JP3457233B2 - Aqueous organic-inorganic composite resin emulsion and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a specific organic-inorganic composite resin aqueous emulsion and a method for producing the same, and more detailed
In some cases, it is a two-pack type coating combination when used in combination with a specific curing agent.
An organic-inorganic composite resin aqueous emulsion capable of forming a coating film excellent in hot water resistance, weather resistance, stain resistance, solvent resistance, alkali resistance, etc.
Manufacturing method .

[0002]

2. Description of the Related Art A coating film in which 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, A coating composition that has excellent stain resistance and is unlikely to cause cracks unlike a coating film in which an organopolysiloxane-based inorganic resin serves as a binder, and therefore the above organic-inorganic composite resin serves as a binder component. Things are getting noticed.

[0003]

However, there is a problem that such a coating composition is inferior in hot water resistance, alkali resistance and the like. The present invention has been made to solve the problems of the prior art, hot water resistance, weather resistance, stain resistance, solvent resistance, to enable you to form a coating film excellent in alkali resistance, etc. An object is to provide a specific organic-inorganic composite resin aqueous emulsion suitable for use in a two- pack type coating composition and a method for producing the same.

[0004]

Means for Solving the Problems As a result of various studies conducted by the present inventors in order to achieve the above-mentioned objects, as a result, a specific organic-inorganic composite resin aqueous emulsion and a curing agent are used in a specific ratio. That a two-component coating composition capable of forming a coating film excellent in hot water resistance, weather resistance, stain resistance, solvent resistance, alkali resistance, etc. can be obtained. The present invention has been completed by finding that an aqueous emulsion can be produced by using a specific raw material compound and adopting a specific method.

That is, the method for producing an organic-inorganic hybrid resin aqueous emulsion of the present invention is as follows: (i) (a) General formula (1) R ¹ _n Si (OR ² ) _4-n (1) (wherein R ¹ Is an organic group having 1 to 8 carbon atoms, R ² is an alkyl group having 1 to 5 carbon atoms, and n is 1 or 2.)
100 parts by mass of at least one organosilane compound selected from the group consisting of organosilanes and partial hydrolysis-condensates thereof, and (b) a silyl group having a silicon atom bonded to a hydrolyzable group or a hydroxyl group. Has a vinyl resin at the terminal or side chain and has an acid value of 20 to 150 m.
5-20 silyl group-containing vinyl resin having a gKOH / g
A mixture of 0 parts by mass of water and acid as the first step
In the presence of the catalyst, the water initially present in the mixture was
Hydrolytic condensation so that 40-80% of the decomposable groups react
The reaction is followed by a second step with water and trialkoxybenzene.
In the mixture in the presence of orchid or organometallic compound catalyst
45-100% of the hydrolyzable groups initially present in
Step of obtaining a solution of organic-inorganic composite resin by hydrolytic condensation reaction until reaction , (ii) Neutralizer and water are added to the solution of organic-inorganic composite resin obtained in step (i), and the mixture is stirred to be an aqueous dispersion. And (iii) in the aqueous dispersion obtained in step (ii), (c) the epoxy group-containing alkoxysilane compound is added to 100 parts by mass of the organic-inorganic composite resin solid content present in the aqueous dispersion. 0.
1 to 10 parts by mass is added and stirred to obtain an organic-inorganic composite resin aqueous emulsion.

[0006]

The organic-inorganic composite resin aqueous emulsion of the present invention is characterized by being obtained by the above-mentioned method for producing an organic-inorganic composite resin aqueous emulsion .

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
First, each raw material component used in the method for producing an organic-inorganic composite resin aqueous emulsion of the present invention will be described.

Component (a) The component (a) is represented by the general formula (1) R ¹ _n Si (OR ² ) _4-n (1) (wherein R ¹ is an organic group having 1 to 8 carbon atoms, R ² is an alkyl group having 1 to 5 carbon atoms, and n is 1 or 2.)
Is at least one organosilane-based compound selected from the group consisting of organosilanes and partially hydrolyzed condensates thereof.

