JP3420163B2 - Paint composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the formation of a coating film comprising a specific organic-inorganic composite resin aqueous dispersion and having excellent hot water resistance, weather resistance, stain resistance, solvent resistance, alkali resistance and the like. The present invention relates to a coating composition suitable for one-component curing type that can be used.

[0002]

2. Description of the Related Art A coating film comprising an organic-inorganic composite resin obtained by subjecting an organosilane and / or a partial hydrolysis-condensation product thereof and a silyl group-containing vinyl resin to a hydrolysis-condensation reaction as a binder has weather resistance and It has excellent stain resistance and is less likely to crack like a coating film using an organopolysiloxane-based inorganic resin as a binder. Therefore, the above-mentioned coating composition using an organic-inorganic composite resin as a binder attracts attention. Is becoming. However, most of such paint compositions are organic solvent paints, which is not preferable from the viewpoint of air pollution and resource saving. On the other hand, in the case of water-based paint, there is a problem that the resulting coating film is inferior in hot water resistance and alkali resistance. Furthermore,
From the viewpoint of storage stability, it is extremely difficult to make these paints into a one-pack type, and three-pack or two-pack type paints are generally used.

[0003]

The present invention has been made against the background of the problems of the prior art as described above. By using an organic-inorganic composite resin aqueous dispersion liquid neutralized with a specific neutralizing agent, storage An object is to provide a water-based coating composition suitable for one-component curing, which has good stability and can form a coating film excellent in hot water resistance, alkali resistance, weather resistance, stain resistance and the like. To do.

[0004]

Means for Solving the Problems The inventors of the present invention have made extensive studies to achieve the above-mentioned object, and as a result, have found that the above-mentioned object can be achieved by the following constitution, and have arrived at the present invention. is there. That is, the present invention is an epoxy group
One-component curable coating material containing no alkoxysilane compound
A method for preparing a composition, comprising : [i] (a) Formula (1), R ¹ _n Si (OR ² ) _4-n (1) [wherein R ¹ is an organic group having 1 to 8 carbon atoms] And R ² is
It is an alkyl group having 1 to 5 carbon atoms, and n is 1 or 2. ] 100 parts by mass of organosilane and / or its partial hydrolyzed condensate, and (b) a hydrolyzable silyl group or a silyl group having a silicon atom bonded to a hydroxyl group, and having an acid value of 20 to 150.
mgKOH / g silyl group-containing vinyl resin 5 to 200
Parts by weight in the presence of water and an acid catalyst as the first step.
Hydrolytic condensation reaction is carried out, and as a second step, water and thoria are added.
Hydrolysis in the presence of lucoxyborane or an organometallic compound catalyst
A hydrolysis-condensation reaction product is obtained by subjecting the resulting hydrolysis-condensation reaction product to [ii] (c) an amino group-containing alkoxysilane compound.
(D) The hydrolysis-condensation reaction product and the nitrogen-containing basic compound having no cross-linking reactivity are defined as the ratio of the number of base equivalents,
Neutralize with a neutralizing agent in the ratio of (3: 7 to 7: 3) ,
It relates to a method for preparing a coating composition, which comprises adding water.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. Component [i] First, each component used for producing the organic-inorganic composite resin of the component [i], which is a hydrolysis-condensation product, will be described.

Component (a) is represented by the formula (1), 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
It is an alkyl group having 1 to 5 carbon atoms, and n is 1 or 2. ] The organosilane and / or its partial hydrolysis-condensation product shown by these. In the above formula, examples of the organic group as R ¹ include an alkyl group, a cycloalkyl group, an aryl group, a vinyl group and the like.

Here, the alkyl group may be linear or branched. Specifically, as the alkyl group, for example, a methyl group, an ethyl group, an n-propyl group,
Examples thereof include alkyl groups such as i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group and octyl group. Preferred alkyl groups have 1 to 4 carbon atoms.
Preferable examples of the cycloalkyl group include a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.

Examples of the aryl group include a phenyl group and the like. Each of these functional groups may optionally have a substituent. Examples of such a substituent include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom and the like), a (meth) acryloyl group, a mercapto group, an alicyclic group and the like. The alkyl group as R ² may be linear or branched. Examples of the alkyl group include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, pentyl group and the like. The preferred alkyl group has 1 to 2 carbon atoms.

Specific examples of the organosilane represented by the above formula (1) include, for example, 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, cyclohexyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane,

Γ-Mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyl Examples include dimethoxysilane and dimethyldipropoxysilane,
Preferred are methyltrimethoxysilane, methyltriethoxysilane, and dimethyldimethoxysilane. These organosilanes can be used alone or in combination of two or more.

