JP2002285088A - Coating-material composition, coated articles, mirror and wall of bathroom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating-material composition that has a high wearing resistance, a low contact angle toward water after the completion of forming film, a low-stain property or haze resistance even in an atmosphere nonexistent of light such as ultraviolet rays. SOLUTION: The composition contains the following (A) and (B) components. (B) component is contained within the range of weight ratio of 0.5-0.95 converted as a solid content against the total weight of (A) and (B). The average primary particle size for the particles over 10 wt.% converted as solid content among (B) component exists within 35-150 nm. (A) component is a hydrolysate and/or partial hydrolysate of an organic silicon alkoxide (R is a 1-8C univalent hydrocarbon group having the same or different kind of substituents or nonsubstituted) shown in the general formula (1): Si(OR)4 , and (B) component is an inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone-based coating material composition having low stain resistance, antifogging property, and durability. The present invention relates to a painted product using the composition, a mirror, and a bath wall.

[0002]

2. Description of the Related Art Conventionally, with the aim of preventing dirt on members constituting a building and fogging of mirrors and glass,
The surface of these materials is made hydrophilic or water-repellent. For example, as a method for imparting hydrophilicity, a method of forming a film made of a hydrophilic resin on the surface, a method of applying a surfactant, and the like are known.

However, even if the surface is made hydrophilic by coating with a hydrophilic resin such as polyvinyl alcohol or applying a surfactant such as sodium alkyl ether sulfate, the effect is temporary, In that the hydrophilicity cannot be maintained over a long period of time. Also, by making the surface water-repellent and splashing water that brings dirt, it may be difficult to get dirt,
In this case, if the water droplets have a size such that they do not fall even on a vertical surface, the water droplets may stay dry at the place and dry and cause contamination.

Therefore, silicone resin is used as a main component,
2. Description of the Related Art A method of applying hydrophilic properties to a base material surface for a long period of time, both indoors and outdoors, by applying and curing an inorganic paint containing a filler on a substrate surface has been performed. In particular, in the case of outdoor use, it is known that by using an optical semiconductor as a filler, superhydrophilic performance can be imparted for a long time by this photocatalytic action.

That is, when light of an excitation wavelength (for example, ultraviolet light having a wavelength of 400 nm) is applied to the above-mentioned optical semiconductor, the optical semiconductor causes the water in the air or the water adhered to the surface of the coating film to undergo hydroxyl radicals due to its photocatalytic action. This hydroxyl radical formation decomposes and removes organic substances that repel water adhering to the surface of the base material and organic substances contained in this surface,
The contact angle of water to the surface of the material is reduced, the familiarity with water is increased, and the hydrophilicity is increased. In other words, there is an effect that the material is easily wetted and the water wettability is improved. From this improvement in hydrophilicity, indoor members can be expected to have an antifogging effect in which glass and mirrors are hardly fogged by water droplets, and in outdoor members, antifouling in which attached dirt is washed away by rainwater. The effect can be expected. Furthermore, a substrate material coated on the surface with a coating containing an optical semiconductor can be provided with an antistatic function by the photocatalytic action of the optical semiconductor, and the antifouling effect can also be expected by this function. It is.

[0006]

As described above, a coating film formed of a silicone-based inorganic paint containing a photo-semiconductor can be formed by the photo-semiconductor in the presence of ultraviolet light, which is light having an excitation wavelength. The effect of improving hydrophilicity can be obtained. However, such an effect is not obtained immediately after the formation of the coating film. Immediately after the film is formed, the contact angle of the coating film with water is high and the hydrophilicity is poor. Moreover, in an environment where there is no light such as ultraviolet rays, the above-mentioned photocatalytic action does not work, so that the effect of improving the hydrophilicity cannot be obtained, the contact angle with water is high forever, and the low pollution or antifouling effect is obtained. There was a problem that it could not be obtained.

On the other hand, a coating film formed of a silicone-based inorganic paint containing silica instead of an optical semiconductor does not provide an optical semiconductor effect regardless of the presence or absence of light such as ultraviolet rays. It was thought that it was not possible to obtain a coating film with improved hydrophilicity.

Further, a coating film generally formed of a silicone-based inorganic paint is excellent in abrasion resistance (hard coat property) and weather resistance, but poor in resistance to an alkaline liquid. For example, when the above-mentioned paint is used for an outer wall, the coating film may be whitened due to an alkali component eluted from concrete. Further, when a coating film is used in a bathroom or a kitchen, a part of the coating film may be eluted by use of a fungicide or an alkaline detergent.

The present invention has been made in view of the above points, has high abrasion resistance, has a low contact angle with water immediately after film formation, and has low pollution or low pollution even in an environment where there is no light such as ultraviolet rays. A coating material composition having anti-fog properties, and painted articles using this coating material composition, mirrors, and bath walls are provided, and have high durability such as alkali resistance and abrasion resistance, It is an object of the present invention to provide a coated product using a coating material composition that can exhibit the effects of antifogging, low contamination, and self-cleaning while maintaining hydrophilicity of the surface for a long time. is there.

[0010]

The coating material composition according to claim 1 of the present invention comprises a coating material composition comprising the following components (A) and (B):
The component (A) and the component (B) are contained in a weight ratio of 0.5 to 0.95 in terms of solid content with respect to the total weight of the components, and 10% by weight of the component (B) in terms of solid content. The above is characterized in that the average primary particle size is in the range of 35 to 150 nm.

Component (A): an organic compound represented by the general formula Si (OR) ₄ (1) (where R is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms). Hydrolyzate and / or partial hydrolyzate of silicon alkoxide (B) Component: Inorganic Filler The invention of Claim 2 is characterized in that in Claim 1, silica is used as the inorganic filler as the (B) component. It is a feature.

The invention of claim 3 is the composition according to claim 1 or 2, wherein the inorganic filler as the component (B) is a mixture containing two or more kinds having different average primary particle diameters. The average primary particle diameter is small, but the average primary particle diameter is 5 to 40 nm.

According to a fourth aspect of the present invention, in any one of the first to third aspects, an optical semiconductor is used as the inorganic filler as the component (B).

According to a fifth aspect of the present invention, there is provided a coated article wherein the coating material composition according to any one of the first to fourth aspects is applied to the surface of a substrate and cured to form a coating film. It is a feature.

The mirror according to claim 6 is a mirror according to claims 1 to 4.
Wherein the coating material composition is applied to the surface and cured to form a coating film.

According to a seventh aspect of the present invention, there is provided a bath wall according to the first aspect.
The coating material composition according to any one of Items 1 to 4, which is applied to the surface and cured to form a coating film.

[0017] The coated article according to claim 8 is characterized in that the coating material composition according to any one of claims 1 to 4 is applied to the surface of a base material and cured to form a film, Treatment with any of alkali, acid, surfactant,
It is characterized by being subjected to a treatment selected from immersion treatment with a heating liquid.

