JP2000007991A - Functional inorganic coating material, its preparation and functional coating product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating material with high water repellency by adding a specific amount of a metal oxide powder having a specific particle size to an inorganic coating material containing a silicone resin as a main component. SOLUTION: A metal oxide powder in which a primary particle size is not more than 30 nm in a number average size is added in an amount 40-80 pts.wt. to total 100 pts.wt. of all condensation compounds and the metal oxide in terms of solid content. The metal oxide is preferably titanium oxide, silicon oxide and aluminum oxide. A silicate resin is a hydrolyzed polycondensate of a mixture containing 0-60 pts.wt. of Si(OR1)4 and/or 20-200 pts.wt. of colloidal silica to 100 pts.wt. of R2Si(OR1)3 and an organosiloxane having a wt. average mol.wt. not less than 900 in terms of polystyrene is more preferable. Wherein R1 and R2 are each a hydrocarbon group. The metal oxide is preferably added during hydrolysis and polymerization processes among preparation processes of the silicone resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a functional inorganic paint having a very high water repellency, a method for producing the paint, and a functional coated product using the same.

[0002]

2. Description of the Related Art Fluorine paints are very well known as functional paints having high water repellency. However, since the fluorine paint has a very soft coating film, it is easily scratched. If dirt enters the scratch, it becomes difficult to remove the dirt even with a water-repellent coating film. On the other hand, an inorganic coating containing a silicone resin as a main component has a higher hardness of a coating film as compared with a fluorine coating and is less likely to be damaged, and has excellent functions such as weather resistance. Then, it was considered to increase the water repellency of such an inorganic paint. That is, by adding a component having high water repellency to such an inorganic coating, the water repellency of the coating film surface is ensured. However, in this method, since a water-repellent component on the surface of the coating film is used, the water-repellent paint has a contact angle with water of about 110 ° at most.

[0003]

The contact angle with water is 110 °.
With such a degree of water repellency, there was a problem that rain streaking and the like became conspicuous and dirt easily adhered. Therefore, an object of the present invention is to increase the water repellency of an inorganic paint containing a silicone resin as a main component.

[0004]

Means for Solving the Problems In order to solve the above problems, the functional inorganic coating of the present invention is an inorganic coating containing a silicone resin as a main component, and has a primary particle diameter (hereinafter, referred to as a number average particle diameter). A powder of a metal oxide having a primary particle diameter of 30 nm or less is used in an amount of 40 to 80 parts by weight on a solid basis with respect to a total of 100 parts by weight of all the condensed compounds and all the metal oxides in the total amount of the paint. It is characterized by containing by weight.

[0005] In the present specification, the amounts of each component of the silicone resin and the amount of the metal oxide in the functional inorganic coating are as follows.
All are on a solids basis. The metal oxide used in the present invention is preferably at least one metal oxide selected from the group consisting of titanium oxide, silicon oxide and aluminum oxide.

[0006] The silicone resin used in the present invention comprises:
The following silicone resin (1) or (2)
preferable. The silicone resin (1) has the following component (A)
including. Component (A): (A₁) General formula R^TwoSi (OR¹)_ThreeIn table
(A)_Two) General
The formula Si (OR¹)_FourAnd / or a silicon compound represented by
Or 20 to 200 parts by weight of colloidal silica;_Three)
General formula R^Two _TwoSi (OR¹) _TwoA silicon compound represented by
0 to 60 parts by weight of a hydrolyzable mixture (wherein
R ¹, R^TwoRepresents a monovalent hydrocarbon group).
A weight average molecular weight of the hydrolyzed polycondensate.
Is adjusted to be 900 or more in terms of polystyrene.
Organosiloxane (hereinafter referred to as “organosiloxane”
Loxane (A) ").

[0007] The silicone resin (2) comprises the following (B):
At least 50 mol% of the hydrolyzable organosilane as a raw material of the component (B) contains the components (C), (D) and (E), and is m = 1. Component (B): represented by the general formula R ³ _m SiX _4-m (I) (where R ³ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , M is an integer of 0 to 3, and X represents a hydrolyzable group.) The hydrolyzable organosilane is dissolved in an organic solvent, water or a mixed solvent thereof per 1 molar equivalent of the hydrolyzable group (X). An organosilane oligomer partially hydrolyzed under conditions using 0.001 to 0.5 mol of water (hereinafter, this may be referred to as "organosilane oligomer (B)"). Component (C): represented by the average composition formula R ⁴ _a Si (OH) _b O _{(4-ab) / 2} ... (II) (where R ⁴ is the same or different and substituted or unsubstituted and has 1 to 1 carbon atoms) 8 represents a monovalent hydrocarbon group, wherein a and b are respectively 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦
3, a number that satisfies the relationship of a + b <4. ), A polyorganosiloxane containing a silanol group in the molecule (hereinafter sometimes referred to as “(silanol group-containing) polyorganosiloxane (C)”). Component (D): silica (hereinafter sometimes referred to as “silica (D)”). Component (E): curing catalyst (this may be hereinafter referred to as “curing catalyst (E)”).

The component (B) of the silicone resin (2) can be prepared by adding the component (D) to an organic solvent, water or a mixed solvent thereof.
In colloidal silica in which the components are dispersed, the hydrolyzable organosilane is partially hydrolyzed under the condition of using 0.001 to 0.5 mol of water per 1 mol equivalent of the hydrolyzable group (X). Preferably, the silica-dispersed organosilane oligomer contains the component (D) in an amount of 5 to 95% by weight as a solid content based on the total amount of the components (B) and (D).

The method for producing a functional inorganic paint of the present invention is a method for producing the functional inorganic paint of the present invention, wherein the metal oxide is added during the hydrolysis and polymerization of the silicone resin. Features. The functionally coated product of the present invention is one in which a functional inorganic coating is formed on the surface of the substrate by applying the functional inorganic coating of the present invention to the substrate.

[0010] The substrate used in the present invention may be metal, glass, hollow, ceramics, cement, concrete, or the like.
G, wood, wood, plastic, inorganic fiber reinforced plastic, each single material of a coating substrate having at least one inorganic coating and / or at least one organic coating on the surface of any one of these substrates, A composite material obtained by combining at least two of these, and
It is preferable that at least two of these are selected from the group consisting of laminated materials.

The coating film on the surface of the coating substrate may be a primer layer.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The functional inorganic coating of the present invention is obtained by adding a metal oxide powder having a primary particle diameter of 30 nm or less to an inorganic coating containing a silicone resin as a main component, on a solid basis.
Total 1 of all condensed compounds and all metal oxides in the total amount of paint
It is presumed that very fine irregularities are formed on the surface of the coating film to be formed by containing 40 to 80 parts by weight with respect to 00 parts by weight. Shows very high water repellency.

To produce the functional inorganic coating of the present invention,
A production method comprising a step of hydrolyzing and polymerizing a silicone resin. In this hydrolysis and polymerization step, a metal oxide powder having a primary particle size of 30 nm or less is used in a total amount of a coating material on a solid basis on a solid basis. It is preferable to add the condensed compound and all metal oxides in an amount of 40 to 80 parts by weight based on 100 parts by weight in total. By adding in this manner, the uniformity of the resin and the metal oxide powder is enhanced, and a paint having higher water repellency can be obtained.

As the powder of the metal oxide, any powder having a primary particle diameter of 30 nm or less may be used. When the primary particle diameter exceeds 30 nm, there is a problem that the irregularities estimated to be formed become too large. The primary particle diameter of the metal oxide powder is preferably 10 nm or less. The metal oxide may be in any form as long as it is in a powder state such as a fine particle powder. The metal oxide is preferably at least one selected from the group consisting of titanium oxide, silicon oxide and aluminum oxide. The reason for this is that these metal oxides are practically and easily available and that those in the form of fine particles can be easily obtained.

