JPH10287846A - Functional inorganic paint and coated product using the same and their use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject coating that forms the coating film excellent in antifog property, antifouling property, resistance to weather, durability and coating film strength by using a specific tetrafunctional silicone resin and a curing accelerator at a certain ratio. SOLUTION: This functional inorganic coating comprises (A) a tetrafunctional silicone resin containing hydrolytic polycondensate of a tetra-functional hydrolytic organosilane of the formula: SiX4 (X is a hydrolyzable group) and a curing accelerator such as a titanium oxide sol dispersed in an organic solvent. The amount of the tetra functional silicone resin is 2-80 pts.wt. per 100 pts.wt. of the whole condensate compounds and the whole curing accelerator in total on the solid basis.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antifogging property, an antifouling property,
The present invention relates to a functional inorganic paint capable of forming a film having excellent functions such as weather resistance, durability, and film strength, a functional coated product using the same, and uses thereof.

[0002]

2. Description of the Related Art Conventionally, as a paint excellent in weather resistance, durability and the like, for example, a silicone-based inorganic paint containing a silicone resin as a base resin (binder resin) is known. The silicone resin contained in the inorganic coating is obtained, for example, by hydrolyzing and polycondensing a hydrolyzable organosilane. Examples of the hydrolyzable organosilane as a raw material include bifunctional ones such as dimethyldimethoxysilane, trifunctional ones such as methyltrimethoxysilane, and tetrafunctional ones such as tetraethoxysilane (also referred to as TEOS or tetraethylorthosilicate). is there.

However, such a silicone-based inorganic paint has the following problems. When the silicone resin contains only a hydrolyzed polycondensate of a difunctional and / or trifunctional hydrolyzable organosilane, the obtained coating film is too soft, and the coating film strength is insufficient. Due to insufficient water wettability, the surface of the coating film is easily clouded or stained by water droplets.

On the other hand, when the silicone resin contains a hydrolyzed polycondensate of a tetrafunctional hydrolyzable organosilane, the coating strength and the coating strength are higher than in the case of only the above-mentioned difunctional and / or trifunctional. Water wettability on the surface is improved. These properties are most excellent when the silicone resin contains only a hydrolytic polycondensate of a tetrafunctional hydrolyzable organosilane.

[0005]

However, a coating containing only a hydrolytic polycondensate of a tetrafunctional hydrolyzable organosilane as a silicone resin is difficult to form a film because the tetrafunctional silicone resin is bulky. At the same time, even if a film can be formed, a normal coating thickness is too hard and cracks are likely to occur. In addition, the curing speed of the coating film is low due to steric hindrance of the tetrafunctional silicone resin, and it takes a very long time to cure the coating film, especially at room temperature.

On the other hand, hydrolyzed polycondensates of bifunctional and trifunctional hydrolyzable organosilanes have the effect of improving the flexibility of the coating film and have a higher curing speed than those of tetrafunctional ones. Therefore, the bifunctional and / or trifunctional hydrolyzable organosilane hydrolyzed polycondensate
In most cases, a hydrolytic polycondensate of a functional hydrolyzable organosilane is used.

However, when a bifunctional and / or trifunctional compound is added, the water wettability of the coating film surface is reduced accordingly. Therefore, in terms of water wettability of the coating film surface, a paint containing only a tetrafunctional silicone resin is most ideal. Therefore, an object of the present invention is to form a thin film to the extent that cracks do not easily occur, and to form a thin film at a high curing speed, despite the fact that only a four-functional silicone resin is included. To provide functional inorganic paints whose coating cured films have excellent functions such as anti-fogging property, anti-fouling property, weather resistance, durability, and coating film strength, and to provide functional coated products using them and their uses. is there.

[0008]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, when the concentration of the tetrafunctional silicone resin is reduced, the film is easily formed and cracks are not easily generated. The inventors have found that a film as thin as possible can be formed, and that the curing speed can be increased by adding a curing accelerator, thereby completing the present invention.

That is, the functional inorganic coating material of the present invention comprises a tetrafunctional hydrolyzable organosilane represented by the general formula SiX ₄ (1) (where X represents the same or different hydrolyzable groups). It contains a tetrafunctional silicone resin containing a hydrolyzed polycondensate and a curing accelerator, and the compounding amount of the tetrafunctional silicone resin is 5% as a total condensed compound equivalent solid content with respect to the total amount of the paint.
0% by weight or less, and the compounding amount of the curing accelerator is 2 to 80 parts by weight based on 100 parts by weight of the total of the solid content in terms of the total condensed compound and the total curing accelerator component in the total amount of the paint. It is.

[0010] Preferably, the curing accelerator is titanium oxide. The titanium oxide is preferably a titanium oxide sol. The titanium oxide sol is preferably of an organic solvent dispersion type. The functional coated article of the present invention has a coating layer of a functional inorganic paint of the present invention having a thickness of 1 μm or less and a cured coating on the surface of the substrate.

The base material may be an inorganic base material, an organic base material, an inorganic-organic composite base material, and at least one inorganic coating and / or at least one organic coating on any one of these base materials. Selected from the group consisting of each single material of the coating base material, a composite material obtained by combining at least two of these materials, and a laminated material obtained by laminating at least two of these materials. Is preferred.

[0012] The base material may be at least one of metal, glass, hollow, ceramics, cement, concrete, wood, wood, plastic, inorganic fiber reinforced plastic, and any one of these base materials. Single material of a coating substrate having at least one inorganic coating and / or at least one organic coating, a composite material obtained by combining at least two of these, and a laminate of at least two of these materials More preferably, it is selected from the group consisting of laminated materials.

[0013] The coating on the surface of the coating substrate may be a primer layer. The functional inorganic paint and the functional coated product of the present invention have a thickness of 1 μm of the functional inorganic paint.
By equipping at least a part with the following coated and cured film, it is preferable to use it for the following applications. Building-related members (eg, glass, etc.), building gates and members for use therewith (eg, gate posts, etc.), building fences, members for use therewith, windows (eg, daylighting windows, etc.) and members for use therewith (Eg, window frames, etc.), automobiles, machinery, road peripherals (particularly traffic signs), advertising towers, outdoor or indoor lighting fixtures and members for use therewith (eg, glass, resin, metal and ceramics) Or a member made of at least one material selected from the group consisting of:

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The silicone resin contained in the functional inorganic coating material of the present invention is a tetrafunctional silicone resin containing a hydrolytic polycondensate of a tetrafunctional hydrolyzable organosilane, and is used as a binder resin and a film-forming component. It is a component that is used and imparts water wettability to a coated and cured coating of a functional inorganic paint to give the coating an antifogging property, an antifouling property by washing with rainwater, and the like.

The form of the tetrafunctional silicone resin is not particularly limited as long as it contains a hydrolyzed polycondensate of a tetrafunctional hydrolyzable organosilane. However, the tetrafunctional hydrolyzable organosilane used as a raw material of the tetrafunctional silicone resin may be one represented by the general formula (1).

X in the general formula (1) is not particularly limited as long as it is the same or different hydrolyzable groups.
For example, alkoxy, acetoxy, oxime,
Examples include an enoxy group, an amino group, an aminoxy group, and an amide group. Among these, an alkoxy group is preferred because of its availability and ease of preparation of the coating. Specific examples of the tetrafunctional hydrolyzable organosilane are not particularly limited. For example, tetrafunctional alkoxysilanes, acetoxysilanes, oximesilanes,
Examples include enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among these,
Alkoxysilanes are preferred because of their availability and ease of preparation of paints.

