JP2564775B2 - Painting method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating method, and more particularly, to the surface of steel, stainless steel, aluminum, ceramics, cement, paper, glass, plastics, inorganic ceramic substrates, etc. The present invention relates to a coating method for forming a coating film having excellent properties, chemical resistance, and adhesion.

[0002]

2. Description of the Related Art Conventionally, paints using an organic polymer such as acrylic emulsion, acrylic resin, urethane resin, polyester resin, etc. as a vehicle have been used for the purpose of surface makeup of base materials. Inferior, there is a problem in the durability of the coating film. Further, a coating composition in which a pigment is dispersed in a dispersion liquid of a hydrolyzed / condensed product of organoalkoxysilane and colloidal silica has been proposed (Japanese Patent Publication No. 53-5042), but the alkali resistance of the coating film is poor. Have the problem. Furthermore, as a composition having excellent weather resistance and alkali resistance, a composition comprising a hydrolysis / condensation product of an organoalkoxysilane, a chelate of a zirconium alkoxide, and a silyl group-containing vinyl resin (Japanese Patent Laid-Open No. 64-1769). ), A composition having improved storage stability of this composition (Japanese Patent Application No. 4-58824) has been proposed, and an acrylic emulsion, an acrylic resin, a urethane resin, which is widely used as an undercoat paint,
The adhesiveness with the epoxy resin sealer is not sufficient,
It has a problem of poor adhesion in a long-term durability test.

[0003]

The present invention has been made against the background of the above-mentioned conventional technical problems, and an inorganic top coating composition excellent in weather resistance, stain resistance and alkali resistance can be applied to various substrates. It is an object of the present invention to provide a coating method that enables close contact for a certain period.

[0004]

According to the present invention, a composition containing the following (a) to (f) as a main component is used as an overcoating paint (A), and a hydrolyzable silyl group is used as an undercoating paint (B-1). It is intended to provide a coating method characterized by using a composition containing a vinyl-based resin as a main component. (A) the general formula _{^{R 1 Si (OR 2) 3}} ( In the formula, R ¹ represents an organic group having 1 to 8 carbon atoms, R ² is an alkyl group or an acyl group having 1 to 4 carbon atoms of 1 to 5 carbon atoms Of the organosilane (hereinafter sometimes referred to as “(a ′) organosilane” or “(a ′) component”) and / or a partial condensate thereof (hereinafter “(a) component”). 100 parts by weight in terms of organosilane, and (b) a diorganosilane represented by the general formula R ¹ ₂ Si (OR ² ) ₂ (wherein R ¹ and R ² are the same as above) (hereinafter, “( b ′) diorganosilane ”or“ (b ′) component ”) and / or its partial condensate (hereinafter referred to as“ (b) component ”) in terms of diorganosilane of 0 to 150 Parts by weight, (c) a hydrolyzable group at the terminal or side chain and / or A silyl group-containing vinyl resin having at least one silyl group having a silicon atom bonded to an acid group in one molecule of the polymer (hereinafter referred to as "(c) silyl group-containing vinyl resin" or "(c) component"). 2 to 300 parts by weight, (d) general formula Zr (OR ³ ) _p (R ⁴ COCHCO
R ⁵ ) _4-p , Ti (OR ³ ) _q (R ⁴ COCHCO
R ⁵ ) _4-q and Al (OR ³ ) _r (R ⁴ COCHCO
R ⁵ ) _3-r (wherein R ³ and R ⁴ are the same or different and are an alkyl group having 1 to 6 carbon atoms, R ⁵ is an alkyl group having 1 to ⁵ carbon atoms or an alkoxy group having 1 to 16 carbon atoms, p 5 To q are integers of 0 to 3 and r is an integer of 0 to 2) at least one metal chelate compound selected from the group of compounds represented by the following (hereinafter referred to as “(d) metal chelate compound” or “( 0.01 to 50 parts by weight of (d) component), 5 to 400 parts by weight of (e) filler based on 100 parts by weight of the total solid content of components (a) to (d), and (f) organic solvent.

Further, the present invention uses the above-mentioned top coating composition (A) and the following (g) to (h) as an undercoat coating composition (B-2).
A coating method characterized by using a composition containing as a main component. (G) Organosilicon compound having at least one mercapto group and at least two alkoxy groups in the molecule (h) Epoxy resin and / or isocyanate prepolymer

Next, the composition constituting the top coating composition (A) used in the present invention and the bottom coating composition (B-1) to
The composition of (B-2) will be described separately.

Topcoat paint (A ) The topcoat paint (A) is composed of a composition containing the above-mentioned components (a) to (f) as main components. Component (a): Component (a) has the general formula R ¹ Si (OR ² ).
It is a hydrolyzate and / or a partial condensate obtained by hydrolyzing and condensing (a ') organosilane represented by ₃ and functions as a binder in the composition of the present invention. . R in such (a ') organosilane
¹ is an organic group having 1 to 8 carbon atoms, such as a methyl group,
Alkyl groups such as ethyl group, n-propyl group, i-propyl group, etc., γ-chloropropyl group, vinyl group,
Examples include a 3,3,3-trifluoropropyl group, a γ-glycidoxypropyl group, a γ-methacryloxypropyl group, a γ-mercaptopropyl group, a phenyl group, and a 3,4-epoxycyclohexylethyl group. Also,
R ^{2 in} (a ′) organosilane is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and examples thereof include methyl group, ethyl group, n-propyl group, i-propyl group and n. -Butyl group, sec-butyl group, tert-butyl group, acetyl group and the like.