The powder of the metal oxide is based on solids,
Total 1 of all condensed compounds and all metal oxides in the total amount of paint
It is added so as to be 40 to 80 parts by weight with respect to 00 parts by weight. If the amount of the metal oxide is less than this range, there is a problem that unevenness is not formed, and if the amount is large, there is a problem that a coating film is not formed. The silicone resin contained in the functional inorganic coating used in the present invention is used as a film-forming component.

As the silicone resin, the component (A) is used in view of the point that it does not deteriorate with time even if a metal oxide is mixed therein, the weather resistance and hardness of the obtained coating film, and the point of maintaining the water repellent effect. Silicone resin (1), which does not deteriorate with time even when mixed with a metal oxide, has room temperature (normal temperature) curability, and has excellent weather resistance, hardness and water repellency of the resulting coating film. From the viewpoint of maintaining the effect, the above (B), (C),
Silicone resin containing components (D) and (E) (2)
It is preferred that These silicone resins (1)
Among them, the silicone resin (1) is particularly preferable from the viewpoint of obtaining a coating film having a higher hardness.

In the following, first, a silicone resin (1)
Each component will be described. As the raw material of the component (A) contained in the silicone resin (1), that is, the organosiloxane (A), the silicon compound (A ₁ )
A hydrolyzable mixture containing (A ₃ ) is used. Silicon compounds other than colloidal silica (A ₁ )
(A ₃₎ of the general formula ^{_{R 2 p Si (OR 1)}} 4-p ... can be grossly represented by (III) (wherein R ^1, R ² represents a monovalent hydrocarbon group, p Is an integer of 0 to 2).

R ² is not particularly limited, and includes, for example, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms. Specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl,
Alkyl groups such as heptyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aralkyl groups such as 2-phenylethyl group, 2-phenylpropyl group and 3-phenylpropyl group; phenyl group and tolyl group Aryl group; alkenyl group such as vinyl group and allyl group; chloromethyl group, γ-chloropropyl group, 3,3,
Halogen-substituted hydrocarbon groups such as 3-trifluoropropyl group; substituted hydrocarbon groups such as γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group, etc. Can be exemplified. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of ease of synthesis or availability.

Further, R ¹ is not particularly limited, and for example, those using an alkyl group having 1 to 4 carbon atoms as a main raw material are used. In particular, tetramethoxysilane, tetraethoxysilane and the like can be exemplified as the tetraalkoxysilane with p = 0, and methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane as the organotrialkoxysilane with p = 1 Phenyltrimethoxysilane, phenyltriethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane. Examples of the diorganodialkoxysilane having p = 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.

These R ¹ and R ² may be the same or different among the silicon compounds (A ₁ ) to (A ₃ ). The organosiloxane (A) is prepared by, for example, diluting the hydrolyzable mixture 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, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, oxalic acid, and other organic acids and inorganic acids, or one or more of them). A necessary amount is added (at this time, the metal oxide powder is also preferably added in a necessary amount).
To 100 ° C.), and a hydrolysis and polycondensation reaction are performed to form a prepolymer. At that time, the weight average molecular weight (Mw) of the obtained prepolymer (hydrolyzed polycondensate) is adjusted to be 900 or more, preferably 1000 or more in terms of polystyrene. When the molecular weight distribution (weight average molecular weight (Mw)) of the prepolymer is smaller than 900, the curing shrinkage at the time of polycondensation of the silicone resin (1) is large, and cracks are easily generated in the coating film after curing. .

The amounts of the raw materials (A ₁ ) to (A ₃ ) used in preparing the organosiloxane (A) are based on the solid content.
(A ₁₎ with respect to 100 parts by weight, (A ₂₎ 20~200
Parts by weight, (A ₃ ) 60 parts by weight or less (preferably 40 parts by weight or less, more preferably 30 parts by weight or less). If the amount of (A ₂ ) used is smaller than the above range, or if the amount of (A ₃ ) used is larger than the above range, there is a problem that the desired hardness of the cured film cannot be obtained (the hardness becomes low). . On the other hand, if the amount of (A ₂ ) is more than the above range, the cured film has too high a cross-linking density and too high a hardness, so that there is a problem that cracks are easily generated.

As the raw material (A ₂ ), the general formula Si
Only one or both of the silicon compound and colloidal silica represented by (OR ¹ ) ₄ are used. Silica has the effect of increasing the hardness of the applied cured film of the functional inorganic paint and improving smoothness and crack resistance.
The colloidal silica that can be used is not particularly limited, and 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 water-dispersible colloidal silica is used, 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 not particularly limited. For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene Ethylene glycol derivatives such as glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. Alternatively, two or more kinds 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.

When colloidal silica is used as at least a part of the raw material (A ₂ ), the amount of the colloidal silica contained in the above-mentioned amount of (A ₂ ) is a part by weight as a silica component. Further, silica may be added to the organosiloxane (A) prepared without using any silica, if necessary, or even if silica is used for the preparation of the organosiloxane (A), Silica may be additionally mixed with the organosiloxane (A) as necessary. As silica that can be used in those cases,
There is no particular limitation, and known ones can be used. In addition, the form of silica at that time is not particularly limited, and may be, for example, the form of the colloidal silica.

Although silica has the above-mentioned effects, if the amount is too large, the cured coating of the functional inorganic coating may be too hard, which may cause cracks in the coating. Therefore, the blending amount of silica in the total amount of the coating material using the silicone resin (1) is preferably 1 to 50% by weight as a solid content with respect to the total amount of the component (A).
More preferably 10 to 50% by weight, still more preferably 1 to 50% by weight.
It is contained in the range of 0 to 30% by weight. This content is 1
When the amount is less than the weight%, a desired film hardness tends to be not obtained. On the other hand, if it exceeds 50% by weight, cracks are likely to occur.

Water is used as a curing agent for the hydrolytic polycondensation reaction of the hydrolyzable mixture, which is a raw material of the organosiloxane (A), and the amount of water is used in the hydrolyzable mixture. per group OR ¹ 1 molar equivalent contained, water 0.01-3.0 mol are preferred, 0.3
1.5 mol is more preferred. As the diluting solvent used in the hydrolysis polycondensation reaction of the hydrolyzable mixture, methanol, ethanol, isopropanol, n-butanol, as described above as the dispersion solvent for colloidal silica,
Lower aliphatic alcohols such as 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. 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 mentioned.

Further, it is preferable that the pH of the organosiloxane (A) is adjusted within a range of 3.8 to 6.
If the pH is within this range, within the above-mentioned range of molecular weight,
The organosiloxane (A) can be used stably. If the pH is out of this range, the stability of the organosiloxane (A) is poor, so that the usable period from the time of preparing the paint is limited. Here, the method for adjusting the pH is not particularly limited. For example, when the pH of the organosiloxane (A) becomes less than 3.8 when the raw materials are mixed, a basic reagent such as ammonia may be used. The pH may be adjusted to a value within the above range, and when the pH exceeds 6, it may be adjusted using, for example, an acidic reagent such as hydrochloric acid. In addition, depending on the pH, when the reaction does not proceed while the molecular weight is small and it takes time to reach the molecular weight range, the organosiloxane (A) may be heated to accelerate the reaction, After the reaction is advanced by lowering the pH with a reagent, the pH may be returned to a predetermined pH with a basic reagent.