Specific examples of the tetrafunctional alkoxysilane are not particularly limited, and include, for example, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane and tetraisopropoxysilane. Further, an organosilane compound generally called a silane coupling agent is also included in the alkoxysilanes.

The tetrafunctional hydrolyzable organosilane may be used alone or in combination of two or more. 4
The functional silicone resin is prepared, for example, by diluting a tetrafunctional hydrolyzable organosilane with a suitable solvent, adding water as a curing agent and, if necessary, a catalyst (for example, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid). Acids and organic acids such as benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, and oxalic acid;
(A kind or two or more kinds) are added by a necessary amount (may be heated (for example, 40 to 100 ° C., if necessary)), and subjected to hydrolysis and polycondensation reaction to form a prepolymer. can do. At this time, the weight average molecular weight (Mw) of the obtained prepolymer is adjusted so as to be preferably 800 or more, more preferably 850 or more, and further preferably 900 or more in terms of polystyrene. Molecular weight distribution of prepolymer (weight average molecular weight (M
When w)) is smaller than 800, the curing shrinkage at the time of polycondensation of the tetrafunctional silicone resin is large, and the cured film tends to crack after curing.

The amount of the tetrafunctional silicone resin in the functional inorganic coating is, for example, not more than 50% by weight, preferably 0.01 to 50% by weight, in terms of the total solid content in terms of the total condensed compound, based on the total amount of the coating. Preferably 0.0
5 to 40% by weight, more preferably 0.1 to 30% by weight
Is the ratio of If the amount is less than the above preferred range, the number of defects in the coating film increases, and a dense film may not be obtained. If the content is more than 50% by weight, the film thickness cannot be reduced to such an extent that cracks do not occur, or the storage stability of the paint cannot be obtained.

The functional inorganic paint of the present invention may also contain colloidal silica as a filler, if necessary, for the purpose of increasing the hardness of the cured coating film and improving smoothness and crack resistance. it can. The colloidal silica that can be used is not particularly limited, but, for example, water-dispersible 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 using water-dispersible colloidal silica,
Water present as a component other than the solid content can be used as a curing agent as described later. The water-dispersible colloidal silica is usually made of water glass, but can be easily obtained as a commercial product. The organic solvent-dispersible colloidal silica can be easily prepared by replacing water of the water-dispersible colloidal silica with an organic solvent. Such an organic solvent-dispersible colloidal silica can be easily obtained as a commercial product similarly to the water-dispersible colloidal silica. In the organic solvent dispersible colloidal silica, the type of the organic solvent in which the colloidal silica is dispersed is, 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 derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol; and one or more selected from the group consisting of these. Can be used. Toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used in combination with these hydrophilic organic solvents.

Although the colloidal silica has the above-mentioned effects, if the amount is too large, the cured coating of the functional inorganic coating may become too hard, which may cause cracks in the coating. Therefore, when colloidal silica is used, the compounding amount thereof is preferably 40% by weight or less, more preferably 35% by weight or less, and still more preferably 30% by weight or less, based on the total amount of the coating material, for example, in terms of silica solid content. Percentage. If the amount of colloidal silica is more than the above range, cracks are likely to occur.

The curing agent used in the hydrolysis polycondensation reaction of the tetrafunctional hydrolyzable organosilane includes:
Water is used, and the amount is preferably 0.01 to 3.0 moles of water, and preferably 0.1 to 3.0 moles per 1 mole equivalent of the hydrolyzable group (X) contained in the tetrafunctional hydrolyzable organosilane.
3 to 1.5 mol is more preferred. As a diluting solvent used in the hydrolysis polycondensation reaction of the tetrafunctional hydrolyzable organosilane, methanol, ethanol, isopropanol, and the like described above as a dispersion solvent of colloidal silica are used.
lower aliphatic alcohols such as n-butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether and ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol and the like. One or two or more selected from the group consisting of these can be used. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone,
Methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be exemplified.

Further, it is preferable that the pH of the tetrafunctional silicone resin is adjusted in the range of 3.8 to 6.
If the pH is within this range, within the aforementioned molecular weight range,
A tetrafunctional silicone resin can be used stably. If the pH is out of this range, the stability of the tetrafunctional silicone resin is poor, so that the usable period from the preparation of the coating is limited. Here, the pH adjusting method is not particularly limited. For example, when mixing the raw materials of the tetrafunctional silicone resin and the pH becomes less than 3.8, a basic reagent such as ammonia is used. The pH may be adjusted to a value within the above range, and when the pH exceeds 6, for example, the pH may be adjusted using an acidic reagent such as hydrochloric acid. In addition, depending on the pH, when the reaction does not proceed with the molecular weight being small and it takes time to reach the molecular weight range, the reaction may be promoted by heating the tetrafunctional silicone resin, After the pH is lowered to proceed the reaction, the pH may be returned to a predetermined value with a basic reagent.

The functional inorganic coating composition of the present invention does not need to contain a curing catalyst, but further promotes the curing of the coating film by accelerating the condensation reaction of the tetrafunctional silicone resin. A catalyst may be included. Examples of the curing catalyst include, but are not particularly limited to, alkyl titanates; carboxylic acid metal salts such as tin octylate, dibutyltin dilaurate, and dioctyltin dimaleate; dibutylamine-2-hexoate, dimethylamine acetate, and ethanolamine acetate. Amine salts such as tetramethylammonium acetate; amines such as tetraethylpentamine; N-β-aminoethyl-γ-aminopropyltrimethoxysilane; N-β-aminoethyl-γ −
Amine silane coupling agents such as aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; lithium acetate, potassium acetate, lithium formate, sodium formate; Alkali metal salts such as potassium phosphate and potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate and titanium tetraacetylacetonate; halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane and trimethylmonochlorosilane; No. However, there is no particular limitation as long as it is effective in promoting the condensation reaction of the tetrafunctional silicone resin.

When the functional inorganic coating composition of the present invention also contains a curing catalyst, the amount thereof is preferably 10% by weight or less, more preferably 8% or less, based on the solid content in terms of the total condensed compound in the total amount of the coating composition. is there. If it exceeds 10% by weight, the storage stability of the functional inorganic paint may be impaired. When the functional inorganic paint of the present invention is heated at a low temperature or left at room temperature, the hydrolyzable groups of the tetrafunctional silicone resin undergo a condensation reaction to form a cured film. Therefore, such a functional inorganic paint is hardly affected by humidity even when it is cured at room temperature. In addition, when a heat treatment is performed, a condensation reaction can be promoted to form a cured film. The curing accelerator contained in the functional inorganic paint of the present invention is a component for accelerating the curing of the coating film (particularly, curing at normal temperature). Such a curing accelerator is not particularly limited, but, for example, 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, cobalt oxide, rhodium oxide In addition to metal oxides such as nickel oxide and rhenium oxide, strontium titanate and the like are preferable because they have a photocatalytic action as an optical semiconductor described later in addition to a hardening promoting action. Among these, the above metal oxides are preferable in that they can be easily used practically,
Among metal oxides, titanium oxide is particularly preferable in view of its curing acceleration performance, photocatalytic performance, safety, availability, and cost. When titanium oxide is used as a curing accelerator, it is better to use an anatase type (anatase type) as the crystal type because the curing acceleration performance and photocatalytic performance are the strongest, and the curing acceleration performance It is preferable in that the photocatalytic performance is expressed in a shorter time.