Examples of the organic group R ¹ having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i
-Alkyl group such as propyl group, γ-chloropropyl group,
Examples thereof include vinyl group, 3,3,3-trifluoropropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group and phenyl group. Examples of the alkyl group R ² having 1 to 5 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group,
Examples thereof include s-butyl group, t-butyl group and i-butyl group.

Specific examples of the organosilane represented by the above general formula (1) include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, γ-chloropropyltrimethoxysilane,
γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3,3
-Trifluoropropyltrimethoxysilane, 3,3
3-trifluoropropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltri Ethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethoxymethylphenylsilane, dimethyldipropoxysilane and the like, preferably, methyltrimethoxy Silane, methyltriethoxysilane and dimethyldimethoxysilane are used.

The component (a) may be a partially hydrolyzed condensate of the above organosilane. It is suitable that the condensate has a polystyrene-equivalent weight average molecular weight of 300 to 5,000, preferably 500 to 3,000. By using a condensate having such a molecular weight, storage stability is not deteriorated, A coating film with good adhesion can be obtained. Further, the partial hydrolysis condensate of organosilane is
An -OH group or -OR ² group bonded to a silicon atom 1 or more, and preferably be those having 3 to 30.

Specific examples of such condensates include, for example, SH60 manufactured by Toray Dow Corning Co., Ltd. as a commercial product.
18, SR2402, DC3037, DC3074, Shin-Etsu Chemical Co., Ltd. KR-211, KR-212, KR-
213, KR-214, KR-216, KR-218,
Toshiba Silicone TSR-145, TSR-16
0, TSR-165, YR-3187 and the like.

In the production method of the present invention, the organosilane and the partial hydrolysis-condensation product thereof as described above may be used alone or in combination of two or more, and may be further used as an organosilane. It is also possible to use one or more silanes and one or more partially hydrolyzed condensates thereof in combination.

In the production method of the present invention, as the component (a), it is possible to use only the organosilane having the n value of 1 in the general formula (1) and / or its partial hydrolysis-condensation product. The mass ratio of the organosilane having an n value of 1 and / or its partial hydrolyzed condensate to the organosilane having an n value of 2 and / or its partially hydrolyzed condensate is 50:50.
It is desirable to use a mixture of ˜100: 0, preferably 60:40 to 95: 5, because the binder polymerizes stably during the production of the binder and a coating film with good crack resistance can be obtained.

Component (b) The component (b) comprises at least one silyl group having a silicon atom bonded to a hydrolyzable group or a hydroxyl group at the end or side chain of the vinyl resin in one molecule of the vinyl resin, It preferably has two or more and has an acid value of 20 to 150 mgKOH /
g, and preferably has a molecular weight of about 1,000 to 50,000.
Is a vinyl resin containing a silyl group.

The silyl group is represented by the general formula (2) -SiX _P (R ³ ) _3-P (2) (wherein, X is an alkoxy group, an acyloxy group, a halogen atom, a ketoximate group, a mercapto group, an alkenyloxy group. Group, a hydrolyzable group such as phenoxy group or a 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 3
Is an integer of 1 to 3).

The silyl group-containing vinyl resin as the component (b) can be prepared, for example, by the general formula (3) H-SiX _P (R ³ ) _3-P (3) (wherein, X, R ³ and p are as described above). The same) and a vinyl-based resin having a carbon-carbon double bond.

Typical examples of the above-mentioned hydrosilane compound include methyldichlorohydrosilane, methyldiethoxyhydrosilane, and methyldiacetoxyhydrosilane. The amount of the hydrosilane compound used is the total number of carbon-carbon double bonds contained in the vinyl resin (not the total number of carbon-carbon double bonds contained in one molecule of the vinyl resin, but the total amount of the vinyl resin used. The total number of carbon-carbon double bonds contained therein is 0.5 to 2 times the number of moles of "total number" used in this specification with the same meaning. .

