JP3218948B2 - Composition for coating - 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 composition, and more particularly to a coating composition having excellent curability and drying properties. ), Workability,
Good film formability and excellent storage stability, on the surface of stainless steel, aluminum, ceramics, cement, paper, glass, plastic, inorganic ceramic substrate, fabric, etc.
The present invention relates to a coating composition suitable for forming a coating film having excellent performance.

[0002]

2. Description of the Related Art In recent years, heat resistance, water resistance, stain resistance, organic chemical resistance, acid resistance, alkali resistance, corrosion resistance, wear resistance,
There is a need for a coating composition that is excellent in weather resistance, moisture resistance, adhesion, and the like and that can form a coating film with high hardness. As a coating composition which satisfies a part of such requirements, a composition comprising a dispersion of a partial condensate of an organosilane and colloidal silica and a silicone-modified acrylic resin (JP-A-60-135465), or an organo A composition comprising a condensate of silane, a chelate compound of zirconium alkoxide, and a hydrolyzable silyl group-containing vinyl resin (JP-A-641-1)
No. 769) or a composition comprising a condensate of an organosilane, colloidal alumina and a hydrolyzable silyl group-containing vinyl resin (US Pat. No. 4,904,72).
No. 1) or a composition comprising a hydrolyzate of an organosilane, a metal chelate compound, and a hydrolyzable or partially condensable silyl group-containing vinyl resin.

[0003] However, Japanese Patent Application Laid-Open No.
Even when a coating film is formed using the coating composition described in Japanese Patent No. 65904 and U.S. Pat. No. 4,904,721, the glossiness of the coating film is reduced by long-term ultraviolet irradiation. . Further, the composition described in JP-A-64-1769 is obtained by adding a condensate of an organosilane, a chelate compound of a zirconium alkoxide and a hydrolyzable silyl group-containing vinyl resin to a hydrophilic organic solvent. However, storage stability is not sufficient, and if the solid content concentration is increased, gelation easily occurs in a short period of time. Further, this composition comprises an alcohol, an ester formed by a condensation reaction between a condensate of organosilane (organopolysiloxane) and a chelate compound, and a SP of a silyl group-containing vinyl resin.
Due to the difference in the values, micro-layer separation occurs, and the copolycondensation between the organopolysiloxane and the silyl group-containing vinyl resin is insufficient.
For example, there are limitations on the drying temperature, coating thickness, coating method, and the like. In addition, there is a problem that glossiness after film formation cannot be obtained as clearly as that of a conventional organic coated plate.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned conventional technical problems, and is directed to a single solvent having one or more solvents mixed and having an SP value of 11 to 15. Alternatively, by using a silyl group-containing vinyl resin synthesized in a mixed solvent, the condensate of the organosilane, the chelate compound, and the hydrolyzable silyl group-containing vinyl resin have good cocondensability, and the micro layer separation is improved. Prevention, uniform reaction, and excellent curability and drying properties, so that it can be used as a general-purpose product at room temperature with a brush or roller coating without any restrictions on drying temperature, coating film thickness, coating method, etc. Excellent in workability and film-forming properties without lifting even in the case of seam-coating or overcoating, so it can be used in a wide range of applications and has a clear image comparable to conventional organic coatings High gloss coating film with transparency, weather resistance, stain resistance, heat resistance, water resistance, seawater resistance, organic chemical resistance, acid resistance, alkali resistance, corrosion resistance, abrasion resistance, weather resistance, It is an object of the present invention to provide a coating composition which is excellent in moisture resistance, adhesion, and the like and can form a coating film having high hardness.