According to a ninth aspect of the present invention, there is provided a coated product in which two or more coating films are laminated on the surface of the substrate, wherein the primer layer in contact with the surface of the substrate is formed of the component (A). The outermost layer is formed of the coating material composition according to any one of claims 1 to 4.

According to a tenth aspect of the present invention, in the ninth aspect, as the component (A), Si (OR) ₄ of the formula (1) is O
It is characterized by using a substance hydrolyzed with 0.001 mol or more of water per 1 mol of R group.

The invention of claim 11 is the invention of claim 9 or 1
0, each of the component (A) forming the primer layer and the coating material composition forming the outermost layer,
Boiling point 100 ° C or higher or vapor pressure 53.3 hPa (40 mm
Hg) (at 25 ° C.) or less in a solvent in an amount of 0.1 to 70% by weight based on the total amount of the component (A) forming the primer layer or the total amount of the coating material composition forming the outermost layer. It is characterized by the following.

[0021]

Embodiments of the present invention will be described below.

In the present invention, the coating material composition comprises:
The following components (A) and (B) are used as essential components.

Component (A): an alkoxide represented by the general formula Si (OR) ₄ (1) (where R is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) (B) Component: Inorganic Filler The component (A) is used as a binder component and a film-forming component of a coating film. (Water wettability) to provide anti-fogging properties and anti-fouling properties by washing with rainwater. The form of the hydrolyzate and / or partial hydrolyzate of the alkoxide of the component (A) is not particularly limited. For example, the form may be a solution or a dispersion.

Here, R in Si (OR) ₄ of the formula (1)
Is not particularly limited as long as it is a monovalent hydrocarbon group, and is preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, and a butyl group. And an alkyl group such as a pentyl group, a hexyl group, a heptyl group and an octyl group. Among the alkyl groups contained in the alkoxy group, those having 3 or more carbon atoms may be linear such as an n-propyl group, an n-butyl group, or an isopropyl group,
It may have a branch such as an isobutyl group or a t-butyl group.

Hydrolysis of alkoxide (partial hydrolysis)
The amount of water required for the reaction is not particularly limited. For example, the amount of water contained in an inorganic filler (water-dispersible colloidal silica or the like) as the component (B) described below is It is preferable to hydrolyze with 0.001 mol or more of water per 1 mol of the OR group in Si (OR) ₄ of the formula (1). If the amount of water is less than 0.001 mol, the desired alkali resistance may not be obtained even if the film-forming property of the coating film is poor, or even if the coating film can be formed. In addition, the catalyst used as needed when hydrolyzing (partially hydrolyzing) the alkoxide is not particularly limited, but an acidic catalyst is preferable from the viewpoint of shortening the time required for the production process. Examples of such an acidic catalyst include, but are not particularly limited to, for example, acetic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, and toluenesulfonic acid. , Organic acids such as oxalic acid, inorganic acids such as hydrochloric acid, nitric acid, and halogenated silane; acidic colloidal silica; acidic sol fillers such as titania sol; and the like. One or more of these may be used. can do. The hydrolysis (partial hydrolysis) of the alkoxide is performed, if necessary,
For example, the heating may be performed at about 40 to 100 ° C.

The hydrolysis (partial hydrolysis) of the alkoxide may be carried out, if necessary, by diluting it with an appropriate solvent. Such solvents are not particularly limited,
For example, methanol, ethanol, isopropanol,
n-butanol, lower aliphatic alcohols such as isobutanol, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol derivatives such as ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol derivatives such as diethylene glycol monobutyl ether, and diacetone alcohol; One or more selected from the group consisting of these can be used. Furthermore, in combination with these hydrophilic organic solvents, toluene, xylene, hexane, ethyl heptane, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone,
One or more kinds such as methyl ethyl ketoxime can be used.

The weight average molecular weight of the component (A) obtained by hydrolyzing (partially hydrolyzing) the above alkoxide is not particularly limited, but is preferably in the range of 500 to 1,000. When the weight average molecular weight is less than 500, the hydrolyzate (partially hydrolyzate) is disadvantageously unstable, and when it exceeds 1,000, the hardness of the formed coating film cannot be sufficiently maintained. And so on.

In the present invention, the inorganic filler of the component (B) is not particularly limited, but it is preferable to use an inorganic oxide such as silica or an optical semiconductor.
These are excellent in chemical stability such as solvent resistance and acid resistance, and dispersibility in the component (A) obtained by hydrolyzing (partially hydrolyzing) the alkoxide.

As the silica, known silica can be used without any particular limitation. The form of silica is not particularly limited, and may be, for example, any of a powder form and a sol form. When silica is used as a sol-like form, that is, when used as colloidal silica, it is not particularly limited, and for example, water-dispersible colloidal silica or non-aqueous organic solvent dispersible colloidal silica such as alcohol can be used. . Generally, such colloidal silica contains 20 to 50% by weight of silica as a solid content, and the amount of silica can be determined from this value.

When water-dispersible colloidal silica is used, water present in the colloidal silica as a component other than solids can be used for the hydrolysis (partial hydrolysis) of the alkoxide. Therefore, it is necessary to add the water of the water-dispersible colloidal silica to the amount of water in the hydrolysis (partial hydrolysis) of the alkoxide. The water-dispersible colloidal silica is usually made of water glass, and a commercially available product can be easily obtained and used.

The organic solvent-dispersible colloidal silica can be easily prepared by substituting the water of the water-dispersible colloidal silica with an organic solvent. As with the water-dispersible colloidal silica, commercially available products can be easily obtained and used for such organic solvent-dispersible colloidal silica. In the organic solvent-dispersible colloidal silica, the type of the organic solvent in which the colloidal silica is dispersed is not particularly limited, but, for example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol. , Ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol derivatives such as ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol derivatives such as diethylene glycol monobutyl ether, and diacetone alcohol, and the like. One or more kinds can be used. Further, in combination with these hydrophilic organic solvents, toluene, xylene,
One or more of hexane, ethyl heptane acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can be used.

On the other hand, an optical semiconductor can impart various functions to a coating film by a photocatalyst, and can further enhance the surface hydrophilicity of the coating film by a photocatalytic effect or maintain the surface hydrophilicity for a long time. This is called a catalyst. Such optical semiconductors include titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide,
Chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, cadmium oxide, copper oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide,
In addition to metal oxides such as cobalt oxide, rhodium oxide, nickel oxide and rhenium oxide, strontium titanate and the like can be mentioned. As the optical semiconductor, only one of these may be used, or two or more thereof may be used in combination.