The component (a) may be a partially hydrolyzed condensate of the organosilane described above. The polystyrene reduced weight average molecular weight of the condensate is, for example, 300 to 5
000, preferably 500 to 3000 is suitable,
By using a condensate having such a molecular weight, a coating film having good adhesion can be obtained without deteriorating storage stability. Further, the partial hydrolysis condensate of organosilane is
An -OH group or -OR ² group bonded to a silicon atom 1 or more, preferably, suitably those having 3 to 30.
Incidentally, in the present invention, all of the —OR ² groups in the above formula (1) are hydrolyzed into only —OH groups, the —OR ² groups do not remain, and they are partially condensed, which is also referred to in the present invention. Included in partially hydrolyzed condensates.

Specific examples of such condensates include commercially available products such as SH6 manufactured by Toray Dow Corning.
018, SR2402, DC3037, DC307
4; Shin-Etsu Chemical Co., Ltd. KR-211, KR-21
2, KR-213, KR-214, KR-216, KR
-218; TSR-145 and T manufactured by Toshiba Silicone Co., Ltd.
SR-160, TSR-165, YR-3187 etc. are mentioned.

In the present invention, the component (a) includes an organosilane having an n value of 1 in the above formula (1) and / or a partially hydrolyzed condensate thereof (a-1), an organosilane having an n value of 2 and / Or its partial hydrolysis-condensation product (a-2) has a mass ratio of, for example, (20:80 to 100: 0), preferably (40:60 to 95: 5), is hydrolyzed and condensed. When reacting, it reacts stably, and a coating film having good crack resistance can be obtained, which is desirable.

Component (b) The component (b) contains at least one silyl group having a silicon atom bonded to a hydrolyzable silyl group or a hydroxyl group at the terminal or side chain of the vinyl resin in one molecule of the resin, preferably at least one. Having 2 or more and an acid value of 20 to 150 mg KOH
/ G, preferably a molecular weight of, for example, about 1000-5
It is a vinyl resin of 0000. The silyl group is represented by the formula (2), —SiX _P (R ³ ) _(3-P) [wherein, X represents an alkoxy group, an acyloxy group, a halogen group, a ketoximate group, a mercapto group, an alkenyloxy group, or a phenoxy group. Hydrolyzable group such as group or hydroxyl group; R
³ is hydrogen or a monovalent hydrocarbon group such as an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, and P is
It is an integer of 1 to 3. ] Is shown.

The silyl group-containing vinyl resin is, for example, represented by the formula (3), (X) _P (R ³ ) _(3-P) Si—H [wherein, X, R ³ and p are represented by the above formula (2). ) Has the same meaning. ] It manufactures by making the hydrosilane compound shown by these and the vinyl resin which has a carbon-carbon double bond react according to a conventional method. In addition, as the above-mentioned hydrosilane compound, for example, methyldichlorohydrosilane, methyldiethoxyhydrosilane, methyldiacetoxyhydrosilane and the like are mentioned as typical ones. The amount of the hydrosilane compound used is appropriately 0.5 to 2 times the molar amount of the carbon-carbon double bond contained in the vinyl resin.

The vinyl-based resin contains (meth) acrylic acid, carboxylic acids such as itaconic acid and fumaric acid, or acid anhydrides such as maleic anhydride as essential vinyl-based monomers, and further contains methyl (meth) acrylate. And (meth) acrylic acid esters such as ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylic acid; 2-hydroxyethyl (meth) acrylate, 2 Hydroxy group-containing vinyl monomers such as hydroxypropyl (meth) acrylate and 2-hydroxy vinyl ether; copolymers with other vinyl monomers selected from the group consisting of acrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, etc. Is preferred, and the (meth) acrylate is used during the production of the copolymer. By radical copolymerization of allyl or diallyl phthalate, carbon in order to hydrosilylation reaction in the vinyl resin - allows the introduction of carbon double bonds.

The above-mentioned carboxylic acid or acid anhydride is
The resulting vinyl-based resin has an acid value of 20 to 150 mgKOH / g, preferably 50, in the constituent monomers of the copolymer.
It is necessary to contain it so as to be ~ 120 mgKOH / g. If the acid value is smaller than the above range, the storage stability of the resulting coating composition will be poor, and conversely if the acid value is large, the water resistance, hot water resistance, etc. of the resulting coating film will be poor, and therefore both are not preferred. Further, as the other production method of the above-mentioned silyl group-containing vinyl resin, a vinyl monomer containing the above-mentioned carboxylic acid or acid anhydride and γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxy Propyltriethoxysilane, β- (meth) acryloxyethyltrimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyl Diethoxysilane, γ- (meth)
Acryloxypropylmethyldipropoxysilane, γ-
Contains a silyl group-containing vinyl compound such as (meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, and γ- (meth) acryloxypropyldiethylmethoxysilane as an essential monomer, and further requires There is also a method of radically polymerizing one or more of the above-mentioned other vinyl-based monomers. Specific examples of these silyl group-containing vinyl resins include Kaneka Zemurask manufactured by Kanebuchi Chemical Co., Ltd. as a commercially available product.

