JPH10273623A - Composition for coating and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for coating, excellent in weather and fouling resistances and further long-term durable adhesion and suitable for forming a film having performances excellent in pigment dispersibility. SOLUTION: This composition for coating comprises (a) an organosilane hydrolyzate represented by the general formula R<1> n Si(OR<2> )4-n (R<1> denotes a 1-8C organic group; R<2> denotes a 1-5C alkyl group or a 1-4C acyl group; (n) is 0-2] and/or its partial condensate and (b) a vinylic copolymer having (b-1) a silyl group having a hydrolyzable group and/or silicon atom bound to hydroxyl group and (b-2) at least one group selected from carboxyl group, hydroxy group, carbonyl group, an acid anhydride group and glycidyl group in one molecule.

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 weather resistance and stain resistance, which is excellent in long-term durability adhesion and pigment. The present invention relates to a coating composition suitable for forming a film having excellent dispersibility.

[0002]

2. Description of the Related Art In recent years, maintenance-free coating materials having excellent weather resistance and stain resistance have been required for materials used for outdoor applications, such as acrylic urethane resin, acrylic silicone resin, and fluorine resin. Organic polymer is used, but from the viewpoint of both weather resistance and stain resistance, an inorganic polymer using an organoalkoxysilane is also used.
Are better. These compositions include, for example, a hydrolyzate / condensate of an organoalkoxysilane or a composition in which colloidal silica is dispersed therein (Japanese Patent Publication No. Sho.
JP-A-3-5042) and a composition comprising a hydrolyzable silyl group-containing vinyl resin (JP-A-64-1769), a partial condensate of organosilane, a silyl group-containing vinyl resin, and a metal chelate. It has been proposed in a composition comprising a compound and a β-diketone and / or β-ketoester (JP-A-4-58824) and a coating method thereof (JP-A-6-329986). These compositions not only have excellent weather resistance and stain resistance, but also have high heat resistance, water resistance, organic chemical resistance, corrosion resistance, abrasion resistance, and high hardness. Can be formed. Compositions based on these organoalkoxysilanes are resistant to heat, light, chemicals, and stains as described above, and are therefore ideally suited as coating materials under severe conditions. So some substrates,
Since long-term adhesion can be secured only to some primers, versatility is poor. In particular, under conditions where light, water, and heat are overlapped, the adhesion decreases over a long period of time.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned conventional technical problems, and is intended to limit the molecular weight of a hydrolyzable silyl group-containing vinyl resin and to provide a carboxyl group, a hydroxy group or a carbonyl group. Alternatively, by using a copolymerizable vinyl resin containing either an acid anhydride or a glycidyl group, the influence of a polar group or a change in SP value occurs, and the adhesion between the composition and a substrate or primer is improved. I do. In addition, the wettability with the pigment is improved, and a composition having good pigment dispersibility can be obtained.
Furthermore, it is transparent, weather resistance, stain resistance, heat resistance, water resistance,
It is widely used as a coating composition that has excellent seawater resistance, organic chemical resistance, acid resistance, alkali resistance, corrosion resistance, abrasion resistance, moisture resistance, etc., and can form a coating film with high hardness. be able to.

[0004]

According to the present invention, there are provided (a) a compound represented by the general formula: R ¹ nSi (OR ² ) 4 -n, wherein R ¹ has 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). Condensate, (b) a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group in one molecule, and (b-2) a carboxyl group, a hydroxy group, a carbonyl group, an acid anhydride A coating composition comprising a vinyl copolymer having at least one group selected from a product or a glycidyl group (hereinafter, these are referred to as "functional groups").

[0005]

Next, the composition of the present invention will be described in detail for each constituent element. Component (a) The component (a) is a hydrolyzate and / or a partial condensate obtained by hydrolyzing and condensing an organosilane represented by the general formula R ¹ nSi (OR ² ) 4-n. In the composition obtained by the invention, it functions as a binder. R ^{1 in} this organosilane has 1 carbon atom.
To 8 organic groups, for example, a methyl group, an ethyl group,
Alkyl groups such as propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, n-hexyl group and n-heptyl group, and other γ-chloropropyl groups, vinyl groups, 3,3 , 3-trifluoropropyl group, γ
-Glycidoxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group, phenyl group, 3,
4-epoxycyclohexylethyl group and the like. R2 in the organosilane has 1 to 5 carbon atoms.
An alkyl group or an acyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an acetyl group, And a propionyl group and a butyryl group.