Of these, metal oxides are preferred in that they can be practically and easily used, and among these metal oxides, titanium oxide is particularly preferred in terms of performance, safety, availability, and cost as a photocatalyst. Is preferred. Here, when titanium oxide is used as a photocatalyst, it is preferable that the crystal type is an anatase type (anatase type), in which the photocatalytic performance is strong, the curing promotion performance of the coating material composition is strong, and the photocatalytic performance is long. It is preferable because it is expressed for a period and is expressed in a short time after light irradiation. It should be noted that a material serving as an optical semiconductor can be used as long as it finally exhibits the properties of the optical semiconductor.

This optical semiconductor is light of an excitation wavelength (for example,
It is known that when exposed to ultraviolet light having a wavelength of 400 nm, it exhibits a photocatalytic effect of generating active oxygen. Since this active oxygen can oxidize and decompose organic substances, by forming a coating film containing an optical semiconductor on the surface of the substrate, a carbon-based soil component attached to the surface of the substrate material (for example, Self-cleaning effect of decomposing carbon fractions and tobacco tar contained in automobile exhaust gas, deodorizing effect of decomposing malodorous components represented by amine compounds and aldehyde compounds, represented by Escherichia coli and Staphylococcus aureus It can be expected to have an antibacterial effect for preventing the generation of bacteria and a fungicidal effect. In addition, when ultraviolet light is applied to a coating film containing an optical semiconductor, the optical semiconductor converts the moisture in the air or the moisture attached to the surface of the coating film into hydroxyl radicals by the photocatalytic action, and the hydroxyl radicals form a base material. By decomposing and removing organic substances repelling water attached to the surface and organic substances contained in the surface, the contact angle of water on the material surface is reduced, the familiarity with water is increased, and the hydrophilicity is increased, that is, wetness is increased. It also has the effect of improving water wettability.

The inorganic filler may be powder, fine powder,
Any form can be used as long as the form is dispersible, such as solution-dispersed sol particles. However, in the case of a sol, particularly a sol having a pH of 7 or less, curing of the coating material composition proceeds in a shorter time, and Excellent convenience in doing. The dispersion medium used in the sol is not particularly limited as long as it can uniformly disperse the fine particles of the inorganic filler, and any aqueous or non-aqueous solvent can be used.

The aqueous solvent is not particularly limited.
For example, in addition to water alone, hydrophilic organic solvents such as methanol, ethanol, isopropanol, n-butanol, lower aliphatic alcohols such as isobutanol, ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monobutyl ether such as acetate A mixed solvent of water with at least one of glycol derivatives, diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether, and diacetone alcohol can be used. Among these aqueous solvents, a water-methanol mixed solvent is preferred in terms of dispersion stability of the photocatalyst and drying of the dispersion medium after application of the coating material composition. When an aqueous sol is used, the sol can also function as an acidic catalyst at the time of hydrolysis of the alkoxide.

The non-aqueous solvent is not particularly limited. For example, those selected from the above-mentioned hydrophilic organic solvents and hydrophobic organic solvents such as toluene and xylene can be used. Among these non-aqueous solvents, methanol is
It is preferable in terms of dispersion stability and drying property of the dispersion medium after coating.

Further, in the coating material composition according to the present invention, the inorganic filler of the component (B) is added to the total weight of the components (A) and (B) in a weight ratio (B / (A + B) in terms of solid content. )) In the range of 0.5 to 0.95, preferably in the range of 0.65 to 0.9. When this weight ratio is less than 0.5,
The effect of the incorporated inorganic filler cannot be sufficiently obtained, and the hydrophilicity cannot be obtained immediately after film formation. Conversely, if the weight ratio exceeds 0.95, the film-forming properties of the coating film deteriorate, which causes deterioration of abrasion resistance or whitening of the coating film. Furthermore, of the component (B), 10% by weight or more in terms of solid content (substantially the upper limit is 10%).
0% by weight) has an average primary particle diameter of 35 to 150 nm.
Must be within the range. Average primary particle size is 35
〜150 nm, but less than 10% by weight, or less than 35 nm only, more than 150 nm only, less than 35 nm and 15
In the case of a mixture having a thickness exceeding 0 nm, the abrasion resistance of the coating film is reduced and the antifogging property is reduced.

As the inorganic filler of the component (B), only one kind may be used, or two or more kinds may be mixed and used. Here, when two or more kinds having different average particle diameters are blended, it is considered that the small ones are arranged between the large average particle diameters and the filling property is enhanced, and the effect of the inorganic filler is more exerted. Excellent antifogging properties, low pollution,
The self-cleaning effect can be obtained. If the average primary particle diameter is particularly small, but is in the range of 5 to 40 nm, the above effect can be further enhanced.

The above components (A) and (B) are blended, and the inorganic filler is uniformly dispersed in a dispersion medium by using various ordinary dispersion methods such as a homogenizer, a disper, a paint shaker, and a bead mill. Thus, a coating material composition can be obtained.

By applying the coating material composition prepared as described above to the surface of the substrate and drying and curing it, a coated article having a coating film formed on the surface can be obtained. At this time, particularly when the base material is a mirror or bath wall, a mirror or bath wall having a coating film formed of a coating material composition on the surface can be obtained. Preferably, the component (A) is applied to the surface of the base material and dried and cured to form a primer layer, and the coating material composition is applied to the surface of the primer layer and dried and cured to form the outermost layer. Things. By forming the primer layer with the component (A) in this way, the durability of the coating film is improved, especially the alkali resistance and abrasion resistance are remarkably improved, and the hydrophilicity of the surface is maintained for a long period of time indoors and outdoors. Is maintained, and the effects of antifogging property, low contamination property, and self-cleaning property can be sufficiently exhibited. In addition, although only two layers, the primer layer and the outermost layer, may be provided, one or more layers of the component (A) or the coating material composition may be provided between the primer layer and the outermost layer.

The coating method is not particularly limited, and examples thereof include brush coating, spray coating, dipping (dipping and dip coating), roll coating, flow coating, curtain coating, knife coating, spin coating, and the like.
An ordinary method such as bar coating can be appropriately selected. However, when a solvent having a low boiling point such as methanol, ethanol, or isopropanol is contained in the above coating material composition, the coating film may be whitened depending on the coating method. Therefore, in order to prevent such whitening of the coating film, a solvent having a boiling point of 100 ° C. or more or a vapor pressure of 53.3 hPa (40 mmHg) (25 ° C.) or less is used in an amount of 0 to the total amount of the coating material composition. It is preferable that the content be contained in the range of 0.1 to 70% by weight. In particular, when a primer layer is formed, it is preferable that the primer layer also contain the solvent described above. In this case, the solvent is added in an amount of 0.1 to the total amount of the component (A).
The content is 1 to 70% by weight. When the above-mentioned solvent is used, it is not necessary to limit the coating method, and it is possible to select an appropriate coating method for a substrate having various shapes and to apply the same, and to prevent whitening of the coating film. And loss of paint such as a coating material composition can be minimized. If the amount of the solvent is less than 0.1% by weight, the above-mentioned effects may not be sufficiently obtained. Conversely, even if the above-mentioned solvent is contained in an amount exceeding 70% by weight, effects higher than the above effects may not be obtained, which is not economically preferable. In addition, boiling point 10
Less than 0 ° C or vapor pressure 53.3 hPa (40 mmHg)
Even if a solvent exceeding (25 ° C.) is used, the above effects may not be sufficiently obtained.