When transparency of the coating film is required, the average primary particle diameter of the curing accelerator is preferably 50 μm or less, more preferably 5 μm or less, and 0.5 μm or less.
More preferably, it is not more than μm. The curing accelerator is
One type may be used alone, or two or more types may be used in combination.

The curing accelerator may be in any form as long as it can be dispersed in the paint, such as powder, fine particle powder, and solution-dispersed sol particles. The curing proceeds in a shorter time, and is excellent in convenience for use. When a sol is used, the dispersion medium may be water or an organic solvent, but an organic solvent is preferable in terms of preparing a paint.

Further, a material which is a raw material of a curing accelerator may be
It is not limited as long as it finally shows the properties of the curing accelerator. As described above, the metal oxide and strontium titanate have a photocatalytic action as an optical semiconductor in addition to the hardening promoting action (these may be hereinafter referred to as a hardening promoting optical semiconductor). It is known that an optical semiconductor generates active oxygen when irradiated with ultraviolet light (photocatalytic property). Since active oxygen can oxidize and decompose organic substances, its properties are used to make use of the properties of carbon-based dirt components attached to painted products (for example, carbon fractions contained in exhaust gas from automobiles, and dust from cigarettes). Self-cleaning effect to decompose, etc .; deodorant effect to decompose malodorous components represented by amine compounds and aldehyde compounds; antibacterial effect to prevent the generation of bacterial components represented by Escherichia coli and Staphylococcus aureus; Obtainable. In addition, dirt such as organic substances repelling water adhered to the coating film surface is decomposed and removed by the photocatalytic action of the optical semiconductor, so that the wettability of the coating film with water is improved, and the anti-fog property and rainwater washing are performed. There is also an effect that antifouling property and the like can be obtained.

Further, the optical semiconductor also has an antistatic function by a photocatalytic action, and an antifouling effect can be obtained by this function. When the curing promoting optical semiconductor is used as a curing accelerator, when the coating film of the functional inorganic paint containing the same is irradiated with light, the surface resistance of the coating film is increased by the action of the curing promoting optical semiconductor contained in the coating film. By lowering, the antistatic effect is exhibited and the coating film surface is less likely to be stained, and the curing promotion action of the curing-promoting optical semiconductor increases the curing speed and the weather resistance as a film. When light is applied to the curing-promoting photo-semiconductor-containing coating film, it is not yet clearly confirmed by what mechanism the surface resistance of the coating film is lowered or the curing of the coating is promoted, It is considered that the electrons and holes generated by the light irradiation act on each other.

It is preferable that a metal is carried on the surface of the optical semiconductor, because the photocatalytic effect and the curing promoting effect of the curing-promoting optical semiconductor become higher. Although the mechanism has not yet been clearly confirmed, the metal is carried on the surface of the curing-promoting optical semiconductor to promote charge separation of the curing-promoting optical semiconductor, and electrons and holes generated by the charge separation are accelerated. This is thought to be related to the decrease in the probability of disappearance.

The metal which may be supported on the surface of the curing promoting optical semiconductor includes, for example, silver, copper, iron, nickel, zinc,
Platinum, gold, palladium, cadmium, cobalt, rhodium, ruthenium and the like are preferable in that the charge separation of the curing promoting optical semiconductor is further promoted. The supported metal may be only one kind or two or more kinds. The amount of metal carried is not particularly limited, but is, for example, 0.1 to 0.1% with respect to the curing promoting optical semiconductor.
It is preferably from 1 to 10% by weight, more preferably from 0.2 to 5% by weight. If the supported amount is less than 0.1% by weight, a sufficient supporting effect tends not to be obtained.
Even if it is carried in excess of the weight%, the effect does not increase so much, and conversely, problems such as discoloration and performance degradation tend to occur.

The method for supporting the metal is not particularly limited, and examples thereof include an immersion method, an impregnation method, and a photoreduction method. Further, a clay crosslinked body in which a curing promoting optical semiconductor is supported between layers may be used. By introducing the curing-promoting optical semiconductor between the layers, the curing-promoting optical semiconductor is supported by the fine particles, and the photocatalytic performance and the curing promoting effect are improved.

The amount of the curing accelerator in the functional inorganic coating is not particularly limited. For example, the total amount of the solid content in terms of the total condensed compound and the total curing accelerator component in the total amount of the coating is 1%.
When described as parts by weight of the curing accelerator with respect to 00 parts by weight, when no metal is supported on the surface of the curing accelerator, preferably 5 to 80 parts by weight, more preferably 10 to 10 parts by weight.
The amount is 50 parts by weight, and preferably 2 to 75 parts by weight, more preferably 5 to 45 parts by weight when a metal is supported on the surface of the curing accelerator. When the compounding amount of the curing accelerator is less than the above range, a sufficient curing promoting function (particularly, the curing promoting function at normal temperature) tends to be difficult to be obtained, and when it is more than the above range, cracks are easily generated. For example, the coating film performance tends to be reduced. In addition, when the metal is carried on the surface of the curing accelerator, the amount of the curing accelerator is not including the supported metal.

The functional inorganic paint of the present invention may be used, if necessary,
Toning is possible by further including a coloring agent such as a pigment or a dye. The pigments that can be used are not particularly limited, but include, for example, carbon black, quinacridone, naphthol red, cyanine blue, cyanine green,
Organic pigments such as Hansa Yellow; inorganic pigments such as titanium oxide, barium sulfate, red iron oxide, and composite metal oxides are preferred, and one or two or more selected from these groups may be used in combination. The dispersion of the pigment is not particularly limited, and may be a usual method, for example, a method of directly dispersing the pigment powder using a dyno meal, a paint shaker, or the like. At that time, a dispersant, a dispersing aid, a thickener, a coupling agent, and the like can be used. The amount of the pigment to be added is not particularly limited because the concealing property varies depending on the type of the pigment.
The amount is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight with respect to parts by weight. When the amount of the pigment is less than 5 parts by weight, the concealing property tends to be deteriorated, and when the amount is more than 80 parts by weight, the smoothness of the coating film may be deteriorated.

The dyes that can be used are not particularly limited, but include, for example, azo, anthraquinone, indicoid, sulfide, triphenylmethane, xanthene, alizarin, acridine, quinone imine,
And thiazole, methine, nitro and nitroso dyes. One kind selected from these groups or a combination of two or more kinds may be used. The amount of the dye added is not particularly limited because the concealing property varies depending on the type of the dye.
It is 80 parts by weight, more preferably 10 to 70 parts by weight.
When the amount of the dye is less than 5 parts by weight, the concealing property tends to be deteriorated, and when it exceeds 80 parts by weight, the smoothness of the coating film may be deteriorated.

The leveling agent, metal powder, glass powder,
Antibacterial agents, antioxidants, ultraviolet absorbers and the like may also be included in the functional inorganic coating as long as the effects of the present invention are not adversely affected. The functional inorganic paint can be used by diluting it with various organic solvents, if necessary, because of easy handling, or it may be diluted with the same organic solvent. The type of the organic solvent can be appropriately selected according to the type of the monovalent hydrocarbon group contained in each component of the silicone resin, the molecular weight of each component of the silicone resin, and the like.
Such an organic solvent is not particularly limited,
For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether; diethylene glycol such as diethylene glycol and diethylene glycol monobutyl ether Derivatives; and toluene,
Xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol and the like can be mentioned, and one or more selected from the group consisting of these can be used. it can. The dilution ratio in the organic solvent is not particularly limited, and the dilution ratio may be appropriately determined as needed.

