JPH06305072A - Building material - Google Patents

Abstract

PURPOSE:To provide a building material holding high design effect without losing a metal feeling, having long-term durability and capable of corresponding to market needs. CONSTITUTION:A building material is based on a metal material processed into a predetermined shape and having a surface subjected to mirror surface finish and constituted by providing an inorg. coating film having transparency on the mirror surface of the metal material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a building material based on a metallic material such as a metallic panel or a rain gutter.

[0002]

2. Description of the Related Art In recent years, with the upsizing of buildings, maintenance-free construction, fashion, etc., panels and rain gutters based on metal-based materials have a high designability that makes use of metallic materials such as stainless steel. With long-term durability,
Moreover, it is required to create panels and rain gutters that have good workability.

In the case of a building material based on a metal-based material such as a metal-based panel, a metal-based material having a mirror-finished surface may be used as the base. This is because the mirror-finished surface enhances the beauty of metal. However, in the case of a metal-based material whose surface is mirror-finished (especially in the case of stainless steel), when the human hand touches it, the appearance of the metal is markedly deteriorated due to the redness of the hand.

An organic coating film is provided on the mirror surface of a metal material,
There are also countermeasures such as making stains inconspicuous and preventing stains, but in the case of an organic coating film, the soft feeling is strong and the sharp metal feeling is lost. in addition,
Rain gutters and panels made by directly processing metallic materials are sea salt, acid rain, air pollutants (sulfurous acid gas, soot,
It is likely that abnormal appearance due to corrosion or contamination will occur due to the influence of automobile exhaust gas, etc., and in severe cases, it will lead to drainage function failure due to perforation, which is not sufficient in terms of long-term durability.

In order to improve this point, an organic coating film is provided on the surface, but the durability is not sufficient. In addition to this, there is a measure to laminate a fluorine-based film, an acrylic-based film, or the like on a metal material, but in this case, it is difficult to deal with various shaped products, and there is a difficulty in processing the film end portion, which is limited. Only the shape can be applied. In addition, especially, the fluorine-based coating which is organic and has excellent weather resistance,
Even if this can be coated well and its long-term durability can be secured to some extent, it will not be possible to join it in a rain gutter, etc. at the time of construction and bonding work to prevent water leakage unless a special method is used. Is a problem.

[0006]

The present invention solves these problems and retains a high designability without losing the metallic feel and has a long-term durability to meet the above market needs. An object is to provide a building material that can be manufactured.

[0007]

In order to solve the above-mentioned problems, a building material according to the present invention is based on a metal material which is processed into a predetermined shape and has a mirror-finished surface, and which is mirror-finished. The structure is such that a transparent inorganic coating film is provided on the mirror surface.

The present invention will be described in more detail below.
Types of building materials of the present invention include, but are not limited to, rain gutters and panels. Examples of the metal material processed into a predetermined shape as the base include, but are not limited to, those made of stainless steel, galvanized steel, aluminum, and the like.

Examples of the mirror surface of the metallic material used in the building material of the present invention include a mirror surface equivalent to a polished mirror surface obtained by polishing with # 500 to # 2000 paper. In the case of the building material of the present invention, a transparent undercoat layer may be provided under a transparent inorganic coating film (hereinafter, appropriately referred to as “transparent inorganic coating film”). As the base layer, an inorganic primer layer, a chemical conversion treatment layer,
Alternatively, a structure in which an inorganic primer layer is laminated on the chemical conversion treatment layer may be mentioned.

The thickness of the transparent inorganic coating film is about 5 to 20 μm, and the thickness of the inorganic primer layer is 0.5 to 10 μm.
The thickness of the chemical conversion treatment layer is about 50 to 100Å.
The transparent inorganic coating film, the inorganic primer layer, or the chemical conversion treatment layer may be colored as long as the transparency is not lost. It can be colored by adding a coloring agent to the coating material. In particular, when both the transparent inorganic coating film and the inorganic primer layer are colored, if the inorganic coating film is of the same color system (similar in saturation) as the inorganic primer layer but has a different lightness, a deep color is obtained. The brightness of the inorganic coating film when colored is both higher and lower than the brightness of the inorganic primer layer.

The following are specific examples of the building material of the present invention. Metallic material-Transparent inorganic coating film Metallic material-Chemical conversion treatment layer-Transparent inorganic coating film Metallic material-Inorganic primer layer-Transparent inorganic coating film Metallic material-Chemical conversion treatment layer-Inorganic primer layer-Transparent inorganic coating film Coating film As the inorganic coating film having transparency of the building material of the present invention (hereinafter, appropriately referred to as "transparent inorganic coating film"), for example, a film formed by using a silicon alkoxide coating material is exemplified. A colorless transparent film and a colored transparent film can be mentioned. In the case of a colored film, a color such as black, brown, or gray is listed. Needless to say, the transparent inorganic coating film is not limited to the example here.

The silicon alkoxide coating film is exemplified by one obtained by applying and curing the following silicon alkoxide coating agent (A) or (B). (A) General formula: (R ¹ ) _m Si (OR ² ) _4-m (I) (In the formula, each R ¹ represents a methyl group, an ethyl group or a phenyl group, and each R ² has a carbon number of 1 to 1. 4 is an alkyl group, and m is 0, 1 or 2.) A silicon alkoxide-based coating agent containing a silicon compound represented by the formula (4) and / or a partial hydrolyzate thereof as a main component.