The above vinyl-based resin contains a carboxylic acid such as (meth) acrylic acid, itaconic acid, fumaric acid or an acid anhydride such as maleic anhydride as an essential vinyl-based monomer unit, and further contains (meth) acrylic acid. Methyl acid, ethyl (meth) acrylate, butyl (meth) acrylate, (meth)
Copolymer containing a vinyl-based monomer unit selected from 2-ethylhexyl acrylate, (meth) acrylic acid ester such as cyclohexyl (meth) acrylic acid, acrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, etc. However, it is also possible to introduce a carbon-carbon double bond for the hydrosilylation reaction into the vinyl-based resin by radically copolymerizing allyl (meth) acrylate or diallyl phthalate during the production of the copolymer. It is possible.

The above carboxylic acid or acid anhydride is
The resulting vinyl resin has an acid value of 20 to 150 mg KOH
/ G, preferably 50 to 120 mgKOH / g, in the copolymer-constituent monomer in an amount sufficient. If the acid value is smaller than the above range, the storage stability of the obtained aqueous emulsion tends to be poor, and conversely, if the acid value is large, the water resistance and hot water resistance of the obtained coating film tend to be poor, and therefore both are not preferable. .

As another method for producing the above silyl group-containing vinyl resin, a vinyl monomer containing the above carboxylic acid or acid anhydride, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) are used. ) A hydroxyl group-containing monomer such as acrylate and 2- hydroxyethyl vinyl ether, and γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, β- (meth) acryl Roxyethyltrimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth)
Acryloxypropylmethyldiethoxysilane, γ-
A silyl group such as (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyldiethylmethoxysilane. There is also a method of radically polymerizing the contained vinyl compound.

Component (c) Component (c) is an alkoxysilane compound having an epoxy group in the molecule and capable of undergoing a hydrolytic condensation reaction. (C)
As a component, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycid Glycidol with xypropyltriisopropenyloxysilane, γ-glycidoxypropyltriiminooxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, γ-isocyanatopropyltriisopropenyloxysilane, etc. Typical examples include adducts.

Next, a method for producing an organic-inorganic composite resin aqueous emulsion will be described. First, in step (i),
Wherein component (a) and (b) is pressurized hydrolysis and condensation reaction of a mixture of components. The mixing ratio of the component (a) and the component (b) is appropriately 5 to 200 parts by mass, preferably 10 to 150 parts by mass, relative to 100 parts by mass of the former. When the latter is less than the above range, the appearance and crack resistance of the coating film obtained, frost damage resistance, alkali resistance, etc. tend to be poor, and the storage stability of the resulting coating composition tends to be poor. On the contrary, if the amount is too large, the resulting coating film tends to have poor weather resistance, stain resistance and the like, which is not preferable.

[0025]

[0026]

[0027]

[0028] Step (i) of the present invention, you performed in the component (a) and (b) two-step as follows components of hydrolytic condensation reaction from the viewpoint of storage stability of the raw Narubutsu. That is, as a first step, in the presence of water and an acid catalyst, (a) component and (b)
40-80% of the hydrolyzable groups initially present in the mixture with the components (percentage based on the number of hydrolyzable groups) ,
It is preferably carried out so that 50 to 70% undergoes a hydrolytic condensation reaction. At this time, 40 to 80 ° C., preferably 45 to
It is preferable to react by stirring at 65 ° C. for 1 to 8 hours. The hydrolysis-condensation reaction is caused by the reaction.
By means such as measuring rucor by gas chromatography
Quantify reaction progress. As the acid catalyst, glass
Acids, inorganic acids such as hydrochloric acid, acetic acid, formic acid, propionic acid, etc.
Organic acids and the like can be mentioned. The amount of acid catalyst added is mixed
A suitable amount is such that the pH of the product is 3-6. Process
In the hydrolysis-condensation reaction of (i), the reaction rate relationship
Then, the reaction of the component (a) mainly occurs first, and then the component (b)
Alternatively, the reaction (condensation) between the component (a) and the component (b)
Grafting reaction) is slow.