The silicone resin (1) does not need to contain a curing catalyst, but may further contain a curing catalyst if necessary for the purpose of accelerating the curing of the coating film by accelerating the condensation reaction of the component (A). Can be included. The curing catalyst is not particularly limited, for example, alkyl titanates; tin octylate, dibutyltin dilaurate,
Carboxylic acid metal salts such as dioctyltin dimaleate; amine salts such as dibutylamine-2-hexoate, dimethylamine acetate, and ethanolamine acetate;
Quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate; amines such as tetraethylpentamine;
Amine silane coupling agents such as N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane; p-toluenesulfonic acid, phthalic acid, hydrochloric acid, etc. Acids; aluminum compounds such as aluminum alkoxides and aluminum chelates; lithium acetate, potassium acetate, lithium formate, sodium formate, potassium phosphate;
Alkali metal salts such as potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate, and titanium tetraacetylacetonate; and halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane, and trimethylmonochlorosilane. However, other than these, there is no particular limitation as long as it is effective for accelerating the condensation reaction of the component (A).

When the silicone resin (1) also contains a curing catalyst, its amount is preferably 10% by weight or less, more preferably 8% by weight, based on the total condensed compound of the organosiloxane (A), based on the solid content. % By weight or less. If it exceeds 10% by weight, the storage stability of the functional inorganic paint may be impaired. When the silicone resin contained in the functional inorganic coating is the silicone resin (1), the functional inorganic coating may be heated at a low temperature or left at room temperature to cause the hydrolyzable groups of the component (A) to be separated from each other. 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. Further, by performing the heat treatment, a condensation reaction can be promoted to form a cured film.

Next, each component of the silicone resin (2) will be described. The component (B) contained in the silicone resin (2), that is, the organosilane oligomer (B)
Is a main component of a base polymer having a hydrolyzable group (X) as a functional group which participates in a curing reaction when forming a cured film of a functional inorganic paint. This is, for example, an organic solvent or water (a mixed solvent of an organic solvent and water may be used).
, One or more hydrolyzable organosilanes represented by the general formula (I), and water (water previously contained in a solvent and / or water separately added) is added to the hydrolyzable organosilane. 0.001 water per mole equivalent of decomposable group (X)
It is obtained by partially hydrolyzing the hydrolyzable organosilane under the condition of using 0.5 mol. When the metal oxide powder is added in the course of hydrolysis and polymerization of the silicone resin (2), for example, it can be added immediately after adding water.

The group R ³ in the hydrolyzable organosilane represented by the general formula (I) is particularly the same or different and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms. Although not limited, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group;
Aralkyl groups such as -phenylethyl group, 2-phenylpropyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; chloromethyl group and γ-chloropropyl group , 3,
Halogen-substituted hydrocarbon groups such as 3,3-trifluoropropyl group; substituted hydrocarbons such as γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group And the like. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of ease of synthesis or availability.

In the general formula (I), the hydrolyzable group X is not particularly restricted but includes, for example, alkoxy, acetoxy, oxime, enoxy, amino, aminoxy, amide and the like. Can be Among these, an alkoxy group is preferred because of its availability and ease of preparation of the organosilane oligomer (B).

Specific examples of the hydrolyzable organosilane include mono-, di-, tri- and tetra-functional alkoxysilanes wherein m in the general formula (I) is an integer of 0 to 3. , Acetoxysilanes, oxime silanes,
Examples include enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are preferable because they are easily available and the organosilane oligomer (B) is easily prepared.

Of the alkoxysilanes, in particular, m = 0
Examples of the tetraalkoxysilane include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane having m = 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and phenyltrimethoxysilane. ,
Examples thereof include phenyltriethoxysilane and 3,3,3-trifluoropropyltrimethoxysilane. Further, as the diorganodialkoxysilane of m = 2,
Examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. Examples of the triorganoalkoxysilane having m = 3 include trimethylmethoxysilane, trimethylethoxysilane, and trimethylisopropoxysilane. And dimethylisobutylmethoxysilane. Further, an organosilane compound generally called a silane coupling agent is also included in the alkoxysilanes.

Of these hydrolyzable organosilanes represented by formula (I), 50 mol% or more (preferably 60 mol% or more, more preferably 70 mol% or more)
Is a trifunctional compound represented by m = 1. This is,
If it is less than 50 mol%, sufficient coating film hardness cannot be obtained, and the drying and curing properties of the coating film tend to be poor. The amount of water used when preparing the organosilane oligomer (B) is as follows:
As described above, 0.001 to 0.5 per mole equivalent of the hydrolyzable group (X) of the hydrolyzable organosilane.
It is in the range of moles, preferably in the range of 0.01 to 0.4 mole. When the amount of water used is less than 0.001 mol,
When a sufficient partial hydrolyzate cannot be obtained and exceeds 0.5 mol, the stability of the partial hydrolyzate deteriorates. Here, the amount of water used in the partial hydrolysis reaction of the hydrolyzable organosilane is the amount of water separately added when only an organic solvent is used as a reaction solvent, and only water or an organic solvent is used as a reaction solvent. When a mixed solvent of a solvent and water is used,
It is the amount of water previously contained in the reaction solvent at least among water previously contained in the reaction solvent and water separately added. If the amount of water is only the water previously contained in the reaction solvent and the amount used is sufficient, it is not necessary to separately add water, but the amount of water was previously contained in the reaction solvent. If water alone is not sufficient for the above usage, it is necessary to separately add water until the usage reaches the above usage. In this case, the amount of water used is the total amount of water previously contained in the reaction solvent and water added separately. In addition, even when only the water previously contained in the reaction solvent is sufficient for the above usage amount, water may be separately added, and in this case, the usage amount of the water is included in the reaction solvent in advance. It is the total amount of water added and water added separately. However, water is separately added so that the total amount does not exceed the upper limit (0.5 mol per 1 mol equivalent of the hydrolyzable group (X)).

The method of partially hydrolyzing the hydrolyzable organosilane is not particularly limited. For example, the hydrolyzable organosilane may be mixed with a reaction solvent (whether the reaction solvent contains no water or If the required amount is not included, add water here. At that time, the partial hydrolysis reaction proceeds at room temperature, but if necessary, heating (for example, 60 to 60) may be performed to promote the partial hydrolysis reaction.
100 ° C.) or a catalyst may be used. The catalyst is not particularly limited, but includes, for example, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid,
One or more organic acids and inorganic acids such as benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, and oxalic acid can be used. .

The organosilane oligomer (B) is adjusted to have a pH in order to stably obtain its performance over a long period of time.
Preferably 2.0 to 7.0, more preferably 2.5 to
6.5, more preferably 3.0-6.0. If the pH is out of this range, the performance continuity of the component (B) is remarkably reduced particularly under the condition that the amount of water used is 0.3 mol or more per 1 mol equivalent of the hydrolyzable group (X). When the pH of the component (B) is outside the above range, the pH may be adjusted by adding a basic reagent such as ammonia or ethylenediamine if the pH is more acidic than the above range. The pH may be adjusted using an acidic reagent such as hydrochloric acid, nitric acid, and acetic acid. However, the adjustment method is not particularly limited.

The component (C) contained in the silicone resin (2), that is, the silanol group-containing polyorganosiloxane (C) is a base polymer having a hydrolyzable group as a functional group subjected to a curing reaction. ) Is a cross-linking agent for forming a three-dimensional cross-link in the cured film by a condensation reaction with the component, and is a component having an effect of absorbing a strain due to the curing shrinkage of the component (B) and preventing the occurrence of cracks.