(B) (a) General formula: (R ³ ) _n SiX _4-n (II) (In the formula, R ³ is a substituted or unsubstituted C 1 to C 8 group, respectively.
Represents a monovalent hydrocarbon group, X represents a hydrolyzable group,
n is an integer of 0-3. (B) a hydrolyzable organosilane represented by the formula (1) is partially hydrolyzed in colloidal silica dispersed in an organic solvent and / or water, and a silica-dispersed oligomer solution of organosilane, and (b) an average composition formula: R ⁴ ) Si (OH) _d O _{(4-cd) / 2} (III) (In the formula, R ⁴ is each a substituted or unsubstituted C 1 to C 8
Represents a monovalent hydrocarbon group, wherein c is 0.2 ≦ c ≦ 2, d is 0.0001 ≦ d ≦ 3, and c + d <4. ) A silicon alkoxide-based coating agent containing, as essential components, a polyorganosiloxane having a silanol group in the molecule thereof and (c) a curing catalyst.

In the case of a colored film, a coloring agent is added to these silicon alkoxide coating agents to form a colored film. The coloring agent is usually an inorganic pigment (composite oxide pigment), for example, black composite oxide pigments such as CuO-MnO-Cr ₂ O ₃ and the like in detail. The colorant is usually a silicon alkoxide-based coating agent 1
It is added in an amount of about 0.5 to 10 parts by weight with respect to 00 parts by weight so that the required transparency can be obtained.

In the case of the present invention, examples of the inorganic primer layer for the underlayer include an inorganic primer layer formed by using the following polysiloxane coating material. (A) the average composition formula ^{_{(R 1) a SiO (4}} -ab) / 2 (OR 2) b ··· (a) formula (In the formula, R ¹ are each a substituted or unsubstituted C 1-8
Represents a monovalent hydrocarbon group, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a represents 0.6 to 1.8.
And b represents the number of hydroxyl groups or alkoxy groups bonded to a silicon atom to be 1 or more, and a + b <4), the polyorganosiloxane (B) organic titanate ester and / or a portion thereof. An inorganic material obtained by applying a primer composition obtained by mixing both components of a hydrolyzate or a primer composition obtained by mixing both components (A) and (b) with an organic solvent (C), followed by baking, drying and curing. It is a primer layer. Usually a transparent film,
A colored film or an opaque film can be formed by adding a coloring agent or a filler.

The organopolysiloxane of component (A) for the primer composition is the main component of the primer composition, and is used to impart adhesiveness, particularly water-resistant adhesiveness, to the primer composition of the present invention. It has one or more hydroxyl groups or alkoxy groups in the molecule and is represented by the average composition formula (a). In the above formula, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, and specific examples thereof include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso- Substituted alkyl groups having 1 to 4 carbon atoms such as butyl group and tert-butyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and tolyl group, and their hydrogen atoms substituted with halogen atoms, cyano atoms, etc. Although what was the like in, among all R ^1, 1 carbon atoms
It is preferable that the alkyl group of 4 to 4 is contained in an amount of 40 mol% or more. R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group and a tert-butyl group, and Is 0.6 to 1.8
And b is a hydroxyl group bonded to a silicon atom in one molecule,
Alternatively, the number is one or more alkoxy groups and a + b <4.

The organopolysiloxane formula (a) containing a hydroxyl group or an alkoxy group is represented by the general formula (R ¹ ) _p
SiY _4-p (wherein R ¹ is the same as above, Y represents Cl or OR ² , R ² is the same as above, p is 0,
1, 2, or 3), each of which is a chlorosilane or an alkoxysilane having a substituted or unsubstituted monovalent hydrocarbon group, or a mixture of two or more thereof is hydrolyzed by an ordinary method under mixing with an organic solvent. It is obtained by decomposing and removing by-product hydrochloric acid, alcohol and the like.

The titanic acid ester as the component (B) for the primer composition and / or its partial hydrolyzate act as a curing catalyst for the polyorganosiloxane (A) having a hydroxyl group or an alkoxyl group. It is also a component for obtaining good adhesion of the primer composition to the substrate. As these titanate esters,
Examples include tetraethyl titanate, tetra (n-propyl titanate), tetraisopropyl titanate, tetra (n-butyl) titanate, tetra (2-ethylhexyl) titanate, and their partial hydrolysates as well. Can be used.

The amount of component (B) used in the primer composition is preferably in the range of 0.1 to 100 parts by weight per 100 parts by weight of (A). If the content of (B) is less than 0.1 part by weight, not only is the film curing slowed but also the water-resistant adhesion is reduced, which is not preferable. On the contrary, if the amount is more than 100 parts by weight, the water-resistant adhesive property is lowered and the coating becomes brittle, which is not preferable.

The organic solvent (C) for the primer composition is a component for forming a film having an appropriate thickness uniformly on the surface of the substrate with good workability. These organic solvents include alcohols such as methanol, ethanol and isopropanol; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as normal hexane and gasoline; carboxylic acids such as ethyl acetate and butyl acetate. Esters; ketones such as acetone and methyl ethyl ketone; ethers such as dimethyl ether and tetrahydrofuran: cyclic polydimethylsiloxane having 3 to 7 silicon atoms, preferably hexamethylcyclopolysiloxane, octamethylcyclopolysiloxane, decamethylcyclopolysiloxane And the like; chain polydimethylsiloxane having 2 to 20 silicon atoms and having a terminal blocked with a trimethylsiloxy group, and the like are exemplified. These solvents may be used alone or in combination of two or more.

When a colored inorganic primer layer is obtained, a colorant is also added to the primer composition. The colorant is usually an inorganic pigment (composite oxide pigment) such as CuO-. Specific examples thereof include black complex oxide pigments such as MnO—Cr ₂ O ₃ . The colorant is usually 0. 100 parts by weight of the primer composition.
It is added within a range of about 5 to 10 parts by weight so that the required transparency can be obtained.