Component [ii] The component [ii] is the aforementioned hydrolysis condensation product [i].
It is a mixture of the following components (c) and (d), which is a neutralizing agent for neutralizing the components, stably dispersing them in water, and improving the storage stability of the coating composition. Component (c) Component (c) is an alkoxysilane having an amino group in the molecule and capable of undergoing a hydrolytic condensation reaction with component [i],
Specifically, formula (4), (R ⁶ —NH—R ⁵ —) _n Si (OR ⁴ ) _4-n [In the formula, R ⁴ is an alkyl group having 1 to 5 carbon atoms, and R ⁵
Is an alkylene group having 1 to 5 carbon atoms, R ⁶ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, or a substituent. Alternatively, it is an unsubstituted amino group, and n is 1 or 2. ] An amino group-containing alkoxysilane represented by the following formula can be preferably used.

R ⁴ may be linear or branched. Examples of the alkyl group as R ⁴ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
Preferable examples are alkyl groups such as n-butyl group, i-butyl group, s-butyl group, t-butyl group and pentyl group.
A preferred alkyl group has, for example, 1 to 2 carbon atoms. The alkylene group as R ⁵ may be linear or branched. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group and the like. The alkyl group having 1 to 5 carbon atoms as R ^{6 is the same} as the above R ⁴ . Further, the cycloalkyl group as R ⁶ includes, for example, a cyclohexyl group and a cycloheptyl group. The aryl group as R ⁶ is, for example, a phenyl group. Further, as the amino group as R ⁶ , those in which one or both of the hydrogen atoms in the amino group are substituted with, for example, the above alkyl group having 1 to 5 carbon atoms are preferable.

Examples of the amino group-containing alkoxysilane represented by the above formula (4) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N- (β-aminoethyl) -γ-amino. Propyltrimethoxysilane, N- (β-aminoethyl) -γ
-Aminopropylmethyldimethoxysilane, N- (β-
Aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-cyclohexyl γ-aminopropyltrimethoxysilane, N-cyclohexyl-γ-aminopropyltriethoxysilane, γ- (2-aminoethyl)-
Aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropylmethyldimethoxysilane, γ
-Anilinopropyltrimethoxysilane and the like.

Component (d) Component (d) is a nitrogen-containing basic compound that is not reactive with the hydrolysis-condensation reaction product of component (i), such as the amino group-containing alkoxysilane compound of component (c). It is a compound. [I]
As long as the compound has no reactivity with the component and can neutralize the component [i] and can be stably dispersed in water, various nitrogen-containing basic compounds conventionally known as neutralizing agents are particularly limited. Available without. Specifically, for example, trimethylamine, alkylamines such as triethylamine and butylamine, triethanolamine, dimethylethanolamine, diethanolamine, monoethanolamine,
Typical examples thereof include alcohol amines such as N-methyldiethanolamine, N, N-dimethylethanolamine and ethylpropanolamine, and volatile nitrogen-containing basic compounds such as morpholine and ammonia.

Next, a method for producing the preferred one-component curable coating composition of the present invention will be described. First, the method for producing the hydrolysis-condensation product of the component [i] will be described. The mixture of the above components (a) and (b) is subjected to hydrolysis and condensation reaction in the presence of water and a catalyst. The mixing ratio of the component (a) and the component (b) is 100 parts by mass of the former,
The latter is suitably 5 to 200 parts by mass, preferably 10 to 150 parts by mass. Incidentally, if the latter is less than the above range, the appearance and crack resistance of the resulting coating film, frost damage resistance, alkali resistance, etc. deteriorate, and conversely, if too much,
The weather resistance and stain resistance of the resulting coating film deteriorate, which is not preferable.

The amount of water is 45% of the hydrolyzable group initially present in the mixture of the components (a) and (b).
To 100%, preferably 50 to 90%, is sufficient to hydrolyze, specifically 0.4 to 1.0 times the total number of hydrolyzable groups in the mixture, preferably 0. .5-
A suitable amount is 0.9 times the number of moles. Further, examples of the catalyst include inorganic acids such as nitric acid and hydrochloric acid, and organic acids such as acetic acid, formic acid, and propionic acid. The amount of the catalyst added is appropriately such that the pH of the mixture becomes 3 to 6. In the hydrolysis condensation reaction, the mixture of the component (a) and the component (b) is reacted in the presence of water and a catalyst at 40 to 80 ° C., preferably 45 to 65 ° C. for 2 to 10 hours while stirring. However, the method is not limited to this method. The amount of water was 45% of the hydrolyzable groups initially present in the mixture of the components (a) and (b).
What is described above makes it possible to form an organic-inorganic composite resin aqueous dispersion (emulsion), that is, the storage stability of the aqueous dispersion as a coating composition is good, and a highly transparent film can be formed. This is because.

