JPH06269732A - Building material - Google Patents

Abstract

PURPOSE:To provide a building material having a long-term durability, realizing high design property and capable of responding to various market needs. CONSTITUTION:The building material comprises a metallic base stock formed by being worked to a specified shape and by being treated with a rugged pattern on the surface as the base, and an inorg. coating film formed on the surface treated with the rugged pattern.

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 metal material such as a metal panel or a metal gutter.

[0002]

2. Description of the Related Art With the advancement of high-grade buildings, maintenance-free construction, fashionable construction, etc., panels and rain gutters based on metal materials have high design characteristics for a long time by taking advantage of metallic material feeling such as stainless steel. It is desired to create panels and rain gutters that are durable and have good workability.

[0003]

For example, a rain gutter and a panel formed by directly shaping a metal material may be affected by sea salt, acid rain, air pollutants (sulfurous acid gas, soot, automobile exhaust gas, etc.). Abnormality in appearance due to corrosion, corrosion, or contamination easily occurs, and in severe cases, perforation results in drainage function failure, 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. Alternatively, in the case of laminating a fluorine-based film, an acrylic film, or the like on a metal material, it is difficult to deal with various shaped products and there is a difficulty in processing the film end portion, so that only a limited shape can be applied. In addition, especially, a fluorine-based film that is organic and has excellent weather resistance can be coated well, and its long-term durability can be secured to some extent,
In rain gutters and the like, joining at the time of construction and bonding work to prevent water leakage are not possible unless a special method is used, and there is a problem of poor workability.

It is an object of the present invention to solve these problems, to provide a building material having long-term durability, high designability, and capable of meeting the above market needs. To do.

[0006]

In order to solve the above-mentioned problems, a building material according to the present invention is based on a metal-based material which is processed into a predetermined shape and has an uneven pattern on its surface. An inorganic coating film is provided on the surface to be applied. Hereinafter, the present invention will be described more specifically.

Types of building materials of the present invention include rain gutters and panels, but it goes without saying that they are not limited to these. 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. The concavo-convex pattern on the surface of the metallic material of the building material of the present invention is not limited to a specific one, and is formed by etching or embossing using a pressure roll, and has a striped or pear-like pattern. Are exemplified. The depth of the unevenness of the pattern varies depending on the type of building material, but is, for example, about 0.5 to 3 mm.

Examples of the inorganic coating film in the building material of the present invention include a silicon alkoxide coating film. The inorganic coating film may be a transparent film or an opaque film, and both the transparent film and the opaque film may be colorless or may be colored. In the case of a colored film, examples of colors include black, brown, and gray. In the case of a colored film, the film has a very excellent design due to the synergistic effect of unevenness and coloring.

The above silicon alkoxide coating film is exemplified by one obtained by coating 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.

As described above, the color of the colored film may be black, brown, gray or the like. These colored films can be realized, for example, by adding a colorant to a silicon alkoxide-based coating agent, and the colorant is usually an inorganic pigment (composite oxide pigment) such as CuO-MnO. Specific examples include black complex oxide pigments such as —Cr ₂ O ₃ .

The colorant is usually added in an amount of about 1 to 50 parts by weight to 100 parts by weight of the silicon alkoxide coating agent. The silicon alkoxide-based coating film is preferably formed by forming an underlayer on the surface of the metal-based material that is the base in advance. The base layer includes a chemical conversion treatment layer, an organic primer layer, and an inorganic primer layer, as well as a laminated structure of these, that is, a layer in which an organic primer layer is laminated on the chemical conversion treatment layer, and a chemical conversion treatment layer. Examples thereof include those in which an inorganic primer layer is laminated.