The method of applying the functional inorganic paint is not particularly limited, and for example, various kinds of ordinary applications such as brush coating, spraying, dipping (dipping), roll, flow, curtain, knife coating, spin coating and the like. You can choose the method. The method for curing the coating film of the functional inorganic paint may be a known method, and is not particularly limited. Further, the temperature at the time of curing is not particularly limited, and can be in a wide range from room temperature to heating temperature according to the desired performance of the cured film and the heat resistance of the optical semiconductor.

The thickness of the cured coating film formed from the functional inorganic coating material may be, for example, about 1 μm or less so that cracks and peeling do not occur, but various functions of the coating film are more effectively exhibited. In order to shorten the curing time at room temperature or to make the applied cured coating adhere and stably stably for a long period, the thickness is preferably 0.001 to 1 μm, more preferably 0.001 to 0.3 μm. Preferably, 0.
001 to 0.1 μm is more preferable.

The substrate to which the functional inorganic paint of the present invention is applied (also the substrate used for the functional coated product of the present invention) is not particularly limited, but examples thereof include inorganic substrates and organic substrates. , An inorganic-organic composite substrate, and a coated substrate having at least one inorganic film and / or at least one organic film on any of these surfaces.

Examples of the inorganic substrate include, but are not particularly limited to, a metal substrate; a glass substrate; an enamel; an inorganic building material such as a water glass decorative plate and an inorganic cured product; and ceramics. The metal substrate is not particularly limited. For example, non-ferrous metals [for example, aluminum (JIS-H4000 etc.), aluminum alloys (duralumin etc.), copper, zinc etc.], iron, steel [for example, rolled steel (JIS) -G3101 etc.), hot-dip galvanized steel (JIS
-G3302 etc.), (rolled) stainless steel (JIS-G
4304, G4305, etc.), tinplate (JIS-G3)
303 etc.) and other metals in general (including alloys).

The glass substrate is not particularly limited, and examples thereof include sodium glass, Pyrex glass, quartz glass, and alkali-free glass. The enamel is obtained by baking and coating a glassy enamel on a metal surface. Examples of the base metal include a mild steel plate, a steel plate, cast iron, and aluminum, but are not particularly limited. The enamel may be a normal enamel, and is not particularly limited.

The water glass decorative board refers to, for example, a decorative board obtained by applying sodium silicate to a cement base such as slate and baking the same. The inorganic hardened material is not particularly limited. For example, a fiber reinforced cement board (J
IS-A5430, etc.), ceramic siding (JIS-
A5422), wood wool cement board (JIS-A5404)
Pulp cement board (JIS-A5414 etc.), slate / wood wool cement laminate board (JIS-A5426)
Gypsum board products (JIS-A6901 etc.), clay roof tiles (JIS-A5208 etc.), thick slate (JIS-A6901 etc.)
A5402), ceramic tile (JIS-A5209)
Etc.), concrete blocks for construction (JIS-A540)
6), terrazzo (JIS-A5411, etc.), prestressed concrete double T slab (JIS-A5412)
Etc.), ALC panel (JIS-A5416 etc.), hollow prestressed concrete panel (JIS-A6511)
Etc.), and all types of base materials obtained by curing and molding inorganic materials such as ordinary bricks (JIS-R1250 etc.).

The ceramic substrate is not particularly limited, and examples thereof include alumina, zirconia, silicon carbide, silicon nitride and the like. As an organic substrate,
Although not particularly limited, for example, plastic, wood,
Examples include wood and paper. As a plastic substrate,
Although not particularly limited, for example, a thermosetting or thermoplastic plastic such as a polycarbonate resin, an acrylic resin, an ABS resin, a vinyl chloride resin, an epoxy resin, and a phenol resin, and these plastics are reinforced with an organic fiber such as a nylon fiber. Fiber reinforced plastic (FRP).

The inorganic-organic composite substrate is not particularly limited.
Fiber reinforced plastics (FRP) reinforced with inorganic fibers such as carbon fibers, and the like. The organic film constituting the coating substrate is not particularly limited, for example, acrylic, alkyd, polyester, epoxy, urethane, acrylic silicone, chlorinated rubber, phenol, melamine, etc. A cured film of a coating material containing an organic resin may be used.

The inorganic coating constituting the coating substrate is not particularly limited, and includes, for example, a cured coating of a coating material containing an inorganic resin such as a silicone resin. When applying the functional inorganic paint of the present invention to a substrate, depending on the material or surface state of the substrate, it may be difficult to obtain adhesion or weather resistance when the functional inorganic paint of the present invention is applied as it is, If necessary, a primer layer may be previously formed on the surface of the base material before forming the coated and cured film of the functional inorganic paint of the present invention. The primer layer is not particularly limited, regardless of whether it is organic or inorganic. Examples of the organic primer layer include nylon resin, alkyd resin, epoxy resin, acrylic resin, and organic modified silicone resin (for example, acrylic silicone resin). , Chloride rubber resin, urethane resin, phenol resin,
A solid content of at least one organic resin selected from the group consisting of polyester resin and melamine resin
A cured resin layer of an organic primer composition containing 0% by weight or more is exemplified. Examples of the inorganic primer layer include a cured resin of an inorganic primer composition containing 90% by weight or more of an inorganic resin such as a silicone resin as a solid content. And the like.

Although the thickness of the primer layer is not particularly limited, it is preferably, for example, 0.1 to 50 μm, and 0.5 to 50 μm.
-10 μm is more preferred. If the thickness is too small, adhesion and weather resistance may not be obtained. If the thickness is too large, foaming may occur during drying. A substrate having at least one organic primer layer and / or inorganic primer layer on its surface is included in the category of the coated substrate. That is, the coating film on the surface of the coating substrate may be the primer layer.

The primer layer may contain a coloring agent such as a pigment or a dye for toning as required. Examples of the colorant that can be used include those described above as those that can be added to the functional inorganic paint. The preferred numerical range of the amount of the coloring agent to be added to the primer layer is the same as in the case of the above-mentioned functional inorganic coating. However, it is not based on 100 parts by weight of the total solid content in terms of the total condensed compound, but the total resin solid content 100
It is specified for parts by weight.

The form of the substrate is not particularly limited, and examples thereof include a film, a sheet, a plate, and a fiber. Further, the base material may be a molded body of a material having these shapes, or a structure partially provided with at least one of the material having the shape or the molded body. The base material may be made of the above-mentioned various materials alone, a composite material obtained by combining at least two of the above-described various materials, or a laminated material obtained by laminating at least two of the above-described various materials. May be.

Since the functional inorganic paint and the functional coated product of the present invention use only a tetrafunctional silicone resin as a film-forming component, the antifogging property, antifouling property, weather resistance,
While exhibiting excellent functions such as durability and coating strength,
Since the curing accelerator is used, the curing of the coating film proceeds in a short time, and the weather resistance of the coating film increases. Therefore, by equipping at least a part of various materials or articles with a coated cured film having a thickness of 1 μm or less of the functional inorganic paint, it can be suitably used for the following applications, for example.