As the second step, water and trialkoxyborane such as trimethoxyborane, triethoxyborane, tripropoxyborane and the like, tri-n-following the first step are further added.
Butoxyethyl acetoacetate zirconium, di-n
-Butoxydi (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (acetylacetoacetate)
Zirconium, tetrakis (ethyl acetoacetate)
Zirconium chelate compounds such as zirconium, titanium diisopropoxybis (acetylacetate) titanium, diisopropoxybis (ethylacetoacetate) titanium chelate compounds, monoacetylacetonate bis (ethylacetoacetate) aluminum, diisopropoxyethylacetate Aluminum acetate, diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, tris (ethylacetoacetate) aluminum,
An organometallic compound catalyst such as an aluminum chelate compound such as tris (acetylacetonato) aluminum is added to carry out hydrolysis and condensation reaction.

In the second step, 4 of the hydrolyzable groups originally present in the mixture of the components (a) and (b) were used.
It is carried out until 5 to 100%, preferably 50 to 90%, undergoes a hydrolytic condensation reaction. The amount of water added in the second stage is
45 to 100%, preferably 50 to 100% of the hydrolyzable groups initially present in the mixture of the components (a) and (b).
90% is a sufficient amount for the hydrolysis and condensation reaction, and specifically, it is 1 times or more of the total number of the hydrolyzable groups remaining after the hydrolysis and condensation reaction in the first step, preferably 1. Amounts that are 2 to 2 times the number of moles are suitable.

The trialkoxyborane and the organometallic compound catalyst used in the second step accelerate the condensation reaction between the components (a) and (b), and the appearance, weather resistance and stain resistance of the coating film,
The hot water resistance and the like can be improved. The amount of trialkoxyborane or the organometallic compound catalyst is 100 parts by mass based on the total amount of the reactant obtained in the first step and the above-mentioned unreacted components (a) and (b). 0.00
1 to 5 parts by mass, preferably 0.005 to 1 part by mass is suitable. If the trialkoxyborane or the organometallic compound catalyst is less than the above range, the condensation reaction tends to be insufficient and the above-mentioned improving effect tends to be unobtainable. On the contrary, if it is too much, the reaction stability and hot water resistance are poor. It tends to become unfavorable.

The hydrolysis-condensation reaction in the second step is 40 to 80 ° C., preferably 45 to 65 ° C., as in the first step.
It is suitable to react for 2 to 5 hours. The hydrolysis-condensation reaction product obtained in step (i) is in a solution state due to the alcohol content produced in the reaction, or due to the alcohol content and an organic solvent which will be described later added as necessary.

In the step (ii), a neutralizing agent is added to the solution of the organic-inorganic composite resin obtained in the step (i), and it is uniformly dispersed and neutralized, and then water is added, or the neutralizing agent is added. And water are added at the same time, and the mixture is forcibly dispersed by stirring to obtain an aqueous dispersion. As a neutralizing agent, triethylamine,
Triethanolamine, dimethylethanolamine, monoethanolamine, N-methyldiethanolamine,
Typical examples are N, N-dimethylethanolamine and morpholine.

The amount of the neutralizing agent added is 50 to 50% of the acid groups of the organic-inorganic composite resin so that a stable aqueous dispersion can be obtained.
An amount that can neutralize 100%, preferably 70 to 90% is suitable. The amount of water added is arbitrarily determined in consideration of the coating workability when the coating composition is used, but normally the solid content of the coating composition is 10 to 5
An amount of about 0% by mass is suitable.

In the water dispersion thus obtained, the alcohol content produced by the above-mentioned hydrolysis condensation reaction remains. Therefore, if the water-dispersed solution is used as it is in the coating composition, the amount of volatile organic components is increased. Therefore, if necessary, the alcohol content may be removed under reduced pressure according to a conventional method.