It is possible to carry out the hydrolysis-condensation reaction of the components (a) and (b) in one step as described above, but the storage stability of the product of the component (i) is From the viewpoint, it is preferable to carry out the reaction in the following two stages. That is, as the first step, in the presence of water and an acid catalyst, (a)
40-80%, preferably 45-70%, of the hydrolyzable groups initially present in the mixture of component and component (b).
Is hydrolyzed and condensed, the reaction is carried out at 40 to 80 ° C., preferably 45 to 65 ° C. for 1 to 8 hours with stirring.

As the second step, following the first step, water and trialkoxyborane such as trimethoxyborane and triethoxyborane; tri-n-butoxyethylacetoacetate zirconium, di-n-butoxydi (ethylacetoacetate) ) Zirconium, zirconium chelate compounds such as tetrakis (ethyl acetoacetate) zirconium, titanium chelate compounds such as diisopropoxybis (acetylacetate) titanium, diisopropoxybis (ethylacetoacetate) titanium, monoacetylacetonate bis (ethylacetate) Acetate) Aluminum, an organometallic compound catalyst such as an aluminum chelate compound such as aluminum diisopropoxyethylacetoacetate is added, and a hydrolysis and condensation reaction is performed.
The amount of water added in the second stage was 45% of the hydrolyzable group initially present in the mixture of the components (a) and (b).
-100%, preferably 50-90% is sufficient for the hydrolysis and condensation reactions.

The trialkoxyborane and the organometallic compound catalyst used in the second step can accelerate the condensation reaction and improve the appearance of the coating film, weather resistance, stain resistance, hot water resistance and the like. The amount of these catalysts is 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of the above-mentioned components (a) and (b) remaining unreacted with the reaction product obtained in the first step, Preferably, 0.005 to 2 parts by mass is suitable. The hydrolysis-condensation reaction in the second stage is the same as in the first stage.
It is suitable to react at -80 ° C for 2 to 5 hours.

The hydrolysis-condensation reaction product is in a solution state due to the alcohol content produced in the reaction, or the alcohol content and an organic solvent which will be described later added as necessary. In the solution of the organic-inorganic composite resin, which is the hydrolysis-condensation reaction product of the component [i] thus obtained,
Add (c) an amino group-containing alkoxysilane compound that is a neutralizing agent for component (ii), and (d) a nitrogen-containing basic compound that has no crosslinking reactivity with the hydrolysis condensation reaction product, and disperse them evenly. After neutralization, water is added, or a neutralizing agent and water are added at the same time and forcedly dispersed by stirring to obtain an aqueous dispersion (emulsion) which is the coating composition of the present invention.

The amount of the neutralizing agent as the component [ii] is 0.4 with respect to the total number of acid group equivalents in the hydrolysis-condensation reaction product of the component [i].
The amount of the base equivalent is about 1.2 to 1.2 times, preferably 0.5 to 1.1 times. When the amount of the neutralizing agent is less than the above range, the storage stability of the coating tends to decrease, and when it is too large, the water resistance of the resulting coating film tends to decrease. The mixing ratio of the component (c) and the component (d), which are components of the neutralizing agent, and the ratio of the number of base equivalents are
(3: 7 to 7: 3) .

If the former is less than the above range, the condensation reaction with the component [i] will be insufficient, and the hot water resistance, alkali resistance, stain resistance, etc. of the resulting coating film will tend to decrease. If the amount is too large, the storage stability of the coating composition tends to decrease, and there is no problem when used as a one-pack type coating composition for a short period of time, but problems tend to occur when the coating composition is stored for a long period of time. Further, the amount of water is arbitrarily determined in consideration of the coating workability of the paint, usually the solid content of the coating composition,
For example, an amount of about 10 to 70% by mass is suitable.

The organic-inorganic composite resin aqueous dispersion, which is the coating composition thus obtained, produces an alcohol component due to the above-mentioned hydrolysis-condensation reaction and remains in the aqueous dispersion. Therefore, when the aqueous dispersion is used as it is as a coating composition, volatile organic components (VOC)
Therefore, the alcohol content may be removed under reduced pressure according to a conventional method. The coating composition of the present invention contains the organic-inorganic composite resin aqueous dispersion (emulsion) described above as a main component, and further, if necessary, to improve storage stability and coating workability of the coating composition. , Organic solvents, fillers,
Dyes and various additives such as curing accelerators, thickeners and pigment dispersants may be added.