The curing method is not particularly limited, and a known method can be used. The temperature at the time of curing is not particularly limited. A wide temperature range from normal temperature to heating temperature can be obtained depending on the presence or absence.

In the present invention, the thickness of the coating film formed by the coating material composition is not particularly limited, and may be, for example, about 0.05 to 10 μm. Stable adhesion to the surface of
In order to be retained and to prevent occurrence of cracks and peeling, the thickness is preferably 0.05 to 2 μm, and 0.1 to 1 μm.
Is more preferred.

After the coating material composition is applied to the surface of the base material and dried and cured as described above, the dried coating film of the coating material composition is treated with steam, alkali, acid, or heated liquid. It is preferable to form the film by performing at least one of the immersion treatments.

The treatment with steam is not particularly limited. For example, a method of exposing a coated product to steam emitted from boiling water for 5 minutes, a method of exposing only a coating film surface to steam, It can be carried out by, for example, spraying steam on the surface of the coating film. This steam has a temperature of 50-200
C., preferably 60 to 100C. If the steam temperature is lower than 50 ° C., the effect of increasing the hydrophilicity of the coating cannot be sufficiently obtained.
Even if the temperature exceeds 0 ° C., the improvement in the effect of increasing the hydrophilicity of the coating film is small, and it is not energy-efficient.
A range of 0 ° C. is preferred. The steam is not particularly limited, but may be, for example, steam or alcohol steam, and the treatment time with the steam is appropriately selected depending on the type, temperature, amount, coating composition, etc. of the steam. Things. The processing time varies depending on the curing conditions of the coating film. It is preferable to shorten the processing time when drying at a low temperature, and to lengthen the processing time when drying at a high temperature. In addition, if the coating film is dried and left for a long time, the processing time may be long due to the curing of the coating film. Therefore, performing the treatment early after drying can shorten the processing time. It is preferred.

The treatment with an alkali is not particularly limited, but can be performed, for example, by immersing the coated product in an alkali solution such as a 5% sodium hydroxide solution. The alkali solution preferably has a pH of 9 or more. If the pH of the alkali solution is less than 9, a long processing time is required, and the processing efficiency is deteriorated. Examples of the alkaline solution include, but are not particularly limited to, aqueous solutions of hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide and calcium hydroxide, aqueous ammonia,
Aqueous solutions of amines can be given, and among them, an aqueous solution of sodium hydroxide is preferred because of its high processing speed. The treatment time with the alkaline solution is appropriately selected depending on the pH, the coating composition, and the like. For example, in the case of a strong alkaline solution having a pH of 12 or more, the treatment time needs to be shortened. The processing time also differs depending on the curing conditions of the coating film. It is preferable to shorten the processing time when the coating film is dried and cured at a low temperature, and to lengthen the processing time when the coating film is dried and cured at a high temperature.

The treatment with an acid is not particularly limited, but can be carried out by immersing the coated article in an acid solution such as immersing the coated article in a hydrochloric acid solution for 10 minutes. The acid solution preferably has a pH of 3 or less,
If the pH of the acid exceeds 3, a long processing time is required, and the processing efficiency is reduced. As the acid solution, hydrochloric acid, sulfuric acid, nitric acid and the like, and aqueous solutions thereof can be used. The method of treating with an acid requires a longer treatment time than the case of treating with an alkali, but the same effect as in the case of treating with an alkali can be obtained.

The immersion treatment in the heating liquid can be carried out, for example, by immersing the coated article in warm water, warm alkaline aqueous solution, warm alcohol or the like. The temperature of these heating liquids is preferably in the range of 50 to 200C. If the temperature of the heating liquid is lower than 50 ° C., the effect of increasing the hydrophilicity of the coating by the heating liquid treatment cannot be sufficiently obtained.
Even if the temperature exceeds ℃, the improvement of the effect of increasing the hydrophilicity of the coating film is small, and it becomes inefficient in terms of energy.
A range of 0 ° C. is preferred. The treatment time by immersion in the heating liquid is appropriately selected depending on the kind, temperature, amount, coating composition and the like of the heating liquid.

By treating the surface of the coating film with a surfactant, a coating film having excellent hydrophilicity can be obtained. This method is not particularly limited,
For example, it can be carried out by immersing the coated product in a 10% solution of a sulfate or sodium dodecylbenzenesulfonate for 5 minutes.

Thus, as described above, the coating material composition is applied to the substrate, dried and cured, and the dried coating film is subjected to the above-mentioned treatment, whereby a coating film can be formed. The coating is subjected to a treatment with steam, an alkali, an acid, a surfactant, or a immersion treatment with a heating liquid, so that the hydrophilicity of the surface is improved. In both cases, therefore, a film having high hydrophilicity can be formed even when there is no light having an excitation wavelength for activating the optical semiconductor. Because of this high hydrophilicity, it is possible to expect an antifogging effect in which glass and mirrors are less likely to be fogged by water droplets in indoor members, and in an outdoor member, the adhered dirt is prevented from being washed by rainwater. It can be expected to have a fouling effect.

[0052]

Next, the present invention will be described specifically with reference to examples. Unless otherwise specified, “parts” means “parts by weight”
“%” Represents “% by weight”. The molecular weight was measured by GPC (gel permeation chromatography) using HLC8020 manufactured by Tosoh Corporation as a measuring instrument to prepare a calibration curve using standard polystyrene and converting it to a converted value.

Example 1 Tetraethoxysilane 208
To this part, 356 parts of methanol was added, and 18 parts of water and 18 parts of 0.01N hydrochloric acid were further mixed, and this was mixed well using a disper. This mixed solution was placed in a 60 ° C.
By heating for a period of time to adjust the weight average molecular weight to 950, a tetrafunctional silicone resin as the component (A) was obtained.
Next, as an inorganic filler of the component (B), a silica sol as a component (B1) having a large average primary particle diameter (trade name “ST-OL” manufactured by Nissan Chemical Industries, Ltd.):
(Particle size: 40 to 50 nm) (in Table 1, it is described as silica 3)
And silica methanol sol as a component (B2) having a small average primary particle diameter (trade name “MA-” manufactured by Nissan Chemical Industries, Ltd.)
ST-M ": particle size of 20 to 30 nm (in Table 1, denoted as silica 2) and the weight ratio of solids in terms of condensed compound B /
(A + B) is 0.75 (however, B = B1 + B2), and the ratio B1 / B of the component (B1) in all inorganic fillers
(Condensation compound conversion) is added so that the weight ratio becomes 0.95 based on the solid content, and after further polymerization reaction at 40 ° C. for 1 hour, it is diluted with methanol so that the total solid content becomes 5%. Thus, a coating material composition was prepared.