In step (iii), component (c) is added to the aqueous dispersion obtained in step (ii) to produce an organic-inorganic composite resin aqueous emulsion. The addition amount of the component (c) is appropriately 0.1 to 10 parts by mass with respect to 100 parts by mass of the solid content of the organic-inorganic composite resin present in the aqueous dispersion. When the amount of component (c) is less than the above range, the curability of the resulting coating film tends to deteriorate, and conversely, when it is more than the above range, hot water resistance, crack resistance, etc. tend to deteriorate. It is not preferable because there is.

The organic-inorganic composite resin aqueous emulsion of the present invention is obtained by the above-mentioned production method and is suitable for use in the two-pack type coating composition of the present invention. The organic-inorganic composite resin aqueous emulsion of the present invention contains, if necessary, an organic solvent, a filler, a dye, and further a curing accelerator for improving storage stability and coating workability when a two-component coating composition is prepared. Various additives such as agents, thickeners, and pigment dispersants can be contained.

Examples of the above 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 ketones such as acetone and methyl ethyl ketone. A solvent or a mixed organic solvent thereof with a hydrophobic organic solvent for various coating materials such as toluene, xylene, ethyl acetate and butyl acetate can be used. These organic solvents can be blended as a solvent in the above step (i) so that the reaction can occur homogeneously.

As the above-mentioned filler, various extender pigments and coloring pigments such as talc, magnesium carbonate, calcium carbonate, barium carbonate, bentonite, titanium oxide, carbon black, red iron oxide and lithopone can be used. Examples of the curing accelerator include tin octylate, dibutyltin dilaurate, dibutyltin dimaleate, organotin compounds such as tributyltin laurate, and amine compounds such as ethylenediamine, diethylenetriamine, piperidine, phenylenediamine, and triethylamine. Among them, organotin compounds are particularly effective.

Next, the organic-inorganic composite resin aqueous emulsion of the present invention
The two-component coating composition containing John will be described. The two- pack type coating composition comprises the above-mentioned organic-inorganic composite resin aqueous emulsion and the amino group-containing alkoxysilane compound which is the component (d), and the organic-inorganic composite resin solid content in the organic-inorganic composite resin aqueous emulsion and (c) )
The component serves as the main agent binder and the component (d) serves as the curing agent.

In the above two-component coating composition, the organic-inorganic composite resin aqueous emulsion and the component (d) are mixed and used immediately before coating. During this mixing, if necessary, an organic solvent for improving the coating workability of the coating composition, a filler, a dye, and further a curing accelerator,
Various additives such as a thickener and a pigment dispersant can also be added.

The component (d) acts as a curing agent, and (c)
In addition to reacting with the epoxy groups of the epoxy group-containing alkoxysilane that is a component, it also undergoes a hydrolytic condensation reaction with the alkoxysilane in the organic-inorganic composite resin, resulting in hot water resistance, alkali resistance, weather resistance, stain resistance, solvent resistance, etc. It forms an excellent coating film.

[0043]

[0044]

[0045]

The component (d) contains an amino group in the molecule.
Alkoxysilane compound capable of hydrolysis and condensation reaction
Examples of such compounds include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, and N- (β- Aminoethyl) -γ-aminopropylmethyldimethoxysilane,
N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-cyclohexyl γ-aminopropyltrimethoxysilane, N-cyclohexyl-γ-
Aminopropyltriethoxysilane , γ -anilinopropyltrimethoxysilane and the like can be mentioned.

The amount of the component (d) to be blended is the solid content of the organic-inorganic composite resin in the organic-inorganic composite resin aqueous emulsion and (c)
An amount of 0.3 to 10 parts by mass, preferably 1 to 7 parts by mass is suitable for 100 parts by mass of the total of the epoxy group-containing alkoxysilane compound as a component. In addition,
If the amount of component (d) is less than the above range, the curability, hot water resistance, alkali resistance, etc. of the resulting coating film will tend to deteriorate, and conversely if it is too high, hot water resistance and crack resistance will tend to deteriorate. .