Specific examples of these (a ') organosilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane and n-propyltrimethoxysilane.
Propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3,3 -Trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4
-Epoxycyclohexylethyltrimethoxysilane,
Examples thereof include 3,4-epoxycyclohexylethyltriethoxysilane, i-butyltrimethoxysilane, and i-butyltriethoxysilane, but methyltrimethoxysilane and methyltriethoxysilane are preferable.

These (a ') organosilanes may be used alone or in combination of two or more. Further, among the above-mentioned (a ′) organosilane,
It is preferable that 80 mol% or more is CH ₃ Si (OR ² ) ₃ .

Component (b): Component (b) has the general formula R ¹ ₂
Si (OR ² ) ₂ [In the formula, R ¹ and R ² are the above (a).
The same as R ¹ and R ² used in the organosilane used as the component] (b ′) a hydrolyzate and / or partial condensate obtained by hydrolyzing and condensing the diorganosilane. In the composition of the present invention, it functions as a binder. R ¹ and R ² of such (b ') in diorganosilane are the same as R ¹ and R ² of the organosilane.

Specific examples of these (b ') diorganosilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane and di-n.
-Propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like can be mentioned, but dimethyldimethoxysilane and dimethyldiethoxysilane are preferable. is there. These (b ') diorganosilanes may be used alone or in combination of 2
One or more species can be used in combination. The proportion of the component (b) in the composition of the present invention is 0 to 150 in terms of (b ') diorganosilane based on 100 parts by weight of the component (a').
The amount is preferably 0 to 100 parts by weight, and if it exceeds 150 parts by weight, the adhesiveness and curability of the resulting coating film will deteriorate.

(C) Silyl group-containing vinyl resin; (c)
The silyl group-containing vinyl resin has a vinyl polymer as a main chain and has at least one silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at the terminal or side chain in one molecule of the polymer. , Preferably two or more, and most of the silyl groups are represented by the following general formula: (In the formula, X is a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group,
Hydrolyzable groups such as amino groups and / or hydroxyl groups, R
⁶ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aralkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 3).

(C) The silyl group-containing vinyl resin is
(A) It may be produced by reacting a hydrosilane compound with a vinyl-based resin having a carbon-carbon double bond, and (b) the following general formula: (Provided that X, R ⁶ and n are the same as above, and R ⁷ is an organic group having a polymerizable double bond) and a vinyl compound. However, the manufacturing method is not limited.

Examples of the hydroxysilane compound used in the production method shown in (a) above include halogenated silanes such as methyldichlorosilane, trichlorosilane and phenyldichlorosilane; methyldiethoxysilane, Alkoxysilanes such as methyldimethoxysilane, phenyldimethoxysilane, trimethoxysilane, triethoxysilane; methyldiacetoxysilane,
Acyloxysilanes such as phenyldiacetoxysilane and triacetoxysilane; methyldiaminoxysilane,
Examples thereof include aminosilanes such as triaminoxysilane, dimethylaminoxysilane, and triaminosilane.

The vinyl-based resin used in the production method (a) is not particularly limited except for the vinyl-based resin containing a hydroxyl group, and examples thereof include methyl (meth) acrylate and (meth) acrylic. Ethyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylic acid ester such as cyclohexyl (meth) acrylate; (meth) acrylic acid, itaconic acid,
Carboxylic acids such as fumaric acid and acid anhydrides such as maleic anhydride; epoxy compounds such as glycidyl (meth) acrylate; amino compounds such as diethylaminoethyl (meth) acrylate and aminoethyl vinyl ether;
(Meth) acrylamide, itaconic acid diamide, α-ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl (meth)
An amide compound such as acrylamide; a vinyl resin obtained by copolymerizing a vinyl compound selected from acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate and the like is preferable.

On the other hand, examples of the silane compound used in the production method shown in (b) include

[0017]

[0018]

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[0019]

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[0020]

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[0021]

[Chemical 4]

And the like. As the vinyl compound used in the production method shown in (b), the vinyl compound used at the time of polymerization of the vinyl resin in the production method of (a) can be used. In addition to those described in the production method (a), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyvinyl ether, vinyl compounds having a hydroxyl group such as N-methylolacrylamide are listed. You can also

Specific examples of the above-mentioned (c) silyl group-containing vinyl resin include, for example, the following general formula: (In the formula, R ⁸ is a hydrogen atom or a methyl group, R ⁹ is a carbon number such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-butyl group, an n-pentyl group, and an n-hexyl group. An alkyl group of 1 to 6, R ¹⁰ is the same as R ⁸ , R ¹¹ is an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group and a butylene group, and R ¹² is the same as R ⁹ . And m / (l + m) = 0.01 to 0.4, preferably 0.02 to 0.2).

The proportion of the (c) silyl group-containing vinyl resin in the composition is 2 to 300 parts by weight, preferably 5 to 100 parts by weight of (a ') organosilane which is a raw material of the component (a). 200 parts by weight, more preferably 10-100
If the amount is less than 2 parts by weight, the alkali resistance of the obtained coating film is low, while if it exceeds 300 parts by weight, the weather resistance of the obtained coating film deteriorates.

(D) Metal chelate compound: The (d) metal chelate compound of the present invention has the general formula Zr (OR ³ ) _p
(R ⁴ COCHCOR ⁵ ) _4-p , Ti (OR ³ ) _q (R
⁴ COCHCOR ⁵ ) _4-q and Al (OR ³ ) _r (R
⁴ COCHCOR ⁵ ) _3-r , which is at least one selected from the group of compounds, and promotes the condensation reaction between the above components (a) and (b) and (c) the silyl group-containing vinyl resin. , (A) and (b) and the component (c) are considered to form a copolymer.