Building-related members or articles, for example, exterior materials (for example, exterior wall materials, tiles such as flat tiles, Japanese tiles, metal tiles, etc.), and metal such as resin rain gutters such as PVC rain gutters and stainless steel rain gutters. Rain gutters such as rain gutters, gates and members for use therein (for example, gates, gate posts, gate walls, etc.), fences (fences) and members for use therein, garage doors,
Home terrace, door, pillar, car port, bicycle parking port, sign post, home delivery post, wiring equipment such as switchboard and switch, gas meter, interphone, TV door phone body and camera lens, electric lock, entrance pole,
Entrance, ventilation fan outlet, glass for buildings, etc .; windows (for example, daylighting windows, skylights, louvers, etc.) and members used therefor (for example, window frames, shutters, blinds, etc.), automobiles, railway vehicles, Aircraft, ships, machinery,
Road peripheral members (for example, soundproof walls, tunnel interior boards, various display devices, guardrails, car stops, railing, traffic signposts and signposts, traffic lights, post cones, etc.), advertising towers, outdoor or indoor lighting fixtures and Member to be used (for example, member made of at least one material selected from the group consisting of glass, resin, metal and ceramics), glass for solar cells, vinyl and glass house for agricultural use, outdoor unit for air conditioner , VHF / UH
Antennas such as F / BS / CS.

The functional inorganic paint of the present invention may be directly applied to at least a part of the above-mentioned various materials or articles and cured, but is not limited thereto. May be applied to the surface of a film substrate and a cured functional film may be attached to at least a part of the above-mentioned various materials or articles. As the material of the base material of such a film, for example, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, vinyl chloride resin, acrylic resin, fluororesin, polypropylene (PP) resin, and composite resin thereof The resin is not particularly limited.

[0052]

The present invention will be described in detail below with reference to examples and comparative examples. In Examples and Comparative Examples, all “parts” represent “parts by weight” and all “%” represent “% by weight” unless otherwise specified. The molecular weight is measured by GPC (gel permeation chromatography) using HLC8020 manufactured by Tosoh Corporation as a measurement model, using a standard polystyrene as a calibration curve, and calculating the converted value. In addition, this invention is not limited to a following example. <Example 1> 90 parts of an organocolloidal silica sol (trade name "OSCAL1432", manufactured by Catalysts & Chemicals, Inc., solid content 30%) in 140 parts of tetraethoxysilane was mixed with methyl alcohol 200 as a diluting solvent. Were mixed and further 90 parts of water were added and stirred. The obtained solution was heated in a 60 ° C. constant temperature bath for 5 hours to adjust the weight-average molecular weight (Mw) of the hydrolysis polycondensate as a reaction product to 1900 to prepare an alcohol solution of the hydrolysis polycondensate. Obtained.

Preparation conditions for the alcohol solution of the hydrolyzed polycondensate: [Water] / (hydrolyzable group X) molar ratio 1.86 ・ Weight average molecular weight 1900 ・ Solid content 12.9% in terms of all condensed compounds Then, a titanium oxide sol (Titanium oxide sol manufactured by Catalysis Kasei Co., Ltd .: trade name "Queen Titanic 11-1020G") as a curing accelerator was added to the total solid content in terms of the total condensed compound in the total amount of the paint and the total curing accelerator component. To 100 parts in total, the amount of the curing accelerator was 20 parts, and the mixture was added and mixed to obtain a functional inorganic paint (1).

This functional inorganic paint (1) is applied to a glass substrate washed with acetone by a spray coating method, and the coated film is dried and cured at room temperature for 150 hours to obtain a functional coated product (1). Was. The cured film had a thickness of 0.1 μm. <Example 2> The procedure of Example 1 was repeated, except that the same amount of titanium oxide powder (titanium oxide manufactured by Ishihara Sangyo Co., Ltd .: trade name “ST-01”) was used as a curing accelerator instead of titanium oxide sol. In the same manner as in Example 1, a functional inorganic paint (2) was obtained.

The functional inorganic coating material (2) is applied to a glass substrate washed with acetone by a spray coating method, and the coating film is dried and cured at room temperature for 150 hours to obtain a functional coated product (2). Was. The cured film had a thickness of 0.1 μm. <Example 3> A functional inorganic paint (3) was obtained in the same manner as in Example 1 except that the same amount of titanium oxide supporting platinum was used instead of the titanium oxide sol as a curing accelerator. Was.

The platinum was loaded on a titanium oxide powder (titanium oxide manufactured by Ishihara Sangyo Co., Ltd .: trade name "ST-01") by a photoelectrodeposition method, and 0.5% was loaded on the titanium oxide.
Next, the functional inorganic coating material (3) was applied to the glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature for 150 hours to obtain a functional coated product (3). . In addition, the thickness of the cured film is 0.1 μm.
Met. <Example 4> A functional inorganic paint (4) was prepared in the same manner as in Example 1 except that the same amount of tetramethoxysilane was used instead of tetraethoxysilane.
I got

However, the conditions for preparing the alcoholic solution of the hydrolyzed polycondensate in the step of preparing this paint were as follows. -[Water] / [Hydrolysable group X] molar ratio 1.86-Weight average molecular weight 3000-Solid content in terms of all condensed compounds 15.7% Next, a glass obtained by washing the functional inorganic paint (4) with acetone The substrate was applied by a spray coating method, and the coating film was dried and cured at room temperature for 150 hours to obtain a functionally coated product (4). In addition, the thickness of the cured film is 0.1 μm.
Met. <Example 5> 60 parts of an isocollanol-dispersed organosilica sol (trade name "OSCAL1432", manufactured by Sekiyu Kasei Kogyo KK, solid content 30%) in 130 parts of tetraethoxysilane and 200 parts of methanol as a diluting solvent And 120 parts of water was further added thereto, followed by stirring. The obtained solution was heated in a 60 ° C. constant temperature bath for 5 hours to adjust the weight average molecular weight (Mw) of the hydrolyzed polycondensate as a reaction product to 3100, thereby preparing an alcohol solution of the hydrolyzed polycondensate. Obtained.

Preparation conditions for the alcohol solution of the hydrolyzed polycondensate: [Water] / [hydrolyzable group X] molar ratio 2.67 • Weight average molecular weight 3100 • Solid content in terms of total condensed compound 10.9% This solution Then, a titanium oxide sol (Titanium oxide sol manufactured by Catalysis Kasei Co., Ltd .: trade name "Queen Titanic 11-1020G") as a curing accelerator was added to the total solid content in terms of the total condensed compound in the total amount of the paint and the total curing accelerator component. Was added and mixed in an amount of 20 parts by weight with respect to 100 parts in total of the above, to obtain a functional inorganic paint (5).

The functional inorganic paint (5) is applied to a glass substrate washed with acetone by a spray coating method, and the coated film is dried and cured at room temperature for 150 hours to obtain a functional coated product (5). Was. The cured film had a thickness of 0.1 μm. <Example 6> A functional inorganic paint (6) was obtained in the same manner as in Example 5, except that the addition amount of the titanium oxide sol used as the curing accelerator was changed to 2 parts.

The functional inorganic coating material (6) is applied to a glass substrate washed with acetone by a spray coating method, and the coating film is dried and cured at room temperature for 150 hours to obtain a functional coated product (6). Was. The cured film had a thickness of 0.1 μm. <Example 7> A functional inorganic paint (7) was obtained in the same manner as in Example 5, except that the addition amount of the titanium oxide sol used as the curing accelerator was changed to 80 parts.