R ⁴ in the above average composition formula (II) representing the silanol group-containing polyorganosiloxane (C) is
There is no particular limitation, and examples thereof include the same ones as R ³ in the formula (I), preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, a vinyl group, a γ-glycidoxypropyl group, Substituted hydrocarbon groups such as γ-methacryloxypropyl group, γ-aminopropyl group, 3,3,3-trifluoropropyl group, and more preferably methyl group and phenyl group. Further, in the above formula (II), a and b are numbers satisfying the above relation, respectively, and a is less than 0.2 or b
Is more than 3, there are inconveniences such as generation of cracks in the cured film of the functional inorganic paint. Also, if a exceeds 2 and 4
In the following cases or when b is less than 0.0001, curing does not proceed well.

The silanol group-containing polyorganosiloxane (C) is not particularly limited.
Methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane,
Alternatively, it can be obtained by hydrolyzing one or a mixture of two or more of the corresponding alkoxysilanes with a large amount of water by a known method. When a silanol group-containing polyorganosiloxane (C) is hydrolyzed by a known method using alkoxysilane, a small amount of an unhydrolyzed alkoxy group may remain. That is, a polyorganosiloxane in which a silanol group and a trace amount of an alkoxy group coexist may be obtained, but in the present invention, such a polyorganosiloxane may be used.

The component (D) of the silicone resin (2), ie, silica (D), has the effect of increasing the hardness of the cured coating of the functional inorganic coating and improving the smoothness and crack resistance. The silica (D) is not particularly limited, and a known silica can be used. The silica (D) is not particularly limited, but can be introduced into the paint by dispersing it in the form of colloidal silica in the reaction solvent used in the preparation of the component (B). It is preferable in terms of film forming properties and simplification of the process. However, it is not limited to this. For example, after the silica (D) is mixed with the component (B) obtained and prepared without the silica (D), the resulting mixture may be introduced into a coating material, or the silica (D) may be added to the paint ( The component (B) may be separately introduced into the paint.

The form of the silica (D) when introduced into the paint is not particularly limited, and may be, for example, a powder form or a colloidal silica form. The colloidal silica is not particularly limited, and for example, those described above as the raw material (A ₂ ) for the organosiloxane (A) can be used. When water-dispersible colloidal silica is used, water present as a component other than the solid content in the colloidal silica is used for hydrolysis of the hydrolyzable organosilane as a raw material of the component (B). (Added to the above-mentioned amount of water used in the hydrolysis) and can be used as a curing agent for a functional inorganic paint.

The silica (D) has the above-mentioned effects, but if the amount is too large, the cured coating of the functional inorganic coating may be too hard, which may cause cracks in the coating. . Therefore, the silica (D) is preferably 5 to 9 as a solid content based on the total amount of the component (B).
The content is 5% by weight, more preferably 10 to 90% by weight, and still more preferably 20 to 85% by weight. If the content is less than 5% by weight, a desired coating hardness tends to be not obtained. On the other hand, if it exceeds 95% by weight,
Cracks are likely to occur.

The component (E), ie, the curing catalyst (E), contained in the silicone resin (2) promotes the condensation reaction between the component (B) and the component (C) to form a coating film of a functional inorganic paint. It is a component to be cured. Examples of the curing catalyst (E) 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; Amine salts such as ethanolamine acetate; quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate; amines such as tetraethylpentamine; N
Amine-based silane coupling agents such as -β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid Aluminum compounds such as aluminum alkoxides and aluminum chelates; alkali metal salts such as lithium acetate, lithium formate, sodium formate, potassium phosphate and potassium hydroxide; tetraisopropyl titanate;
Titanium compounds such as tetrabutyl titanate and titanium tetraacetylacetonate; and halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane and trimethylmonochlorosilane. However, other than these, there is no particular limitation as long as it is effective for promoting the condensation reaction between the component (B) and the component (C).

The proportion of the components (B) and (C) in the silicone resin (2) is not particularly limited.
For example, in terms of the total solid content in terms of the total condensed compound,
For a total of 100 parts by weight of the components (B) and (C),
0.5-99.5 parts by weight of component (B), component 99.
5 to 0.5 part by weight is preferred, and component (B) 2.5 to 9
More preferably, 7.5 parts by weight, 97.5 to 2.5 parts by weight of the component (C), 5 to 95 parts by weight of the component (B), and 9 of the component (C)
5 to 5 parts by weight are more preferred. When the component (B) is less than 0.5 parts by weight (the component (C) exceeds 99.5 parts by weight), the curability at room temperature is poor, and sufficient film hardness tends not to be obtained. On the other hand, the component (B) exceeds 99.5 parts by weight (the component (C) is less than 0.5 part by weight).
, The curability is unstable and a good coating film may not be obtained.

In the silicone resin (2), the mixing ratio of the component (E) is not particularly limited. For example, based on the solid content, the total amount of the component (B) and the total condensation of the component (C) are converted. The total amount is preferably in the range of 0.0001 to 10 parts by weight, more preferably in the range of 0.0005 to 8 parts by weight, and still more preferably in the range of 0.0007 to 5 parts by weight, based on 100 parts by weight in terms of the compound. Within range. If the amount of (E) is less than 0.0001 part by weight, the room-temperature curability tends to decrease, and sufficient film hardness tends not to be obtained. 1
If the amount exceeds 0 parts by weight, the heat resistance and weather resistance of the cured film may be reduced, and the hardness of the cured film may be too high to cause cracks.

When the silicone resin contained in the functional inorganic coating is the silicone resin (2), the functional inorganic coating has a hydrolyzable group of the organosilane oligomer (B) and a polyorganosiloxane (C). In the presence of a curing catalyst (E), a silanol group undergoes a condensation reaction when left at room temperature or heated at a low temperature 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, a heat treatment can promote a condensation reaction to form a cured film.

The functional inorganic paint used in the present invention can be toned by further containing a coloring agent such as a pigment or a dye, if necessary. The pigment that can be used is not particularly limited. For example, organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and Hansa yellow; titanium oxide;
Inorganic pigments such as barium sulfate, red iron oxide, and composite metal oxides are preferred, and one or a combination of two or more selected from these groups may be used. The pigment has a larger particle diameter than the metal oxide powder. 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. And more preferably 10 to 70 parts by weight. When the amount of the pigment is less than 5 parts by weight, the concealing property tends to deteriorate, and when the amount exceeds 80 parts by weight, the smoothness of the coating film may deteriorate.

The dyes that can be used are not particularly limited.
Dyes of thiazole type, methine type, nitro type, nitroso type and the like can be mentioned. One or more of these groups may be used in combination. The amount of the dye added is not particularly limited because the concealing property varies depending on the type of the dye. And 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.

Incidentally, a leveling agent, metal powder, glass powder,
Antibacterial agents, antioxidants, ultraviolet absorbers and the like may also be included in the functional inorganic coating within a range that does not adversely affect the effects of the present invention. The functional inorganic paint can be used by diluting it with various organic solvents, if necessary, for ease of handling, or 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 for producing the functional inorganic paint is not particularly limited, and the components may be mixed using a usual method and apparatus. Regarding the form of each component when introduced into the paint, liquid itself, a solution dissolved in a solvent, a liquid such as a dispersion liquid dispersed in a dispersion medium, a solid state such as a powder, etc. Regardless, it is not particularly limited. When each component is introduced in the form of a solution or dispersion, the solvent or dispersion medium is, for example, water, the above-mentioned organic solvent, or
Mixtures of water and the above-mentioned organic solvents can be used. Each component may be added separately, or two or more components may be mixed in advance and then mixed with the remaining components,
All the components may be mixed at the same time, and there is no particular limitation on the timing of addition or mixing. Primary particle size 3
When a metal oxide powder having a diameter of 0 nm or less is added in the course of hydrolysis and polymerization of the silicone resin, a substance to be hydrolyzed such as water can be added immediately after the addition.