Examples of the organic solvent include alcohols such as methanol, ethanol, propanol and butanol, alcohol ethers such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, hydrophilic organics such as acetone and methyl ethyl ketone. A solvent or a mixed organic solvent thereof with a hydrophobic organic solvent for various paints such as toluene, xylene, ethyl acetate and butyl acetate can be used. These organic solvents can be blended as a solvent so that the reaction can occur uniformly during the production of the above-mentioned component [i]. The content of the organic solvent in the coating composition is, for example, 0 to 20% by mass, preferably 0 to 10% by mass.

Examples of the filler include talc, barium carbonate, calcium carbonate, barium carbonate, bentonite,
Various extender pigments for paints such as titanium oxide, carbon black, red iron oxide, and lithopone, and coloring pigments can be used.
The amount of the filler compounded is 0 to 70% by mass, preferably 0 to 50% by mass, based on the solid content of the coating composition. Examples of the curing accelerator include tin octylate, dibutyltin dilaurate, dibutyltin dimaleate, organotin compounds such as tributyltin laurate, amine compounds such as ethylenediamine, diethylenetriamine, piperidine, phenylenediamine and triethylamine, and reactive with amino groups. Compounds containing epoxy groups in the molecule
object,

Alkyl glycidyl ethers and esters such as butyl glycidyl ether, polyoxyethylene glycidyl ether, Cardura E (trade name, manufactured by Shell Co.), butylphenyl glycidyl ether, cycloepoxy compounds, Epicoat 815, 828, 834 (oiled shell Epoxy Co., Ltd.) and the like, and these emulsions are typical.

The coating composition of the present invention is applied to the surface of an object to be coated by a coating means such as brush, spray, roll, dipping, etc., and baked at room temperature or at a temperature of 300 ° C. or less to form a cured coating film. Is possible. As the article to be coated, inorganic ceramic substrates, various metal substrates such as stainless steel and aluminum, glass substrates, plastic substrates and paper substrates can be used.

[0035]

EXAMPLES The present invention will now be described in more detail with reference to examples. In the examples, "parts" and "%" are based on mass unless otherwise specified. Reference Example 1 < Preparation of silyl group-containing vinyl resin solution (a)> 100 parts of ethylene glycol monobutyl ether was added to a reactor equipped with a reflux condenser and a stirrer, and heated to 100 ° C while stirring. Next, 50 parts of isobutyl methacrylate and 31.5 parts of 2-ethylhexyl methacrylate.
Part, γ-methacryloxypropyltrimethoxysilane 1
A mixed solution of 0 parts, 8.5 parts of acrylic acid and 2.5 parts of t-butylperoxy 2-ethylhexanoate was added dropwise at 100 ° C. over 3 hours, then heated to 105 ° C. and maintained for 2 hours. , The reaction was terminated. The obtained silyl group-containing vinyl resin solution (ii) had a solid content concentration of 50%, an acid value of the resin of 65 mgKOH / g, and a number average molecular weight of 10,000.

Reference Example 2 < Preparation of silyl group-containing vinyl resin solution (b)> To a reactor equipped with a reflux condenser and a stirrer, 100 parts of ethylene glycol monobutyl ether was added and heated to 100 ° C. with stirring. . Next, 51 parts of isobutyl methacrylate, 35 parts of 2-ethylhexyl methacrylate, γ
-Methacryloxypropyltrimethoxysilane 6.5
Part, 7.5 parts of methacrylic acid and 2.5 parts of t-butylperoxy 2-ethylhexanoate were added dropwise at 100 ° C. over 3 hours, then heated to 105 ° C. and maintained for 2 hours. The reaction was completed. The resulting silyl group-containing vinyl resin solution (b) had a solid content concentration of 50%, an acid value of the resin of 50 mgKOH / g, and a number average molecular weight of 9000.