The functional inorganic coating material (7) is applied to a glass substrate washed with acetone by a spray coating method, and the coating film is dried and cured at room temperature for 150 hours to obtain a functional coated product (7). Was. The cured film had a thickness of 0.1 μm. <Example 8> A functionally coated product (8) was obtained in the same manner as in Example 5, except that an aluminum substrate was used instead of the glass substrate as the base material. <Example 9> A functionally coated product (9) was obtained in the same manner as in Example 5, except that an acrylic substrate was used instead of the glass substrate as the base material. <Example 10> A functional inorganic paint (10) was obtained in the same manner as in Example 5, except that the addition amount of the titanium oxide sol used as the optical semiconductor was changed to 5 parts.

The functional inorganic paint (10) is applied to an aluminum substrate washed with acetone by a spray coating method,
By drying and curing the coating at room temperature for 150 hours,
A functionally coated product (10) was obtained. The cured film had a thickness of 0.1 μm. Example 11 To 170 parts of tetraethoxysilane, 50 parts of an acidic colloidal silica isopropanol-dispersed organosilica sol (trade name "OSCAL1432", manufactured by Catalysts & Chemicals, Inc., solid content 30%), and 100 parts of methanol as a diluting solvent Were mixed, and 180 parts of water was further added, followed by stirring. By heating the obtained liquid in a 60 ° C. constant temperature bath for 5 hours, the weight-average molecular weight (Mw) of the hydrolysis polycondensate as a reaction product was adjusted to 3600 to prepare an alcohol solution of the hydrolysis polycondensate. Obtained.

Preparation conditions for the alcohol solution of the hydrolyzed polycondensate: [Water] / [hydrolyzable group X] molar ratio 3.06 • Weight average molecular weight 3600 • Solid content in terms of total condensed compound 12.8% This solution And titanium oxide sol as a curing accelerator (Titanium oxide sol manufactured by Ishihara Sangyo Co., Ltd .: trade name "STS-01")
To a total of 100 parts of the total solid content in terms of the total condensed compound and all the curing accelerator components in the total amount of the coating composition, so that the amount of the curing accelerator becomes 20 parts.
1) was obtained.

This functional inorganic paint (11) was applied to a glass substrate washed with acetone by a spray coating method,
By drying and curing the coating at room temperature for 150 hours,
A functionally coated product (11) was obtained. The cured film had a thickness of 0.1 μm. <Example 12> 90 parts of an isocollanol-dispersed organosilica sol (trade name "OSCAL1432", manufactured by Catalysts & Chemicals, Inc., solid content 30%) in 100 parts of tetraethoxysilane and 100 parts of isopropanol as a diluting solvent , And 200 parts of water were further added thereto, followed by stirring. The obtained liquid is placed in a 60 ° C.
By heating for a period of time, the weight average molecular weight (Mw) of the hydrolyzed polycondensate as a reaction product was adjusted to 6000 to obtain an alcohol solution of the hydrolyzed polycondensate.

Conditions for preparing alcohol solution of hydrolyzed polycondensate: [Water] / [hydrolyzable group X] molar ratio 5.78 ・ Weight average molecular weight 6000 ・ Solid content 11.4% in terms of total condensed compound And titanium oxide sol as a curing accelerator (Titanium oxide sol manufactured by Ishihara Sangyo Co., Ltd .: trade name "STS-01")
To a total of 100 parts of the total solid content in terms of the total condensed compound and all the curing accelerator components in the total amount of the coating composition, so that the amount of the curing accelerator becomes 20 parts.
2) was obtained.

This functional inorganic paint (12) was applied to a glass substrate washed with acetone by a spray coating method.
By drying and curing the coating at room temperature for 150 hours,
A functionally coated product (12) was obtained. The cured film had a thickness of 0.1 μm. <Example 13> 60 parts of isopropanol-dispersed organosilica sol (trade name “OSCAL1432”, manufactured by Catalysts & Chemicals, Inc., solid content 30%) in 100 parts of tetraethoxysilane and 100 parts of isopropanol as a diluting solvent , And 60 parts of water was further added thereto, followed by stirring. By heating the obtained liquid in a 60 ° C. constant temperature bath for 5 hours, the weight average molecular weight (Mw) of the hydrolysis polycondensate as a reaction product was adjusted to 1800, and the alcohol solution of the hydrolysis polycondensate was removed. Obtained.

Preparation conditions for the alcohol solution of the hydrolyzed polycondensate: [Water] / [hydrolyzable group X] molar ratio 1.73 • Weight average molecular weight 1800 • Solid content 14.6% in terms of total condensed compound Then, a titanium oxide sol (Titanium oxide sol manufactured by Catalysis Kasei Co., Ltd .: trade name "Queen Titanic 11-1020G") as a curing accelerator was added to the total solid content in terms of the total condensed compound in the total amount of the paint and the total curing accelerator component. The functional inorganic paint (13) was obtained by adding and mixing the curing accelerator in an amount of 20 parts with respect to 100 parts in total.

This functional inorganic paint (13) was applied to a glass substrate washed with acetone by a spray coating method.
By drying and curing the coating at room temperature for 150 hours,
A functionally coated product (13) was obtained. The cured film had a thickness of 0.1 μm. <Example 14> A functionally coated product (14) was obtained in the same manner as in Example 13, except that the film thickness after curing of the coating film was changed to 1.0 µm. <Example 15> In Example 13, the coating method was changed to a spin coating method, and the film thickness after curing of the coating film was changed to 0.01 μm.
Except having changed to m, the same operation as Example 13 was performed to obtain a functionally coated product (15). <Example 16> In Example 13, the coating method was changed to the spin coating method, and the thickness of the cured film was set to 0.05 μm.
Except having changed to m, the same operation as Example 13 was performed, and the functional coating product (16) was obtained. <Example 17> A functional coated product (17) was obtained in the same manner as in Example 13, except that the thickness of the cured film was changed to 0.03 µm. <Example 18> In Example 13, a pigment (white pigment manufactured by Ishihara Sangyo Co., Ltd.) was added to the functional inorganic paint (13) in an amount of 45 parts based on 100 parts by weight of the total condensed compound in the total amount of the paint.
The functional inorganic paint (18) was obtained by adding a part thereof.

The functional inorganic coating material (18) was applied to a glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature for 150 hours to obtain a functional coated product (18). . The cured film had a thickness of 0.1 μm. <Comparative Example 1> A functional inorganic paint for comparison (1) was obtained in the same manner as in Example 1 except that no curing accelerator was used.