The method of applying the functional inorganic paint is not particularly limited, and may be, for example, a usual various application 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 metal oxide.

The thickness of the cured coating film formed from the functional inorganic coating material is not particularly limited.
The thickness is preferably about 0 μm. However, in order that the various functions of the coating film can be more effectively exerted, the coated cured film can be stably adhered and held for a long period, and cracks and peeling do not occur. 01-5 μm, preferably 0.05-2
μm is more preferred.

The substrate to which the functional inorganic paint is applied (also the substrate used for the functional coated product of the present invention) includes
Although not particularly limited, for example, an inorganic base material, an organic base material, an inorganic-organic composite base material, and at least one inorganic coating film and / or at least one organic coating film on any of these surfaces Paint substrates and the like can be mentioned.

Examples of the inorganic substrate include, but are not particularly limited to, a metal substrate; a glass substrate; an enamel; a water glass decorative plate, an inorganic building material such as 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 restricted but includes, for example, sodium glass, Pyrex glass, quartz glass, alkali-free glass and the like. 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 it. 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-A6208 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 refers to all 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 a functional inorganic paint to a substrate, depending on the material and surface condition of the substrate, if the functional inorganic paint is applied as it is, it may be difficult to obtain adhesion and weather resistance,
If necessary, a primer layer may be previously formed on the surface of the base material before forming the applied cured coating of the functional inorganic paint. The primer layer is not particularly limited, regardless of whether it is organic or inorganic. Examples of the organic primer layer include a nylon resin, an alkyd resin, an epoxy resin, an acrylic resin, and an organic modified silicone resin (for example, an acrylic silicone resin). , A cured resin layer of an organic primer composition containing at least one organic resin selected from the group consisting of a chlorinated rubber resin, a urethane resin, a phenol resin, a polyester resin, and a melamine resin in a solid content of 10% by weight or more. Examples of the inorganic primer layer include a cured resin layer of an inorganic primer composition containing 90% by weight or more of a solid content of an inorganic resin such as a silicone resin.

The thickness of the primer layer is not particularly limited, but 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 usable coloring agents 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, although based on the solid content, it is defined not for 100 parts by weight of the total condensed compound but for 100 parts by weight of the total resin in the total amount of the primer composition.

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 including 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-mentioned various materials, or a laminated material obtained by laminating at least two of the above-described various materials. May be.

The functional inorganic paint and the functional coated product of the present invention have a property of decomposing dirt (when an optical semiconductor material such as titanium oxide is used as a metal oxide), a water repellency as well as a surface hydrophilicity from the beginning of film formation. (When an optical semiconductor material such as titanium oxide is used as the metal oxide), functions such as rainwater washability and antifogging properties are exhibited. For this reason, the weather resistance of the coating film is enhanced, and the effect of reducing the adhesion of dirt is also obtained. By equipping at least a part of various materials or articles with a coated and cured coating of a 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 Members for use (for example, members made of at least one material selected from the group consisting of glass, resin, metal, and ceramics), solar cell glass, agricultural vinyl and glass houses, and air conditioner outdoor units , VHF / UH
Antennas such as F / BS / CS.

The functional inorganic paint according to the present invention may be applied directly 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,
A resin such as an acrylic resin, a fluororesin, a polypropylene (PP) resin, or a composite resin thereof may be used, but is not particularly limited.

[0066]

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 was measured by GPC (gel permeation chromatography) using a standard curve of standard polystyrene using HLC8020 manufactured by Tosoh Corporation as a measuring model, and measuring the converted value. In addition, this invention is not limited to a following example.

First, Examples and Comparative Examples using the silicone resin (1) containing the component (A) will be described. 100 parts of methyltrimethoxysilane <Example 1> material (A _1), the raw material (A ₂₎ as 10 parts tetraethoxysilane, also raw material (A ₂₎ as IPA organosilica sol is acidic colloidal silica (trade name " OS
CAL1432 ", manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content 30
%), 30 parts of dimethyldimethoxysilane as the raw material (A ₃ ), and 100 parts of isopropyl alcohol (which may be abbreviated as IPA in this specification) as a diluting solvent, and 90 parts of water are further added. Stirred. By heating the obtained liquid in a 60 ° C. constant temperature bath for 5 hours, the weight average molecular weight (M
By adjusting w) to 1500, an alcohol solution of an organosiloxane was obtained.

Preparation conditions of the organosiloxane alcohol solution: [Water] / [OR ¹ ] molar ratio: 1.73; weight average molecular weight: 1500; solid content in terms of all condensed compounds: 23.3%. Titanium oxide (Nippon Aerosil Co., Ltd.) as powder (hereinafter simply referred to as “metal oxide”)
Titanium oxide: trade name "P-25" primary particle diameter 21n
m), based on the solid content, is added and mixed in such an amount that the metal oxide becomes 50 parts with respect to 100 parts in total of all the condensed compounds and all the metal oxide components in the total amount of the coating composition. (1) was obtained.

This functional inorganic paint (1) was applied by brush to a glass substrate washed with acetone, and the paint was applied at 30 ° C.
After drying and curing for 1 hour at 150 ° C., drying was performed at 150 ° C. for 1 hour to obtain a functionally coated product (1). The cured film had a thickness of 0.5 μm. <Example 2> In Example 1, instead of titanium oxide, silicon oxide powder (silicon oxide manufactured by Nippon Aerosil Co., Ltd .: trade name "AEROSOL300") was used in place of titanium oxide.
Example 1 except that the same amount of (primary particle diameter 7 nm) was used.
In the same manner as in the above, a functional inorganic paint (2) was obtained.

The functional inorganic paint (2) was applied by brush to a glass substrate washed with acetone, and the paint was dried and cured at room temperature for 1 hour to obtain a functional coated product (2). In addition, the thickness of the cured film is 0.5 μm.
Met. <Example 3> In Example 1, titanium oxide was used in an amount of 70 parts based on the solid content based on 100 parts of the total of all the condensed compounds and all the metal oxide components in the total amount of the paint. Except for the above, a functional inorganic paint (3) was obtained in the same manner as in Example 1.

The functional inorganic paint (3) was applied to a glass substrate washed with acetone by a brush, and the paint was dried and cured at room temperature for 1 hour to obtain a functional coated product (3). In addition, the thickness of the cured film is 0.5 μm.
Met. <Example 4> In Example 2, titanium oxide was used in an amount of 65 parts on a solids basis with respect to a total of 100 parts of all the condensed compounds and all metal oxide components in the total amount of the paint. Except for the above, a functional inorganic paint (4) was obtained in the same manner as in Example 2.

The functional inorganic paint (4) was applied to a glass substrate washed with acetone by a brush, and the paint was dried and cured at room temperature for 1 hour to obtain a functional coated product (4). In addition, the thickness of the cured film is 0.5 μm.
Met. <Example 5> In Example 4, silicon oxide powder (silicon oxide manufactured by Nippon Aerosil Co., Ltd .: trade name “AEROSOL300”) was used instead of titanium oxide as the metal oxide.
Example 4 except that the same amount of (primary particle diameter 7 nm) was used.
In the same manner as in the above, a functional inorganic paint (5) was obtained.

The functional inorganic paint (5) was applied to a glass substrate washed with acetone with a brush, and the paint was dried and cured at room temperature for 1 hour to obtain a functional coated product (5). In addition, the thickness of the cured film is 0.5 μm.
Met. <Example 6> In Example 4, the same amount of aluminum oxide powder (aluminum oxide manufactured by Nippon Aerosil Co., Ltd .: trade name "Aluminum oxide C", primary particle diameter: 13 nm) was used instead of titanium oxide as the metal oxide. Except for the above, a functional inorganic paint (6) was obtained in the same manner as in Example 4.