Example 1 (a) Hydrolyzed condensate of methyltrimethoxysilane (SR2402 manufactured by Toray Dow Corning Co., Ltd .; solid content 100%) was added to a reactor equipped with a reflux condenser and a stirrer.
3 parts, 8 parts of methyltrimethoxysilane, 1.7 parts of dimethyldimethoxysilane, 25 parts of (b) silyl group-containing vinyl resin solution (a), 10 parts of isopropanol, and after mixing, ion exchange 3.0 parts of water and 0.05 parts of 1N hydrochloric acid were added, and the mixture was reacted at 60 ° C. for 3 hours. Next, 0.3 part of monoacetylacetonate bis (ethylacetoacetate) aluminum and 0.8 part of ion-exchanged water were added, and the mixture was further reacted at 60 ° C. for 3 hours. Then, as a neutralizing agent, (c) N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane (0.5 part), (d) triethylamine (0.5 part) and water (37 parts) were added, and the mixture was mixed at 50 ° C. for 1 hour. After stirring for an hour, under reduced pressure (133x10 ² Pa (100 torr)),
The solvent was removed. Then, a clear coating was produced by adjusting the dilution with water to a solid concentration of 35%. The amount of the neutralizing agent is 0.5 times as much as the total number of equivalents of acid groups in the hydrolysis-condensation reaction product, and the ratio of the equivalents of bases of the component (c) and the component (d) is (3: 7).

[0038]Example 2 In a reactor equipped with a reflux condenser and a stirrer, (a) phenyl
Hydrolyzed condensate of rutrimethoxysilane (Toray Dauko
DC3074 manufactured by Erning Co., Ltd .; solid content 100%)
25 parts, 8 parts of methyltrimethoxysilane, (b) Si
25 parts of vinyl resin solution (a) containing ril group and isop
After adding 10 parts of lopanol and mixing, deionized water
Add 2.0 parts and 1 part hydrochloric acid 0.05 parts at 60 ° C for 3:00
Reacted for a while. Then, 0.5 parts of triethoxyborane
Add 0.5 parts of deionized water and react at 60 ° C for 3 hours
Let Then, as a neutralizing agent, (c) N- (β-amido
Noethyl) -γ-aminopropyltrimethoxysilane
0.8 parts and (d) N, N-dimethylethanolamine
0.3 parts and 40 parts of water were added and stirred at 50 ° C. for 1 hour.
Decompression (133x10²The solvent was removed under Pa. Then
Adjust the dilution with water to a solid concentration of 35%, and
A rear coating was produced. The neutralizing agent is a hydrolytic condensation
1.1 times the base equivalent based on the total number of acid group equivalents in the reaction product.
It is the amount that becomes a number, and the base equivalent of the components (c) and (d)
The number ratio was (5: 5).

[0039]Example 3 In a reactor equipped with a reflux condenser and a stirrer, (a) methyl
30 parts of trimethoxysilane, dimethyldimethoxysila
And (b) silyl group-containing vinyl resin solution
25 parts of (b) and 5 parts of isopropanol are added and mixed.
Then, 5.2 parts of ion-exchanged water and 0.05 part of 1N hydrochloric acid
In addition, the mixture was reacted at 60 ° C. for 3 hours. Then monoaceti
Ruacetonate bis (ethylacetoacetate) aluminum
Add 0.3 parts of Ni and 1.5 parts of deionized water, and add 6 more parts.
The reaction was carried out at 0 ° C for 3 hours. Then ethylene glycol
5 parts of monobutyl ether and (c) γ-a as a neutralizing agent
0.5 parts of minopropyltriethoxysilane and (d) N,
Add 0.4 parts N-dimethylethanolamine and 50 parts water.
After stirring at 50 ° C for 1 hour, depressurization (133x10²Pa)
The solvent was removed underneath. Next, add water to a solids concentration of 35%.
Dilution was adjusted so as to obtain a clear paint.
The neutralizing agent is the total number of acid group equivalents in the hydrolysis condensation reaction product.
To the base equivalent number of 0.6 times,
The base equivalent number ratio of the components (c) and (d) is (3: 7).
Met.

[0040]Example 4 In a reactor equipped with a reflux condenser and a stirrer, (a) phenyl
Hydrolyzed condensate of alkyl and alkylalkoxysilane (East
SH6018 manufactured by Re Dow Corning Co., Ltd .; solid content 1
00%, Si-OH functional group system) 18 parts, methyltri
2 parts methoxysilane and dimethyldimethoxysilane 1.
5 parts, (b) silyl group-containing vinyl resin solution (ii)
Add 6 parts and 3 parts isopropanol, mix, and then
60 parts of exchanged water and 0.05 part of 1N hydrochloric acid were added,
The reaction was carried out at 0 ° C for 3 hours. Then monoacetylacetone
Tobis (ethyl acetoacetate) aluminum 0.
Add 3 parts and 0.2 parts of ion-exchanged water, and further at 3 hours at 60 ° C.
Reacted for a while. Then, as a neutralizing agent, (c) N- (β
-Aminoethyl) -γ-aminopropylmethyl dimethoxy
0.5 parts of silane and (d) N, N-dimethyl ethanol
Add 0.4 parts of amine and 50 parts of water and stir at 50 ° C for 1 hour
After that, decompression (133x10²The solvent was removed under Pa. Next
Then, adjust the dilution with water to a solid concentration of 35%.
I made a clear paint. The neutralizing agent is
1.0 times as much salt as the total number of acid group equivalents in the decondensation reaction product
The amount of the base equivalent number, and the salt of the component (c) and the component (d)
The base equivalent number ratio was (3: 7).