The method of coating the primer composition includes, for example, spray coating, roll coating and dip coating, and is not particularly limited. The baking and drying temperature of the primer composition is preferably in the range of 50 to 250 ° C, and 10
More preferably, it is in the range of 0 to 250 ° C. Examples of the chemical conversion treatment layer for the underlayer include the following. When an inorganic primer layer is also provided, a chemical conversion treatment layer is formed below the inorganic primer layer.

The chemical conversion coating used in the present invention is
It refers to a film obtained by ordinary chromate treatment and phosphate conversion treatment. The chemical conversion coating is chromate chromate,
Chromate phosphate, zinc phosphate, calcium phosphate, iron phosphate and the like. Especially for stainless steel and aluminum substrates,
Chromate treatment is preferable, and in particular, chromate treatment containing silica powder or colloidal silica is preferable in order to secure long-term adhesion with the silicon compound film used in the present invention.
In addition, trivalent chromium ions may be contained in the total chromium component, but Cr ³⁺ / Cr ⁶⁺ ≦ 1 is preferable. A portion of the water-soluble organic resin may be included, but the amount of the organic resin added is 5
% Or less is good. If an amount exceeding 5% is added, the stability of the chromate solution may be deteriorated, and in terms of performance, the adhesion may be deteriorated and long-term durability may be adversely affected. Further, the chemical conversion treatment film preferably has a total chromium content of 5 mg / m ² or more. If less than 5 mg / m ² ,
Adversely affects the adhesion to the silicon compound film and the corrosion resistance. The treatment method is not particularly limited to dipping treatment, coating treatment and the like, but when the amount of treatment is too large, it is colored and is conspicuous even when the silicon compound as the second layer is coated. Therefore, the treatment method is preferably 30 mg / m ² or less. The temperature at that time may be, for example, normal temperature. Drying of the treated film after coating may be performed at room temperature, but it is better to dry at 50 ° C. or higher for workability. It is preferably 80 ° C to 120 ° C.

After the underlayer is formed, a silicon alkoxide-based coating layer is formed. In order to form this silicon alkoxide coating layer, the silicon alkoxide coating agent-A or silicon alkoxide coating agent-B described below is used. The silicon alkoxide coating agent-A contains a silicon compound represented by the general formula (I) and / or a partial hydrolyzate thereof as a main component. This silicon alkoxide-based coating agent-A is prepared by, for example, diluting a mixture containing the following components (i), (ii) and (iii) as a main component with an appropriate solvent and adding a curing agent and a required amount of a catalyst. Weight average molecular weight Mw obtained by hydrolysis and polycondensation reaction is 500 to 3,000 in terms of polystyrene.
It is preferably 0 and has a molecular weight distribution Mw / Mn of 1.1 to 3.0 (Mn is a number average molecular weight). More preferably Mw
= 600 to 3,000, and Mw / Mn = 1.2 to 1.8
Is. When the weight average molecular weight and the molecular weight distribution are smaller than the above ranges, the curing shrinkage during polycondensation tends to be large, or the coating film tends to be cracked after baking. Further, when the weight average molecular weight and the molecular weight distribution are larger than the above range, the reaction is too slow to be hardened, or even when hardened, a soft coating film is formed, or the leveling property of the coating film is very poor. I tend to become.

(I): Silicon compound represented by m = 0 in the general formula (I) and colloidal silica 20 to 20
0 parts by weight. (Ii): 100 parts by weight of a silicon compound represented by m = 1 in the general formula (I). (Iii): 0 to 80 parts by weight of a silicon compound represented by m = 2 in the general formula (I).

The colloidal silica is used by dispersing the fine particle silica component in water, an organic solvent such as methanol or a mixed solvent thereof, and as long as they are colloidal, the particle size, the solvent species, etc. It is not particularly limited. The content of the colloidal silica in the component (i) is the weight part including the dispersion medium. The curing agent used as necessary in the silicon alkoxide coating agent-A is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid, and organic acids such as formic acid, acetic acid and chloroacetic acid. An acidic catalyst such as a dilute solution of 1), a basic catalyst described later, or the like can be used alone or in combination of two or more kinds. Further, when silica sol is used as the component (i), the silica sol exhibits acidity, and this serves as a catalyst, so that nothing needs to be added as a catalyst.

Silicon Alkoxide Coating Agent-A
Can be stably used within the above-mentioned molecular weight range by adjusting its pH value to 3.8 to 6.0. If the pH value is outside the above range, the coating agent-
The stability of A may be deteriorated and the usable period after preparation of the paint may be limited. Here, the pH value adjusting method is not particularly limited, but for example, when the pH value becomes less than 3.8 when the coating agent-A raw material is mixed, a basic reagent such as ammonia is used within the above range. The pH value may be adjusted to the above pH value. If the pH value exceeds 6.0, the pH value may be adjusted using an acidic reagent such as hydrochloric acid. Further, depending on the pH value, if the reaction does not proceed while the molecular weight remains small and it takes time to reach the molecular weight range, the coating agent-A may be heated to accelerate the reaction, or the acidic reagent may be used. The pH value may be lowered to proceed the reaction, and then the pH value may be returned to a predetermined pH value with a basic reagent.

Even if the pH value is adjusted as described above, or even if the pH value is not adjusted, until use,
Or at least at the time of use, in the coating agent-A,
By adding a basic catalyst, the condensation reaction can be promoted and the number of crosslinking points in the coating film can be increased, so that a coating film having good crack resistance can be stably obtained. Further, by promoting the crosslinking reaction, the curing time can be shortened or the curing temperature can be lowered, which is economical.