The functional inorganic paint (6) was applied by brush to a glass substrate washed with acetone, and the paint was dried and cured at room temperature for 1 hour to obtain a functional coated product (6). In addition, the thickness of the cured film is 0.5 μm.
Met. 100 parts of methyltrimethoxysilane <Example 7> material (A _1), the raw material (A ₂₎ as 10 parts tetraethoxysilane, also raw material (A ₂₎ as IPA organosilica sol is acidic colloidal silica (trade name " OS
CAL1432 ", manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content 30
%), And 90 parts of IPA as a diluting solvent were mixed,
Further, 90 parts of water was added and stirred. The obtained liquid is
The mixture was heated in a constant temperature bath for 5 hours to adjust the weight average molecular weight (Mw) of the organosiloxane (A) as a reaction product to 1,000 to obtain an alcohol solution of the organosiloxane.

Preparation conditions of alcohol solution of organosiloxane: [Water] / [OR ¹ ] molar ratio 2.08 ・ Weight average molecular weight 1000 ・ Solid content in terms of total condensed compounds 20.3% Titanium oxide (titanium oxide manufactured by Nippon Aerosil Co., Ltd .: trade name "P-25", primary particle diameter: 21 nm) is 100 parts in total of all condensed compounds and all metal oxide components in the total amount of the paint on a solid content basis. In addition, a functional inorganic paint (7) was obtained by adding and mixing an amount of 50 parts of the metal oxide.

This functional inorganic paint (7) was applied by brush to a glass substrate washed with acetone, and the paint was heated at 30 ° C.
After drying and curing for 1 hour at 150 ° C., the coating was dried at 150 ° C. for 1 hour to obtain a functionally coated product (7). The cured film had a thickness of 0.5 μm. <Example 8> A functionally coated product (8) was obtained in the same manner as in Example 7, except that an aluminum substrate was used instead of the glass substrate as the base material.

Next, prior to the following examples, the components (B) and (C) of the silicone resin (2) used for them were prepared as follows. At that time, the colloidal silica (D) was introduced by dispersing it in the preparation solution of the component (B). (Preparation Example of Component B): <Preparation Example B-1> In a flask equipped with a stirrer, a heating jacket, a condenser, and a thermometer, IPA-dispersed colloidal silica sol IPA-ST (particle diameter: 10 to 20 nm;
Solid content 30%, moisture 0.5%, manufactured by Nissan Chemical Industry Co., Ltd.)
100 parts, 68 parts of methyltrimethoxysilane, and 1 part of water
0.8 part of the mixture was charged, and a partial hydrolysis reaction was carried out at 65 ° C. for about 5 hours with stirring, followed by cooling to obtain a silica dispersion solution of the organosilane oligomer (B-1). This had a solid content of 36% in terms of total condensed compounds when left at room temperature for 48 hours.

Preparation conditions of B-1 silica dispersion solution: 0.4 mol of water per 1 mol equivalent of hydrolyzable group ・ Silica content in silica dispersion solution of B-1 47.2% ・ m Preparation Example B-2> In a flask equipped with a stirrer, a heating jacket, a condenser, and a thermometer, IPA-dispersed colloidal silica sol IPA-ST (particle diameter 10 to 10) was used. 20 nm,
Solid content 30%, moisture 0.5%, manufactured by Nissan Chemical Industry Co., Ltd.)
100 parts, 68 parts of methyltrimethoxysilane, 18 parts of dimethyldimethoxysilane, 2.7 parts of water, and 0.1 part of acetic anhydride are charged, and the mixture is partially hydrolyzed at 80 ° C. for about 3 hours while stirring. After performing the decomposition reaction, by cooling, a silica dispersion solution of the organosilane oligomer (B-2) was obtained. This product had a solid content of 39.5% in terms of total condensed compounds when left at room temperature for 48 hours.

Preparation conditions of B-2 silica dispersion solution: ・ mol number of water per mole equivalent of hydrolyzable group 0.1 mol ・ silica content in silica dispersion solution of B-2 40.2% ・ m = Mol% of hydrolyzable organosilane of 1 = 77 mol% (Preparation example of component C): <Preparation example C-1> A solution prepared by dissolving 220 parts (1 mol) of isopropoxysilane in 150 parts of toluene was charged.
108 parts of a 1% hydrochloric acid aqueous solution was added dropwise over 20 minutes, and methyltriisopropoxysilane was hydrolyzed at 60 ° C. with stirring. After 40 minutes from the end of the dropwise addition, the stirring was stopped, and the reaction solution was transferred to a separating funnel and allowed to stand, and then separated into two layers.
The mixed solution of the lower layer of water and isopropyl alcohol containing a small amount of hydrochloric acid was separated and removed, the remaining hydrochloric acid in the remaining toluene resin solution was removed by washing with water, and toluene was further removed under reduced pressure. By diluting the product with isopropyl alcohol, a weight average molecular weight (Mw) of about 200
0 silanol group-containing polyorganosiloxane (C-
An isopropyl alcohol solution of 1) was obtained. The solid content in terms of the total condensed compound in this solution is 40%. The silanol group-containing polyorganosiloxane (C
It has been confirmed that -1) satisfies the average composition formula (II).

<Preparation Example C-2> 1000 parts of water and 50 parts of acetone were charged into a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, and a thermometer, and further 44.8 parts of methyltrichlorosilane (0. 3 mol), 38.7 parts (0.3 mol) of dimethyldichlorosilane and 84.6 parts (0.4 mol) of phenyltrichlorosilane.
(4 mol) dissolved in 200 parts of toluene was hydrolyzed at 60 ° C. while dripping under stirring with a solution. Forty minutes after the completion of the dropwise addition, the stirring was stopped, and the reaction solution was transferred to a separating funnel and allowed to stand, and then separated into two layers. The lower layer of aqueous hydrochloric acid is separated and the remaining water and hydrochloric acid remaining in the toluene solution of organopolysiloxane are removed together with excess toluene by vacuum stripping to obtain a weight average molecular weight (Mw) of about 3,000. A toluene solution of the silanol group-containing polyorganosiloxane (C-2) was obtained. The solid content in terms of the total condensed compound in this solution is 60%. Further, it has been confirmed that the silanol group-containing polyorganosiloxane (C-2) in this solution satisfies the above average composition formula (II).

(B) and (C) obtained as described above.
The following examples were performed using each solution of the components. <Example 9> 70 parts of a silica dispersion solution of B-1 (about 25 parts in terms of total condensed compound equivalent solids) and 30 parts of C-1 isopropyl alcohol solution (12 parts in terms of total condensed compound equivalent solids) And 1 part of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as a curing catalyst (E), and then titanium oxide (titanium oxide manufactured by Nippon Aerosil Co., Ltd .: trade name “P -2
5) The primary particle diameter of 21 nm) is added and mixed on a solid content basis in an amount of 50 parts of the metal oxide with respect to 100 parts of the total of all the condensed compounds and all the metal oxides in the total amount of the paint. A functional inorganic paint (9) was obtained.

This functional inorganic paint (9) was applied by brush to a glass substrate washed with acetone, and the paint was applied at 30 ° C.
After drying and curing for 1 hour at 150 ° C., drying was performed at 150 ° C. for 1 hour to obtain a functionally coated product (9). The cured film had a thickness of 0.5 μm. <Example 10> In Example 9, as a metal oxide,
Instead of titanium oxide, silicon oxide powder (silicon oxide manufactured by Nippon Aerosil Co., Ltd .: trade name "AEROSOL300")
Example 9 except that the same amount of (primary particle diameter 7 nm) was used.
In the same manner as in the above, a functional inorganic paint (10) was obtained.