The comparative functional inorganic paint (1) was applied to a glass substrate washed with acetone by a spray coating method, and the coating was dried and cured at room temperature for 150 hours to obtain a functional paint (1) for comparison. ) Got. The cured film had a thickness of 0.1 μm. <Example 19> After thoroughly washing the hood of Toyota Sprinter (automobile; 1990 model) with acetone, the functional inorganic paint (18) obtained in Example 18 was cured by spray coating to obtain a cured coating thickness. It was applied to a thickness of 0.05 μm and dried and cured at room temperature for 24 hours to obtain a functionally coated product (19). Example 20 A part (10 m ² ) of the south side of the main building of Matsushita Electric Works, Ltd. (building; Kadoma City, Osaka) was washed with hydrofluoric acid, and further sufficiently washed with acetone. A functional inorganic paint (18) is applied by a spray coating method so as to have a cured coating thickness of 0.1 μm, and is dried and cured at about 20 ° C. at an outside temperature for 24 hours to obtain a functional coated product (20).
I got <Example 21> A lighting window (model M) manufactured by Matsushita Electric Works, Ltd.
WT2025JH), a functional inorganic paint (18) obtained in Example 18 was applied by a spray coating method so as to have a cured film thickness of 0.1 μm, and dried and cured at room temperature for 24 hours. A functionally coated product (21) was obtained. <Example 22> A part of the entire glass (about 250 cm) of the draft in the intermediate laboratory on the site of Osaka Kadoma, Matsushita Electric Works, Ltd.
² ) The functional inorganic paint (18) obtained in Example 18
Was applied by a spray coating method so as to have a cured coating thickness of 0.1 μm, and was dried and cured at room temperature for 24 hours to obtain a functionally coated product (22). <Example 23> The functional inorganic paint obtained in Example 18 (approximately 1400 cm ² ) was applied to a part of a road sign (approximately 1400 cm ² ) with a size of 600 mmφ and a height of 1200 mm inside Matsushita Electric Works Osaka Kadoma. 18) was applied by a spray coating method so as to have a cured coating thickness of 0.5 μm, and was dried and cured at room temperature for 24 hours to obtain a functionally coated product (23). <Example 24> The functional inorganic paint (18) obtained in Example 18 was spray-coated on a window glass (1 m ² , 6 mm thick) of a building on the site of Osaka Kadoma, Matsushita Electric Works, Ltd. By applying the cured coating to a thickness of 1.0 μm and drying and curing at room temperature for 24 hours, a functional coated product (2
4) was obtained. <Example 25> The functional inorganic substance obtained in Example 18 was applied to a part of the entire glass, poles, and fixtures of a road lighting fixture (model YA32020) installed at the main gate of Matsushita Electric Works, Ltd. Osaka Kadoma. The coating material (18) was applied by a spray coating method so as to have a cured film thickness of 0.1 μm, and was dried and cured at room temperature for 24 hours to obtain a functional coated product (25). <Example 26> Fuji-type fluorescent light fixture (model FA22) installed in a kitchen of an in-house cafeteria on the site of Osaka Kadoma, Matsushita Electric Works, Ltd.
063), the functional inorganic paint (18) obtained in Example 18 was applied to a part of the reflection plate by a spray coating method to obtain a cured coating film thickness of 0.
It was applied so as to have a thickness of 1 μm, and was dried and cured at room temperature for 24 hours to obtain a functionally coated product (26). <Example 27> In Example 1, as a curing accelerator,
A functional inorganic paint (27) was obtained in the same manner as in Example 1 except that the same amount of strontium titanate (a reagent manufactured by Furuuchi Chemical Co., Ltd.) was used instead of the titanium oxide sol.

This functional inorganic paint (27) was applied to a glass substrate washed with acetone by a spray coating method.
By drying and curing the coating at room temperature for 150 hours,
A functionally coated product (27) was obtained. The cured film had a thickness of 0.1 μm. <Example 28> In Example 1, as a curing accelerator,
Instead of titanium oxide sol, a 1: 1 mixture by weight of titanium oxide (trade name “ST-01” manufactured by Ishihara Sangyo Co., Ltd.) and zinc oxide (trade name “reagent ZnO” manufactured by Nacalai Tesque, Inc.) Was used in the same manner as in Example 1 except that the same amount was used to obtain a functional inorganic paint (28).

This functional inorganic paint (28) was applied to a glass substrate washed with acetone by a spray coating method.
By drying and curing the coating at room temperature for 150 hours,
A functionally coated product (28) was obtained. The cured film had a thickness of 0.1 μm. <Example 29> A functional inorganic paint (29) was obtained in the same manner as in Example 1, except that the same amount of tetra-n-propoxysilane was used instead of tetraethoxysilane.

However, the conditions for preparing the alcohol solution of the hydrolyzed polycondensate in the step of preparing this paint were as follows. -[Water] / [hydrolyzable group X] molar ratio 2.36-Weight average molecular weight 1500-Solid content in terms of total condensed compound 11.3% Spray this functional inorganic paint (29) on a glass substrate washed with acetone. It was applied by a coating method, and the coating was dried and cured at room temperature for 150 hours to obtain a functionally coated product (29). In addition, the thickness of the cured film is 0.1 μm.
m. <Example 30> A functional inorganic paint (30) was prepared in the same manner as in Example 1 except that no colloidal silica was used and 10 parts of 0.1N HCl was used instead. I got

However, the conditions for preparing the alcohol solution of the hydrolyzed polycondensate in the step of preparing this coating material were as follows. -[Water] / [hydrolyzable group X] molar ratio 2.06-Weight average molecular weight 2000-Solid content in terms of all condensed compounds 7.61% Spray this functional inorganic paint (30) on a glass substrate washed with acetone. The functional coating product (30) was obtained by applying the coating method and drying and curing the coating film at room temperature for 150 hours. In addition, the thickness of the cured film is 0.1 μm.
m. <Example 31> A functional inorganic paint (31) was obtained in the same manner as in Example 1, except that the amount of tetraethoxysilane was changed to 350 parts.

However, the conditions for preparing the alcohol solution of the hydrolyzed polycondensate in the step of preparing the paint were as follows. -[Water] / [hydrolyzable group X] molar ratio 1.86-Weight-average molecular weight 2000-Solid content 48% in terms of total condensed compounds This functional inorganic paint (31) is spray-coated on a glass substrate washed with acetone. Then, the coated film was dried and cured at room temperature for 150 hours to obtain a functionally coated product (31). In addition, the thickness of the cured film is 0.1 μm.
m. <Example 32> An epoxy-based primer (Isamu Paint Co., Ltd., trade name "E-1") was applied to the surface of a glass plate washed with acetone.
Primer ") was applied to a thickness of about 10 μm, and then the functional inorganic paint (1) obtained in Example 1 was cured to a thickness of 0.1 μm.
It was applied by a spray coating method so as to have a thickness of 1 μm, and then dried and cured at room temperature for 150 hours to obtain a functionally coated product (32). <Comparative Example 2> A comparative functional inorganic paint (2) was obtained in the same manner as in Example 1 except that the addition amount of the curing accelerator was changed to 1 part.

The comparative functional inorganic paint (2) was applied to a glass substrate washed with acetone by a spray coating method, and the coated film was dried and cured at room temperature for 150 hours to obtain a comparative functional coated product (2). ) Got. The cured film had a thickness of 0.1 μm. Comparative Example 3 A comparative functional inorganic paint (3) was obtained in the same manner as in Example 1, except that the amount of the curing accelerator was changed to 85 parts.

The comparative functional inorganic paint (3) was applied to a glass substrate washed with acetone by a spray coating method, and the coated film was dried and cured at room temperature for 150 hours to obtain a comparative functional paint (3). ) Got. The cured film had a thickness of 0.1 μm. <Comparative Example 4> A comparative functional coated article (4) was obtained in the same manner as in Example 1 except that the thickness of the cured film was changed to 3 µm. <Comparative Example 5> A comparative functional inorganic paint (5) was obtained in the same manner as in Example 1, except that the amount of tetraethoxysilane was changed to 400 parts.

However, the conditions for preparing the alcohol solution of the hydrolyzed polycondensate in the step of preparing this paint were as follows. -[Water] / [hydrolyzable group X] molar ratio 0.65-Weight average molecular weight 2500-Solid content in terms of total condensed compounds 60% This functional inorganic paint for comparison (5) is sprayed on a glass substrate washed with acetone. It was applied by a coating method, and the coating film was dried and cured at room temperature for 150 hours to obtain a functional coated product for comparison (5). The cured film had a thickness of 0.1 μm.