[0005]

The present invention SUMMARY OF THE INVENTION may, (a) the general formula R ¹ _n Si (OR ²⁾ in _4-n (wherein, R ¹ is 1 to 8 carbon atoms
R ² represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and n is 0 to 2). 100 parts by weight of condensate in terms of organosilane, (b)
A silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, which is polymerized using a single or mixed solvent having an SP value of 11 to 15, is at least one terminal or side chain in one molecule of the polymer. 4 to 500 parts by weight of a silyl group-containing vinyl resin solution having one piece in terms of solid content,
(C) General formula M (OR ³ ) _p (R ⁴ COCH ₂ CO
R ⁵ ) _q (wherein, M is a metal atom, R ³ and R ⁴ are the same or different and are an alkyl group having 1 to 6 carbon atoms, and R ⁵ is an alkyl group having 1 to 6 carbon atoms or 1 to 16 carbon atoms. An alkoxy group, p and q are integers of 0 to 4), 0.01 to 100 parts by weight of an organometallic compound represented by the general formula R ⁴ COCH ₂ COR ⁵ (where R is an integer). ^{4 to} R
⁵ is the same as described above), and provides a coating composition containing the β-diketones and / or β-ketoesters represented by (c) in an amount of 2 mol or more per 1 mol of the organometallic compound. is there.

[0006]

Next, the composition of the present invention will be described in detail for each constituent element. Component (a) component (a) is a general formula _{^{R 1 n Si (OR 2)}} 4-n represent organosilane hydrolysis is, the hydrolyzate obtained by condensation and / or partial condensate, It functions as a binder in the composition obtained in the present invention. R ^{1 in} this organosilane has 1 to 8 carbon atoms.
And an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and γ
-Chloropropyl group, vinyl group, 3,3,3-trifluoropropyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group,
Examples include a phenyl group and a 3,4-epoxycyclohexylethyl group. R ² in the organosilane is
An alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl Group, acetyl group and the like.

Specific examples of these organosilanes include tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-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, 3,4-epoxycyclohexyl Ethyltriethoxysilane, dimethylmethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane,
Di-i-propyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like can be mentioned, and preferred are methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane.

[0008] These organosilanes can be used alone or in combination of two or more. Further, among the above organosilanes, preferably 40
Mole% or more, more preferably 50 mole% or more of CH
₃ Si if a (OR ²⁾ ₃ is preferred. In addition,
The weight average molecular weight of the component (a) is preferably from 800 to 1
00,000, more preferably 1,000 to 50,000.
00.

(B) Silyl group-containing vinyl resin (b) The silyl group-containing vinyl resin is composed of a silicon polymer having a main chain composed of a vinyl polymer and having a terminal or a side chain bonded to a hydrolyzable group and / or a hydroxyl group. A polymer containing at least one, and preferably two or more, silyl groups having atoms in a molecule of a polymer, and a single or mixed solvent having an SP value of 11 to 15 It is polymerized using a solvent, and most of the silyl groups are represented by the following general formula. (Wherein X is a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group,
A hydrolyzable group such as an amino group and / or a hydroxyl group;
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 m is an integer of 1 to 3. )

(B) The silyl group-containing vinyl resin is
(A) a hydrosilane compound may be produced by reacting a hydrosilane compound with a vinyl resin having a carbon-carbon double bond, and (b) a hydrolyzable group and / or hydroxyl group-containing vinyl compound represented by the following general formula: And various vinyl-based compounds may be produced, and the production method is not limited. (However, X, R ⁶ and m are the same as above, and R ⁷ is an organic group having a polymerizable double bond.)

Here, as the hydrosilane compound used in the production method shown in the above (a), for example, halogenated silanes such as methyldichlorosilane, trichlorosilane and phenyldichlorosilane; methyldiethoxysilane, methyl Alkoxysilanes such as dimethoxysilane, phenyldimethoxysilane, trimethoxysilane and triethoxysilane; acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane and triacetoxysilane; methyldiaminoxysilane, triaminoxysilane; Examples include aminosilanes such as dimethylaminoxysilane and triaminosilane.