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.

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
3Si (OR ² ) 3 is preferable. 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. Such a hydrolyzate and / or a partial condensate thereof can be prepared and used in advance. In the present invention, the silane compound of the component (a) and the components (b) to (g) described later are usually used. When blending the ingredients,
By adding an appropriate amount of water, (a)
The components can also be hydrolyzed and condensed.

Component (b) The component (b) is a silyl group (hereinafter simply referred to as "silyl group") having a main chain composed of a vinyl polymer and having a silicon atom bonded to a terminal or side chain thereof with a hydrolyzable group and / or a hydroxyl group. At least one, preferably two or more, silyl groups) in one molecule of the polymer, and further has at least one kind of functional group. In the present invention, the silyl group is generally represented by the following general formula. —Si (R ⁶ ) 3-mXm (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. )

The component (b) may be produced by reacting (a) a hydrosilane compound with a vinyl resin having a carbon-carbon double bond, and (b) a hydrolysis represented by the following general formula. The polymer may be produced by polymerizing a vinyl compound having a functional group and / or a hydroxyl group with various vinyl compounds, and the production method is not limited. ^{R 7 -Si (R 6) 3} -mXm ( although, X, R ^6, m are as defined above, 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.

On the other hand, as the hydrolyzable group and / or hydroxyl group-containing vinyl compound used in the production method shown in (b), for example, CH ₂ ＣＨCH (CH ₃ ) Si (OCH
₃ ) ₂ , CH ₂ ＣＨCHSi (OCH ₃ ) ₃ , CH ₂ ＣＨCH
(CH ₃ ) SiCl ₂ , CH ₂ ＣＨCHSiCl ₃ , CH ₂ =
CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₂ , CH ₂ ＣC
HCOO (CH ₂ ) ₃ Si (CH ₃₎ (OCHR ₃ ) ₃ , C
H ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ , CH ₂
ＣＨCHCOO (CH ₂ ) ₃ SiCl ₃ , CH ₂ ＣC (C
H ₃ ) COO (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ ,
CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (CH ₃ )
(OCH ₃ ) ₂ , CH ₂ ＣC (CH ₃ ) COO (C
H ₂ ) ₃ SiCl ₂ , CH ₂ ＣC (CH ₃ ) COO (C
H ₂ ) ₃ SiCl ₃ ,

[0012]

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[0013]

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[0014]

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[0015]

Embedded image And the like. There is no particular limitation on the copolymerizable monomer used in the production method shown in (a) or (b). For example, (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, (meth) Acrylic acid or derivatives thereof can be mentioned.
Specific examples of (meth) acrylates or derivatives thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic acid. Acid
c-butyl, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n-hexyl (meth) acrylate, isohexyl (meth) acrylate, n- (meth) acrylate -Heptyl,
Isoheptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, (meth) ) N-decyl acrylate, isodecyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate,
(Meth) acrylates such as 4-methylcyclohexyl (meth) acrylate and 4-tert-butylcyclohexyl (meth) acrylate; amide compounds such as (meth) acrylamide; 2-methoxyethyl (meth) acrylate , 2-methoxypropyl (meth) acryle
3-methoxypropyl (meth) acrylate, 2-
Methoxybutyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) ) (Meth) acrylates of alkoxy (poly) alkylene glycol such as acrylate, carboxyethyl acrylate, etc .; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate
3-hydroxybutyl (meth) acrylate, 4-
Hydroxybutyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate And other polyvalent alcohol mono (meth) acrylates: ethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, butylene glycol di (meth) acrylate
Glycerin di (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol, 1,
4-cyclohexanedioldi (meth) acrylate,
Polyhydric alcohol poly (meth) acrylates such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate; succinic acid [2- (meth) acryloyloxyethyl], succinic Acid di [2- (meth) acryloyloxyethyl],
Mono [2- (meth) acryloyloxyethyl adipate], di [2- (meth) acryloyloxyethyl adipate], mono [2- (meth) acryloyloxyethyl phthalate], di [2- (meta) phthalate ) Acryloyloxyethyl] and the like, and (poly) esters of hydroxyalkyl (meth) acrylate;
Amino group-containing (meth) such as 2-aminoethyl (meth) acrylate, 2- (n-methylamino) ethyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate Acrylates; Epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate; dicarboxyl-containing derivatives such as fumaric acid, methylfumaric acid, maleic acid, and methylmaleic acid; maleic anhydride, anhydride Acid anhydride-containing derivatives such as methylmaleic acid; α-chloroacrylonitrile, α
Methacrylonitrile derivatives such as trifluoromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, cyancabinylidene;
N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethylacrylamide,
Acrylamide derivatives such as N-methoxy (meth) acrylamide, N-ethoxy (meth) acrylamide and diacetone acrylamide; acrylic acid, α-chloroacrylic acid, α-methylacrylic acid, α-methoxyacrylic acid, α-ethoxyacryl An acrylic acid derivative such as an acid can be used. In the present invention, (b)
The component further has a functional group. For this purpose, among the copolymerizable monomers described above, an acrylic acid derivative, a dicarboxyl group-containing derivative, a hydroxy-containing (meth) acrylate derivative, an acrylamide derivative, It is necessary to use either an acid anhydride-containing derivative or a glycidyl group-containing derivative. Among these functional group-containing monomers, dicarboxyl group derivatives, hydroxy group-containing (meth) acrylate derivatives, and acid anhydride-containing derivatives are preferred. These functional group-containing monomers are used in an amount of 0.1% by weight or more, preferably 0.2% by weight or more, based on the solid content of the component (b).

