JP2001122971A - Method for producing organic and inorganic composite resin aqueous emulsion and composition for coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an organic and inorganic composite resin aqueous emulsion for a coating composition forming a coated film excellent in frostproof, resistance to boiling water, weatherproof, stain resistance and the like and to obtain a coating composition including the aqueous emulsion. SOLUTION: This organic and inorganic composite resin aqueous emulsion is obtained by (i) a process wherein a mixture of (a) 100 pts.wt. both or one of an organosilane represented by formula (1) (R1)nSi(OR2)4-n [wherein R1 is 1-18C organic group; R2 is a 1-5C alkyl group; n is 0, 1 or 2] and a condensate of partially hydrolyzate of the organosilane, (b) 1-240 pts.wt. silyl group- containing organic compound represented by formula (2) and (c) 5-200 pts.wt. silyl group-containing vinyl resin having a hydrolyzable silyl group or a silyl group having a silicon atom bonging to a hydroxyl group and having 20-150 mgKOH/g acid value and (ii) a process wherein a neutralizer and water are added into a solution of the reaction product of the process (i).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an aqueous emulsion of an organic-inorganic composite resin, and to a method for containing the aqueous emulsion, which is free from frost damage, hot water, weather, stain, solvent, and solvent. The present invention relates to a coating composition that forms a coating film having excellent alkalinity and the like.

2. Description of the Related Art A coating material comprising an organic-inorganic composite resin obtained by subjecting an organosilane and / or a partially hydrolyzed condensate thereof and a silyl group-containing vinyl resin to a hydrolytic condensation reaction as a binder has a weather resistance and a resistance to weather resistance. Attention has been paid to forming a coating film having excellent stainability and the like. However,
Such a coating composition has a problem that frost damage resistance and hot water resistance are inferior.

[0002]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and uses water as a solvent, and has resistance to frost damage, hot water resistance, weather resistance, solvent resistance, and water resistance. It is an object of the present invention to provide a method for producing an aqueous emulsion of an organic-inorganic composite resin for forming a coating film having excellent alkalinity and the like, and a coating composition containing the aqueous emulsion.

[0003]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that the above object can be achieved by the following constitution, and have reached the present invention. That is, the present invention relates to the following inventions. In the first invention, (i) (a) Formula (1) (R
¹ ) _n Si (OR ² ) _{4-n 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 one or both of the organosilane represented by the formula (1)

[0004]

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Wherein R ¹ and R ² have the same meanings as above, A is (CH ₂ ) _m , m is an integer of 1 to 8, and n is 0, 1 or 2. A silyl group-containing organic compound represented by the formula (1), and (c) a hydrolyzable silyl group or a silyl group having a silicon atom bonded to a hydroxyl group, and an acid value of 20 to 150 mgK.
A step of subjecting a mixture consisting of 5 to 200 parts by mass of an OH / g silyl group-containing vinyl resin to a hydrolysis condensation reaction,
Next, (ii) the reaction product solution obtained in step (i)
It is intended to provide a method for producing an aqueous emulsion of an organic-inorganic composite resin, comprising a step of adding a neutralizing agent and water. Further, a second invention provides a coating composition containing the organic-inorganic composite resin aqueous emulsion obtained in the first invention.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Each component used for producing the organic-inorganic composite resin aqueous emulsion of the first invention will be described. <Component (a)> The 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, R ² is an alkyl group having 1 to 5 carbon atoms, and n
Is 1 or 2. And / or a partially hydrolyzed condensate thereof. R ¹ in the above formula
Is an organic group having 1 to 8, preferably 1 to 6 carbon atoms.
Examples of the organic group include an alkyl group, an alkenyl group, a cycloalkyl group, and an aryl group. Here, the alkyl group may be linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group,
Alkyl groups such as a pentyl group, a hexyl group, a heptyl group and an octyl group are preferred. Preferred alkyl groups have, for example, 1 to 4 carbon atoms.