Then, the coating material composition was dropped on the surface of a glass plate and applied by a spin coater.
It was baked at 250 ° C. for 30 minutes. Furthermore, this coating film surface is
The coating was obtained by exposing to steam at 00 ° C. for 10 minutes.

(Example 2) In Example 1, (B1)
Component B1 / B in all inorganic fillers (however, B
= B1 + B2) (in terms of a condensed compound) except that the weight ratio was 0.15 based on the solid content.
A coating material composition was prepared in the same manner as in Example 1.

The coating composition was applied and treated with steam in the same manner as in Example 1 to obtain a coating.

Example 3 In Example 1, the weight ratio B / (A + B) of the component (B) was 0.9 (where B = B1 + B2) in terms of a condensed compound. A coating material composition was prepared in the same manner as in Example 1 except that the ratio B1 / B (in terms of a condensed compound) in all the inorganic fillers was added so that the weight ratio was 0.8 based on the solid content. .

The coating composition was applied and treated with steam in the same manner as in Example 1 to obtain a coating.

Example 4 In Example 3, the component (B) was added so that the weight ratio B / (A + B) of the solid in terms of the condensed compound was 0.5 (B = B1 + B2). A coating composition was prepared in the same manner as in Example 3, except that

Then, the coating material composition was applied and treated with steam in the same manner as in Example 1 to obtain a film.

Example 5 In Example 1, silica sol (trade name "ST-ZL" manufactured by Nissan Chemical Industries, Ltd .; particle size: 70 to 100 n) was used as the component (B1) of the component (B).
m ") (in Table 1, denoted as silica 4), except that a coating material composition was prepared in the same manner as in Example 1.

The coating composition was applied and treated with steam in the same manner as in Example 1 to obtain a coating.

Example 6 In Example 1, silica sol (trade name “ST-O” manufactured by Nissan Chemical Industries, Ltd .; particle size: 10 to 20 nm) was used as component (B2) of component (B).
(Denoted as silica 1 in Table 1) and (B
Example 1 Example 1 except that the ratio B1 / B (where B = B1 + B2) (in terms of a condensed compound) in the total inorganic filler of the component 1) was added so that the weight ratio was 0.15 based on the solid content. A coating material composition was prepared in the same manner as described above.

Then, the coating material composition was applied and treated with steam in the same manner as in Example 1 to obtain a film.

(Example 7) In Example 6, the weight ratio B / (A + B) of the solid in terms of the condensed compound was 0.5 (provided that B = B1 + B2).
A coating material composition was prepared in the same manner as in Example 6, except that it was added so as to be as follows.

Then, the coating material composition was applied and treated with steam in the same manner as in Example 1 to obtain a film.

Example 8 The procedure of Example 1 was repeated, except that the coating film after firing was not treated with steam.

Example 9 The procedure of Example 5 was repeated, except that the coating film after firing was not treated with water vapor.

(Embodiment 10) In Embodiment 1, (B)
As the component (B2), alumina sol (trade name “Alumina sol 520” manufactured by Nissan Chemical Industries, Ltd .: particle size 10)
A coating material composition was prepared in the same manner as in Example 1 except that (〜20 nm) (in Table 1, indicated as alumina 1) was used.

Then, the coating material composition was applied and treated with steam in the same manner as in Example 1 to obtain a film.

(Embodiment 11) In Embodiment 1, (B)
Titanium oxide aqueous sol as an optical semiconductor (solid content 25%, average primary particle diameter 10 to 20 n) as the component (B2) among the components
m) A coating material composition was prepared in the same manner as in Example 1 except for using titania 1 in Table 1.

Then, the coating material composition was applied and treated with steam in the same manner as in Example 1 to obtain a film.

(Example 12) In Example 1, (B)
The component does not contain silica methanol sol as the component (B2), and the component (B) is all silica sol (trade name “ST-OL” manufactured by Nissan Chemical Industries, Ltd .: particle size 40 to 50 n).
m), and the ratio B1 / B (B = B1 + B2, B2 = 0) (in terms of condensed compound) in the total inorganic filler of the component (B1) is added such that the weight ratio becomes 1 based on the solid content. A coating material composition was prepared in the same manner as in Example 1 except for the above.

Then, the coating material composition was applied and treated with steam in the same manner as in Example 1 to obtain a film.

(Comparative Example 1) In Example 1, the component (B) was added so that the weight ratio B / (A + B) of the solid was 0.25 (where B = B1 + B2) in terms of the condensation compound. A coating material composition was prepared in the same manner as in Example 1, except that

Then, the coating material composition was applied and treated with steam in the same manner as in Example 1 to obtain a film.

Comparative Example 2 In Example 10, (B)
The weight ratio of solids in terms of condensed compound is B / (A + B)
Is 0.25 (however, B = B1 + B2), and the ratio B1 / B (in terms of condensed compound) in the total inorganic filler of the component (B1) is added so that the weight ratio becomes 0.15 based on the solid content. A coating material composition was prepared in the same manner as in Example 10 except for the above.

Then, the coating material composition was applied and treated with steam in the same manner as in Example 1 to obtain a film.

(Comparative Example 3) In Example 1, the component (B) was added so that the weight ratio B / (A + B) of the solid was 0.99 (where B = B1 + B2) in terms of the condensation compound. A coating material composition was prepared in the same manner as in Example 1, except that

Then, the coating material composition was applied and treated with steam in the same manner as in Example 1 to obtain a film.

Comparative Example 4 In Example 6, all of the component (B) was a silica sol (trade name “S” manufactured by Nissan Chemical Industries, Ltd.).
(TO): particle diameter of 10 to 20 nm), and the weight ratio B / (A + B) of the solid component in component (B) is 0.5 in terms of condensation compound.
(However, B = B2) and the ratio B1 / B (B1 = 0) (in terms of condensed compound) of the component (B1) in the total inorganic filler is added so that the weight ratio becomes 0 based on the solid content. A coating composition was prepared in the same manner as in Example 6, except that

Then, the coating material composition was applied and treated with steam in the same manner as in Example 1 to obtain a film.

With respect to the coating films obtained in Examples 1 to 12 and Comparative Examples 1 to 4, the contact angle of water and the abrasion resistance of the coating surface immediately after film formation were measured, and the performance was evaluated.

(Contact angle of water immediately after film formation) This measurement was carried out by dropping 0.2 cm ³ of distilled water on the surface of the film and observing it with a magnifying camera.

(Test of abrasion resistance = hard coat property) Using a traverse abrasion tester, a canvas cloth was brought into contact with the surface of a coating film, and reciprocated 1000 times (load: 9.8 kPa).
(100 g / cm ² ) and a stroke of 100 mm) to carry out a wear test. Then, the degree of occurrence of scratches on the coating film surface after the abrasion test was observed with an optical microscope, and evaluated according to the following criteria.