The basic catalyst used as necessary in the coating agent-A is not particularly limited, but examples thereof include amines such as triethanolamine; γ-aminopropyltriethoxysilane, N- (β-amino). Ethyl) -γ-aminopropyltriethoxysilane, N-
Aminosilanes such as (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane; inorganic acids (eg hydrochloric acid, nitric acid, phosphoric acid, etc.) or organic acids (eg,
Examples thereof include salts of formic acid, acetic acid, propionic acid, etc.) such as ammonia, trimethylamine, triethylamine, n-butylamine, etc., or a metathesis salt of a salt of an inorganic acid or an organic acid with a quaternary ammonium salt. These types,
The amount added is not particularly limited.

Silicon Alkoxide Coating Agent-A
In addition to the above components, if necessary, a filler other than the silica sol (for example, an inorganic filler such as alumina sol or fumed silica), a diluting solvent, a thickener, a surfactant, an ultraviolet absorber, etc. One or more of various additives may be included. The diluting solvent is not particularly limited, but examples thereof include alcohols such as methanol, ethanol, and isopropanol (also referred to as IPA); cellosolves such as ethylene glycol, methyl cellosolve, ethyl cellosolve, and butyl cellosolve. These may be used alone or in combination of two or more.

Silicon alkoxide coating agent-A
The coating method of is not particularly limited, for example, spray coating, roll coating, flow coater coating,
Examples include dip coating. Also, the drying and baking conditions after coating are not particularly limited, but are 60 to 200 ° C.
It is preferable to carry out the process in a moderate degree. In the above composition, if the proportion of the component (i) is less than 20 parts by weight or more than 200 parts by weight, there is a problem that crack resistance is poor. When the amount of the component (ii) exceeds 80 parts by weight, the coating film is too soft to be practical.

Next, the silicon alkoxide type coating agent-B will be described. This coating agent-B is
The following components (a), (b) and (c) are essential components. (A) General formula (R ³ ) _n SiX _4-n (II) (In the formula, R ³ is each a substituted or unsubstituted C 1 to C 8
Represents a monovalent hydrocarbon group, X represents a hydrolyzable group,
n is an integer of 0-3. ) A silica-dispersed oligomer solution of organosilane, which is obtained by partially hydrolyzing a hydrolyzable organosilane represented by the formula (4) in colloidal silica dispersed in an organic solvent and / or water.

(B) Average composition formula (R ⁴ ) Si (OH) _d O _{(4-cd) / 2} (III) (In the formula, R ⁴ is a substituted or unsubstituted C 1 to C 8
Represents a monovalent hydrocarbon group, wherein c is 0.2 ≦ c ≦ 2, d is 0.0001 ≦ d ≦ 3, and c + d <4. ) A polyorganosiloxane having a silanol group in the molecule represented by the formula (1).

(C) Curing catalyst. The silica-dispersed oligomer as the component (a) used in the silicon alkoxide-based coating agent-B is the main component of the base polymer having the hydrolyzable group X, which is involved in the curing reaction during film formation. This is obtained by adding the above-mentioned general formula (II) to an organic solvent and / or water in which colloidal silica is dispersed.
With one or more of the hydrolyzable organosilanes represented by the formula (1), water in the dispersion liquid or water added separately,
It can be obtained by partially hydrolyzing this hydrolyzable organosilane.

Specific examples of R ^{3 in} the general formula (II) representing a hydrolyzable organosilane include methyl, ethyl,
Alkyl groups such as propyl, butyl, pentyl, hexyl, heptyl, octyl; cycloalkyl groups such as cyclopentyl, cyclohexyl; aralkyl groups such as 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl; aryls such as phenyl and tolyl Group: Alkenyl group such as vinyl, allyl; Halogen-substituted hydrocarbon group such as chloromethyl, γ-chloropropyl, 3,3,3-trifluoropropyl; γ-methacryloxypropyl, γ-glycidoxypropyl, 3, Substituted hydrocarbon groups such as 4-epoxycyclohexylethyl, γ-mercaptopropyl and the like can be mentioned. Among these, an alkyl group having 1 to 4 carbon atoms or a phenyl group is preferable from the viewpoint of ease of synthesis and availability.

Examples of the hydrolyzable group X include an alkoxyl group, an acetoxy group and an oxime group [-O-N = C (-
R ')-R], enoxy group [-OC (-R) = C (-
R ")-R '], amino group, aminoxy group [-ON"
(-R) -R '], amide group [-N (-R')-CO-
R] (wherein R, R ′ and R ″ are, for example, a hydrogen atom or a monovalent hydrocarbon group, etc.) and the like.Easy availability and easy preparation of a silica dispersion oligomer solution. Therefore, an alkoxyl group is preferable.

Examples of such hydrolyzable organosilanes are mono-, di-, tri-, and tetra-functional alkoxysilanes in which n in the general formula (II) is an integer of 0 to 3. , Acetoxysilanes, oxime silanes, enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Since it is easily available and a silica dispersion oligomer solution is easily prepared,
Alkoxysilanes are preferred.

Particularly, tetramethoxysilane, tetraethoxysilane and the like can be exemplified as the tetraalkoxysilane of n = 0, and methyltrimethoxysilane, methyltriethoxysilane and methyltriethoxysilane can be exemplified as the organotrialkoxysilane of n = 1. Isopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,
Examples include 3,3,3-trifluoropropyltrimethoxysilane and the like. Examples of the diorganodialkoxysilane with n = 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. Examples of the triorganoalkoxysilane with n = 3 Is trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane,
Dimethylisobutyl methoxysilane etc. can be illustrated. Furthermore, the organosilane compound generally called a silane coupling agent is also included in the alkoxysilanes.