The alkenyl group may be linear or branched. Preferable examples of the alkenyl group include alkenyl groups such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and an octenyl group. Preferred alkenyl groups have 2 to 4 carbon atoms. Preferred examples of the cycloalkyl group include a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group. Further, as the aryl group, for example, a phenyl group and the like are preferably mentioned. Each of the above functions may optionally have a substituent. As such a substituent, for example, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom and the like), a mercapto group, an epoxy group, an amino group, a cycloalkyl group and the like are preferably exemplified. Examples of the organic group having such a substituent include a γ-chloropropyl group and 3,3,3
-Trifluoropropyl group, γ-glycidoxypropyl group, γ-mercaptopropyl group, 3,4-epoxycyclohexylethyl group, γ-aminopropyl group and the like.

[0008] When the R ¹ there are a plurality, these R ₁
May be the same or different. R ² in the formula is an alkyl group having 1 to 5 carbon atoms. The alkyl group may be linear or branched. As such an alkyl group,
For example, methyl group, ethyl group, n-propyl group, i-
Alkyl groups such as propyl, n-butyl, i-butyl, sec-butyl, t-butyl, and pentyl are preferred. Preferred alk groups have, for example, 1-2 carbon atoms. When a plurality of R ² are present, these R ² may be the same or different. As the organosilane represented by the above formula (1), 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, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropylto Silane, γ-
Mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, dimethyldimethoxysilane, Dimethyl diethoxy silane, diethyl dimethoxy silane, diethyl diethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, methyl phenyl dimethoxy silane, dimethyl dipropoxy silane and the like, preferably methyl trimethoxy silane, methyl triethoxy silane , Dimethyldimethoxysilane. These organosilanes
One type may be used alone, or two or more types may be used in combination.

The component (a) may be a partially hydrolyzed condensate of the organosilane described above. The polystyrene equivalent weight average molecular weight of the condensate is, for example, 300 to 5
000, preferably 500 to 3000, and the use of a condensate having such a molecular weight can provide a coating film having good adhesion without deteriorating storage stability. Furthermore, partial hydrolysis condensate of organosilane, a -OH group or -OR ² group bonded to a silicon atom 1 or more,
Preferably, those having 3 to 30 are suitable. As a specific example of such a condensate, as a commercial product, for example,
SH6018, SR240 manufactured by Dow Corning Toray
2, DC3037, DC3074; KR-211, KR-212, KR-213, KR-2 manufactured by Shin-Etsu Chemical Co., Ltd.
14, KR-216, KR-218; TSR-145, TSR-160, TSR-16 manufactured by Toshiba Silicone Co., Ltd.
5, YR-3187 and the like. In the present invention, the formula (R ¹ ) ₃ Si () is used in combination with the component (a) for the purpose of improving the storage stability of the coating composition and improving the crack resistance and the like of the obtained coating film. OR ² ) [wherein, R ¹ and R ² have the same meanings as in formula (1) of the component (a). And the organosilane represented by the formula (a)
It is also possible to mix in a range not exceeding 20 parts by mass with respect to parts by mass. Specific examples of such an organosilane include, for example, methoxytrimethylsilane, ethoxytrimethylsilane, ethoxydiphenylmethylsilane, and the like. <Component (b)> The component (b) is represented by the formula (2),

[0010]

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[0011] wherein, R ¹ and R ² are the same meaning as R ¹ and R ² of component (a) of the formula (1), A, (C
H ₂ ) _m , m is an integer of 1 to 8, and n is 0, 1 or 2
It is. And a silyl group-containing organic compound represented by the formula:
Specific examples of these silyl group-containing compounds include 1,3,
5-N-tris (2-trimethoxysilylethyl) isocyanurate, 1,3,5-N-tris (3-triethoxysilylpropyl) isocyanurate, 1,3,5-
N-tris (3-trimethoxysilylpropyl) isocyanurate, 1,3,5-N-tris (3-methyl-3
-Dimethoxysilylpropyl) isocyanurate, 1,
3,5-N-tris (3-dimethyl-3-methoxysilylpropyl) isocyanurate and the like. These silyl group-containing organic compounds can be used alone or in combination.
Two or more kinds may be used in combination. As a commercially available product of such a silyl group-containing organic compound, for example, Y-11597 manufactured by Nihon Unica Co., Ltd. and the like can be mentioned.