The functional inorganic paint (10) was applied to a glass substrate washed with acetone with a brush, and the paint was dried and cured at room temperature for 1 hour to obtain a functional coated product (10). In addition, the thickness of the cured film is 0.5 μm.
m. <Example 11> In Example 9, as a metal oxide,
A functional inorganic paint (in the same manner as in Example 9) except that the same amount of aluminum oxide powder (aluminum oxide manufactured by Nippon Aerosil Co., Ltd .: aluminum oxide C, primary particle diameter: 13 nm) was used in place of titanium oxide. 1
1) was obtained.

The functional inorganic paint (11) was applied by brush to a glass substrate washed with acetone, and the paint was dried and cured at room temperature for 1 hour to obtain a functional coated product (11). In addition, the thickness of the cured film is 0.5 μm.
m. Example 12 The functional inorganic paint (7) obtained in Example 7 was spray-coated on a window glass (1 m ² , 6 mm thick) of a building on the site of Matsushita Electric Works, Ltd. Osaka Kadoma. Coated to a cured film thickness of 0.1 μm, and dried and cured at room temperature for 24 hours to obtain a functional coated product (12)
I got <Example 13> 50 parts of a silica dispersion solution of B-2 (about 20 parts in terms of total condensed compound equivalent solid) and 50 parts of a C-2 toluene solution (in terms of total condensed compound equivalent solid of 30 parts)
Parts) and N-β-aminoethyl- as a curing catalyst (E).
After mixing 2 parts of γ-aminopropylmethyldimethoxysilane, titanium oxide (titanium oxide manufactured by Nippon Aerosil Co., Ltd .: trade name “P-25”, primary particle diameter 21 nm) as a metal oxide was used on a solid content basis. A functional inorganic paint (13) was obtained by adding and mixing an amount of 50 parts of the metal oxide to 100 parts of the total of all the condensed compounds and all the metal oxide components in the whole amount of the paint.

The functional inorganic paint (13) was applied to a glass substrate washed with acetone by a spray coating method.
The coated film was dried and cured at room temperature for 5 hours to obtain a functionally coated product (13). The cured film had a thickness of 0.2 μm. <Example 14> An organosilane oligomer (B-) containing no silica was prepared in the same manner as in Preparation Example B-1 except that colloidal silica was not used at all.
A solution of 3) was obtained. This product had a solid content of 70% in terms of the total condensed compound when left at room temperature for 48 hours.

Next, in Example 13, 70 parts of the solution of the organosilane oligomer (B-3) obtained above (solid content in terms of total condensed compound was 49 parts) instead of 50 parts of the silica dispersion solution of B-2. Part), and when this solution is mixed with a toluene solution of C-2, a curing catalyst, and a metal oxide, IPA-dispersed colloidal silica sol IPA-
ST (particle size: 10 to 20 nm, solid content: 30%, water content: 0.1%)
A functional inorganic paint (14) was obtained in the same manner as in Example 13, except that 100 parts of 5% (manufactured by Nissan Chemical Industries, Ltd.) was added.

By using this functional inorganic paint (14) and performing the same operation as in Example 13, a functional coated product (14) was obtained. <Example 15> A functionally coated product (15) was obtained in the same manner as in Example 7, except that a polycarbonate plate was used instead of the glass substrate as the base material. <Example 16> In Example 7, an epoxy-based primer (Isamu Co., Ltd .: trade name "E-1 Primer") was applied to a surface of a glass plate washed with acetone in a film thickness of about 10 µm. A functionally coated product (16) was obtained by performing the same operation as in Example 7 except that the functional inorganic paint (7) was applied. 100 parts of methyltrimethoxysilane <Example 17> material (A _1), the raw material (A ₂₎ as 10 parts tetraethoxysilane, also raw material (A ₂₎ as IPA organosilica sol is acidic colloidal silica (trade name " O
SCAL1432 ", manufactured by Catalyst Chemical Industry Co., Ltd., solid content 3
(0%), 90 parts of dimethyldimethoxysilane as a raw material (A ₃ ), 100 parts of IPA as a diluting solvent, 90 parts of water were further added, and the mixture was stirred. Titanium oxide (Nippon Aerosil (Nippon Aerosil) Titanium oxide (trade name: P-25, primary particle size: 21 nm), based on the solid content, based on 100 parts of the total of all the condensed compounds and all the metal oxide components in the total amount of the coating material, Was added and mixed. By heating the obtained liquid in a 60 ° C. constant temperature bath for 5 hours, the weight average molecular weight (Mw) of the organosiloxane (A) as a reaction product was set to 1500.
To obtain a functional inorganic paint (17).

Preparation conditions of functional inorganic paint (17): [Water] / [OR ¹ ] molar ratio 1.73 ・ Weight average molecular weight 1500 ・ Solid content in terms of total condensed compound 23.3% 17) was applied by brush to a glass substrate washed with acetone, and the coating was dried and cured at room temperature for 1 hour to obtain a functionally coated product (17). The cured film had a thickness of 0.5 μm.

Example 18 A stirrer, a heating jacket,
In a flask equipped with a condenser and thermometer, place IPA
Dispersed colloidal silica sol IPA-ST (particle size 10 to 10)
20 nm, solid content 30%, water content 0.5%, manufactured by Nissan Chemical Industries, Ltd.) 100 parts, and methyltrimethoxysilane 68
Part, water 10.8 parts, and titanium oxide as a metal oxide (titanium oxide manufactured by Nippon Aerosil Co., Ltd .: trade name "P-2
5) The primary particle diameter of 21 nm) was calculated based on the solid content as 100
Of the organosilane oligomer (B-3) by adding a quantity of 50 parts by weight of the metal oxide to the mixture, performing a partial hydrolysis reaction at 65 ° C. for about 5 hours with stirring, and then cooling. )) A metal oxide-containing silica dispersion solution was obtained. This had a solid content of 36% in terms of total condensed compounds when left at room temperature for 48 hours.

Preparation conditions of silica dispersion solution of B-3: ・ mol number of water per mole equivalent of hydrolyzable group 0.4 mol ・ silica content in silica dispersion solution of B-3 47.2% ・ m = 1 mol% of hydrolyzable organosilane of 100 mol% 70 parts of this metal oxide-containing silica dispersion solution of B-3 (approximately 20 parts as a solid content in terms of total condensed compound, 50 parts as a total metal oxide) And 30 parts of an isopropyl alcohol solution of C-1 (12 parts as a solid content in terms of total condensed compounds)
And N-β-aminoethyl-γ- as a curing catalyst (E).
By mixing with 1 part of aminopropylmethyldimethoxysilane, a functional inorganic paint (18) was obtained.

This functional inorganic paint (18) was applied by brush to a glass substrate washed with acetone, and the paint was applied for 30 minutes.
After drying and hardening at 150 ° C. for 1 hour, it was dried at 150 ° C. for 1 hour to obtain a functional coated product (18). The cured film had a thickness of 0.5 μm. <Comparative Example 1> In Example 1, instead of titanium oxide, silicon oxide powder (silicon oxide manufactured by Nippon Aerosil Co., Ltd .: trade name “AEROSOL OX5”) was used as the metal oxide.
Comparative inorganic paint (1) was obtained in the same manner as in Example 1 except that the same amount of “0” primary particle diameter of 50 nm) was used.