Of the hydrolyzable organosilane represented by the general formula (II), 50 mol% or more is preferably a trifunctional one represented by n = 1, and more preferably 60 mol% or more. And most preferably 70 mol% or more. When the content of the trifunctional compound represented by n = 1 is less than 50 mol%, sufficient coating film hardness cannot be obtained and the dry curability may be poor.

The colloidal silica in the component (a) is essential for increasing the hardness of the cured coating of the silicon alkoxide coating agent-B containing the component (a). As such colloidal silica, water dispersibility,
Alternatively, non-aqueous organic solvent-dispersible colloidal silica such as alcohol can be used. Generally, such colloidal silica dispersions contain 20 to 20% silica as solids.
The content of silica is 50% by weight, and the content of silica can be determined from this value. Further, when the water-dispersible colloidal silica is used, water present as a component other than the solid content can be used for the hydrolysis of the hydrolyzable organosilane in the component (a). These are usually made from water glass, but such colloidal silica dispersions are readily available commercially.

The organic solvent-dispersed colloidal silica is
It can be easily prepared by replacing the water of the water-dispersible colloidal silica with an organic solvent. Such an organic solvent-dispersed colloidal silica can be easily obtained as a commercial product like the water-dispersible colloidal silica.
The type of organic solvent in which the colloidal silica is dispersed is, for example, methanol, ethanol, isopropanol,
lower aliphatic alcohols such as n-butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether and acetic acid ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether, or diacetone alcohol Can be mentioned. These may be used alone or in combination of two or more. 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 used.

Component (a) is a colloidal silica of 5-9.
It is preferably contained in the range of 5% by weight. The range is more preferably 10 to 90% by weight, and most preferably 20 to 85% by weight. When the content is less than 5% by weight,
If the desired coating hardness cannot be obtained, and if it exceeds 95% by weight, it may be difficult to uniformly disperse the silica, which may cause inconvenience such as gelation of the component (a).

The silica-dispersed oligomer of component (a) can usually be obtained by partially hydrolyzing a hydrolyzable organosilane in water-dispersed colloidal silica or organic solvent-dispersed colloidal silica. The amount of water used relative to the hydrolyzable organosilane is such that the hydrolyzable group (X)
0.001 to 0.5 mol of water is preferable to 1 mol.
If it is less than 0.001 mol, a sufficient partial hydrolyzate cannot be obtained, and if it exceeds 0.5 mol, the stability of the partial hydrolyzate may deteriorate. The method of partial hydrolysis is not particularly limited, but it is sufficient to mix the hydrolyzable organosilane and colloidal silica and add and mix the required amount of water, at which time the partial hydrolysis reaction proceeds at room temperature. To do.
You may heat at 60-100 degreeC in order to accelerate a partial hydrolysis reaction. Furthermore, for the purpose of promoting the partial hydrolysis reaction, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid,
An organic or inorganic acid such as citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid or oxalic acid may be used as a catalyst.

The component (a) has a pH value of the liquid of 2.0 to 7.0, preferably 2.5 to 6.5, more preferably 3.0 in order to obtain stable performance for a long period of time. It is good to set it to ~ 6.0. If the pH is out of this range, especially when the amount of water used is 0.3 mol or more per 1 mol of the hydrolyzable group (X), the long-term performance deterioration of the component (a) may be remarkable. When the pH of the component (a) is outside this range, it may be adjusted by adding a basic reagent such as ammonia or ethylenediamine if it is on the acidic side of this range, and on the basic side, hydrochloric acid may be added. It may be adjusted using an acidic reagent such as nitric acid or acetic acid. However, the adjusting method is not particularly limited.

The polyorganosiloxane having a silanol group, which is the component (b), is an important component characterizing the present invention. Such component (b) has the above-mentioned average composition formula (II
It is represented by I). In formula (III), R ⁴ is represented by the above formula (I
The same as R ^{3 in} I) is exemplified, but preferably,
Alkyl group having 1 to 4 carbon atoms, phenyl group, vinyl group, γ
-Substituted hydrocarbon groups such as glycidoxypropyl group, γ-methacryloxypropyl group, γ-aminopropyl group and 3,3,3-trifluoropropyl group, more preferably methyl group or phenyl group. In the formula (III),
c and d are numbers satisfying the above relationship, and c
Is less than 0.2 or d is more than 3, there is an inconvenience such as cracking of the cured film, and c is more than 2 d
Is less than 0.0001, curing does not proceed favorably.

As the polyorganosiloxane having such a silanol group, for example, one or more kinds of known compounds such as methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, or an alkoxysilane corresponding thereto are known. It can be obtained by hydrolyzing with a large amount of water according to the above method. When a polyorganosiloxane having a silanol group is hydrolyzed by a known method using an alkoxysilane, a small amount of unhydrolyzed alkoxyl group may remain. That is, a polyorganosiloxane in which a silanol group and an extremely small amount of an alkoxyl group coexist may be obtained, but in the present invention, such a polyorganosiloxane can also be used.