The vinyl resin used in the production method shown in (a) is not particularly limited, except for the vinyl resin containing a hydroxyl group. For example, methyl (meth) acrylate, (meth) acryl Ethyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylic acid esters 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;
Amide compounds such as (meth) acrylamide, itaconic acid diamide, α-ethylacrylamide, crotonic acid amide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl (meth) acrylamide; acrylonitrile, styrene, α-methylstyrene, vinyl chloride A vinyl resin obtained by copolymerizing a vinyl compound selected from vinyl acetate, vinyl propionate and the like is preferred.

On the other hand, examples of the hydrolyzable group and / or hydroxyl group-containing vinyl compound used in the production method shown in (b) include, for example,

[0014]

[0015]

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

Specific examples of the above silyl group-containing vinyl resin (b) include a trialkoxysilyl group-containing acrylic polymer represented by the following general formula. [Wherein, 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 having 1 to 6 groups, 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, a butylene group, and R ¹² is the same as R ⁹ . And t / (s + t) = 0.01 to 0.4, preferably 0.02 to 0.2. The number average molecular weight of the silyl group-containing vinyl resin (b) is preferably from 2,000 to
100,000, more preferably 4,000 to 50,
000.

The silyl group-containing vinyl resin (b) is a solvent of one kind or a mixture of two or more kinds,
It is obtained by polymerization in a single or mixed solvent having a P value of 11 to 15, preferably 11 to 14. The solvent used for the polymerization preferably has an SP value of 11 to 1.
The 5 alcohols can be used alone or as a mixture with two or more of ethers, ketones, esters, aromatic hydrocarbons and the like. SP value of mixed solvent δ
Is obtained by the following equation. The formula used is one quoted from the solvent handbook. The value at 25 ° C. is used as the δ value of each solvent. δ _mix = (x ₁ V ₁ δ ₁ + x ₂ V ₂ δ ₂ + ... x _n V
_{n δ n) / (x 1} V 1 + x 2 V 2 ··· + x n V n) wherein, x represents a molar fraction, V is a molecular volume of mixture components.

When the SP value of the solvent alone or the mixed solvent is less than 11, the difference in SP value between the alcohol and ester formed by the hydrolysis and condensation of the organosiloxane and the silyl group-containing vinyl resin solution is large. Insufficient condensation. In addition, a solvent having an SP value of less than 11 easily dissolves the polymer and causes lifting when a seam is applied at the time of coating or when a layer is repeatedly applied. Furthermore, the curability and the drying property are poor, and the glossiness cannot be obtained as bright as that of a conventional organic coated plate. On the other hand, a solvent having an SP value of more than 15 is not used as a general solvent for coatings and coatings, and when water is used, the silyl group-containing vinyl resin obtained by emulsion polymerization is (a) In the reaction using the components (c) to (c), synthesis with an organosiloxane cannot be performed, which is inappropriate.

In the present invention, the component (b) is S
After polymerization using a solvent having a P value of 11 to 15, the solvent is used without being separated. Here, the proportion of the solvent in the component (b) is 50% by weight or more.

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

Specific examples of ethers include tetrahydrofuran and dioxane; specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone; specific examples of esters include ethyl acetate; Propyl acetate, butyl acetate, propylene carbonate and the like, and specific examples of the aromatic hydrocarbons include xylene and toluene.

The proportion of (b) the silyl group-containing vinyl resin (solid content) in the composition is 4 to 500 parts by weight, preferably 7 to 500 parts by weight, per 100 parts by weight of the organosilane used as the raw material of the component (a). 250 parts by weight, and less than 4 parts by weight,
The alkali resistance of the obtained coating film is low. On the other hand, when it exceeds 500 parts by weight, the weather resistance of the obtained coating film is deteriorated.

(C) Organometallic Compound The (c) organometallic compound of the present invention comprises the component (a) and the component (b)
It is considered that they act to form a co-condensate with the component.