Immediately after mixing the above two-component coating composition, the surface of the article to be coated is coated with a coating means such as a brush, spray, roll or dipping, and baked at room temperature or at a temperature of 300 ° C. or less. It is possible to form a cured coating film. It should be noted that the object to be coated can be applied to various objects such as an inorganic ceramic substrate, various metal substrates such as stainless steel and aluminum, a glass substrate, a plastic substrate, and a paper substrate.

[0049]

EXAMPLES The present invention will be described in more detail below with reference to preparation examples, examples and comparative examples. In the description of preparation examples, examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.

Preparation Example 1 <Preparation of silyl group-containing vinyl resin solution (a)> A reactor equipped with a reflux condenser and a stirrer was charged with 100 parts of ethylene glycol monobutyl ether and heated to 100 ° C with stirring. Warmed. Next, 50 parts of isobutyl methacrylate, 31.5 parts of 2-ethylhexyl methacrylate, 10 parts of γ-methacryloxypropyltrimethoxysilane, 8.5 parts of acrylic acid and t-butylperoxy-2-ethylhexanoate were added to this reactor. A mixed solution consisting of 5 parts was added dropwise at 100 ° C. over 3 hours, and then 1 part was added.
The temperature was raised to 05 ° C. and maintained for 2 hours to complete the reaction. The resulting silyl group-containing vinyl resin solution (a) has a solid content concentration of 50% and an acid value of the resin of 65 mgKOH / g.
And the number average molecular weight was 10,000.

Preparation Example 2 <Preparation of silyl group-containing vinyl resin solution (b)> 100 parts of ethylene glycol monobutyl ether was placed in a reactor equipped with a reflux condenser and a stirrer, and the mixture was heated to 100 ° C. with stirring. Warmed. Next, 50 parts of isobutyl methacrylate, 31.5 parts of 2-ethylhexyl methacrylate, 8.5 parts of γ-methacryloxypropyltrimethoxysilane, 10.5 parts of acrylic acid and t- were added to this reactor.
A mixed solution consisting of 2.5 parts of butylperoxy 2-ethylhexanoate was added dropwise at 100 ° C over 3 hours, then heated to 105 ° C and maintained for 2 hours to terminate the reaction. The resulting silyl group-containing vinyl resin solution (b) is
The solid content concentration is 50% and the acid value of the resin is 80 mg KO.
It was H / g and the number average molecular weight was 10,000.

Example 1 (a) In a reactor equipped with a reflux condenser and a stirrer, (a) a partial hydrolysis-condensation product of methyltrimethoxysilane (SR2402 manufactured by Toray Dow Corning Co., Ltd., solid content 100%)
23 parts, 8 parts of methyltrimethoxysilane and 1.7 parts of dimethyldimethoxysilane, (b) 25 parts of the silyl group-containing vinyl resin solution (a) obtained in Preparation Example 1 and 10 parts of isopropanol were charged and mixed. After that, deionized water 3.
0 part and 0.05 part of 1N hydrochloric acid were added and reacted at 60 ° C. for 3 hours (70% of the hydrolyzable groups were hydrolyzed and condensed.
Response: Methanol produced by hydrolysis condensation reaction is gas chromatographed.
Quantitative method) . Next, 0.3 part of monoacetylacetonate bis (ethylacetoacetate) aluminum (aluminum chelate D manufactured by Kawaken Fine Chemicals Co., Ltd.) and 0.8 part of ion-exchanged water were added, and the mixture was further reacted at 60 ° C. for 3 hours. In the obtained reaction product, 80% of the initially present hydrolyzable groups had undergone a hydrolytic condensation reaction .