Silicon alkoxide type coating agent-B
The curing catalyst which is the component (c) of (1) accelerates the condensation reaction between the component (a) and the component (b) to cure the coating. Such a catalyst is not particularly limited, but examples thereof include alkyl titanate, tin octylate,
Metal salts of carboxylic acids such as dibutyltin dilaurate and dioctyltin dimaleate; amine salts such as dibutylamine-2-hexoate, dimethylamine acetate, ethanolamine acetate; carboxylic acid quaternary ammonium salts such as tetramethylammonium acetate; tetraethylene Amines such as pentamine; N-β-aminoethyl-γ
-Amine-based silane coupling agents such as aminopropyltrimethoxysilane and N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid, hydrochloric acid; aluminum alkoxides, aluminum chelates, etc. Aluminum compounds of
Examples thereof include alkali metal hydroxides such as potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate and titanium tetraacetylacetonate; halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane and trimethylmonochlorosilane. However, other than these catalysts, any catalyst can be used as long as it is effective in promoting the condensation reaction between the component (a) and the component (b), and there is no particular limitation.

The mixing ratio of the component (a) and the component (b) is such that the total amount of the component (a) and the component (b) is 100 parts by weight and the component (b) is 1 to 99 parts by weight. ) 9
9 to 1 part by weight, more preferably component (a) 5 to 9
95 to 5 parts by weight of component (b) to 5 parts by weight, particularly preferably component (b) to 10 to 90 parts by weight of component (a).
90 to 10 parts by weight. When the amount of the component (a) is less than 1 part by weight, the room temperature curability is poor, and sufficient coating hardness cannot be obtained. On the other hand, when the component (a) exceeds 99 parts by weight,
The curability may be unstable and a good coating film may not be obtained.

The amount of the component (c) added is 0.0001 to 10 with respect to 100 parts by weight of the total of the components (a) and (b).
It is preferably part by weight, more preferably 0.00
05 to 8 parts by weight, and particularly preferably 0.0007 to
5 parts by weight. If the addition amount of the component (c) is less than 0.0001 parts by weight, it may not be cured at room temperature, and if it exceeds 10 parts by weight, heat resistance and weather resistance may be deteriorated.

The hydrolyzable group contained in the silica-dispersed oligomer of component (a) and the silanol group of component (b) are
In the presence of the curing catalyst of the component (c), the condensation reaction is performed at room temperature or low temperature (for example, a temperature of 100 ° C. or less) to form a cured film. Therefore, unlike the moisture-curing type coating composition, the silicon alkoxide-based coating agent-B used in the present invention is hardly affected by humidity even when cured at room temperature. On the other hand, the heat treatment can accelerate the condensation reaction to form a cured film.

Silicon alkoxide type coating agent-B
In addition to the above components, if necessary, various fillers (inorganic fillers such as alumina sol and fumed silica) other than the silica sol, diluting solvents, thickeners, surfactants, ultraviolet absorbers, etc. One or more kinds of additives may be contained.
The diluting solvent is not particularly limited, but for example, methanol, ethanol, isopropanol (IP
Alcohols such as A); ethylene glycol monomethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and other cellosolves. These may be used alone or in combination of two or more. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, etc. can also be used.

Silicon alkoxide type coating agent-B
The storage method for the components is (a), (b) and (c)
It is common to take three packaging forms in which each is stored separately, but the mixed component of the component (a) and the component (c) and the component (b) are divided into two packaging forms, and both are mixed at the time of use. Alternatively, all the components may be mixed and stored in one container in one packaging form.

Silicon alkoxide type coating agent-B
Can be coated by a usual coating method, and various coating methods such as brush coating, spray coating, roll coating, flow coater coating and dip coating can be selected. The curing conditions are preferably 5 to 200 ° C., and 10 to 15
0 ° C is more preferable. If it is less than 5 ° C, it becomes difficult to cure, and if it exceeds 200 ° C, foaming may occur. The coating thickness of the second layer is preferably 3 μm or more after curing. If it is less than 3 μm, pinholes are likely to be formed, and the anticorrosion property may be deteriorated.

[0054]

In the case of the building material of the present invention, since the inorganic coating film having high durability is provided on the surface of the metal material as the base, the long-term durability is sufficient, and the fluorine-based film, the acrylic Unlike the case of laminating a metal-based material on a metal-based material, it can handle various shapes, and it does not require special bonding work to prevent water leakage as in the case of an organic fluorine-based coating The decrease is not a problem.

In the case of the present invention, the surface of the metallic material is mirror-finished and has a strong metallic feeling, and since the inorganic coating film is transparent and has a hard feeling, the metallic feeling is maintained without being impaired. In the case of the present invention, in addition, the inorganic coating film is less likely to be touched by the hands and is less likely to get dirty.

[0056]

EXAMPLES Examples and comparative examples of the present invention will be shown below.
The present invention is not limited to the examples below. In the following, as a general rule, “part” means “part by weight” and “%” means “% by weight”.

Table 1 shows the treatment for forming the chemical conversion treatment layer used in the examples. Table 2 shows the primer composition for the inorganic primer layer used in the examples. The primer composition shown in Table 2 was obtained as follows. Preparation of Silicone Resin Solution (S-1) 70 parts of methyltrichlorosilane, 6 parts of dimethyldichlorosilane and 3 parts of tetrachlorosilane were mixed with 85 parts of toluene, and this was mixed with 200 parts of water in a container equipped with a reflux condenser and n. -In a mixed solution with 50 parts of butanol, the temperature was kept at 50 ° C or lower and the mixture was added dropwise with stirring to carry out hydrolysis and condensation.