In the present invention, the component (b) is used after being polymerized using a solvent without separating the solvent. Here, the proportion of the solvent in the component (b) is 50% by weight or more.
The type of solvent used is not particularly limited, and alcohols, ethers, ketones, esters, aromatic hydrocarbons and the like can be used.

The amount of component (b) used in the present invention is 4 to 500 parts by weight, preferably 7 to 250 parts by weight, more preferably 10 to 10 parts by weight, per 100 parts by weight of component (a).
0 parts by weight. Further, in order to enhance the weather resistance of the hydrolyzable silyl group-containing vinyl resin, an ultraviolet ray stable group and / or an ultraviolet ray absorbing group may be copolymerized. Examples thereof include sterically hindered amine compounds, salicylic acid compounds, benzophenone compounds, benzotriazoles, triazine compounds, phenolic compounds and the like, in which a polymerizable unsaturated group is introduced, and the amount of monomer used is (b) ) Component is usually 1 to 20% by weight, preferably 1 to 10% by weight, and more preferably 1 to 5% by weight, based on all the monomers.

(C) Organometallic Compound The component (c) of the present invention can be used to promote the action of forming a cocondensate of the component (a) and the component (b). A preferred compound as the component (c) can be represented by the general formula M (OR ³ ) p (R ⁴ COCH ² COR ⁵ ) q.

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

Specific examples of the component (c) include zirconium tetrabutoxyzirconium, zirconium tri-n-butoxyethylacetoacetate, zirconium di-n-butoxybis (ethylacetoacetate), and n-butoxytris (ethylacetoacetate). Zirconium compounds such as zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis ( Acetyl acetate) titanium, diisopropoxy bis (acetyl acetate) titanium, tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetra t- butoxy, tetrakis (2-ethylhexyl oxy) titanium compounds such as titanium; diisopropoxy ethyl acetoacetate aluminum, diisopropoxy acetylacetonate aluminum, diisopropoxy bis (ethylacetoacetate)
Aluminum compounds such as aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, and monoacetylacetonate bis (ethylacetoacetate) aluminum are exemplified. Among these components (c), preferred are zirconium tri-n-butoxyethylacetoacetate, titanium diisopropoxybis (acetylacetonate), aluminum diisopropoxyethylacetoacetate, and aluminum tris (ethylacetoacetate). . These components (c) are:
These can be used alone or in combination of two or more. Further, as the component (c), partial hydrolysates of these organometallic compounds can also be used.

The proportion of the component (c) in the composition is based on 100 parts by weight of the organosilane as the raw material of the component (a).
0.01 to 100 parts by weight, preferably 0.1 to 80 parts by weight, more preferably 0.5 to 50 parts by weight;
If the amount is less than 01 parts by weight, the formation of a co-condensate of the component (a) and the component (c) is insufficient, and the weather resistance of the coating film is deteriorated. This is not preferred because the properties may deteriorate 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 2COR 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 R ⁴ constituting the organometallic compound (c).
And is the same as R ^5.