(D) R ³ and R ⁴ in the metal chelate compound are the same or different and each is an alkyl group having 1 to 6 carbon atoms,
Specifically, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group,
Examples include n-pentyl group and phenyl group. Also, R
⁵ is an alkyl group having 1 to 6 carbon atoms similar to the above,
Alkoxy group having 1 to 16 carbon atoms, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-
Examples thereof include butoxy group, sec-butoxy group, t-butoxy group, lauryl group and stearyl group. Further, in the metal chelate compound (d), p to q are integers of 0 to 3, r is 0 to 2
Indicates an integer.

Specific examples of these (d) metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, Tetrakis (n-
Zirconium chelate compounds such as propyl acetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethyl acetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, Titanium chelate compounds such as diisopropoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonato aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonato) aluminum , Tris (ethylacetoacetate) aluminum, tris (acetylacetonate) Aluminum, mono acetyl acetonate bis (ethyl acetoacetate), and the like of aluminum chelate compounds such as aluminum. Among these (d) metal chelate compounds, preferred are tri-n-butoxyethylacetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, diisopropoxyethylacetoacetate aluminum, tris (ethylacetoacetate).
Aluminum. These (d) metal chelate compounds may be used alone or in combination of two or more. Further, as the component (d), a partial hydrolyzate of these metal chelate compounds can also be used.

The proportion of the metal chelate compound (d) in the composition is 0.01 to 50 parts by weight, preferably 0.1 to 100 parts by weight of the organosilane (a ') which is a raw material of the component (a). -50 parts by weight, more preferably 0.5-10
If it is less than 0.01 parts by weight, (a)-
Formation of a copolymer of the component (b) and the component (c) is insufficient, and the weather resistance of the coating film deteriorates. On the other hand, when it exceeds 50 parts by weight, the storage stability of the composition deteriorates, and Cracks may occur in the obtained coating film, which is not preferable.

(E) Filler: The (e) filler is used for exhibiting various properties such as coloring, thickening of the coating film obtained, prevention of ultraviolet ray transmission to the base, imparting corrosion resistance, and heat resistance. It is a thing. Examples of the filler (e) include water-insoluble pigments such as organic pigments and inorganic pigments, or particulates other than pigments,
Examples thereof include fibrous or scale-like metals and alloys, and oxides, hydroxides, carbides, nitrides and sulfides thereof. Specific examples of the filler (e) include particulate, fibrous or scaly iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, Chromium oxide, manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, carbonic acid Calcium, magnesium carbonate, barium sulfate, bentonite, mica, zinc green, chrome green, cobalt green, viridian, Guinea green, cobalt chrome green, shale green, green soil, manganese green, pigment green, ultramarine blue, dark blue, pigment green, rock Ultramarine, cobalt blue,
Cerulean blue, copper borate, molybdenum blue, copper sulfide,
Cobalt purple, mars purple, manganese purple, pigment violet, lead suboxide, calcium leadate, zinc yellow, lead sulfide, chrome yellow, ocher, cadmium yellow, strontium yellow, titanium yellow, litharge, pigment yellow, cuprous oxide, cadmium red , Selenium red, chrome vermillion, red iron oxide, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead zinc white, bunchson white, lead phthalate, manganese white, Lead sulfate, graphite, bone black, diamond black,
Thermatomic black, vegetable black, potassium titanate whiskers, molybdenum disulfide, etc. can be mentioned.

The average particle diameter or average length of these (e) fillers is usually 50 to 50,000 nm, preferably 100 to 5,000 nm. The ratio of the component (e) in the composition is 5 to 400 parts by weight, preferably 10 to 300 parts by weight, and more preferably 20 to 200 parts by weight based on 100 parts by weight of the total solid content of the components (a) to (d). Parts by weight. 5
If the amount is less than 100 parts by weight, the coloring effect is insufficient, while 400
If it exceeds the weight part, the adhesiveness will decrease.

(F) Organic solvent: The (f) organic solvent mainly mixes the components (a) to (e) uniformly to adjust the solid content of the composition used in the top coating composition (A) of the present invention. At the same time, it can be applied to various coating methods to improve the dispersion stability and storage stability of the composition. The (f) organic solvent is not particularly limited as long as it can uniformly mix the components (a) to (e),
For example, alcohols, aromatic hydrocarbons, ethers,
Ketones, esters and the like are preferable.

Of these, examples of alcohols include monohydric alcohols and dihydric alcohols, and among these, the monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

Specific examples of the aromatic hydrocarbons are benzene, toluene, xylene, etc., specific examples of the ethers are tetrahydrofuran, dioxane, etc., and specific examples of the ketones are acetone, methyl ethyl ketone, methyl. Isobutyl ketone, diisobutyl ketone, etc., specific examples of esters include ethyl acetate,
Examples thereof include propyl acetate, butyl acetate, propylene carbonate and the like. These (f) organic solvents may be used alone or in combination of two or more.
The ratio of the organic solvent (f) in the composition is not particularly limited, and an amount that adjusts the total solid content concentration according to the purpose of use is used.

The composition constituting the top coating composition (A) of the present invention contains the above-mentioned components (a) to (f) as main components, but usually (a) to (d) and (f) components are used. (A ') constituting the component (a) and / or constituting the component (b) (b') when preparing a composition containing
Water is added for the hydrolysis / condensation of diorganosilane. The amount of water used is usually 1.2 to 3.0 mol, preferably 1.3 to 1 mol of (a ') organosilane.
To 2.0 mol, and usually 0.8 to 2.0 mol, and preferably 0.9 to 1 mol of (b ') diorganosilane.
It is about 1.5 mol.