“○”: No scratches “△”: Several scratches occurred per 1 cm ² “×”: Many scratches occurred and peeled off The results of the above tests are shown in Table 1.

[0087]

[Table 1]

In Table 1, the silicas 1 to 4, alumina 1, and titania 1 indicate the following as described above.

Silica 1: Silica sol (trade name “ST-O” manufactured by Nissan Chemical Industries, Ltd .: particle size of 10 to 20 nm) Silica 2: Silica methanol sol (Nissan Chemical Industries, Ltd.)
Product name “MA-ST-M”: particle size 20 to 30 nm) Silica 3: silica sol (product name “ST-OL” manufactured by Nissan Chemical Industries, Ltd .: particle size 40 to 50 nm) Silica 4: silica sol (Nissan Chemical Alumina 1: alumina sol (trade name “Alumina Sol 520” manufactured by Nissan Chemical Industries, Ltd .: particle size 10 to 20 nm) manufactured by Kogyo Co., Ltd. Titania 1: titanium oxide Water sol (solid content: 25%, average primary particle diameter: 10 to 20 nm) As shown in Table 1, all of Examples 1 to 12 have generally good abrasion resistance, and contact with water immediately after film formation. It is confirmed that the corner is low. In contrast, (B)
Comparative Examples 1 and 2, in which the proportions of the components were small, had good abrasion resistance, but the contact angles to water immediately after film formation were as high as 67 ° and 60 °, respectively. In Comparative Example 3 in which the component (A) was extremely small, the abrasion resistance was extremely poor. Comparative Example 4 containing only an inorganic filler having a small average primary particle diameter had good abrasion resistance, but had a high contact angle to water immediately after film formation, at 71 °.

Next, another embodiment will be described.

Example 13 Tetraethoxysilane 20
356 parts of methanol was added to 8 parts, 18 parts of water and 18 parts of 0.01 N hydrochloric acid were further mixed, and the mixture was mixed well using a disper. This mixed solution was placed in a 60 ° C.
By heating for a period of time, (A)
The components were obtained. Next, a component (B) having a large average primary particle diameter is added to the component (A) as an inorganic filler of the component (B).
1) Silica sol (trade name “ST-OL” manufactured by Nissan Chemical Industries, Ltd .: particle size of 40 to 50 nm) (in Table 2, expressed as silica 3) in terms of a condensed compound, the weight ratio of solids B /
(A + B) was added so as to be 0.75 (B = B1), and the polymerization reaction was further carried out at 40 ° C. for 1 hour, followed by dilution with methanol so that the total solid content was 5%. A coating material composition for forming a surface layer was obtained.

Then, a mirror and a soda lime silicate glass plate (hereinafter, referred to as a glass plate) were used as a base material, and the surface of each of these was polished with a cerium oxide-based abrasive and further washed with pure water. Thereafter, the component (A) for forming a primer layer was dropped on this surface, applied by a spin coater, and baked at 250 ° C. for 15 minutes. afterwards,
When the substrate temperature reached 40 ° C., the coating material composition for forming the outermost layer was dropped on the surface of each of the primer layers of the mirror and the glass plate and applied by a spin coater, and two inorganic coating films were formed. To obtain a mirror and a glass plate.

(Example 14) In Example 13,
As the inorganic filler of the component (B), silica methanol sol which is a component (B2) having a small average primary particle diameter (trade name “MA-ST-M” manufactured by Nissan Chemical Industries, Ltd .: particle size: 20 to
30 nm) (in Table 2, denoted as silica 2), and (B
Example 13 Example 13 was repeated except that the ratio B1 / B (where B = B1 + B2) (in terms of condensed compound) in the total inorganic filler of the component 1) was added so that the weight ratio was 0.95 based on the solid content. A coating material composition was prepared in the same manner as described above.

Then, using this coating material composition and the component (A), a mirror and a glass plate having two inorganic coating films were obtained in the same manner as in Example 13.

(Example 15) In Example 14, (B
Example 14 Example 14 was repeated except that the ratio B1 / B (where B = B1 + B2) (in terms of a condensed compound) in the total inorganic filler of the component 1) was added so that the weight ratio was 0.15 based on the solid content. A coating material composition was prepared in the same manner as described above.

Then, using this coating material composition and the component (A), a mirror and a glass plate having two inorganic coating films were obtained in the same manner as in Example 13.

(Example 16) In Example 14,
The component (B) is converted into a condensed compound in terms of a weight ratio of solids B / (A
+ B) is 0.9 (however, B = B1 + B2) and (B
1) A coating material composition was prepared in the same manner as in Example 14, except that the ratio B1 / B (in terms of condensed compound) in all the inorganic fillers of the component was added to be 0.8.

Using this coating material composition and the component (A), a mirror and a glass plate having two inorganic coating films were obtained in the same manner as in Example 13.

(Embodiment 17) In Embodiment 16,
The component (B) is converted into a condensed compound in terms of a weight ratio of solids B / (A
+ B) was prepared in the same manner as in Example 16 except that the addition was performed so that (B = B1 + B2) was 0.5.

Using this coating material composition and the component (A), a mirror and a glass plate having two inorganic coating films were obtained in the same manner as in Example 13.

(Embodiment 18)
Silica sol as the component (B1) of the component (B) (trade name “ST-ZL” manufactured by Nissan Chemical Industries, Ltd .: particle size 70 to 1)
00 nm) (in Table 2, denoted as silica 4), except that a coating material composition was prepared in the same manner as in Example 14.

Then, using this coating material composition and the component (A), a mirror and a glass plate having two inorganic coating films were obtained in the same manner as in Example 13.

(Example 19) Using a coating material composition prepared in the same manner as in Example 13 and the component (A), a mirror and a glass plate having two inorganic coating films in the same manner as in Example 13 I got

The surface of the fired coating film was exposed to steam at 100 ° C. for 10 minutes to obtain a coating film.

(Example 20) In Example 14,
Alumina sol (trade name “alumina sol 520” manufactured by Nissan Chemical Industries, Ltd .; particle size: 10 to 20 nm) (in Table 2, denoted as alumina 1) as the (B2) component of the (B) component, is used. In the same manner as in Example 14, a coating material composition was prepared.

Then, using this coating material composition and the component (A), a mirror and a glass plate having two inorganic coating films were obtained in the same manner as in Example 13.

(Example 21) In Example 14,
Titanium oxide aqueous sol as an optical semiconductor (solid content 25%, average primary particle diameter 10 to 10) as component (B2) of component (B)
A coating material composition was prepared in the same manner as in Example 14, except that 20 nm (in Table 2, denoted as titania 1) was used.

Then, using this coating material composition and the component (A), a mirror and a glass plate having two inorganic coating films were obtained in the same manner as in Example 13.