(C) R ³ and R ⁴ in the organometallic compound
Are the same or different alkyl groups having 1 to 6 carbon atoms, specifically, ethyl group, n-propyl group, i-propyl group, n
-Butyl group, sec-butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ⁵ is an alkyl group having 1 to 6 carbon atoms as described above,
16 alkoxy groups such as methoxy, ethoxy,
Examples include an n-propoxy group, an i-propoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group, a lauryl group, and a stearyl group. Further, p to q in the organometallic compound (c) represent an integer of 0 to 4.

Specific examples of these organometallic compounds (c) include tetrabutoxyzirconium, tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium,
n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate)
Zirconium compounds such as zirconium, tetrakis (acetylacetoacetate) zirconium and tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diisopropoxy bis (Acetylacetate) titanium compounds such as titanium, tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetra-t-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropane Aluminum propoxyacetylacetonate, aluminum isopropoxybis (ethylacetoacetate), isopropoxybis (acetylacetonate) aluminum Miniumu, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, mono-acetylacetonate ·
Aluminum compounds such as bis (ethyl acetoacetate) aluminum and the like can be mentioned. Preferred among these (c) organometallic compounds are zirconium tri-n-butoxyethyl acetoacetate, titanium diisopropoxybis (acetylacetonate), aluminum diisopropoxyethyl acetoacetate, and aluminum tris (ethylacetoacetate). It is. These organometallic compounds (c) may be used alone or in combination.
A mixture of more than one species can be used. Further, as the component (c), partial hydrolysates of these organometallic compounds can also be used.

The proportion of the organometallic compound (c) in the composition is 0.01 to 100 parts by weight, preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the organosilane as the raw material of the component (a).
When it is less than 0.01 part by weight, the formation of a co-condensate of the component (a) and the component (c) is insufficient, and When the amount exceeds 100 parts by weight, the storage stability of the composition deteriorates, and cracks may occur in the resulting coating film.

Component (d) The component (d) used in the present invention has the general formula R ⁴ COCH
Β-diketones and / or β represented by ₂ COR ⁵
-Ketoesters, which act as a stability improver for the composition of the present invention. That is, the above (a) to
(B) By coordinating to a metal atom in an organometallic compound (zirconium, titanium and / or aluminum compound) present in a composition containing the component as a main component, (a) It is considered that it acts to control the condensation reaction of component (b) and / or component (b), and acts to improve the storage stability of the resulting composition. R ⁴ constituting the component (d)
And R ⁵ are the same as those of the above (c) organometallic compound.
It is similar to the ⁴ and R ^5.

Specific examples of the (d) β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, and acetoacetate. -N-butyl, acetoacetate-sec-butyl, tert-butyl acetoacetate, 2,4-hexane-dione, 2,4
-Heptane-dione, 3,5-heptane-dione, 2,
4-octane-dione, 2,4-nonane-dione, 5-
Methyl-hexane-dione and the like can be mentioned.
Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketones and / or β-ketoesters can be used alone or as a mixture of two or more. (D) β-diketones and / or β
The amount of the ketoester is 2 mol or more, preferably 3 to 20 mol, per 1 mol of the organometallic compound (c), and when it is less than 2 mol, the storage stability of the obtained composition is poor.

Component (e) The composition of the present invention contains the above-mentioned components (a) to (d) as a main component, and usually, a composition containing the components (a) to (d) is prepared. At this time, (e) water is added to the organosilane constituting the component (a). (E) The amount of water used is
It is usually about 0.5 to 3.0 mol, preferably about 0.7 to 2.0 mol, per 1 mol of the organosilane.

(F) Component The total solid content of the composition of the present invention is preferably 50% by weight or less, and the total solid content is adjusted according to the purpose of use. At that time, if necessary, (f) an organic solvent is added. (F) The organic solvent is not particularly limited as long as it mainly mixes the components (a) to (d) uniformly. Examples thereof include alcohols, aromatic hydrocarbons, ethers, ketones, and esters. It is an organic solvent having an SP value of 11 to 15, which can be added, and is preferably one kind or a mixture of two or more kinds. For the purpose of impregnating a thin film forming substrate, the total solid content concentration is usually 5 to 30% by weight. When used for forming a thick film or dispersing a filler (g) described later, the total solid content concentration is usually 20 to 50% by weight, preferably 30% by weight.
When the content exceeds 50% by weight, the storage stability of the composition deteriorates, which is not preferable.