<Component (c)> As the component (c), at least one hydrolyzable silyl group at the terminal or side chain or a silyl group having a silicon atom bonded to a hydroxyl group is preferably contained in one molecule of the resin. 2 or more and the acid value is 2
0 to 150 mgKOH / g, for example, having a molecular weight of about 10
Suitably, it is a vinyl-based resin having a molecular weight of 00 to 50,000. The silyl group of the formula ^{_{(3) -SiX P (R 3}} ) (3-P)
[In the formula, X is a hydrolyzable group such as an alkoxy group, an acyloxy group, a halogen group, a ketoximate group, an amino group, an acid amide group, an amideoxy group, a mercapto group, an alkenyloxy group, a phenoxy group or a hydroxyl group; ³ is hydrogen or a monovalent hydrocarbon group such as an alkyl group, an aryl group, or an aralkyl group having 1 to 10 carbon atoms; P is an integer of 1 to 3; ]. The silyl group-containing vinyl resin is, for example, represented by the formula (4) (X _P ) (R ³ )
_(3-P) Si-H wherein X, R ³ and P have the same meanings as above. And a vinyl resin having a carbon-carbon double bond according to a conventional method,
It is produced by reacting.

The hydrosilane compound includes:
For example, typical examples include methyldichlorohydrosilane, methyldiethoxyhydrosilane, methyldiacetoxyhydrosilane, and methyldiaminooxyhydrosilane. The amount of the hydrosilane compound to be used is 0.5 to 0.5% based on the carbon-carbon double bond contained in the vinyl resin.
The use of twice the molar amount is appropriate. The vinyl resin,
(Meth) acrylic acid, itaconic acid, carboxylic acid such as fumaric acid or acid anhydride such as maleic anhydride is contained as an essential vinyl monomer, and further, methyl (meth) acrylate,
(Meth) acrylic acid esters such as ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylic acid; epoxy compounds such as glycidyl (meth) acrylate; acrylonitrile; It is a copolymer of a vinyl monomer selected from the group consisting of styrene, α-methylstyrene, vinyl acetate, vinyl propionate, and the like. In the production of the copolymer, allyl (meth) acrylate, diallyl phthalate, etc. By copolymerization, it is possible to introduce a carbon-carbon double bond into a vinyl resin for a hydrosilylation reaction.

The above carboxylic acid or acid anhydride is
The acid value of the vinyl resin obtained in the constituent monomer of the copolymer is from 20 to 150 mgKOH / g, preferably from 50 to 150 mgKOH / g.
It needs to be contained so as to be 120 mgKOH / g. When the acid value is smaller than the above range, the storage stability of the obtained aqueous emulsion is deteriorated, and when it is larger, the water resistance of the obtained coating film is deteriorated.
Further, as other production methods, the above-mentioned vinyl monomer containing the above-mentioned carboxylic acid or acid anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyvinyl ether, etc. A hydroxyl group-containing monomer, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, β- (meth) acryloxyethyltrimethoxysilane, β- (meth) acryloxyethyltri Ethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ
-Silyl such as (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, and γ- (meth) acryloxypropyldiethylmethoxysilane There is also a method of radically polymerizing a group-containing vinyl compound. Specific examples of these silyl group-containing vinyl resins include, for example, commercially available products such as Kanekazemurakku manufactured by Kaneka Chemical Industry Co., Ltd.

Next, a method for producing the aqueous organic-inorganic composite resin emulsion of the first invention will be described. First, in the step (i), the component (a), the component (b), and the component (c) are subjected to a hydrolysis and condensation reaction in the presence of, for example, water and a catalyst. The mixing ratio of each component is as follows:
The component (b) is suitably used in an amount of 1 to 240 parts by weight, preferably 15 to 150 parts by weight, and the component (c) is appropriately used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight. is there. If the amount of the component (b) is less than the above range, the obtained coating film has poor frost damage resistance and the like, whereas if it is too large, the obtained coating film has poor weather resistance and the like.
When the component (c) is less than the above range, the storage stability and appearance of the obtained coating film, crack resistance, alkali resistance, etc. are deteriorated. It is not preferable because it becomes worse. The amount of water is determined in step (i)
In the mixture of the component (a), the component (b) and the component (c), 45 to 100% of the hydrolyzable functional group, preferably 50 to 100%
An appropriate amount is 0.45 to 1.0 equivalent, preferably 0.5 to 0.9 equivalent, per equivalent of the hydrolyzable functional group so that 80% undergoes hydrolysis and condensation reactions.