As the organic primer layer for the underlayer,
For example, a primer layer formed by applying the following primer composition may be mentioned. That is, silicone-modified epoxy resin 40 to 60 parts by weight melamine resin 3 to 5 parts by weight inorganic color pigment and / or extender pigment 11 to 23 parts by weight One or more organic solvents capable of dissolving the above 12 to 44 Parts by weight (however, the total content (PWC) of the above pigments is 35 to 45% by weight based on the total solid content of the primer composition.
Is. The primer layer which applied and hardened the primer composition which mix | blended each component of 1) was mentioned.

The silicone-modified epoxy resin which is a component of the primer composition is not particularly limited,
For example, silicone-modified epoxy resin was alternating structure of epoxy resins with chelate ligand functional groups: (- (epoxy) - (P _A) - (epoxy) - (P _B)
-) _{N and the} like.

The molecular weight of the silicone-modified epoxy resin is not particularly limited, but it may be two, one having a number average molecular weight of 5,000 to 10,000 and one having a number average molecular weight of 20,000 to 40,000. It is preferable to use different types together. In this invention, the excellent adhesion of the primer to the stainless steel substrate is due to the following reasons (1) and (2).

(1) Since the epoxy resin is modified to contain appropriate epoxy groups and hydroxyl groups, the hydrogen bonding force between the epoxy resin and the stainless steel substrate is strong. (2) As shown in Chemical Formula 1 below, the silicone-modified epoxy resin forms an oxane bond with the hydroxyl group on the surface of the stainless steel substrate, and at the same time imparts the property of bridging by the reaction with the resin functional group and only strengthens the initial adhesion. In addition, the secondary (evaluation after accelerated deterioration of the coating film) adhesion can also be maintained.

[0017]

[Chemical 1]

The melamine resin, which is a component of the primer composition, is used for thermal crosslinking. Examples of the melamine resin include, but are not limited to, methylrolled melamine and trimethylrolled melamine. Inorganic coloring pigment which is a component of the primer composition and / or
Alternatively, of the extender pigments, the inorganic color pigment is not particularly limited, and examples thereof include a calcined pigment such as titanium oxide. The extender pigment is not particularly limited, and examples thereof include talc; rust preventive pigments such as aluminum phosphomolybdate. However, the content (hereinafter, referred to as “PWC”) of the inorganic color pigment or the extender pigment (total when used together) is 35 with respect to the total solid content of the primer composition.
~ 45% by weight. When PWC is out of this range,
This is because problems arise in adhesion and water resistance.

The solvent capable of dissolving the silicone-modified epoxy resin and the melamine resin, which are components of the primer composition, is not particularly limited, but examples thereof include alcohol solvents, glycol solvents, aromatic hydrocarbon solvents and the like. Can be mentioned. More specific examples of these solvents.
It is as follows. Alcohol-based solvent: butyl alcohol, etc.

Glucol type solvent: butyl cellosolve, methoxypropanol and the like. Aromatic hydrocarbon solvent: xylene, toluene, etc. As the solvent, only one kind may be used, or two or more kinds may be used in combination. The primer composition may contain various additives as needed. The additive is not particularly limited, and examples thereof include a titanate coupling agent, an antisettling agent, a dispersant, and the like.

When the alcohol solvent, the glycol solvent and the aromatic hydrocarbon solvent are used in combination as the solvent and the additive is used, the composition of each component of the primer composition is not particularly limited. However, the following examples are given. Silicone-modified epoxy resin 40.0 to 60.0 parts by weight Melamine resin 3.0 to 5.0 parts by weight Inorganic coloring pigment 7.0 to 13.0 parts by weight Body pigment 4.0 to 10.0 parts by weight Alcohol-based Solvent 6.0 to 10.0 parts by weight Glucol-based solvent 7.0 to 11.0 parts by weight Aromatic hydrocarbon solvent 9.0 to 13.0 parts by weight Additive 0.5 to 1.5 parts by weight Primer composition The method of coating the material on the stainless steel substrate is not particularly limited, and examples thereof include spray coating, roll coating, and dip coating.