The composition of the present invention may optionally contain a metal oxide sol for the purpose of improving the hardness of the resulting coating film. Examples of the metal oxide sol include organosilica sol, alumina sol, tin sol, zirconium sol, antimony pentoxide sol, and the like.The cocondensation reaction may be performed in the presence of these metal oxide sols, or the mixture may be mixed after the reaction. May be.

Further, the composition of the present invention is separately provided with the following properties in order to exhibit various properties such as coloring, thickening of a coating film, prevention of ultraviolet transmission to a base, imparting corrosion resistance, and heat resistance.
(G) It is also possible to add and disperse a filler. Examples of the filler (g) include, for example, water-insoluble pigments such as organic pigments and inorganic pigments, and particles, fibrous or scale-like metals and alloys other than pigments, and oxides, hydroxides and carbides thereof. , Nitrides, sulfides and the like. Specific examples of the filler (g) include particles, fibers, and scales of iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, and 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, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, mica, zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, shere green, green earth , Manganese green, pigment green, ultramarine,
Navy blue, Pigment green, Rock ultramarine, Cobalt blue, Cerulean blue, Copper borate, Molybdenum blue, Copper sulfide, Cobalt purple, Mars purple, Manganese purple, Pigment violet, Lead oxide, Calcium plumbate, Zinc yellow, Lead sulfide, Chromium Yellow, loess, cadmium yellow, strontium yellow, titanium yellow, litharge, pigment yellow, cuprous oxide, cadmium red, selenium red, chrome vermillion, bengala, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, Lead silicate, zircon oxide, tungsten white, lead zinc white, bunchison white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black,
Examples include thermatomic black, vegetable black, potassium titanate whisker, and molybdenum disulfide.

The average particle size or average length of the filler (g) is usually 50 to 50,000 nm, preferably 100 to 5,000 nm. The proportion of the component (g) in the composition is about 10 to 300 parts by weight based on 100 parts by weight of the total solids of the components (a) to (d). Further, in curing the composition 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 in combination. is there.

Examples of the curing accelerator include alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate and carbonic acid; alkaline compounds such as sodium hydroxide and potassium hydroxide; alkyltitanic acid, phosphoric acid, p-
Acidic compounds such as toluenesulfonic acid and phthalic acid; various modifications used as curing agents for ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, metaphenylenediamine, ethanolamine, triethylamine, and epoxy resin Amine, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ- (2-
Amine 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 = CHCOO)
C 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 = CHCOO)
C ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CH
Carboxylic acid type organotin compounds such as COOC ₈ H ₁₇ ) ₂ and Sn (OCOC ₈ H ₁₇ ) ₂ ; (C ₄ H ₉ ) ₂ Sn
(SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₄ H ₉ ) ₂ Sn
(SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn
(SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn
(SCH ₂ CH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂
Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ S
n (SCH ₂ COOC ₁₂ H ₂₅ ) ₂ ,

[0036] Mercaptide-type organotin compounds such as; Sulfide-type organotin compounds such as;

(C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ S
nO, or (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ S
An organic tin compound such as a reaction product of an organic tin oxide such as nO and an ester compound such as ethyl silicate, dimethyl maleate, diethyl maleate, and dioctyl phthalate is used. The proportion of these curing accelerators in the composition is 100% solids of the composition of the present invention.
It is used in an amount of usually 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on parts by weight.

The composition of the present invention may further contain other known dehydrating agents such as methyl orthoformate, methyl orthoacetate, and tetraethoxysilane, various surfactants,
Silane coupling agent, titanium coupling agent, dye,
Additives such as dispersants, thickeners and leveling agents can also be added.