The comparative inorganic paint (1) was applied by brush to a glass substrate washed with acetone, and the paint was dried and cured at room temperature for 1 hour to obtain a comparative coated product (1). In addition, the thickness of the cured film is 0.5 μm.
Met. Comparative Example 2 A comparative inorganic paint (2) was obtained in the same manner as in Example 1 except that 15 parts of titanium oxide were used.

By using this comparative inorganic paint (2) and performing the same operation as in Example 1, the comparative coated product (2) was obtained.
I got Comparative Example 3 A comparative inorganic paint (3) was obtained in the same manner as in Example 1 except that 60 parts of titanium oxide was used.

Using the comparative inorganic paint (3), the same operation as in Example 1 was carried out to obtain a comparative coated product (3).
I got <Comparative Example 4> In Example 1, instead of titanium oxide, silicon oxide powder (silicon oxide manufactured by Nippon Aerosil Co., Ltd .: trade name “OX50”, primary particle size 4) was used in place of titanium oxide.
Comparative Inorganic Paint (4) was obtained in the same manner as in Example 1 except that the same amount of 0 nm) was used.

The same operation as in Example 1 was carried out using this comparative inorganic paint (4) to obtain a comparative coated product (4).
I got <Comparative Example 5> A comparative inorganic paint (5) was obtained in the same manner as in Example 1, except that no metal oxide was used.

By using this comparative inorganic paint (5) and performing the same operation as in Example 1, a comparative coated product (5) was obtained.
I got The coating film performance of the coated product obtained as described above was evaluated by the following method. <Evaluation method> (Adhesion): Evaluated by a boiling test described in JIS-K5400. When there was no problem, “○” was given, when there was a change in appearance, “△”, and when peeling occurred, “×” was given.

(Contact angle): The contact angle between water and the coating film was evaluated by measuring it immediately after the preparation of the coating 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. The larger the contact angle, the higher the water repellency. Table 1 shows the results.

[0098]

[Table 1]

As shown in Table 1, all of Examples 1 to 18 had a contact angle with water of 120 ° or more and exhibited good water repellency. It was also confirmed that the adhesiveness was excellent.

[0100]

The functional inorganic coating composition according to any one of the first to fifth aspects of the present invention is characterized in that a metal oxide powder having a primary particle diameter of 30 nm or less is obtained by mixing all condensed compounds and metal oxides in the total coating composition on a solid basis. 40 to 80 parts by weight with respect to the total of 100 parts by weight, so that it is excellent in water repellency and hardly adheres dirt, and because it is inorganic, it is hard to be scratched, weather resistance, durability and the like. It is possible to form an excellent functional coating film. Further, since this coating film can be toned in various colors, it has a high design and a wide range of use.

According to the second aspect of the present invention, the effect of high weather resistance is further added. According to the invention of claim 3,
Further, there is an additional effect that the metal oxide hardly deteriorates with time, and the weather resistance, hardness, and water repellency maintaining property of the coating film are further improved. According to the invention of claims 4 and 5, further,
It is hard to cause deterioration with time due to the metal oxide, and has the effect of further improving the curability at room temperature (normal temperature), the weather resistance of the coating film, the hardness, and the retention of the water repellent effect. Therefore, it can be used in a wide range of drying and curing conditions or temperature range. Therefore, not only can a substrate having a shape difficult to evenly apply heat, a substrate having a large dimension or a substrate having poor heat resistance be coated, but also when performing a coating operation outdoors or the like. Since it can be painted even when it is difficult to apply heat, its industrial value is high.

According to the sixth aspect of the present invention, the water repellency of the inorganic coating having excellent functionality as described above can be enhanced. By adding the metal oxide during the hydrolysis and polymerization process of the silicone resin, the uniformity as a film is increased, and the weather resistance, durability and functionality as a coating film are further improved. According to the invention of claims 7 to 9, it is possible to enhance the water repellency of the inorganic coating film having the above-mentioned excellent functionality.

According to the ninth aspect of the present invention, the effect that the adhesion is further improved is added.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Meiji Goto 1048 Kadoma Kadoma, Osaka Prefecture Matsushita Electric Works, Ltd. (Reference) 4J038 DL021 DL031 HA216 HA246 HA446 JA43 JC13 JC30 JC38 JC41 KA04 NA03 NA07 PA06 PA07 PA19 PC02 PC03 PC04 PC06 PC08

Claims (9)

[Claims] 1. An inorganic coating containing a silicone resin as a main component, wherein a metal oxide powder having a primary particle diameter of 30 nm or less in number average particle diameter is completely condensed in a total amount of the coating on a solid basis. A functional inorganic coating, comprising 40 to 80 parts by weight based on 100 parts by weight of the total of the compound and the metal oxide. 2. The functional inorganic paint according to claim 1, wherein the metal oxide is at least one metal oxide selected from the group consisting of titanium oxide, silicon oxide and aluminum oxide. 3. The functional inorganic paint according to claim 1, wherein the silicone resin is a silicone resin containing the following component (A). Component (A): 100 parts by weight of a silicon compound represented by the general formula R ² Si (OR ¹ ) ₃ , based on the general formula Si (OR ¹ )
A silicon compound and / or colloidal silica from 20 to 200 parts by weight represented by _4, the general formula R ^{₂ 2} Si (O
A hydrolyzable polycondensate of a hydrolyzable mixture containing a silicon compound represented by R ¹ ) ₂ (0 to 60 parts by weight), wherein R ¹ and R ^{2 each} represent a monovalent hydrocarbon group; The weight average molecular weight of this hydrolyzed polycondensate is 90 in terms of polystyrene.
An organosiloxane adjusted to be 0 or more. 4. The silicone resin comprises the following (B):
The silicone resin comprising the components (C), (D) and (E), wherein at least 50 mol% of the hydrolyzable organosilane as the raw material of the component (B) is an organosilane having m = 1. 3. The functional inorganic paint according to 2. Component (B): represented by the general formula R ³ _m SiX _4-m (I) (where R ³ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , M is an integer of 0 to 3, and X represents a hydrolyzable group.) The hydrolyzable organosilane is dissolved in an organic solvent, water or a mixed solvent thereof per 1 molar equivalent of the hydrolyzable group (X). An organosilane oligomer partially hydrolyzed under conditions using 0.001 to 0.5 mol of water. Component (C): represented by the average composition formula R ⁴ _a Si (OH) _b O _{(4-ab) / 2} ... (II) (where R ⁴ is the same or different and substituted or unsubstituted and has 1 to 1 carbon atoms) 8 represents a monovalent hydrocarbon group, wherein a and b are respectively 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦
3, a number that satisfies the relationship of a + b <4. ), Polyorganosiloxanes containing silanol groups in the molecule. Component (D): silica. Component (E): curing catalyst. 5. The component (B) is obtained by dissolving the hydrolyzable organosilane in the colloidal silica obtained by dispersing the component (D) in an organic solvent, water or a mixed solvent thereof. (X) water 0.001 to 1 molar equivalent
Partially hydrolyzed under the condition of using 0.5 mol,
The functionality according to claim 4, wherein the component (D) is a silica-dispersed organosilane oligomer containing 5 to 95% by weight as a solid content based on the total amount of the component (B) and the component (D). Inorganic paint. 6. A method for producing a functional inorganic coating according to claim 1, wherein the metal oxide is added during the hydrolysis and polymerization of the silicone resin. Production method of functional inorganic paint. 7. A functionally coated article, wherein a functional inorganic coating according to any one of claims 1 to 5 is applied to a substrate to form a functional inorganic coating on the surface of the substrate. 8. 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 7, wherein the functionally coated article is selected from the group consisting of: 9. The functional coated product according to claim 8, wherein the coating film on the surface of the coating substrate is a primer layer.