The coating amount of the primer is preferably 5 to 1
The thickness is 00 μm, more preferably 15 to 40 μm. 5μ
When it is less than m, the hiding power to the base is lost,
This is because there is a problem in adhesion, and when it exceeds 100 μm, problems such as foaming tend to occur during baking, which is not preferable. The baking and drying temperature of the primer composition is preferably in the range of 50 to 200 ° C.
It is more preferably in the range of 20 to 180 ° C.

Examples of the chemical conversion treatment layer for the underlayer include the following chemical conversion treatment films. The chemical conversion coating used in the present invention refers to a coating obtained by ordinary chromate treatment and phosphate chemical conversion treatment. Examples of the chemical conversion coating include chromate chromate, chromate phosphate, zinc phosphate, calcium phosphate, iron phosphate and the like. In particular, chromate treatment is preferable for stainless steel and aluminum substrates, and chromate treatment containing silica powder or colloidal silica is preferable for ensuring long-term adhesion with the silicon compound coating used in the present invention. In addition, although it may contain trivalent chromium ions in the total chromium component, Cr ³⁺ / Cr ⁶⁺ ≤
1 is preferred. Although it may contain a part of a water-soluble organic resin,
The amount of organic resin added is preferably 5% or less. 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 it is less than 5 mg / m ² , the adhesion to the silicon compound coating and the corrosion resistance are adversely affected. 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.

The chemical conversion coating alone does not have water resistance (for example, Cr ⁶⁺ flows out) for a long period of time, and has insufficient corrosion resistance. After the primer layer is formed, the silicon alkoxide-based coating layer is formed. In order to form this silicon alkoxide coating layer, a silicon alkoxide coating agent-A or a silicon alkoxide coating agent-B described below is formed.
Is used.

Silicon alkoxide type coating agent-A
Is a silicon compound represented by the general formula (I) and /
Alternatively, the main component is a partial hydrolyzate thereof.
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 catalyst in required amounts. The weight average molecular weight Mw obtained by hydrolysis and polycondensation reaction is 500 to polystyrene equivalent.
3,000 and molecular weight distribution Mw / Mn of 1.1 to 3.0
(Mn is a number average molecular weight) is preferable. More preferably Mw = 600 to 3,000 and Mw / Mn = 1.2
Is about 1.8. 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 a fine particle silica component in water, an organic solvent such as methanol, or a mixed solvent thereof. As long as they are colloidal, the particle size, solvent type, 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,
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 group, respectively.
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 the hydrolyzable organosilane are 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 are 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.

In particular, 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 film 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 such polyorganosiloxane having a silanol group, for example, one or more kinds of known compounds such as methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, and alkoxysilanes 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 compounding 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 relative 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.

[0055]

In the case of the present invention, since a highly durable inorganic coating film is formed on the surface of the metal material as the base,
It is sufficient in terms of long-term durability, and since it is a coating film, it can handle various shaped products unlike the case of laminating a fluorine-based film, an acrylic film, etc. on a metal material, and an organic fluorine-based coating. There is no need for special bonding work to prevent water leaks, and workability deterioration does not pose a problem. Since the inorganic coating film is formed on the surface of the uneven pattern, the adhesion area is increased and the anchoring effect improves the adhesiveness, and the uneven pattern appears on the surface, so high designability is also realized. .

[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”. The primer composition P-1 used in the following examples is shown in Table 1 and below. Table 2 also shows the treatment for forming the chemical conversion treatment layer used in the following examples.

Primer Composition P-1 As the primer composition P-1, E-1 baking primer F-039 manufactured by Isamu Paint Co., Ltd. was used. This E-1
The baking primer F-039 was prepared by the following procedure. First, a silicone-modified epoxy resin having an alternating structure of an epoxy resin with chelate-coordinating functional groups (having a molecular weight of 5,000 to 10,000 and 20,000)
To 50 parts of 0 to 40,000 and 50 parts of melamine resin, 23 parts of a mixed solvent of butyl alcohol, butyl celloslub and xylene in a weight ratio of 8: 9: 6 is added as a solvent, and 1000 rpm by a disper. Stir for 15 minutes. After 15 minutes, a total of 7 parts of titanium oxide as an inorganic color pigment and talc and aluminum phosphomolybdate as an extender pigment are added with further stirring. After that, stirring is continued for about 10 minutes to perform rough kneading. The liquid after the rough kneading is dispersed in a sand grind mill, and after the dispersion is completed, 5 parts of xylene is added to obtain a primer F-039.