[0041]Comparative Example 1 In a reactor equipped with a reflux condenser and a stirrer, (a) methyl
Hydrolysis condensate of trimethoxysilane (Toray Dowkoh
SR2402 manufactured by Ning Co., Ltd .; solid content 100%) 2
3 parts, 8 parts of methyltrimethoxysilane, dimethyl dime
1.7 parts of toxysilane and (b) silyl group-containing vinyl
25 parts of resin solution (a), 10 parts of isopropanol
After adding and mixing, 3.0 parts of deionized water and 1N salt
0.05 part of acid was added and reacted at 60 ° C. for 3 hours. Next
And monoacetylacetonate bis (ethylacetoacetate
Tate) 0.3 part aluminum and 0.8 part ion-exchanged water
Was added and the mixture was further reacted at 60 ° C. for 3 hours. Then neutralize
As an agent, (d) 0.9 parts of triethylamine and 37 parts of water
Was added, and the mixture was stirred at 50 ° C for 1 hr, and then depressurized (133x10²P
a) The solvent was removed underneath. Then, solid content concentration of 35
Dilution is adjusted so that
It was The neutralizing agent is the acid group equivalent in the hydrolysis condensation reaction product.
The amount is 1.0 times the number of base equivalents of the total number.
It was

Comparative Example 2 In a reactor equipped with a reflux condenser and a stirrer, (a) 30 parts of methyltrimethoxysilane, 10 parts of dimethyldimethoxysilane, and (b) silyl group-containing vinyl resin solution (b). And 25 parts of isopropanol and 5 parts of isopropanol were added and mixed, and then 5.2 parts of ion-exchanged water and 0.05 part of 1N hydrochloric acid were added and reacted at 60 ° C. for 3 hours. Next, 0.3 parts of aluminum monoacetylacetonate bis (ethylacetoacetate) and 1.5 parts of ion-exchanged water were added, and a further 6 parts were added.
The reaction was carried out at 0 ° C for 3 hours. Then, 5 parts of ethylene glycol monobutyl ether and 1.5 parts of (c) γ-aminopropyltriethoxysilane and 50 parts of water were added as a neutralizing agent, and the mixture was stirred at 50 ° C. for 1 hour, and then depressurized (133 × 10 ² P
a) The solvent was removed underneath. Then, solid content concentration of 35
The clear coating was manufactured by adjusting the dilution so as to be 100%. The amount of the neutralizing agent was 1.0 times as many as the number of equivalents of acid groups in the hydrolysis-condensation reaction product. Each of the obtained coating compositions was subjected to a storage stability test and a coating film appearance test, coating film performance test of hardness, hot water resistance, stain resistance, weather resistance, and alkali resistance, and the results are shown in Tables 1 and 2, respectively.
It is shown in the bottom row.

<Storage Stability Test> Each paint was stored at 50 ° C. for one month, and then the change in viscosity and the appearance of the paint were visually examined. <Coating film performance test> As a material, gypsum slag perlite plate (thickness 12 mm)
Polyisocyanate prepolymer solution sealer "V Seran # 100 Sealer" (trade name, manufactured by Dainippon Paint Co., Ltd.) (100% diluted with a solution of butyl acetate: xylene = 1: 1) was applied to the surface of 90-100g / m ²
Spray coating was performed so that the (wet mass) was obtained. This is 10
It was dried at 0 ° C. for 5 minutes. Then, as a base paint, an acrylic silicone resin-based paint "V-Seran # 500 Enamel" (trade name, manufactured by Dainippon Paint Co., Ltd.) (40% diluted with a solution of butyl acetate: xylene = 1: 1) was applied at a coating amount of 80. ~
Spray coating was performed so that the weight became 90 g / m ² (wet mass). This was dried at 120 ° C. for 15 minutes. Then, each clear coating composition of Examples 1 to 4 and Comparative Examples 1 and 2 was spray-coated so that the applied amount was (130 ± 10) g / m ² (wet mass). This was dried at 80 ° C for 12 minutes, and then dried at room temperature for another 3 days, and coated plate A and 20 ° C.
Each coated plate B was dried for one week. The test method and evaluation were based on the following.