The performances of the paints and coated articles obtained as described above were evaluated by the following methods. <Evaluation method> (Coating film performance): Evaluated by a boiling test described in JIS-K5400.

(Wetability with water): Evaluation was made by measuring the contact angle between water and the cured film. The contact angle was measured by dropping 0.2 cc of distilled water on the surface of the coating film and then observing it with a magnifying camera. (Evaluation of a product coated on an article or the like): The evaluation was made based on the difference in stains between the painted portion and the unpainted portion after 3 months from the painting. The results are shown in Tables 1 and 2.

[0081]

[Table 1]

[0082]

[Table 2]

In Examples 19 to 26, adhesion of dirt on the painted portion was hardly observed as compared with the unpainted portion.

[0084]

The functional inorganic coating material of the present invention has a low concentration, despite containing only a four-functional silicone resin, and is easy to form into a film. It can be formed. In addition, since a curing accelerator is included, the curing time of the coating film is shortened, so that the weather resistance of the coating film is high, and the coating film is hardly damaged. This curing acceleration effect is particularly remarkable at room temperature as compared with the case where no curing accelerator is used. Since the paint of the present invention is an inorganic paint, the performance of the coating film is hardly impaired by the addition of a curing accelerator. Since only four-functional silicone resins are included, the formed cured coating film has antifogging property, antifouling property, weather resistance, durability,
Excellent functions such as coating film strength. Further, it can be toned in various colors.

The functional inorganic paint of the present invention can control various functions, curing performance, coating film properties, etc. according to the intended use by changing the ratio of the resin and the curing accelerator contained therein. it can. The functional inorganic coating material of the present invention can be cured not only by heat but also at room temperature, and can be used in a wide range of dry curing conditions or temperature. Therefore, not only can a substrate having a shape difficult to apply heat uniformly, a substrate having a large size or a substrate having poor heat resistance be coated, but also when performing a coating operation outdoors or the like. If it is difficult to apply heat,
Its industrial value is high because it can be painted even if it does not take a long time to cure.

Since the functional coated article of the present invention is provided with a coated and cured film of the above-mentioned functional inorganic coating on the surface of the substrate, it is excellent in functions such as antifogging property, antifouling property and coating film strength. At the same time, the curing time of the coating film at ordinary temperature can be shortened as compared with the case where no curing accelerator is used. Further, the performance of the coating film is hardly impaired by the addition of a curing accelerator, the weather resistance, the durability and the like are excellent, and the film is hardly damaged. Since the thickness of the applied cured film is within the above-mentioned specific range and is thin, cracks are unlikely to occur. Further, since it can be manufactured using the above-mentioned functional inorganic paint capable of toning in various colors, the design is high and the range of use is wide.

The functional coated product of the present invention can be prepared by changing the ratio of the resin and the curing accelerator contained in the functional inorganic coating used for the production thereof to obtain various functionalities, curing performance, It is possible to control the characteristics of the coating film. The functional coated article of the present invention can be produced using the above-mentioned functional inorganic paint which is not only heat-curable but also can be cured at room temperature and is fast, so that it can be produced in a wide range of drying and curing conditions or temperature. Therefore, it is possible to use a base material having a shape that is difficult to apply heat evenly, a base material having a large size, a base material having poor heat resistance, and the like. Its industrial value is high because it can be manufactured in places where long time cannot be spent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 5/00 C09D 5/00 Z 7/12 7/12 Z

Claims (24)

[Claims] 1. A tetrafunctional compound comprising a hydrolytic polycondensate of a tetrafunctional hydrolyzable organosilane represented by the general formula: SiX ₄ (1) (where X represents the same or different hydrolyzable groups). It contains a silicone resin and a curing accelerator, and the compounding amount of the tetrafunctional silicone resin is 5% as the total solid content in terms of the total condensation compound with respect to the total amount of the paint.
0% by weight or less, and the compounding amount of the curing accelerator is 2 to 80 parts by weight based on 100 parts by weight of the total of the solid content in terms of the total condensed compound and the total curing accelerator component in the total amount of the paint. Is a functional inorganic paint. 2. The functional inorganic paint according to claim 1, wherein the curing accelerator is titanium oxide. 3. The titanium oxide is a titanium oxide sol,
The functional inorganic paint according to claim 2. 4. The functional inorganic paint according to claim 3, wherein the titanium oxide sol is of an organic solvent dispersion type. 5. A functionally coated product comprising a coating layer comprising a cured coating having a thickness of 1 μm or less of the functional inorganic coating according to any one of claims 1 to 4 on the surface of a substrate. 6. The base material may be an inorganic base material, an organic base material, an inorganic-organic composite base material, or at least one layer of an inorganic coating and / or at least one layer of an organic material on any one of these base materials. Selected from the group consisting of each single material of a coating substrate having a coating, a composite material obtained by combining at least two of these materials, and a laminated material obtained by laminating at least two of these materials. The functionally coated article according to claim 5, wherein 7. The base material may be metal, glass, hollow, ceramics, cement, concrete, wood, wood, plastic, inorganic fiber reinforced plastic, or any one of these base materials. A single material of a coating substrate having at least one inorganic coating and / or at least one organic coating, a composite material obtained by combining at least two of these, and a laminate of at least two of these materials The functionally coated article according to claim 6, wherein the functionally coated article is selected from the group consisting of: 8. The functional coated product according to claim 6, wherein the coating film on the surface of the coating substrate is a primer layer. 9. A building-related member comprising at least a part of the functional inorganic paint according to any one of claims 1 to 4 and a cured coating having a thickness of 1 μm or less. 10. The building-related member according to claim 9, which is glass. 11. A building gate provided with at least a part of the functional inorganic paint according to any one of claims 1 to 4 having a cured coating having a thickness of 1 μm or less. 12. A portal for use in the portal according to claim 11. 13. A building fence provided at least in part with a cured coating of the functional inorganic coating according to any one of claims 1 to 4 having a thickness of 1 μm or less. 14. A member for use in the fence according to claim 13. 15. A window provided at least in part with a cured coating of the functional inorganic paint according to any one of claims 1 to 4 having a thickness of 1 μm or less. 16. The window according to claim 15, which is a daylighting window. 17. A window frame for use in a window according to claim 15. 18. An automobile comprising at least a part of the functional inorganic paint according to any one of claims 1 to 4, which is provided with a cured coating having a thickness of 1 μm or less. 19. A mechanical device comprising at least a part of the functional inorganic paint according to any one of claims 1 to 4, which is provided with a cured coating having a thickness of 1 μm or less. 20. A road peripheral member comprising at least a part of the functional inorganic paint according to any one of claims 1 to 4 and a cured coating having a thickness of 1 μm or less. 21. The road peripheral member according to claim 20, which is used as a traffic sign. 22. An advertising tower comprising at least a part of the functional inorganic paint according to any one of claims 1 to 4 and a cured coating having a thickness of 1 μm or less. 23. A luminaire comprising at least a part of the functional inorganic paint according to any one of claims 1 to 4, which is provided with a cured coating having a thickness of 1 μm or less. 24. A member used for the lighting apparatus according to claim 23, wherein the member is made of at least one material selected from the group consisting of glass, resin, metal and ceramics.