For the purpose of improving the storage stability of the top coating composition (A) of the present invention, (i) the general formula R ⁴ COCH ₂
Β-diketones represented by COR ⁵ and / or β-
It is possible to add ketoesters. That is, the component (i) is added to the metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound) (d) present in the composition containing the components (a) to (f) as the main components. Coordination suppresses the action of promoting the condensation reaction of the components (a) to (b) and / or (c) by these metal chelate compounds, and improves the storage stability of the resulting composition. It is considered that (I) R ⁴ and R ⁵ constituting the component, R ⁴ constituting the (d) above metal chelate compound
And is the same as R ^5.

Specific examples of the (i) β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetic acid-n-propyl, acetoacetic acid-i-propyl and acetoacetic acid. -N-butyl, acetoacetate-sec-butyl, acetoacetate-t-butyl, 2,4-hexane-dione, 2,4
-Heptane-dione, 3,5-heptane-dione, 2,
4-octane-dione, 2,4-nonane-dione, 5-
Methyl-hexane-dione etc. can be mentioned.
Of these, ethyl acetoacetate and acetylacetone are particularly preferable. These (i) β-diketones and / or β-ketoesters may be used alone or in combination.
It is also possible to use a mixture of two or more species. Such (i)
β-diketones and / or β-ketoesters are
(D) 2 mol or more, preferably 3 to 20 mol, relative to 1 mol of the metal chelate compound, and less than 2 mol results in poor storage stability of the resulting composition. The method of using the component (i) is as follows: the composition comprising the components (a) to (f)
A method of adding the component (i), (a) to (d),
Examples include a method of adding the component (i) to the composition comprising the component (f), and then mixing and dispersing the component (e).

Furthermore, in order to cure the composition constituting the top coating composition (A) of the present invention faster, a curing accelerator may be used depending on the curing conditions, and in order to cure at a relatively low temperature, It is more effective to use a curing accelerator together.

As such a curing accelerator, naphthenic acid,
Alkali metal salts such as octylic acid, nitrous acid, sulfurous acid, aluminic acid and carbonic acid; alkaline compounds such as sodium hydroxide and potassium hydroxide; alkyl titanic acid, phosphoric acid, p
-Acidic compounds such as toluenesulfonic acid and phthalic acid; ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, metaphenylenediamine, ethanolamine, triethylamine, various used as a curing agent for epoxy resin Modified amine, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ- (2-
Amino-based compounds such as aminoethyl) -aminopropylmethyldimethoxysilane and γ-anilinopropyltrimethoxysilane, (C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ ,
_{(C 4 H 9) 2 Sn} (OCOCH = CHCOOCH 3) 2,
_{(C 4 H 9) 2 Sn} (OCOCH = CHCOOC 4 H 9)
_{2, (C 8 H 17)} 2 Sn (OCOC 11 H 23) 2, (C
_{8 H 17) 2 Sn (OCOCH} = CHCOOCH 3) 2, (C
_{8 H 17) 2 Sn (OCOCH} = CHCOOC 4 H 9) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC
_{8 H 17) 2, Sn (} OCOCC 8 H 17) carboxylic acid type organotin compounds such as _{2; (C 4 H 9)} 2 Sn (SCH 2 CO
_{O) 2, (C 4 H} 9) 2 Sn (SCH 2 COOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 COO) 2, (C 8 H 17) 2
_{Sn (SCH 2 CH 2 COO)} 2, (C 8 H 17) 2 Sn (S
CH ₂ COOCH ₂ CH ₂ OCOCH ₂ S) ₂ , (C ₈ H
₁₇ ) ₂ Sn (SCH ₂ COOCH ₂ CH ₂ CH ₂ CH ₂ O
COCH ₂ S) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC
_{8 H 17) 2, (C} 8 H 17) 2 Sn (SCH 2 COOC
₁₂ H ₂₅ ) ₂ ,

[0039] Mercaptide type organotin compounds such as; Sulfide type organotin compounds such as;

(C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ Sn
O, organotin oxides such as (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO and ethyl silicate, ethyl silicate 40, dimethyl maleate, diethyl maleate,
Organotin compounds such as reaction products with ester compounds such as dioctyl phthalate are used. The proportion of these curing accelerators in the composition is usually 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the solid content of the composition of the present invention.

The composition used in the top coating composition (A) of the present invention contains the above-mentioned components (a) to (f), and the total solid content concentration thereof is usually 20 to 60% by weight. The total solid content concentration is adjusted appropriately according to the purpose of use.

In addition, in the composition constituting the top coating composition (A) of the present invention, other known dehydrating agents such as methyl orthoformate, methyl orthoacetate and tetraethoxysilane, various surfactants, and silane cups other than the above Additives such as ring agents, titanium coupling agents, dyes, dispersants, thickeners and leveling agents can also be added.

In addition, the composition constituting the top coating composition (A) of the present invention may contain an organic solvent other than the above-mentioned (f) organic solvent. Any solvent may be used as long as it does not cause precipitation when the component (d) is mixed, and may be any of aliphatic hydrocarbons, aromatic hydrocarbons, halogenated carbonized hydrocarbons used in general paints, coating agents and the like. Examples thereof include hydrogens, ketones, esters, ethers, ketone ethers, ketone esters, ester ethers, and the like. Specific examples thereof include benzene, toluene, xylene, methyl acetate, ethyl acetate, propyl acetate. , Butyl acetate, isoamyl acetate and the like. These organic solvents are
Usually, about 100 parts by weight or less is used per 100 parts by weight of the composition of the present invention.