Specific examples of the component (d) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate,
N-butyl acetoacetate, sec-butyl acetoacetate, t-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. 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. This component (d) is the component (c) 1
It is 2 mol or more, preferably 3 to 20 mol, per mol, and if it is less than 2 mol, the storage stability of the obtained composition is inferior.

Component (e) The composition of the present invention contains the above-mentioned components (a) to (d) as a main component. 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. An organic solvent 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 the purpose of forming a thick film or dispersing a filler (g) described later, the total solid content concentration is usually 20 to 5%.
The content is 0% by weight, preferably 30 to 45% by weight, and if it exceeds 50% by weight, the storage stability of the composition deteriorates, which is not preferable.

The composition of the present invention contains
For the purpose of improving the hardness of the thin film, a metal oxide sol can be added as needed. 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 contains
Separately add and disperse (g) filler to develop various properties such as coloring, thickening, heat resistance, ultraviolet absorption, antibacterial properties, antifungal properties, anti-algal properties, antistatic properties, etc. It is also possible to make it. Examples of the filler (g) include non-water-soluble pigments such as organic pigments and inorganic pigments, and particulate, fibrous or scale-like ceramics, metals and alloys, and oxides and hydroxides thereof, other than pigments. , Carbides, 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, shale green, green earth, manganese green, pigment green, ultramarine, navy blue, pigment green, rock ultramarine, cobalt blue, cerulean blue, boric acid Copper, molybdenum blue, copper sulfide, cobalt purple, mars purple,
Manganese purple, Pigment violet, Lead suboxide, Calcium plumbate, Zinc yellow, Lead sulfide, Chrome 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, bunchesone white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide, etc. be able to.

The proportion of the component (g) in the composition is from (a) to
10 to 30 parts by weight based on 100 parts by weight of the total solid content of the component (d)
It is about 0 parts by weight. 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;
Alkyl titanic acid, phosphoric acid, p-toluenesulfonic acid,
Acidic compounds such as phthalic acid; ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, metaphenylenediamine, ethanolamine,
Triethylamine, various modified amines used as curing agents for epoxy resins, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropylmethyldimethoxy Silanes, amine compounds such as γ-anilinopropyltrimethoxysilane, zirconium compounds, titanium compounds, aluminum compounds as described in component (c), (C ₄ H ₉ ) ₂ Sn (OCOC)
_{11 H 23) 2, (C} 4 H 9) 2 Sn (OCOCH = CHCOO
CH ₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH ＝ CHCOO)
C ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC11H23)
2, (C8 H17) 2 Sn (OCOCH = CHC
OOCH ₃ ) ₂ , (C ₈ H17) 2 Sn (OCOCH =
CHCOOC4 H9) 2, (C8 H17) ₂ Sn
(OCOCH = CHCOOC ₈ H ₁₇ ) ₂ , Sn (OCOC
Carboxylic acid type organotin compounds such as C 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 (SC
H ₂ CH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SC
H ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CO
OC ₁₂ H ₂₅ ) ₂ ,

[0029] 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, or _{(C 4 H 9) 2 SnO} , organotin oxide and ethyl silicate, such as _{(C 8 H 1 7) 2} SnO, dimethyl maleate, diethyl maleate, a reaction product of an ester compound such as dioctyl phthalate An organic tin compound such as is used. The proportion of these curing accelerators in the composition is usually 0.1 to 15 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the solid content of the composition of the present invention.
5 to 10 parts by weight are used.

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,
Dispersant, thickener, leveling agent, or highly functional (light-absorbing, anti-corrosive, anti-bacterial, anti-mold, conductive, insulating)
An organic additive for imparting an acid may be added.

Further, the composition of the present invention may contain an organic solvent other than the above (f) organic solvent, and 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 are preferably one kind or a mixture of two or more kinds. These organic solvents can be used in the composition 100 of the present invention.
Usually, about 100 parts by weight or less based on parts by weight is used.

The constitution of the coating material of the present invention is as follows.
Substrate / invented coating composition or substrate /
Composed of a primer / invented coating composition.
The base material varies depending on the application. For example, inorganic ceramic bases including metals such as iron, aluminum, and stainless steel, cement, concrete, ALC, flexible boards, mortar, slates, gypsum, ceramics, and bricks. Wood; Pheno
Resin molded products such as metal, epoxy, polyester, polyethylene, polypropylene, polycarbonate and ABS;
Plastic films such as polyethylene, polycarbonate, polyethylene terephthalate, polypropylene, polyimide, polyurethane, polyvinyl alcohol; base materials such as wood, paper, glass, etc., and deteriorated coating films for repainting And so on.