Further, the composition of the present invention may contain an organic solvent other than the above (f) organic solvent. The organic solvent does not cause precipitation when the above composition is mixed. Any solvent may be used, and there is no particular limitation as long as it is used for general paints, coating agents, and the like.Examples include alcohols, aromatic hydrocarbons, ethers, ketones, and esters. Can be mentioned. As described above, these organic solvents have an SP value of 11 or a mixture of two or more.
~ 15 organic solvents are preferred. These organic solvents are generally used in an amount of about 100 parts by weight or less based on 100 parts by weight of the composition of the present invention.

In preparing the composition of the present invention, a composition containing the above components (a) to (d) may be prepared. For example, the following preparation methods are preferred. To a solution comprising (a) the organosilane constituting the component, (b) a vinyl resin containing a silyl group, and (c) an organometallic compound, 0.1 to 3 mol of water is added to 1 mol of the organosilane, A method comprising forming a composition comprising components (a) to (c), and then adding (d) β-diketones and / or β-ketoesters.

Organosilane 1 Constituting Component (a)
The hydrolysis / condensation reaction is carried out by adding 0.1 to 3 mol of water to the mol, and then (b) a silyl group-containing vinyl resin,
(C) A method in which an organometallic compound is added and mixed, a condensation reaction is further performed to form a composition comprising the components (a) to (c), and then the component (d) is added.

An organosilane constituting the component (a),
(C) A solution obtained by adding the organometallic compound and the component (d) is subjected to hydrolysis and condensation reaction by adding 0.01 to 3 mol of water to 1 mol of the organosilane to carry out a hydrolysis / condensation reaction. ~
A method comprising forming a composition comprising the component (c) and then adding the component (d).

The composition of the present invention is applied on the surface of a substrate as an object by a coating method such as a brush, a roller, a spray, a dipping, a bar code, an applicator or the like in a single application to a thickness of about 10 to 100 μm. A coating film having a thickness of about 2 to 200 μm can be formed by 3 to 3 coatings, and dried at normal temperature of about 5 to 40 ° C. under a normal environment, or 30
It is possible to form a coating film by leaving or heating and drying at a temperature of about 200 ° C. for about 10 minutes to 1 day. Substrates on which the composition of the present invention is coated include, for example, stainless steel, aluminum, ceramics, cement, concrete, ALC, paper, glass, plastic, inorganic ceramic substrates, and fabrics.

In coating the substrate, conventionally known acrylic resins, epoxy resins, and urethane resins are used for the purpose of improving the adhesion to the substrate, or filling, smoothing, and film-forming the porous substrate. Alternatively, it is possible to use a base material on which a primer such as a polyester resin is formed in advance. Further, in order to enhance the abrasion resistance and gloss of a coating film formed using the composition of the present invention containing (g) a filler, a clear layer of the present composition may be formed. No. 4,986,997, U.S. Pat.
It is also possible to form a clear layer containing a siloxane resin as an essential component, such as a stable dispersion of colloidal silica and a siloxane resin described in Japanese Patent No. 027,073.

[0045]

EXAMPLES The present invention will be described more specifically with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the examples, parts and% are by weight unless otherwise specified. Various measurements in the examples are as follows.

(Polymer, composition) The storage stability of the composition was sealed in a glass bottle at room temperature without adding a curing accelerator at room temperature, and the presence or absence of gelation was visually determined. For those which did not cause gelation, a coaxial double cylindrical high shear viscometer, Rheomat 115 [contraves
(Manufactured by K.K.), and those having a change rate of 20% or less were judged as no change (（), those having a change rate of more than 20%, and those gelled were judged as x. Here, the viscosity of the polymer (composition) was measured using the above-mentioned coaxial double cylindrical high shear viscometer, Rheoma.
The viscosity was measured by t115 (manufactured by Contrabes), and the viscosity at a shear rate of 500 sec ^-1 was measured.