The produced polymethylsiloxane was washed with water to remove by-produced hydrogen chloride. This is heated under pressure to remove the water present as part of the solvent,
% Silicone resin toluene solution was obtained. Preparation of Silicone Resin Solution (S-2) 33 parts of methyltrichlorosilane, 28 parts of dimethyldichlorosilane, and 75 parts of phenyltrichlorosilane were mixed with 130 parts of toluene, and this was mixed with 150 parts of water in a container equipped with a reflux condenser. In a mixed solution with 70 parts of acetone, the temperature was adjusted to 5
While maintaining the temperature at 0 ° C or lower, the mixture was added dropwise with stirring to carry out hydrolysis and condensation.

The polymethylphenylsiloxane produced was washed with water to remove by-produced hydrogen chloride. This is heated under pressure to remove water present as part of the solvent,
A toluene solution of silicone resin having a concentration of 50% was obtained. Primer composition For the silicone resin toluene solution S-1 or 2,
As shown in Table 2, the titanate ester and the solvent were added to prepare primer compositions P-1 to P-3.
It should be noted that only the primer composition P-2 was prepared by adding 3 parts of CuO—MnO—Cr ₂ O ₃ composite oxide fine particulate pigment for black as a colorant to 100 parts of a black transparent film. Become.

[0060]

[Table 1]

[0061]

[Table 2]

The silicon alkoxide-based coating agents used in the following Examples and Comparative Examples are A-shown below.
1, A-2, B-1 are used. Preparation of Silicon Alkoxide Coating Agent-A (A-1) 100 parts of methyltrimethoxysilane, 20 parts of tetraethoxysilane, IPA organosilica sol (trade name "OS
CAL1432 ", manufactured by Catalysts & Chemicals Industry Co., Ltd., SiO ₂ content 30%) 150 parts, dimethyldimethoxysilane 40
And 100 parts of isopropyl alcohol (IPA) were mixed, and 200 parts of water was further added and stirred. By adjusting the molecular weight Mw to 1200 in a constant temperature bath at 60 ° C., a silicon alkoxide coating agent A-1 was prepared.
Got The molecular weight is GPC (gel permeation chromatography, manufactured by Tosoh Corporation: HLC802).
0) was used to prepare a calibration curve with standard polystyrene, and measurement was performed.

Silicon Alkoxide Coating Agent-A
Preparation of (A-2) 100 parts of methyltrimethoxysilane, 10 parts of tetraethoxysilane, IPA organosilica sol (trade name "OS
CAL1432 ", manufactured by Catalysts & Chemicals Industry Co., Ltd., SiO ₂ content 30%) 110 parts, dimethyldimethoxysilane 20
Parts and 100 parts of isopropyl alcohol (IPA) were mixed. To this mixed solution, 1 part of 1N hydrochloric acid and 5 parts of water were added as a catalyst to prepare S-1 liquid.

To 100 parts of this S-1 solution, 0.3 part of powdered silica (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.) was added. Using a disper, glass beads were added in the container and dispersed at 2000 rpm for 15 minutes to obtain S
-2 liquid was tightly stoppered and stored at 25 ° C for 3 days. When using,
To 100 parts of S-2 liquid, 27 parts of water, 27 parts of IPA and 0.2 part of 1N hydrochloric acid as a catalyst were added, and the mixture was heated to 500 at 25 ° C.
A silicon alkoxide coating agent A-2 was obtained by stirring at rpm for 10 minutes.

Silicon alkoxide coating agent-B
Preparation of (B-1) Preparation of component (a) Isopropanol-dispersed colloidal silica sol IPA-ST (particle size 10 to 20 μm, solid content 30%, Nissan Chemical Co., Ltd.) in a flask equipped with a stirrer, heating jacket, condenser and thermometer. (Manufactured by Kogyo Co., Ltd.) 100 parts, methyltrimethoxysilane 65 parts, and water 5.05 parts are added and stirred to carry out a partial hydrolysis reaction at 65 ° C. for 5 hours, and then cooled to obtain a component ( a) was obtained. This product had a solid content of 36% when left to stand at room temperature for 48 hours. The preparation conditions for this component (a) are as follows.

Molar number of water to 1 mol of hydrolyzable group: 0.1 mol Silica content: 47.2% Mol% of hydrolyzable group-containing organosilane of n = 1: 100 mol% component Preparation of (b) A mixed solution of 220 parts (1 mol) of methyltriisopropoxysilane and 160 parts of toluene was weighed and charged into a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer, and then, 105 parts of a 1% aqueous hydrochloric acid solution was added dropwise to the above-mentioned stirred mixed solution over 30 minutes to hydrolyze methyltriisopropoxysilane. After a lapse of 40 minutes from the completion of the dropping, the stirring was stopped and the lower layer mixed solution of water and isopropyl alcohol containing a small amount of hydrochloric acid separated into two layers was separated. Then, the remaining residual hydrochloric acid in the solution containing toluene and the resin is removed by washing with water, and the toluene is further removed under reduced pressure, followed by diluting with isopropyl alcohol to give an average molecular weight of about 2
000 silanol group-containing polyorganosiloxane (polymer silanol) (component (b)) in 40% isopropyl alcohol was obtained. The molecular weight is GPC (gel permeation chromatography, Tosoh Corporation).
(Manufactured by: HLC-802UR), a calibration curve was prepared using standard polystyrene and measured.

In use, 3 parts of # 200 manufactured by Nippon Aerosil Co., Ltd. as fumed silica was added to 100 parts of the component (a) obtained above, and then treated with a sand mill at 1000 rpm for 20 minutes. To the obtained liquid, 0.5 part of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane and 1 part of dibutyltin dilaurate were added as a curing catalyst for the component (c) to prepare a liquid A '. This liquid A'and a silanol group-containing polyorganosiloxane (component (b)) obtained above in a 40% isopropyl alcohol solution have a weight ratio of component (a) and component (b) of 50:50. By thus mixing, a silicon alkoxide coating agent B-1 was obtained.