Appearance: Visual judgment of the appearance of the coating film formed on the coated plate Hardness: Pencil hardness measured according to JIS K 5400 Hot water resistance: The coated plate is immersed in water at 80 ° C. and visually judged for abnormal appearance of the coating film Evaluation criteria ○ ・ ・ ・ No change △ ・ ・ ・ Minor changes such as decrease in gloss and whitening × ・ ・ ・ Changes such as decrease in gloss and whitening Large stain resistance: After applying red and black magic ink (registered trademark) After 24 hours, it was wiped with a cloth wet with n-butanol, and the decontamination property was visually judged. Evaluation criteria ◎ ・ ・ ・ Complete removal ○ ・ ・ ・ Very slight pollution △ ・ ・ ・ Little pollution × ・ ・ ・ Significant pollution

Weather resistance: Sunshine weather-Ohmeter 3000 hours evaluation standard ○: No change in coating appearance, gloss retention rate 95% or more △: slight change in coating appearance, gloss retention rate 80
~ 94% × ... Remarkable coating change, gloss retention rate less than 80% Alkali resistance: 4 each coated plate in saturated slaked lime alkali aqueous solution
After soaking at 0 ° C. for 10 days, the coating film surface was visually evaluated. Evaluation criteria ○ ・ ・ ・ No change △ ・ ・ ・ Slight turbidity on film surface × ・ ・ ・ Sky turbidity on coating film surface

[0046]

[Table 1] Table 1

[0047]

[Table 2] Table 2

As is clear from Table 1, the coating compositions of Examples 1 to 4 of the present invention had good storage stability and excellent coating film performance. On the other hand, in Comparative Example 1 in which the amino group-containing alkoxysilane compound was not blended as the neutralizing agent, the storage stability was good, but the hardness, hot water resistance, stain resistance, weather resistance, and alkali resistance were poor. Also,
In Comparative Example 2 in which only the amino group-containing alkoxysilane compound was blended as the neutralizing agent, the storage stability was poor and the alkali resistance was poor.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuyoshi Tsuneta 1-981 Shimonagata, Nishinasuno-cho, Nasu-gun, Tochigi Prefecture (56) References JP-A-10-36514 (JP, A) JP-A-10-36515 (JP, A) JP 2001-115023 (JP, A) JP 2000-207121 (JP, A) JP 10-195381 (JP, A) JP 11-349815 (JP, A) JP 11-71527 (JP, A) JP 10-88065 (JP, A) JP 9-227835 (JP, A) JP 2-208310 (JP, A) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) C09D 183/00-183/16 C09D 185/04 C08G 77/00-77/62 C09D 143/04 C08L 83/00-83/16 C08L 85/04

Claims (3)

(57) [Claims] 1. Epoxy group-containing alkoxysilane compound
A method for preparing a one-component curable coating composition containing no : [i] (a) Formula (1), R ¹ _n Si (OR ² ) _4-n (1) [wherein R ¹ is R ² is an organic group having 1 to 8 carbon atoms,
It is an alkyl group having 1 to 5 carbon atoms, and n is 1 or 2. ] 100 parts by mass of organosilane and / or its partial hydrolyzed condensate, and (b) a hydrolyzable silyl group or a silyl group having a silicon atom bonded to a hydroxyl group, and having an acid value of 20 to 150.
mgKOH / g silyl group-containing vinyl resin 5 to 200
Parts by weight in the presence of water and an acid catalyst as the first step.
Hydrolytic condensation reaction is carried out, and as a second step, water and thoria are added.
Hydrolysis in the presence of lucoxyborane or an organometallic compound catalyst
A hydrolysis-condensation reaction product is obtained by subjecting the resulting hydrolysis-condensation reaction product to [ii] (c) an amino group-containing alkoxysilane compound.
(D) The hydrolysis-condensation reaction product and the nitrogen-containing basic compound having no cross-linking reactivity are defined as the ratio of the number of base equivalents,
Neutralize with a neutralizing agent in the ratio of (3: 7 to 7: 3) ,
A method for preparing a coating composition, which comprises adding water. 2. The component (a) is represented by the formula: R ¹ Si (OR ² ) ₃ [wherein R ¹ and R ² have the same meanings as in the formula (1). An organosilane and / or its partially hydrolyzed condensate (a-1) represented by], wherein, R ¹ ₂ Si (OR ²⁾ ₂ wherein, R ¹ and R ^2, the equation (1) Have the same meaning. ] The mass ratio with the organosilane and / or its partial hydrolysis-condensation product (a-2) represented by
The method of claim 1, which is 100: 0). 3. A hydrolysis-condensation product of the component [i], a neutralizing agent of the component [ii] is added in an amount of 0.4 to 1.2 with respect to the total number of acid group equivalents in the component [i]. Add in an amount that doubles the number of base equivalents.
The method according to claim 1 or 2, further comprising :