The coating properties were as follows. For the gloss, a 60-degree specular gloss according to JIS K5400 was evaluated using a variable-angle gloss meter (manufactured by Tokyo Denshoku Co., Ltd.). When judging the appearance, when the coating film is viewed with a fluorescent lamp, those with a clear reflection like a mirror surface have a sharp image, those with a thin fluorescent lamp are considered as glossy blur, and those with no fluorescent lamp reflected. Was determined to be glossy. The resistance to organic chemicals (solvent resistance) was determined by dropping 2 cc of i-propanol on the coating film, wiping it with a cloth 5 minutes later, and observing the state of the coating film. Those with no dripping marks on the coating ○
It was determined.

The weather resistance is based on JIS K5400,
3,000 hours irradiation test with a weather meter,
The state of the coating film was observed. Maintains gloss with glossy coating film, no change in color, good for coating film surface not chalked, bad for glossy surface change, bad for glossy coating, change to gloss color difference Those that did not exist were determined to have no change.
The stain recovery property (stain resistance) is determined by applying a paste mixed with carbon black / kerosene (weight ratio) = 1/2 on the coating film, leaving it to stand at room temperature for 24 hours, washing with a sponge, and washing with water. The state of recovery of the contamination of the membrane was observed.が な い indicates no contamination, ○ indicates slight contamination, and × indicates significant contamination.

The lifting was carried out twice in an atmosphere of 5 to 40 ° C. using an applicator, and swelling and shrinkage of the coating film were visually confirmed. For the drying property, the surface of the coating film was observed after a tack test by touch with a finger, and those having no fingerprints and no stickiness were judged as OK, and those with fingerprints and sticky were judged as NG.

Reference Example 1 [Preparation of Silyl Group-Containing Vinyl Resin ~] In a reactor equipped with a reflux condenser and a stirrer, 90 parts of i-propanol was heated to 80 ° C, and 70 parts of methyl methacrylate was added thereto. 2-ethylhexyl methacrylate 15
Part, γ-methacryloxypropyltrimethoxysilane 1
5 parts were added dropwise and mixed well. A solution obtained by dissolving 4 parts of azobisisovaleronitrile in 10 parts of i-propanol was added dropwise to the mixture over 30 minutes.
The reaction was carried out for an hour to obtain a silyl group-containing vinyl resin solution (a) having a solid content of 50%. The SP value of the solvent at this time was 12.0.

Similarly, 50 parts of i-propanol was added to 80 parts.
After heating to 70 ° C., 70 parts of methyl methacrylate, 15 parts of 2-ethylhexyl methacrylate, 15 parts of γ-methacryloxypropyltrimethoxysilane, and 40 parts of methyl ethyl ketone were dropped and mixed well, and azobisisovaleronitrile 4 was added to the mixture. A part thereof dissolved in 5 parts of i-propanol was added dropwise over 30 minutes, and the mixture was further reacted at 80 ° C. for 5 hours to obtain a silyl group-containing vinyl resin solution (b) having a solid content concentration of 50%. The SP value of the solvent at this time was 11.1.

Similarly, 60 parts of butyl acetate and 30 parts of i-propanol were heated to 80 ° C., and 58 parts of methyl methacrylate, 30 parts of n-butyl acrylate, and 12 parts of γ-methacryloxypropyltrimethoxysilane were added dropwise. Mix well. A solution obtained by dissolving 4 parts of azobisisovaleronitrile in 10 parts of butyl acetate was added dropwise to the mixture over 30 minutes, and the mixture was further reacted at 80 ° C. for 5 hours to obtain a silyl group-containing vinyl resin having a solid content of 50%. A solution (c) was obtained. The SP value of the solvent at this time was 10.0.