In the case of the silicon alkoxide type coating agent used in the examples, a colorant is blended. The colorant may be mixed at any time, either midway or last, and is not limited to a specific timing. Silicon alkoxide coating agent-C-1 This is silicon alkoxide coating agent A-1 itself, and a colorless and transparent film is obtained.

[0069] The silicon alkoxide-based coating agent -C-2 silicon alkoxide-based coating agent A-1, CuO-MnO- Cr 2 O 3 composite oxide particulate pigment for black based as a colorant silicon alkoxide-based coating agent 1
It is added in a ratio of 1.5 parts with respect to 00 parts, and a transparent black coating film can be formed.

Silicon alkoxide coating agent-C-3 In addition to the silicon alkoxide coating agent A-1, a black CuO—MnO—Cr ₂ O ₃ composite oxide fine particle pigment as a coloring agent is added to the silicon alkoxide coating agent 1
It is added at a ratio of 4 parts with respect to 00 parts, and a darker color coating film can be formed as compared with the case of using the coating agent-C-2.

Silicon Alkoxide Coating Agent-C-4 In addition to the silicon alkoxide coating agent A-2, a black CuO—MnO—Cr ₂ O ₃ composite oxide fine particle pigment as a coloring agent is added to the silicon alkoxide coating agent 1
It is added at a ratio of 4 parts with respect to 00 parts, and a transparent black coating film can be formed.

Silicon alkoxide coating agent-C-5 This is silicon alkoxide coating agent B-1 itself, and a colorless and transparent film is obtained. The silicon alkoxide-based coating agent -C-6 silicon alkoxide-based coating agent B-1, CuO-MnO- Cr 2 for blackish as a colorant O ₃ composite oxide particulate pigment is silicon alkoxide-based coating agent 1
It is added at a ratio of 4 parts with respect to 00 parts, and a transparent black coating film can be formed.

-Examples 1 to 24-In Examples, according to Tables 3 and 4, a metal base material molded into a building material was used, and a chemical conversion treatment layer, an inorganic primer layer and a transparent inorganic coating film were sequentially formed to construct the building. I got the materials. Degreasing was performed before forming the chemical conversion treatment layer. Degreasing is
For example, after performing alkaline degreasing, it was washed with ion-exchanged water and then dried at 120 ° C. for 10 minutes. The thickness of the chemical conversion treatment layer is about 80Å.

For the inorganic primer layer, a primer composition is applied so as to have a film thickness of 4 to 6 μm, the setting time is kept for 5 minutes, baking is performed at 150 ° C. for 30 minutes, and the temperature is cooled to room temperature. Then, the silicon alkoxide coating is applied. The agent was spray coated to a film thickness of about 10 μm, and baking was carried out at 150 to 180 ° C. for 15 to 30 minutes to form a transparent inorganic coating film.

It should be noted that # 700 and # 1000 in the table indicate the degree of polishing of the mirror surface of the surface.
It shows that the mirror surface is the same as the polished mirror surface obtained by polishing with No. 1000 paper. -Comparative Examples 1 to 6- The building materials of Comparative Examples are as shown in Table 5, and the organic coating film is an acrylic coating film.

[0076]

[Table 3]

[0077]

[Table 4]

[0078]

[Table 5]

The building materials obtained in the above Examples and Comparative Examples were examined for coating adhesion, corrosion resistance, weather resistance, and appearance evaluation according to whether or not a handprint remained after being touched by human hands. . The adhesion of the coating film was confirmed by immersing the stainless steel-coated article in boiling water for 5 hours, air-drying it, and using an adhesive tape (cellophane tape) within 3 hours.

Corrosion resistance is determined by salt spray test 2,000.
The condition after 0 hours was visually evaluated. Weather resistance is ice-
With the Per UV tester, make the following conditions 1 cycle (8 hours + 4 hours = 12 hours 1 cycle) UV test
The situation after the irradiation time of 1,000 hours was evaluated. Test conditions Time: 8 hours 4 hours UV irradiation: Yes (100 mW / cm ² ) No Temperature: 63 ° C. 35 ° C. Humidity: 50% 90% or more (with condensation) The results are shown in Tables 6-8.

[0081]

[Table 6]

[0082]

[Table 7]

[0083]

[Table 8]

As can be seen from Tables 6 to 8, the building materials of Examples had sufficient coating film adhesion, corrosion resistance, and weather resistance, and moreover, the shape of the hand, even when touched by a person, was small. Everything was excellent in appearance evaluation, and was confirmed to be superior to conventional building materials. Of course, it was also visually confirmed that the building materials of the examples had a metallic feeling not inferior to the building materials of Comparative Examples 1 to 3.

[0085]

EFFECTS OF THE INVENTION In the case of the building material of the present invention, since the inorganic material coating film having high durability is provided on the surface of the metal material as the base, long-term durability is sufficient and the fluorine-based film Unlike the case of laminating acrylic film, etc. on a metal material, it can be applied to various shapes, and it does not require special adhesion work to prevent water leakage as in the case of organic fluorine-based coating. In addition, the inorganic coating film is transparent and rich in hard feeling, and the metallic feeling generated by the mirror surface of the base metallic material is not impaired and high design is realized. And
Moreover, the inorganic coating film is hard to touch and does not become dirty, and can sufficiently meet the market needs.

Claims (1)

[Claims] 1. A building material, which is based on a metal material which is processed into a predetermined shape and whose surface is mirror-finished, on which a transparent inorganic coating film is provided on the mirror-finished mirror surface. .