In preparing the composition constituting the top coating composition (A) of the present invention, for example, the following preparation methods are preferable. (A ') organosilane constituting the component (a),
(B ') diorganosilane constituting the component (b),
(A) a solution containing (c) a silyl group-containing vinyl resin, (d) a metal chelate compound, and (f) an organic solvent.
1.2 to 3 mol of water per 1 mol of organosilane,
(B ') 0.8 to 2 mol of water is added to 1 mol of diorganosilane to carry out hydrolysis / condensation reaction, and (a) to
After forming a composition comprising the components (d) and (f),
(E) A method of mixing and dispersing the filler.

1 mol of (a ') organosilane is added to a solution comprising (a') organosilane which constitutes (a) component, (b ') diorganosilane which constitutes (b) component, and (f) organic solvent. To 1.2 to 3 mol of water, (b ')
0.8 to 2 mol of water is added to 1 mol of diorganosilane to perform a hydrolysis / condensation reaction, and then (c) a silyl group-containing vinyl resin and (d) a metal chelate compound are added and mixed, Further, a condensation reaction is carried out, (a) to (d),
A method of forming a composition comprising the component (f) and then mixing and dispersing the filler (e).

A solution containing (a ') organosilane constituting component (a), (b') diorganosilane constituting component (b), (d) metal chelate compound and (f) organic solvent is added to Hydrolysis / condensation reaction is carried out by adding 1.2 to 3 moles of water to 1 mole of a ') organosilane and 0.8 to 2 moles of water to 1 mole of (b') diorganosilane, and (C) A silyl group-containing vinyl resin is added and mixed, and a condensation reaction is further carried out to obtain (a) to (d),
A method of forming a composition comprising the component (f) and then mixing and dispersing the filler (e).

Undercoat paint (B) The undercoat paint (B) used in the present invention functions to develop long-term adhesion between the overcoat paint (A) and various base materials, and is a hydrolyzable silyl compound. Undercoat paint (B-1) composed of a composition containing a group-containing vinyl resin as a main component, or (g) one or more mercapto groups and 2 in a molecule.
An undercoat paint (B-2) comprising an organosilicon compound having one or more alkoxy groups and (h) a composition containing an epoxy resin and / or an isocyanate prepolymer as a main component is used.

Undercoat paint (B-1); Undercoat paint (B-
The composition constituting 1) is a solution of the above-mentioned (c) silyl group-containing vinyl-based resin in (f) an organic solvent, one obtained by emulsifying and dispersing this component (c) in an aqueous medium, and (c) containing a silyl group. Emulsion polymerization of vinyl resin in aqueous medium, JP-A-3-4
Composite polymer particles in which a continuous phase organic polymer and polysiloxane coexist in a single particle described in JP-A-5628, and (meth) acrylic acid alkyl ester monomer described in JP-A-4-57868 as a main component And an emulsion obtained by condensing an alkoxysilane compound in the presence of a copolymer latex. The composition forming the undercoat paint (B-1) is a known additive such as the above-mentioned (e) filler, dehydrating agent, surfactant, coupling agent, dye, dispersant, thickener, and leveling agent. Can be blended. Further, in order to cure the undercoat paint (B-1) faster, a curing accelerator used in the above-mentioned overcoat paint (A) can be used in combination.

Undercoat paint (B-2); Undercoat paint (B)
Another composition that can be suitably used as is a composition containing the above-mentioned components (g) to (h) as a main component. Specific examples of the composition constituting the undercoat paint (B-2) include the following compositions. The following primer composition described in JP-A-1-83580 (g) 1 to 100 parts by weight of an organosilicon compound having at least one mercapto group and at least two alkoxy groups in the molecule (h-1) in the molecule 100 parts by weight of an isocyanate prepolymer having 2 or more isocyanate groups but not having a urethane bond (h-2) 100 parts by weight or less of epoxy resin-modified silicone resin (as solid content) (j) Organotin compound and / or Organic acid salt of tin 0.01 to 30 parts by weight

The following primer composition described in JP-A-4-59081 (g) 1 to 100 parts by weight of an organosilicon compound having at least one mercapto group and at least two alkoxy groups in a molecule (h-3 ) 100 parts by weight of an epoxy compound having two or more epoxy groups in the molecule (k) General formula Ti (OR) ₄ (wherein R is a carbon number of 1 to 6)
5 to 200 parts by weight of a titanic acid ester represented by (a monovalent hydrocarbon group of

Substrate There is no particular limitation on the substrate used in the coating method of the present invention. For example, a surface-untreated steel plate, a conventionally known plated steel plate such as zinc plating, zinc / aluminum plating, and aluminum plating,
Steel sheets that have been conventionally treated with chemical conversion liquids such as zinc phosphate, aluminum phosphate, calcium phosphate, etc., steel sheets with anticorrosion primer treatments such as zinc rich paint, wash primer, epoxy primer, etc. Treated or untreated aluminum substrate, ceramics, cement, paper, glass, plastics, concrete, precast concrete, lightweight cellular concrete (ALC), refractory mortar, extruded cement, cement mortar, resin mortar, slate, asbestos slate, Wood wool cement, pulp cement, wood chip cement, asbestos cement perlite, asbestos cement calcium silicate, glass fiber reinforced concrete, pulp cement perlite, slag gypsum cement, gypsum plastic Terpolymers, mention may be made of dolomite plaster, plasterboard, a ceramic substrate such as bricks. In addition, in the case of a porous substrate such as a ceramic substrate,
It is also possible to use a base material that has been sealed with a conventionally known sealer, such as an acrylic emulsion type, an acrylic urethane resin type, or an epoxy resin type. Among these base materials, metal building materials and ceramic base materials used for interior and exterior construction are suitable.