Next, 0.95 parts of triethylamine and 40 parts of water were added, and the mixture was stirred at 50 ° C. for 1 hour.
It was added 2 parts of γ--glycidoxypropylmethyldiethoxysilane, further 1 hour stirring, the organic-inorganic composite resin (acid value 20 mgKOH / g) aqueous Emaruji ® emission (solid concentration 3
5% ) was obtained.

Example 2 In a reactor equipped with a reflux condenser and a stirrer, (a) 25 parts of a partially hydrolyzed condensate of an alkoxysilane (DC3074 manufactured by Toray Dow Corning Co., Ltd., solid content 100%) and methyl were used. 8 parts of trimethoxysilane, (b) 25 parts of the silyl group-containing vinyl resin solution (a) obtained in Preparation Example 1 and 10 parts of isopropanol were charged and mixed, and then 2.0 parts and 1 part of ion-exchanged water were added. Add 0.05 parts of normal hydrochloric acid to 60
Reaction was carried out at ℃ for 3 hours (70% of the hydrolyzable groups were
Decondensation reaction) . Next, 0.5 part of triethoxyborane and 0.5 part of ion-exchanged water were added, and the mixture was further reacted at 60 ° C. for 3 hours. In the obtained reaction product, 75% of the initially present hydrolyzable groups had undergone a hydrolytic condensation reaction.

Next, 0.8 part of N, N-dimethylethanolamine and 50 parts of water were added, and after stirring at 50 ° C. for 1 hour, 2 parts of (c) γ-glycidoxypropyltrimethoxysilane was added. , stirred for an additional 1 hour to obtain an organic-inorganic composite resin (acid value 20 mgKOH / g) aqueous Emaruji ® emission (solid concentration 35%).

Example 3 In a reactor equipped with a reflux condenser and a stirrer, (a) 30 parts of methyltrimethoxysilane and 10 parts of dimethyldimethoxysilane, (b) the silyl group-containing vinyl resin solution obtained in Preparation Example 2 was added. (B) 16 parts and 5 parts of isopropanol were charged and mixed, then, 5.2 parts of ion-exchanged water and 0.05 part of 1N hydrochloric acid were added, and the mixture was reacted at 60 ° C. for 3 hours (addition).
65% of the water-decomposable group is a hydrolytic condensation reaction) . Next, 0.3 part of monoacetylacetonate bis (ethylacetoacetate) aluminum (aluminum chelate D manufactured by Kawaken Fine Chemicals Co., Ltd.) and 1.5 parts of ion-exchanged water were added, and the mixture was further reacted at 60 ° C. for 3 hours. In the obtained reaction product, 80% of the initially present hydrolyzable groups had undergone a hydrolytic condensation reaction.

Then, 5 parts of ethylene glycol monobutyl ether and 1.0 of N, N-dimethylethanolamine.
Parts and 60 parts of water were added, and the mixture was stirred at 50 ° C. for 1 hour, and then methanol produced by the reaction was added under reduced pressure to 50-65.
Removed at ° C. Next, (c) 2.5 parts of γ-glycidoxypropyltrimethoxysilane was added, and the mixture was further stirred for 1 hour to prepare an organic-inorganic composite resin (acid value 26 mgKOH / g).
To obtain an aqueous Emaruji ® emission (solid concentration 35%).

Comparative Example 1 In a reactor equipped with a reflux condenser and a stirrer, (a) 30 parts of methyltrimethoxysilane and 10 parts of dimethyldimethoxysilane, and (b) a vinyl resin solution containing a silyl group (Kanebuchi Chemical Industry ( Kaneka Zemulac Co., Ltd., acid value 0, solid content 50%) 16 parts, and isopropanol 16 parts are charged and mixed, and then 5.4 parts of ion-exchanged water and 0.05 part of 1N hydrochloric acid are added. And reacted at 60 ° C. for 3 hours (hydration).
70% of the decomposable groups are hydrolytically condensed) . Next, 5 parts of ion-exchanged water was added, the mixture was further reacted at 60 ° C. for 3 hours, 5 parts of ethylene glycol monobutyl ether and 40 water were added, and the mixture was stirred at 50 ° C. for 1 hour. Then, the methanol produced by the reaction was removed under reduced pressure at 50 to 65 ° C. As a result, the reaction product was separated and precipitated and could not be made into a paint.