[0058]

[Table 1]

[0059]

[Table 2]

The silicon alkoxide coating agents used in the following examples and comparative examples are as follows. Silicon alkoxide coating agent-A (A-1)
Preparation 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 type 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.

Mol number of water per mol of hydrolyzable group: 0.1 mol Silica content: 47.2% Mol% of hydrolyzable group-containing organosilane with 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 placed in 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 were 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.

Silicon Alkoxide Coating Agent-A
Preparation of (A-3) A silicon alkoxide coating agent 1 was prepared by adding a black-colored CuO—MnO—Cr ₂ O ₃ composite oxide fine particle pigment as a colorant to the silicon alkoxide coating agent A-1.
It was compounded in a ratio of 3 parts to 00 parts. Silicon alkoxide coating agent-A (A-4)
Preparation silicon alkoxide-based coating agent A-2, CuO-MnO- Cr 2 for blackish as a colorant O ₃ composite oxide particulate pigment silicon alkoxide-based coating agent 1
It was compounded in a ratio of 3 parts to 00 parts.

Silicon Alkoxide Coating Agent-B
(B-2) Preparation of silicon alkoxide-based coating agent B-1 of, CuO-MnO-Cr ₂ for blackish as a colorant O ₃ composite oxide particulate pigment silicon alkoxide-based coating agent 1
It was compounded in a ratio of 3 parts to 00 parts. Silicon alkoxide coating agent-A (A-5)
The prepared silicon alkoxide-based coating agent A-1 was mixed with 35 parts of a black CuO—MnO—Cr ₂ O ₃ composite oxide pigment as a colorant per 100 parts of the silicon alkoxide-based coating agent.

Silicon Alkoxide Coating Agent-A
Preparation of (A-6) In the silicon alkoxide coating agent A-2, a black CuO—MnO—Cr ₂ O ₃ composite oxide pigment as a colorant is used in a ratio of 35 parts per 100 parts of the silicon alkoxide coating agent. Blended in. Silicon alkoxide-based coating agent-B (B-3)
Preparation silicon alkoxide-based coating agent B-1, a CuO-MnO-Cr ₂ O ₃ composite oxide pigments for black-based blended at a ratio of 35 parts per 100 parts of silicon alkoxide-based coating agent as a coloring agent.

Silicon Alkoxide Coating Agent-B
Preparation of (B-3) The timing of adding the colorant may be during the adjustment or at the final stage, and is not limited to a specific stage. In the examples, B-1 to B-3 were cured at room temperature. When 3 parts of the coloring agent is added, it becomes a transparent film, and when 35 parts of the coloring agent is added, it becomes an opaque film. -Examples 1 to 6-In Examples 1 to 6, as shown in Table 3, a silicon alkoxide-based coating is used after forming a building material and using a metal base material having an uneven pattern on the surface, followed by surface treatment. Using the agent, a transparent inorganic coating film was formed on the surface having an uneven pattern. The pear ground pattern has a depth of 2 mm and the striped pattern has a depth of 2.5 mm, and the pattern is formed by roll molding.

Degreasing was performed before forming the underlayer. Degreasing was performed, for example, by performing alkaline degreasing, washing with ion-exchanged water, and then drying at 120 ° C. for 10 minutes. When P-1 was used as the primer composition, the film thickness was 20 μm by spray coating, and baking was performed at 150 ° C. for 20 minutes.
I went for a minute. Silicon alkoxide coating agent A-
1 is spray-painted, the film thickness is 25 μm, and baking is 1
It was carried out at 50 to 180 ° C. for 15 to 30 minutes.