Coating Method In the present invention, the undercoat paint (B) is first applied to the surface of the base material.
[(B-1) and / or (B-2)] is applied, and then the above-mentioned topcoat paint (A) is applied. At this time, the means for applying the undercoat paint (B) on the surface of the base material is a brush, a spray, a roll coater, a flow coater, dipping, etc., and a dry film thickness of about 5 to 100 μm by one application,
A coating film having a dry film thickness of about 10 to 300 μm can be formed by coating 2-3 times, and it can be dried at room temperature or 30 to 30 μm.
A coating film can be formed by heating at a temperature of about 200 ° C. for about 1 to 60 minutes and drying. Also,
The means for applying the topcoat paint (A) on the surface of the base material after the undercoat paint (B) has been applied is one-time application by brush, spray, roll coater, flow coater, screen printing, gravure printing, dipping, etc. 5 in dry film thickness
~ 50μm, dry film thickness 10 ~ 15 after 2-3 coats
A coating film having a thickness of about 0 μm can be formed, and the coating film can be formed by drying at room temperature or by heating at a temperature of about 30 to 200 ° C. for about 1 to 60 minutes and drying.

The basic coating film constitution of the coated article obtained by the coating method of the present invention is as shown in FIG.
In addition, as shown in FIG. 2, a sealer is provided between the base material and the undercoat to improve the sealing of the base material and / or the adhesion to the base material, and the gloss is improved as shown in FIG. For the purpose, a coating layer containing an organoalkoxysilane condensate as a main component, such as a composition comprising an organotrialkoxysilane condensate as described in JP-A-63-117074 and colloidal silica, is provided as the uppermost layer. The coating composition may be different. It should be noted that FIGS. 1a and 2 to 3 show a single color finish painting tone, and FIG. 1b shows a tile tone. In addition to this, as a painted product, it is possible to apply a patterning paint of multiple colors such as granite tone and painting.

[0054]

The present invention will be described in more detail with reference to the following examples, but the invention is not limited to the following examples. In the examples, parts and% are based on weight unless otherwise specified. In addition, various measurements in the examples are as follows.

The number average molecular weight and the weight average molecular weight were measured by the gel permeation chromatography (GPC) method under the following conditions. The sample was prepared by using tetrahydrofuran as a solvent, dissolving 0.1 g of the silyl group-containing vinyl resin in 100 cc of tetrahydrofuran, and dissolving 1 g of the organopolysiloxane in 100 cc of tetrahydrofuran. The standard polystyrene used was Standard Polystyrene manufactured by Pressure Chemical Co., USA. Equipment: Waters, USA, high temperature high speed gel permeation chromatogram (Model 150-C ALC / GPC) column: Showa Denko KK, SHODEX A80M,
Length 50 cm Measurement temperature; 40 ° C Flow rate; 1 cc / min

The adhesion is in accordance with JIS K5400,
After a cross-cut test using 25 squares of 2 mm square, a tape peeling test was conducted, and the residual rate of the squares was shown. The pencil hardness was based on the pencil hardness according to JIS K5400. Regarding the weather resistance, an irradiation test was carried out by a weather meter according to JIS K5400 for 2,000 hours, and the state of the coating film was observed. The salt spray was based on JIS K5400, and the state of the coating film was observed after a 1,000-hour test with a salt spray tester. In the exposure test, the appearance of the coating film and the adhesion were tested after conducting a tilted exposure test at 45 degrees on the south surface for one year in the Okinawa area.

Reference Example 1 (Preparation of silyl group-containing vinyl resin) 90 parts of methyl methacrylate, 40 parts of n-butyl acrylate, 20 parts of γ-methacryloxypropyltrimethoxysilane were placed in a reactor equipped with a reflux condenser and a stirrer. Parts and 130 parts of xylene are added and mixed, and then stirred at 80 ° C.
Azobisisovaleronitrile 4 was added to this mixture after heating to
Part dissolved in 10 parts xylene was added dropwise over 30 minutes, and the mixture was further reacted at 80 ° C. for 5 hours to give a solid content concentration of 50.
% Silyl group-containing vinyl resin (a) was obtained. The polystyrene-reduced number average molecular weight of this silyl group-containing vinyl resin by gel permeation chromatography is 1
It was 2,000 and was estimated to contain an average of 6 silyl groups per molecule of polymer.

Reference Example 2 (Preparation of Topcoat Paint) In the same reactor as in Reference Example 1, 100 parts of (a ') methyltrimethoxysilane, 30 parts of (b') dimethyldimethoxysilane, and (c) of Reference Example 1 were used. Vinyl resin containing silyl group 5
After adding 0 parts, (d) diisopropoxyaluminum ethyl acetoacetate 20 parts and (f) isopropanol 40 parts and mixing, 30 parts ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature, (I) 20 parts of acetylacetone was added to obtain a resin solution having a solid content concentration of 35%. For the solid content of 100 parts of the resin solution obtained,
70 parts of titanium oxide and 1.5 parts of a cellulosic thickener were added and mixed and dispersed by a ball mill to obtain a top coating composition (b). To 100 parts of this topcoat paint (b), 1 part of dibutyltin dimaleate was added to prepare a topcoat paint (b ').

