversion system, wherein the compound (A) contains a group of Si, Al, Ti, Sn, and W. Selecting at least one metal and oxygen, the compound (B) being an oxide of at least one metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Ga, Zr, Y, In, and Hf At least one selected from the group consisting of inorganic salts and organic salts. The coating composition according to claim 24, which comprises the material (I-1) as the compound (A), the material (I-2) as the compound (B), and a solvent. The material (I-1) is at least one compound selected from the group consisting of cerium oxide, alkali ceric acid salt, aluminum oxide, and amorphous titanium oxide, and/or the precursors, and the foregoing material (I-2) Selecting at least one selected from the group consisting of oxides, inorganic salts and organic salts of at least one metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Ga, Zr, Y, In, and Hf The compound (I-2) is formulated in an amount of 30% by mass or more based on the mass of the material (I-1) and the mass of the oxide of the material (I-2). It is 70% by mass or less. The coating composition according to claim 25, wherein the material (I- is the mass of the mass of the material (I-1) and the amount of the oxide of the material (I-2). 2) The amount of the oxide conversion system is 30% by mass or more and 50% by mass or less. The coating composition according to claim 25, wherein the material (I-2) is blended in an amount of more than 30% by mass and not more than 70% by mass in terms of the oxide-forming component. The coating composition according to claim 27, wherein the material (I-2) is blended in an amount of more than 30% by mass and less than 50% by mass in terms of the oxide-forming component. . Applying as described in any one of claims 25 to 28 In the cloth composition, the material (I-1) is a particle having a number average particle diameter of 10 nm or more and 100 nm or less calculated by measuring 100,000 times of the field of view by a scanning electron microscope. The coating composition according to any one of claims 25 to 29, which does not contain a photocatalyst material. The coating composition according to claim 24, which comprises the material (II-1) which is one of the compounds (A), and the material (II-2) which is the compound (B), as described above. The material (II-3) of one of the compounds (A) and the solvent, the material (II-1) is a photocatalyst material, and the material (II-2) contains Cr, Mn, Fe, Co, Ni, At least one compound selected from the group consisting of oxides, inorganic salts and organic salts of at least one metal selected from the group consisting of Cu, Ga, Zr, Y, In and Hf, the material (II-3) being oxidized by oxidation At least one compound selected from the group consisting of ruthenium, alkali ruthenate and amorphous titanium oxide further comprises, as a material of the compound (A), and as an alumina of any component, relative to the aforementioned material (II- 1) the mass, the amount of the oxide of the material (II-2), the amount of the oxide of the material (II-3), and the mass of the alumina, and the material (II-1) is more than 0. The mass % is less than 20% by mass, and the material (II-2) is blended in the oxide conversion system to more than 35 masses. The amount of the material (II-3) is adjusted to be more than 10% by mass and not more than 65% by mass in terms of oxides, and the amount of the alumina-based compound is 0% by mass or more and 10% by mass. The following is made. The coating composition according to claim 31, wherein the photocatalyst material is anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide, zinc oxide, tin oxide, and crystallinity. At least one photocatalyst material selected from the group consisting of tungsten oxide and amorphous tungsten oxide. The coating composition according to claim 31, wherein the material (II-1) has a thickness of 10 nm or more calculated by measuring 100,000 times of the field of view by using a scanning electron microscope. And particles having a number average particle diameter of 100 nm or less. The coating composition according to claim 24, which comprises the material (III-1) as the compound (A), the material (III-2) as the compound (B), and a solvent. The material (III-1) is a photocatalyst material, and the material (III-2) is at least selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Ga, Zr, Y, In, and Hf. a compound selected from the group consisting of a metal oxide and an inorganic salt, and the mass of the mass of the material (III-1) and the oxide of the material (III-2) III-2) It is prepared by the oxide conversion system exceeding 50 mass % and not exceeding 99 mass %. a coating composition as described in claim 34, The photocatalyst material is selected from the group consisting of anatase titanium oxide, rutile titanium oxide, brookite titanium oxide, zinc oxide, tin oxide, crystalline tungsten oxide, and amorphous tungsten oxide. A photocatalytic material. The coating composition according to claim 34 or claim 35, further comprising cerium oxide, alkyl cerate, alkali cerate, alumina, amorphous titanium oxide, titanium peroxide, hydrogen At least one material selected from the group consisting of alumina and gibbsite (III-3). The coating composition according to claim 36, wherein the mass of the material (III-1), the amount of the oxide of the material (III-2), and the material (III-3) are the same. In the mass of the oxide-converted amount, the material (III-2) is blended in an amount of more than 50% by mass and not more than 99% by mass. The coating composition according to claim 37, wherein the material (III- is the mass of the mass of the material (III-1) and the amount of the oxide of the material (III-2). 2) It is prepared by blending the oxide conversion amount to 56% by mass or more and 90% by mass or less. The coating composition according to claim 36, wherein the mass of the material (III-1), the oxide of the material (III-2), and the material (III-3) are the same. The material (III-2) is blended in an amount of 56% by mass or more and 90% by mass or less based on the mass of the oxide. The coating composition according to any one of the present invention, wherein the material (III-2) is blended in an amount of more than 50% by mass based on the oxide-forming component. Up to 99 quality % formed. The composite material according to any one of the present invention, wherein the material (III-2) is blended in an amount of more than 56% by mass and 90% by mass based on the oxide-forming component. The following is made. The coating composition according to any one of claims 34 to 41, wherein the material (III-1) has a surface length of 200,000 times measured by a scanning electron microscope. The calculated number average particle diameter of 10 nm or more and 100 nm or less. The coating composition according to any one of claims 24 to 42, wherein the compound (B) is at least one compound selected from the group consisting of an oxide of Zr or Hf and an inorganic salt. The coating composition according to any one of claims 24 to 42, wherein the compound (B) contains Cr, Mn, Fe, Co, Ni, Cu, Ga, Zr, Y, In And an amorphous oxide of at least one metal selected from the group consisting of Hf or an oxide particle or an inorganic salt having an average crystal diameter of less than 10 nm. The coating composition according to claim 44, wherein the compound (B) contains an amorphous oxide of Zr or Hf or an oxide particle or an inorganic salt having an average crystal diameter of less than 10 nm. A method of producing a composite material, which comprises applying the coating composition according to any one of claims 24 to 46 to a surface of a substrate by (a) The surface is heated at 300 ° C or lower, (b) dried at room temperature, or (c) before The surface of the substrate is heated at more than 300 and less than 1000 ° C for 2 to 60 seconds to form a surface layer. A composite material obtained by the production method as described in claim 46 of the patent application.