Depending on the base material, a surface treatment, a base adjustment, and a treatment for providing design properties may be performed. For example, in the case of metal, there are polishing, degreasing, plating, chromating, flame treatment, coupling treatment, etc., and in the case of plastic, blasting, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge. Treatment, UV irradiation treatment, plasma treatment, ion treatment, etc., polishing, filling, patterning, etc. for ceramic substrates, polishing, filling, insect repellent treatment for wood, filling, insect repellent treatment, etc. for paper In the case of an old coating film for coating, there may be mentioned, for example, keren.

The coating specifications differ depending on the condition of the base material and the coating method. For example, in the case of metal,
If it is necessary to prevent rust, a primer may be used. In the case of a ceramic base material, the concealing property varies depending on the characteristics of the base material (surface roughness, impregnation, alkalinity, etc.).
Is used. In the case of repainting of a deteriorated coating film, use a primer if the old coating film is significantly deteriorated. In the case of other substrates such as plastic, wood, paper, glass, etc., use a primer according to the application. May or may not be present.
When there is no primer, it is desirable that the vinyl resin in the organosilane resin contains at least 0.5% by weight of a carboxyl group, a hydroxy group, a carbonyl group, an acid anhydride or a glycidyl group.
More preferably, the surface treatment is performed. The primer layer is not particularly limited as long as it functions to adhere the substrate to the invented coating composition.
Select according to the purpose of painting. One or two or more primers may be used. The primer may be a paint containing a coloring component such as a pigment, or may be a clear paint that does not contain a coloring component. Further, a dedicated curing accelerator may be used in combination. The type of primer is, for example, in the case of metal, alkyd resin, amino alkyd resin, epoxy resin, polyester resin, acrylic resin,
Polyurethane resin and fluorine resin. In ceramics-based substrates, alkyd resins, amino alkyd resins, epoxy resins, polyurethane resins, acrylic resins, polyester resins, acrylic emulsions, epoxy emulsions,
For polyurethane emulsion, polyester emulsion, plastic, epoxy resin, acrylic urethane resin, acrylic resin, polyester resin, acrylic emulsion, epoxy emulsion, polyurethane emulsion, polyester emulsion, for wood, nitrocellulose-slacker, alkyd resin, aminoalkyd For resin, polyester resin, paper, epoxy resin, polyurethane resin, acrylic resin, polyester resin, acrylic emulsion, epoxy emulsion, polyurethane emulsion, polyester emulsion,
In the case of old coating films such as polyvinyl alcohol and carboxymethyl cellulose, epoxy resins, acrylic resins, epoxy emulsions, acrylic emulsions and urethane emulsions can be used. The coating composition developed to any of the above primers can be adhered,
Preferred are epoxy resins, acrylic resins, polyurethane resins and polyester resins. Depending on the application, adhesion under severe conditions such as water or temperature change is required. In this case, the resin can be modified with a functional group.
Examples of the functional group and bonding type include a hydroxy group, a carboxyl group, a carbonyl group, an amide group, an amine group, a glycidyl group, an alkoxysilyl group, an ether bond, an ester bond and the like.

The coating method depends on the purpose of coating, such as brush,
, Dipping, sink coating, spray, roll coater, flow coater, centrifugal coater, ultrasonic coater,
Screening process, electrodeposition coating, vapor deposition coating and the like.

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 1 to 3 are preferable. 1. To a solution comprising the components (a), (b) and (c), 0.1 to 3 mol of water is added per 1 mol of the organosilane to give a composition comprising the components (a) to (c). After forming, a method of adding the component (d).

2. 0.1 to 3 mol of water is added to 1 mol of the organosilane constituting the component (a) to carry out hydrolysis / condensation reaction, and then the components (b) and (c) are added and mixed, followed by condensation. A method in which a reaction is carried out to form a composition comprising the components (a) to (c), and then the component (d) is added.

3. To a solution obtained by adding the organosilane constituting the component (a), the component (c), and the component (d), 0.01 to 3 mol of water is added with respect to 1 mol of the organosilane. A method comprising performing a condensation reaction to form a composition comprising components (a) to (c), and then adding the component (d).