Reference Example 3 (Preparation of Topcoat Paint) In the same reactor as in Reference Example 1, 100 parts of (a ') methyltrimethoxysilane, 20 parts of (b') dimethyldimethoxysilane, 25 parts of ion-exchanged water, 0 0.1 N hydrochloric acid water
After adding 01 parts and mixing, the mixture was heated to 60 ° C. with stirring and reacted at the same temperature for 3 hours to give a weight average molecular weight of 1.
200 organopolysiloxane solutions were obtained. In this solution, (c) silyl group-containing vinyl resin 30 of Reference Example 1 was added.
Parts, (d) aluminum tris (ethylacetoacetate) 15 parts, and (f) isopropanol 40 parts,
After reacting at 60 ° C. for further 4 hours, the mixture was cooled to room temperature and (f) ethylene glycol monobutyl ether 40 was added.
And (i) 20 parts of acetylacetone were added to obtain a resin solution having a solid content concentration of 35%. To 100 parts of the solid content of the obtained resin solution, 70 parts of titanium oxide and 1.5 parts of a cellulosic thickener were added and mixed and dispersed by a ball mill to obtain a top coating composition (c). To 100 parts of this topcoat paint (C),
2 parts of dioctyl tin dimaleate was added as a curing accelerator to prepare a top coating composition (c).

Reference Example 4 (Preparation of Topcoat Paint) In the same reactor as in Reference Example 1, (a ′) 100 parts of methyltrimethoxysilane, (c) 25 parts of the silyl group-containing vinyl resin of Reference Example 1, ( d) 20 parts of tributoxyzirconium ethyl acetoacetate and (f) 10 parts of ethylene glycol monobutyl ether were added and mixed, 23 parts of ion-exchanged water was added, and the mixture was reacted at 60 ° C. for 4 hours.
After cooling to room temperature, 14 parts of (i) acetylacetone was added to obtain a resin solution having a solid content concentration of 35%. To 100 parts of the solid content of the obtained resin solution, 70 parts of titanium oxide and 1.5 parts of a cellulosic thickener were added and mixed and dispersed by a ball mill to obtain a top coating composition (d). To 100 parts of this topcoat paint (d), 2 parts of dibutyltin dimaleate as a curing accelerator was added to prepare a topcoat paint (d ').

Reference Example 5 (Preparation of Undercoat Paint) In a reactor similar to that of Reference Example 1, methyl methacrylate 10 was added.
0 parts, 30 parts of 2-ethylhexyl methacrylate, 5 parts of methacrylic acid, 25 parts of γ-methacryloxypropyltrimethoxysilane and 130 parts of xylene were added and mixed, and then the mixture was heated to 80 ° C. with stirring, and azobis was added to this mixture. A solution prepared by dissolving 4 parts of isovaleronitrile in 10 parts of xylene was added dropwise over 30 minutes and further reacted at 80 ° C. for 5 hours to obtain a silyl group-containing vinyl resin having a solid content concentration of 50%. The number average molecular weight of this resin by GPC is 15,0.
It was estimated to have an average of 10 silyl groups per polymer molecule. 50 parts of amorphous silica and 1 part of titanium oxide to 100 parts of solid content of this resin solution
00 parts was added and mixed and dispersed by a ball mill, and xylene was added to obtain an undercoat paint (e) having a solid content concentration of 55%.
To 100 parts of this undercoat paint (e), 0.3 part of dibutyltin dilaurate was added to prepare an undercoat paint (e ').

Reference Example 6 (Preparation of undercoat paint) Reflux condenser, nitrogen inlet, thermometer, monomer addition device,
To a stainless steel autoclave equipped with a stirrer, 100 parts of ion-exchanged water and 0.5 part of sodium persulfate as a polymerization initiator were charged, the gas phase part was replaced with nitrogen gas for 15 minutes, and the temperature was raised to 80 ° C. 50 parts of ion-exchanged water in a separate container,
Polyoxyethylene alkylphenyl ether sulfate ammonium salt 1.0 part, sodium alkylbenzene sulfonate 0.5 part, n-butyl acrylate 50
Parts, 28 parts of methyl methacrylate, 20 parts of styrene and 2 parts of acrylic acid were mixed to prepare a pre-emulsion, which was added dropwise to the autoclave over 4 hours. After the dropping is completed,
The mixture was further stirred at 85 ° C for 3 hours and then cooled to 25 ° C to terminate the reaction. The polymerization conversion rate of the obtained emulsion was 99%. The temperature of this emulsion is 25
The pH was adjusted to 7 while maintaining the temperature at 0 ° C, 10 parts of methyltriethoxysilane was added, and the mixture was vigorously stirred for 30 minutes.
Then, the temperature was raised to 60 ° C. and the reaction was carried out for 3 hours to obtain a silyl group-containing vinyl resin emulsion. To 60 parts of the solid content of this emulsion, 90 parts of titanium oxide, 5 parts of a dispersant (Rohm & Haas Company, Orotan 731SD), 3 parts of a thickener (Fuji Chemical Co., A-5000), a plasticizer (yeast) 3 parts of Texanol (manufactured by Man Chemical Co., Ltd.) were mixed and dispersed by a ball mill, and then ion-exchanged water was added to prepare an undercoat paint (he) having a solid content concentration of 55%.

Reference Example 7 (Preparation of Undercoat Paint) A reactor similar to that of Reference Example 1 was charged with 100 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 200 and 300 parts of γ-mercaptopropyltrimethoxysilane.
The mixture was heated and stirred in a nitrogen atmosphere for 4 hours. Then, 100 parts of tetrabutoxytitanium, 100 parts of xylene and 100 parts of tetramethoxysilane were added and stirred to prepare an undercoat paint (g).