Example 22 The procedure of Example 13 was repeated except that the dilution was carried out using a mixed solvent of methanol / propylene glycol methyl ether acetate (PGM-Ac) = 1/1 (weight ratio). In the same manner as in Example 13, a coating material composition was prepared.

A mirror having a two-layer inorganic coating film and a glass plate were prepared in the same manner as in Example 13 except that the coating material composition and the component (A) were used and the coating was performed by spraying. I got

(Example 23) In Example 13, the dilution was carried out with methanol / diacetone alcohol (DAA) = 1 /.
A coating material composition was prepared in the same manner as in Example 13, except that the mixing was performed using a 1 (weight ratio) mixed solvent.

A mirror having a two-layer inorganic coating film and a glass plate were prepared in the same manner as in Example 13 except that the coating material composition and the component (A) were used and applied by spraying. I got

(Example 24) A mirror having a single inorganic coating film was prepared using a coating material composition prepared in the same manner as in Example 13 except that the primer layer was not formed. And a glass plate was obtained.

(Comparative Example 5) In Example 14, (B)
The weight ratio of solids in terms of condensed compound is B / (A + B)
Was 0.25 (however, B = B1 + B2), except that the coating material composition was prepared in the same manner as in Example 14.

Then, using this coating material composition and the component (A), a mirror and a glass plate having two inorganic coating films were obtained in the same manner as in Example 13.

Comparative Example 6 In Example 14, (B)
The weight ratio of solids in terms of condensed compound is B / (A + B)
Is 0.99 (provided that B = B1 + B2), and the ratio B1 / B of the component (B1) in the total inorganic filler (provided that B = B1 + B2).
A coating material composition was prepared in the same manner as in Example 14, except that (B1 + B2) (condensation compound equivalent) was added so that the weight ratio was 0.95 based on the solid content.

Then, using this coating material composition and the component (A), a mirror and a glass plate having two inorganic coating films were obtained in the same manner as in Example 13.

Comparative Example 7 No coating was applied to either the mirror or the glass plate.

Examples 13 to 25 and Comparative Examples 5 to 7
The performance of the mirror and the glass plate obtained in the above was evaluated as follows.

(State of Coating Film) The coating film formed on the surface of the mirror and the glass plate was visually observed to check for whitening. Those in which no whitening was observed in the coating film were evaluated as good.

(Test of abrasion resistance = hard coat property) Using a traverse abrasion tester, a canvas cloth was brought into contact with the outermost layer surface of a glass plate and slid 1000 times (load 9.
8 kPa (100 g / cm ² ), stroke 100 m
m) to carry out a wear test. And
The degree of occurrence of scratches on the outermost layer surface after the abrasion test was observed with an optical microscope, and evaluated according to the following criteria.

“○”: No scratches “△”: Several scratches occurred per 1 cm ² “×”: Many scratches occurred and peeled (contact angle) Contact of the outermost surface of the glass plate surface with 0.3 mg of water droplet Use a contact angle meter (Kyowa Interface Science Co., Ltd. “CA
-DT ").

(Water film area = anti-fog test) Even if steam hits the surface of the mirror or the glass plate, the fogging is prevented if the water film is formed on the surface of the mirror or the glass plate in advance. The visibility is improved. Therefore, the anti-fogging property can be evaluated by applying water to the surface of the mirror or the glass plate and checking whether or not the water film formed by the water is retained for a long time. Then, after the mirror and the glass plate were immersed in water and pulled up, the area of the formed water film was measured, and the mirror and the glass plate were placed in a thermo-hygrostat at a temperature of 35 ° C. and a relative humidity of 75%.
After standing for 0 minutes, the retained water film area was measured, and the ratio of the water film area after standing to the water film area after lifting was calculated. Those less than were evaluated as "x".

(Bathroom Exposure Test) Mirrors were installed in bathrooms of six households of ordinary households, and the antifogging property after one month was evaluated by measuring the water film area as described above.

(Alkali Test 1) A glass having a coating film formed on its surface was placed in a 1% by weight aqueous sodium hydroxide solution for 12 hours.
After dipping for 24, 36, and 48 hours, the presence or absence of the coating film was observed using an atomic force microscope ("Nanopix 1000" manufactured by Seiko Instruments Inc.).

(Alkali test 2) A mirror having a coating film formed on its surface was transferred to Johnson &Johnson's"moldkiller" by 12,
After dipping for 24, 36, and 48 hours, the presence or absence of the coating film was observed using an atomic force microscope ("Nanopix 1000" manufactured by Seiko Instruments Inc.).

(Water Film Area after Alkali Test 2) The antifogging property after the alkali test 2 was evaluated by measuring the water film area.

(Stain resistance ΔE) A glass plate previously coated with a white enamel paint was used, and a primer layer and an outermost layer were formed on the surface of the glass plate. Then, after exposing this glass plate to the outdoors for one month, a color difference meter (“X-rightSP-8” manufactured by Nippon Lithographic Equipment Co., Ltd.) is used.
8 ").

Tables 2 to 4 show the results of the above tests.

[0130]

[Table 2]

[0131]

[Table 3]

[0132]

[Table 4]

In Tables 2 to 4, silicas 2 to 4, alumina 1 and titania 1 indicate the following as described above.

Silica 2: Silica methanol sol (trade name “MA-ST-M” manufactured by Nissan Chemical Industries, Ltd .: particle size 20 to
Silica 3: Silica sol (trade name “ST-OL” manufactured by Nissan Chemical Industries, Ltd .: particle size 40 to 50 nm) Silica 4: Silica sol (trade name “ST-ZL” manufactured by Nissan Chemical Industries, Ltd .: particle size) 70-100 nm ") Alumina 1: Alumina sol (trade name" Alumina sol 520 "manufactured by Nissan Chemical Industries, Ltd .: Particle size: 10-20 nm) Titania 1: Titanium oxide aqueous sol (solid content: 25%, average primary particle size: 10-20 nm) As can be seen from Tables 2 to 4, it is confirmed that Examples 13 to 24 are all excellent in abrasion resistance, antifogging property and stain resistance as compared with Comparative Examples 5 to 7.

It is also confirmed that Examples 13 to 23 in which the primer layer was formed with the component (A) had better alkali resistance of the coating film than Example 24 in which the primer layer was not formed. .

[0136]

As described above, the coating material composition according to claim 1 of the present invention is a coating material composition containing the above components (A) and (B), wherein the component (B) is
The component (A) and the component (B) are contained in a weight ratio of 0.5 to 0.95 in terms of solid content with respect to the total weight of the components, and 10% by weight of the component (B) in terms of solid content. Since the average primary particle diameter of the above is in the range of 35 to 150 nm, it is excellent in abrasion resistance and has a low water contact angle immediately after film formation, is excellent in hydrophilicity, and forms a coating film having good antifogging property. Is what you can do.