In the present invention, 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. A clear resin containing a siloxane resin as an essential component such as a stable dispersion of colloidal silica and a siloxane resin described in U.S. Pat. Nos. 3,986,997 and 4,027,073. It is also possible to form layers.

[0037]

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.

Reference Example 1 In a reactor equipped with a reflux condenser and a stirrer, 80 parts of xylene was heated to 80 ° C, and methyl methacrylate 70 was added thereto.
And 15 parts of 2-ethylhexyl methacrylate, 15 parts of γ-methacryloxypropyltrimethoxysilane, and 0.5 part of maleic anhydride were added dropwise and mixed well. To this mixture, 4 parts of azobisisovaleronitrile was added with 1 part of butyl acetate.
The solution dissolved in 0 parts was added dropwise over 30 minutes.
The reaction was carried out at 0 ° C. for 5 hours to obtain a hydrolyzable silyl group-containing vinyl resin solution (a) having a solid content of 50%. Also,
A cut of maleic anhydride and a drop of 0.05 part were synthesized to obtain hydrolyzable silyl groups (f) and (g). Reference Example 2 In a reactor equipped with a reflux condenser and a stirrer, 40 parts of i-propanol was heated to 80 ° C, and methyl methacrylate 70 was heated.
Parts, 2-ethylhexyl methacrylate 15 parts, γ-methacryloxypropyltrimethoxysilane 15 parts, 2-
After 1.0 part of hydroxyethyl methacrylate and 40 parts of methyl ethyl ketone 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 mixture was further reacted at 80 ° C. for 5 hours to obtain a silyl group-containing vinyl resin solution (b) having a solid content of about 50%. Reference Example 3 In a reactor equipped with a reflux condenser and a stirrer, 40 parts of i-propanol was heated to 80 ° C, and methyl methacrylate 70 was heated.
, 15 parts of 2-ethylhexyl methacrylate, 15 parts of γ-methacryloxypropyltrimethoxysilane, 0.5 part of carboxy acrylate, and 40 parts of methyl ethyl ketone were added dropwise, mixed well, and then azobisisovalero was added to the mixture. A solution obtained by dissolving 4 parts of nitrile in 10 parts of i-propanol was added dropwise over 30 minutes.
For 5 hours to obtain a silyl group-containing vinyl resin solution (c) having a solid content of about 50%. Reference Example 4 In a reactor equipped with a reflux condenser and a stirrer, 40 parts of i-propanol was heated to 80 ° C, and methyl methacrylate 70 was heated.
Parts, 2-ethylhexyl methacrylate 15 parts, γ-methacryloxypropyltrimethoxysilane 15 parts, glycidyl methacrylate 1.0 part, methyl ethyl ketone 4
After 0 parts were dropped and mixed well, a solution obtained by dissolving 4 parts of azobisisovaleronitrile in 10 parts of i-propanol was added dropwise to this mixture over 30 minutes, and further reacted at 80 ° C. for 5 hours to obtain a solid content. A silyl group-containing vinyl resin solution (d) having a concentration of about 50% was obtained. Reference Example 5 In a reactor equipped with a reflux condenser and a stirrer, 50 parts of i-propanol was heated to 80 ° C, and methyl methacrylate 40 was heated.
, 30 parts of n-butyl acrylate, 10 parts of carboxyethyl acrylate and 15 parts of γ-methacryloxypropyltrimethoxysilane were added dropwise and mixed well. To this mixture, a solution prepared by dissolving 4 parts of azobisisovaleronitrile in 40 parts of butyl acetate 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 compound having a solid content of about 50%. A resin solution (e) was obtained. Reference Example 5 80 parts of xylene was heated to 80 ° C. in a reactor equipped with a reflux condenser and a stirrer, and methyl methacrylate 70 was added thereto.
And 15 parts of 2-ethylhexyl methacrylate and 15 parts of γ-methacryloxypropyltrimethoxysilane were added dropwise and mixed well. A solution obtained by dissolving 4 parts of azobisisovaleronitrile in 10 parts of butyl acetate was added to 30 parts of this mixture.
Over a period of minutes, and further reacted at 80 ° C. for 5 hours.
A hydrolyzable silyl group-containing vinyl resin solution (F) having a solid content of 50% was obtained. Reference Example 6 In a reactor equipped with a reflux condenser and a stirrer, 80 parts of xylene was heated to 80 ° C, and methyl methacrylate 70 was added thereto.
And 15 parts of 2-ethylhexyl methacrylate, 15 parts of γ-methacryloxypropyltrimethoxysilane, and 0.05 part of maleic anhydride were added dropwise and mixed well. A solution obtained by dissolving 4 parts of azobisisovaleronitrile in 10 parts of butyl acetate was added dropwise to this mixture over 30 minutes, and the mixture was further reacted at 80 ° C. for 5 hours to obtain a hydrolyzable silyl group containing 50% solids. A vinyl resin solution (g) was obtained.