Reference Example 8 (Preparation of Epoxy Resin Modified Silicone Resin Solution) In a reaction vessel equipped with a stirrer, a distillation device and a chemical solution addition device,
350 parts of water and 50 parts of methanol are charged, and 7 parts of dimethyldichlorosilane, 40 parts of methyltrichlorosilane, 48 parts of diphenyldichlorosilane, 78 parts of phenyltrichlorosilane and 95 parts of toluene are added so that the temperature becomes 50 ° C. or lower while stirring. A mixture with and was added dropwise to carry out a hydrolysis / condensation reaction. The produced methylphenyl polysiloxane was washed with water to remove by-produced hydrogen chloride. This was heated under reduced pressure to remove water remaining as a part of the solution to obtain a silicone resin solution having a solid content concentration of 50%. Then, in a reactor similar to the above, a bisphenol A epichlorohydrin type epoxy resin 70 having an epoxy equivalent of 250 was used.
Parts, 5 parts of phthalic anhydride, 10 parts of linseed oil fatty acid and 75 parts of toluene were charged, the temperature was gradually raised to 230 ° C. with stirring, and the toluene was distilled off. Then, the mixture was heated at 230 ° C. for 5 hours, 50 parts of the above silicone resin and toluene in an amount such that the total solid content concentration became 50% were added, and the mixture was stirred until the solution became transparent to obtain an epoxy-modified silicone resin solution.

Reference Example 9 (Preparation of Undercoat Paint) 75 parts of isocyanate prepolymer represented by the following formula, 25 parts of butyl acetate, 20 parts of epoxy modified silicone resin solution obtained in Reference Example 8, γ-mercaptopropyltrimethoxysilane 12 parts, dibutyltin dilaurate 0.5
Parts and 30 parts of ethyl acetate are mixed, and the undercoat paint (h)
I got

[0066]

Examples 1 to 5 and Comparative Examples 1 to 7 Under the coating specifications shown in Table 1, various base materials were coated with an undercoat paint and a top coat paint and dried to prepare coated products, and various physical properties were measured. The slate plate (JIS A5043F) was applied as it was, and SUS304 was applied after the degreasing treatment. The results are shown in Table 1.

[0068]

[Table 1]

The paint types of the sealer used in Table 1 are as follows. V-Seran # 100; Dainippon Paint Co., Ltd., solvent-type acrylic urethane type Campe Color Sealer; Kansai Paint Co., Ltd., acrylic emulsion type vinylose surfacer; Dainippon Paint Co., Ltd., vinyl chloride resin type mighty Eposealer: Dainippon Paint Co., Ltd., epoxy resin type Nippe AC White Sealer: Nippon Paint Co., Ltd.
Solvent-based acrylic Mighty Grand Sealer; Dainippon Paint Co., Ltd., acrylic resin Eponix # 20 undercoat; Dainippon Paint Co., Ltd., epoxy resin

[0070]

EFFECTS OF THE INVENTION According to the coating method of the present invention, the adhesion of the inorganic top-coat paint having excellent durability to various substrates is significantly improved, and the excellent durability and the good adhesion are obtained for a long period of time. It is possible to manufacture painted products.

[Brief description of drawings]

FIG. 1 is a basic coating film configuration diagram of a coated article obtained by a coating method of the present invention.

FIG. 2 is a coating film configuration diagram of a coated product obtained by the coating method of the present invention.

FIG. 3 is a coating film configuration diagram of a coated product obtained by the coating method of the present invention.

Claims (2)

(57) [Claims] 1. The following (a) to (1) as the topcoat paint (A):
An undercoat paint (B-
As 1), a coating method comprising using a composition containing a hydrolyzable silyl group-containing vinyl resin as a main component. (A) the general formula _{^{R 1 Si (OR 2) 3}} ( In the formula, R ¹ represents an organic group having 1 to 8 carbon atoms, R ² is an alkyl group or an acyl group having 1 to 4 carbon atoms of 1 to 5 carbon atoms 100 parts by weight of an organosilane hydrolyzate represented by the formula) and / or a partial condensate thereof in terms of organosilane, (b) the general formula R ¹ ₂ Si (OR ² ) ₂ (wherein R ¹ and R ² is the same as above) 0 to 150 parts by weight of a diorganosilane hydrolyzate and / or a partial condensate thereof represented by diorganosilane, (c) a hydrolyzable group at the terminal or side chain and / or Alternatively, 2 to 300 parts by weight of a silyl group-containing vinyl resin having at least one silyl group having a silicon atom bonded to a hydroxyl group in one molecule of the polymer, (d) General formula Zr (OR ³ ) _p (R ⁴ COCHCO
R ⁵ ) _4-p , Ti (OR ³ ) _q (R ⁴ COCHCO
R ⁵ ) _4-q and Al (OR ³ ) _r (R ⁴ COCHCO
R ⁵ ) _3-r (wherein R ³ and R ⁴ are the same or different and are an alkyl group having 1 to 6 carbon atoms, R ⁵ is an alkyl group having 1 to ⁵ carbon atoms or an alkoxy group having 1 to 16 carbon atoms, p 5 To q is an integer of 0 to 3, r is an integer of 0 to 2) 0.01 to 50 parts by weight of at least one metal chelate compound selected from the group of compounds represented by: (e) filling 5 to 400 parts by weight per 100 parts by weight of the total solid content of components (a) to (d), and (f) organic solvent 2. A coating method comprising using the top coating composition (A) according to claim 1 and using a composition containing the following (g) to (h) as a main component as the under coating composition (B-2). . (G) Organosilicon compound having at least one mercapto group and at least two alkoxy groups in the molecule (h) Epoxy resin and / or isocyanate prepolymer