Similarly, 65 parts of xylene, 2 parts of butyl acetate
5 parts was heated to 80 ° C., 70 parts of methyl methacrylate,
15 parts of 2-ethylhexyl methacrylate and 15 parts of γ-methacryloxypropyltrimethoxysilane were added dropwise,
After mixing well, 4 parts of azobisisovaleronitrile dissolved in 10 parts of xylene was added dropwise to the mixture over 30 minutes, and the mixture was further reacted at 80 ° C. for 5 hours to obtain a 50% solids-containing silyl group. A vinyl resin (d) was obtained. The SP value of the solvent at this time was 8.7.

Examples 1 to 7, Comparative Examples 1 to 5 A reactor equipped with a stirrer and a reflux condenser was charged with 80 parts of methyltrimethoxysilane, 20 parts of dimethyldimethoxysilane,
(B) 40 parts of polyacryl silicon [solid content concentration 50%, (a) of Reference Example 1], (c) 8 parts of ethyl acetoacetate aluminum diisopropylate, and (f) 5 parts of i-propanol were added and mixed. Thereafter, (e) 20 parts of ion-exchanged water was added, and the mixture was reacted at 60 ° C. for 4 hours. After cooling to room temperature, (d) 30 parts of acetylacetone was added,
A coating composition A was obtained. Using a similar reactor,
Compositions B to L shown in Tables 1 and 2 were obtained. The results are shown in Tables 1 and 2.

Fillers, additives, and pigments are added to the compositions A to J at the ratios shown in Tables 3 and 4, glass beads are added, and the mixture is kneaded using a sand mill. j was obtained. A slate board (JIS A5043F) is coated with a general-purpose epoxy resin and then a general-purpose acrylic resin in a dry weight of 5% each.
^{On a} substrate coated and dried at 0 g / m ² , the above compositions a to j containing 15% of dibutyltin dilaurate as a curing agent
- adding propanol solution of 10%, paint mixed well, dry weight 50 g / m ² was applied, allowed to stand at room temperature for 7 days to prepare a test piece. Tables 3 and 4 show the results of various tests performed using these test pieces. In addition, since the compositions K and L were gelled, a coating could not be produced.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

[Table 4]

*) In Table 3, the titanium oxide is titanium oxide (white).

[0061]

Industrial Applicability The coating composition of the present invention has excellent curability and drying properties and can be applied without causing lifting due to recoating, so that it has a high versatility, a high gloss and a sharp finish. The coating film is a good coating film, has excellent storage stability, is transparent, has excellent physical properties such as organic chemical resistance, weather resistance, and stain resistance, and has high hardness.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 183/07

Claims (2)

(57) [Claims] (1) The general formula R ¹ _n Si (OR ² ) _4-n
(Wherein, R ¹ is an organic group having 1 to 8 carbon atoms, and R ² is an organic group having 1 carbon atom.
Represents an alkyl group of from 5 to 5 or an acyl group of from 1 to 4 carbon atoms, and n is from 0 to 2). (B) a polymer 1 having a SP value of 11 to 15 and having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, which is polymerized using a single or mixed solvent, at the terminal or in the side chain; 4 to 500 parts by weight, in terms of solids, of a silyl group-containing vinyl resin solution having at least one silyl group-containing molecule, (c) a general formula M (OR ³ ) _p (R ⁴ COCH ₂ CO
R ⁵ ) _q (wherein, M is a metal atom, R ³ and R ⁴ are the same or different and are an alkyl group having 1 to 6 carbon atoms, and R ⁵ is an alkyl group having 1 to 6 carbon atoms or 1 to 16 carbon atoms. An alkoxy group, and p and q are integers of 0 to 4) in an amount of 0.01 to 100 parts by weight, and (d) a general formula R ⁴ COCH ₂ COR ⁵ (wherein R ^{4 to} R
⁵ is the same as described above), a coating composition comprising β-diketones and / or β-ketoesters represented by (c) in an amount of 2 mol or more per 1 mol of the organometallic compound. 2. The above component (a) is converted to an organosilane in an amount of 1%.
The component (b) is used in an amount of 7 to 100 parts by weight in terms of solid content.
2. The coating composition according to claim 1, wherein the amount is 250 parts by weight.
object.