-Examples 7 to 12-In Examples 7 to 12, as shown in Table 4, Example 1 except that the silicon alkoxide-based coating agent was A-2.
Approximately the same as ~ 6. -Examples 13 to 18-In Examples 13 to 18, as shown in Table 5, substantially the same as Examples 1 to 6 except that the silicon alkoxide-based coating agent was B-1.

-Examples 19 to 24-In Examples 19 to 24, as shown in Table 6, substantially the same as Examples 1 to 6 except that the silicon alkoxide coating agent was A-3. -Examples 25 to 30-In Examples 25 to 30, as shown in Table 7, substantially the same as Examples 1 to 6 except that the silicon alkoxide-based coating agent was A-4.

-Examples 31 to 36-Examples 31 to 36 were almost the same as Examples 1 to 6 except that the silicon alkoxide coating agent was B-2 as shown in Table 8. -Examples 37 to 42-In Examples 37 to 42, as shown in Table 9, substantially the same as Examples 1 to 6 except that the silicon alkoxide-based coating agent was A-5.

-Examples 43 to 48-In Examples 43 to 48, as shown in Table 10, substantially the same as Examples 1 to 6 except that the silicon alkoxide coating agent was A-6. -Examples 49 to 54-In Examples 49 to 54, as shown in Table 11, substantially the same as Examples 1 to 6 except that the silicon alkoxide-based coating agent was B-3.

Comparative Example 1 In Comparative Example 1, as shown in Table 12, the same procedure as in Example 1 was performed except that there was no uneven pattern. -Comparative Example 2-In Comparative Example 2, as shown in Table 12, the same procedure as in Example 3 was performed except that there was no uneven pattern.

Comparative Example 3 In Comparative Example 3, as shown in Table 12, the same procedure as in Example 5 was carried out except that there was no uneven pattern. -Comparative Example 4-In Comparative Example 4, as shown in Table 12, the same procedure as in Example 6 was carried out except that there was no uneven pattern.

Comparative Example 5 Comparative Example 5 was the same as Comparative Example 1 except that an organic coating film was formed from an acrylic-silicon coating material instead of the silicon alkoxide coating film. The coating materials, the corrosion resistance and the weather resistance of the building materials obtained in the above Examples and Comparative Examples were examined.

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 adhesive tape (cellophane tape) within 3 hours. The corrosion resistance was visually evaluated after 2,000 hours from the salt spray test.
The weather resistance was evaluated with an ice-per UV tester after performing a test under the following conditions as one cycle (8 hours + 4 hours = 12 hours for one cycle) up to a UV irradiation time of 1,000 hours.

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 also shown in each table.

[0080]

[Table 3]

[0081]

[Table 4]

[0082]

[Table 5]

[0083]

[Table 6]

[0084]

[Table 7]

[0085]

[Table 8]

[0086]

[Table 9]

[0087]

[Table 10]

[0088]

[Table 11]

[0089]

[Table 12]

As can be seen from the tables, the building materials of the examples have sufficient coating adhesion, corrosion resistance and weather resistance, and are superior to the building materials of the comparative examples. confirmed.

[0091]

In the case of the present invention, since a highly durable inorganic coating film is formed on the surface of the metal material as the base, it has sufficient long-term durability, and since it is a coating film, the film is Unlike the case of laminating on a metal material, it can be used for various shapes, and it does not require special adhesion work to prevent water leakage, and it does not pose a problem of workability deterioration. Since it is formed on the surface of the uneven pattern, the adhesion area is increased and the anchoring effect improves the adhesion, and since the uneven pattern is exposed on the surface, high designability can be realized. The building materials are very useful.

Claims (1)

[Claims] 1. A building material, which is based on a metal-based material that is processed into a predetermined shape and has an uneven pattern on its surface, and has an inorganic coating film on the surface having the uneven pattern.