Comparative Example 2 (a) A partial hydrolysis-condensation product of methyltrimethoxysilane (SR2402 manufactured by Toray Dow Corning Co., Ltd., solid content 100%) was placed in a reactor equipped with a reflux condenser and a stirrer.
23 parts, 8 parts of methyltrimethoxysilane and 1.7 parts of dimethyldimethoxysilane, (b) 20 parts of the silyl group-containing vinyl resin solution (b) obtained in Preparation Example 2 and 10 parts of isopropanol were charged and mixed. After that, deionized water 2.5
Parts and 1 part of 1N hydrochloric acid were added and reacted at 60 ° C. for 3 hours (56% of the hydrolyzable groups were hydrolyzed and condensed.
O) . Next, 0.3 part of triethoxyborane and 0.8 part of ion-exchanged water were added, and the mixture was further reacted at 60 ° C. for 3 hours. Then, N, N-dimethylethanolamine 0.8
Parts and 37 parts of water were added, and the mixture was stirred at 50 ° C. for 1 hour to prepare an organic-inorganic composite resin (acid value 20 mgKOH / g) aqueous emulsion.
Was obtained ® emission (solid concentration 32%).

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

The two- pack type coating composition using the organic-inorganic composite resin aqueous emulsion obtained by the production method of the present invention has a coating film excellent in hot water resistance, alkali resistance, weather resistance and stain resistance. Can be formed.

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hiroharu Sasaki 7-1414-46 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 9-176489 (JP, A) JP 11-92536 (JP, A) JP 10-77322 (JP, A) JP JP-A-11-279408 (JP, A) JP-A-11-209475 (JP, A) JP-A-11-343419 (JP, A) JP-A-11-349815 (JP, A) JP-A-9-227835 (JP , A) JP-A-10-226768 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 83/00-83/16 C09D 183/00-183/16 C08G 77/00 -77/62 WPI / L (QUESTEL)

Claims (2)

(57) [Claims] (I) (a) General 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 an alkyl group having 1 to 5 carbon atoms, and n is 1 or 2.)
100 parts by mass of at least one organosilane compound selected from the group consisting of organosilanes and partial hydrolysis-condensates thereof, and (b) a silyl group having a silicon atom bonded to a hydrolyzable group or a hydroxyl group. Has a vinyl resin at the terminal or side chain and has an acid value of 20 to 150 m.
5-20 silyl group-containing vinyl resin having a gKOH / g
A mixture of 0 parts by mass of water and acid as the first step
In the presence of the catalyst, the water initially present in the mixture was
Hydrolytic condensation so that 40-80% of the decomposable groups react
The reaction is followed by a second step with water and trialkoxybenzene.
In the mixture in the presence of orchid or organometallic compound catalyst
45-100% of the hydrolyzable groups initially present in
Step of obtaining a solution of organic-inorganic composite resin by hydrolytic condensation reaction until reaction , (ii) Neutralizer and water are added to the solution of organic-inorganic composite resin obtained in step (i), and the mixture is stirred to be an aqueous dispersion. And (iii) in the aqueous dispersion obtained in step (ii), (c) the epoxy group-containing alkoxysilane compound is added to 100 parts by mass of the organic-inorganic composite resin solid content present in the aqueous dispersion. 0.
A method for producing an organic-inorganic composite resin aqueous emulsion, comprising the step of adding 1 to 10 parts by mass and stirring to obtain an organic-inorganic composite resin aqueous emulsion. 2. An organic-inorganic composite resin aqueous emulsion obtained by the production method according to claim 1 .