Further, in the invention of claim 2, since silica is used as the inorganic filler as the component (B), a coating having low pollution or anti-fog properties even in an environment where no light such as ultraviolet rays is present. A film can be formed.

The invention of claim 3 is characterized in that, as the inorganic filler as the component (B), those having different average primary particle diameters are two.
A mixture containing more than one kind, and the average primary particle diameter of the mixture having a small average primary particle diameter is 5 to 40.
Since a film having a thickness of nm is used, a coating film having excellent abrasion resistance and having a low contact angle with water immediately after film formation and having good anti-fog properties can be formed.

Further, in the invention of claim 4, since an optical semiconductor is used as the inorganic filler as the component (B), a coating material having low pollution or anti-fog properties in an environment where light such as ultraviolet rays is present. A film can be formed.

In the coated article according to the fifth aspect, the coating material composition according to any one of the first to fourth aspects is applied to the surface of the substrate and cured to form a coating film. It is excellent in abrasion resistance, has a low contact angle with water immediately after film formation, is excellent in hydrophilicity, and can exhibit a good antifogging effect.

The mirror according to claim 6 is the same as that of claims 1 to 4.
The coating material composition according to any of the above is applied to the surface and cured to form a coating film, so that it has excellent abrasion resistance, and has a low contact angle to water immediately after film formation and has excellent hydrophilicity. And a good antifogging effect.

The wall of the bath according to claim 7 is the same as that of claim 1.
The coating material composition according to any one of to 4 is applied to the surface and cured to form a coating film, so that the coating material composition is excellent in abrasion resistance and has a low contact angle with water immediately after film formation and a low hydrophilicity. And can exhibit a good antifogging effect.

Further, the coated article according to claim 8 is characterized in that the coating material composition according to any one of claims 1 to 4 is applied to the surface of a substrate and cured to form a coating, Treatment with any of alkali, acid, surfactant,
Since the treatment selected from the immersion treatment with the heating liquid has been performed, when the optical semiconductor is contained in the coating material composition, the activity of the optical semiconductor present on the coating film surface can be enhanced by the above treatment. The effect of the optical semiconductor can be exhibited to a high degree, and the effect of the optical semiconductor can be sufficiently obtained while maintaining the wear resistance of the coating film. Is not included, the hydrophilicity of the surface of the coating film can be improved by the above treatment, and a coating film having high hydrophilicity can be formed.

The coated article according to claim 9 is a coated article in which two or more coating films are laminated on the surface of the substrate, wherein the primer layer in contact with the surface of the substrate is formed of the component (A). Since the outermost layer is formed of the coating material composition according to any one of claims 1 to 4, the durability of the coating film is improved, particularly the alkali resistance and abrasion resistance are remarkably improved. It can maintain the hydrophilicity of the surface for a long period of time regardless of whether it is outdoors or outdoors, and can sufficiently exhibit the effects of antifogging, low contamination, and self-cleaning.

The invention according to claim 10 uses, as the component (A), a product obtained by hydrolyzing Si (OR) ₄ of the formula (1) with 0.001 mol or more of water per 1 mol of the OR group. Therefore, it is possible to prevent deterioration of the film forming property of the coating film and decrease in the alkali resistance of the coating film.

Further, the invention of claim 11 provides that the component (A) forming the primer layer and the coating material composition forming the outermost layer each have a boiling point of 100 ° C. or higher or a vapor pressure of 53.3 hPa (40 mmHg) (25 mm). ° C) or less, since the solvent is contained in an amount of 0.1 to 70% by weight based on the total amount of the component (A) forming the primer layer or the total amount of the coating material composition forming the outermost layer, the solvent has various shapes. In addition, it is possible to select an appropriate coating method for the base material having the above, prevent whitening of the coating film, and minimize the loss of paint.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Motoharu Haruna 1048 Kazuma Kadoma, Osaka Prefecture Matsushita Electric Works Co., Ltd. F-term (reference) 4F100 AA20C AG00 AK52B AK52C AT00A BA03 BA07 BA10A BA10C CA23C EH46 GB08 GB90 JL06 JL07 YY00C 4J038 DL021 HA166 HA216 HA446 NA04 NA05 NA06 NA11 PB02 PC03

Claims (11)

[Claims] 1. In a coating material composition containing the following components (A) and (B), the component (B) has a weight ratio of 0 to the total weight of the components (A) and (B) in terms of solid content. In the range of 0.5 to 0.95,
(B) A coating material composition characterized in that the component (B) has an average primary particle size of 35 to 150 nm in terms of solid content of 10% by weight or more. Component (A): an organosilicon alkoxide represented by the general formula Si (OR) ₄ (1) (where R is the same or different, substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) Hydrolyzate and / or partial hydrolyzate (B) component: inorganic filler 2. As the inorganic filler as the component (B),
The coating material composition according to claim 1, wherein the coating material composition comprises silica. 3. The inorganic filler as the component (B),
A mixture comprising two or more kinds having different average primary particle diameters, wherein the mixture has a small average primary particle diameter and an average primary particle diameter of 5 to 40 nm. Item 3. The coating material composition according to Item 1 or 2. 4. The inorganic filler as the component (B),
4. An optical semiconductor comprising: an optical semiconductor;
The coating material composition according to any one of the above. 5. A coated article, wherein the coating composition according to claim 1 is applied to a surface of a substrate and cured to form a coating film. 6. A mirror, wherein the coating material composition according to claim 1 is applied to the surface and cured to form a coating film. 7. A bath wall, wherein the coating material composition according to any one of claims 1 to 4 is applied to a surface and cured to form a coating film. 8. A coating material formed by applying and curing the coating material composition according to claim 1 on a surface of a substrate, and adding a vapor, an alkali, an acid, and a surfactant to the coating film. A coated article characterized by being subjected to any one of treatments and immersion treatment with a heating liquid. 9. In a coated article having two or more coating films laminated on the surface of a substrate, a primer layer in contact with the surface of the substrate is formed of the following component (A), and the outermost layer is an outermost layer.
A coated article formed of the coating material composition according to any one of claims 1 to 4. Component (A): an organosilicon alkoxide represented by the general formula Si (OR) ₄ (1) (where R is the same or different, substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) Hydrolyzate and / or partial hydrolyzate 10. As the component (A), Si of the formula (1)
The coated product according to claim 9, wherein (OR) ₄ is obtained by using a product hydrolyzed with 0.001 mol or more of water per 1 mol of an OR group. 11. A component (A) for forming a primer layer,
And each of the coating material compositions forming the outermost layer have a boiling point of 100 ° C. or higher or a vapor pressure of 53.3 hPa (25
C) or lower solvent forms a primer layer (A)
The coated article according to claim 9 or 10, comprising 0.1 to 70% by weight based on the total amount of the components or the total amount of the coating material composition forming the outermost layer.