Examples 1 to 5 and Comparative Examples 1 to 2 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 a silyl group-containing vinyl resin solution (a) to (d) [solid content concentration 50%], (c) 8 parts of ethyl acetoacetate aluminum diisopropylate, (f) i-
After adding and mixing 5 parts of propanol, (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, and the coating composition was added. Obtained. In the same manner, coating compositions 1 to 3 were obtained in the proportions shown in Table 2.

Examples 6 to 10 and Comparative Examples 3 to 4 Coating compositions obtained in Examples 1 to 10
26 parts by weight of titanium oxide and 0.5 parts by weight of a cellulose-based thickener were added to 0 parts by weight (solid content), glass beads were added, and the mixture was kneaded using a sand mill to obtain compositions A to G. .

Test Examples Using the compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 4, tests were performed as follows. Coating method When there is a primer on various base materials (ceramic base material in the case of paint, metal or plastic in the case of clear), apply a special primer at a dry weight of 5 to 50 g / m2,
Dry in a hot air drying oven at a plate temperature of 80-100 ⇒ for about 10 minutes. Further, 10% of an n-butanol solution containing 15% of dibutyltin dilaurate was added as a curing agent to paints A to G and clear-a to g, and a well-mixed paint was applied at a dry weight of 10 to 50 g / m2, followed by hot air drying. The sample was dried in a furnace at a sheet temperature of 80 to 120 ⇒ for about 10 minutes to prepare a test piece.
Tables 3 and 4 show the results of various tests performed using these test pieces as shown below. The method of confirming the color-separation property was as follows: a glass plate was painted with an applicator of 150 μm, and then painted from above. An applicator of 100 μm was drawn in the vertical direction in the direction described above, and it was visually confirmed whether there was any difference in color. When there was a difference in color, it was evaluated as x, and when there was no difference, it was evaluated as ○. Pigment sedimentation The composition was sealed and stored at room temperature without adding a curing accelerator in a glass bottle, and then visually judged. × indicates that there is sedimentation and does not redisperse, 、 indicates that there is sedimentation and redisperses,
A sample without sedimentation was marked with a circle. Solvent resistance 2 cc of xylene was dropped on the coating film, and one minute later, it was wiped off with a cloth and the state of the coating film was observed. Those with no dripping marks on the coating ○
It was determined. Weather resistance According to JIS K5400, weather meter
The irradiation test was performed for 000 hours, and 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. Stain resistance A paste mixed with carbon black / kerosene (weight ratio) = 1/2 is applied on the coating film, left at room temperature for 24 hours, washed with a sponge, and observed for the recovery state of the coating film's contamination. did.が な い indicates no contamination, ○ indicates slight contamination, and × indicates significant contamination. Adhesion The coating film was stored in 60 ⇒ warm water and tested for 10 days and 1 month. As a test method, a peel test using a 2 mm grid was performed according to JIS K5400.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

EFFECT OF THE INVENTION The coating composition of the present invention is excellent in storage stability and pigment dispersion, and has excellent curability and drying properties.
It is a high-gloss, clear finish film with a clear feeling,
A coating film having excellent physical properties such as organic chemical resistance, weather resistance, and stain resistance, and having high hardness can be formed.

Claims (2)

[Claims] (1) The general formula R ¹ nSi (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.
An alkyl group of 5 to 5 carbon atoms or an acyl group of 1 to 4 carbon atoms, and n is 0 to 2).
(B-1) a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group in one molecule;
-2) carboxyl group, hydroxy group, carbonyl group,
A coating composition comprising a vinyl copolymer having at least one group selected from an acid anhydride and a glycidyl group. 2. A cured product obtained by applying the coating composition of claim 1 on the surface of a substrate and drying the composition.