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 is suitably such that the pH of the composition becomes 3 to 6. Examples of the catalyst include trialkoxyboranes such as trimethoxyborane, triethoxyborane, and tripropoxyborane, zirconium tri-n-butoxyethylacetoacetate, zirconium di-n-butoxydi (ethylacetoacetate), and zirconium n-butoxytris (ethyl). Zirconium chelate compounds such as zirconium acetoacetate, zirconium tetrakis (acetylacetoacetate), and zirconium tetrakis (ethylacetoacetate); titanium chelates such as diisopropoxybis (acetylacetate) titanium and diisopropoxybis (ethylacetoacetate) titanium Compound: aluminum monoacetylacetonate bis (ethylacetoacetate) aluminum, diisopropoxyethyl acetoacetate aluminum, diisoprop Po carboxymethyl acetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, tris (ethylacetoacetate) aluminum, tris metal catalysts of the aluminum chelate compounds such as (acetylacetonate) aluminum can be used. The amount of the trialkoxy borane or the metal catalyst is determined by comparing the components (a), (b) and (c)
0.001 to 2 parts by mass is appropriate for 100 parts by mass of the total amount of the components.

The hydrolysis-condensation reaction is carried out by mixing the components (a), (b) and (c) in the presence of water and a catalyst to form a mixture.
A method in which the reaction is carried out at -80 ° C, preferably 45-65 ° C for 2-10 hours is suitable, but not limited to this method. In the hydrolysis and condensation reaction of the step (i), initially, the reaction of the component (a) mainly occurs due to the reaction rate, and the component (b), the component (c), or
The reaction between component (a), component (b) and component (c) (grafting reaction by condensation reaction) is slow. As described above, in step (i), the hydrolysis and condensation reaction
When the content of the hydrolyzable functional group in the mixture of the component (a), the component (b) and the component (c) is 45 to 100%, the storage stability of the product is good and a highly transparent film can be formed. This is because Note that the process (i) is performed in one stage as described above in (a).
The component, the component (b), and the component (c) can be subjected to a hydrolysis-condensation reaction, but the reaction is preferably performed in the following two steps from the viewpoint of storage stability of the product. That is, in the first stage, 40 to 80%, preferably 50 to 7% of the hydrolysis functional group in the mixture of the component (a), the component (b) and the component (C).
The reaction is performed in the presence of water and a catalyst as described above so that 0% undergoes hydrolysis and condensation reactions.

In the second step, water and a catalyst are further added following the first step to effect hydrolysis and condensation. The amount of water is
After the reaction in the first stage, 1 equivalent or more, preferably 1.2 to
2.0 equivalents are appropriate. The hydrolysis condensate reaction in the second stage is carried out at 40 to 80 ° C., preferably 4 ° C., as in the first stage.
It is appropriate to react at 5 to 65 ° C for 2 to 5 hours.
The hydrolysis-condensation reaction product obtained in the second step is in a solution state by the produced alcohol component or an organic solvent added thereto as required, which will be described later. Subsequent to the step (i), in the step (ii), a neutralizing agent is added to the solution of the organic-inorganic composite resin, which is the reactant obtained in the step (i), and the solution is uniformly dispersed and neutralized. Or a neutralizing agent and water are added at the same time, followed by forced emulsification by stirring and emulsification.

The amount of the neutralizing agent is set to 50 to 100 of the acid groups in the organic-inorganic composite resin so that a stable emulsion can be obtained.
%, Preferably an amount that neutralizes 70 to 100%. In addition, as a neutralizing agent, triethylamine, triethanolamine, dimethylethanolamine, monoethanolamine, N-methyldiethanolamine, N,
Representative examples include N-dimethylethanolamine, morpholine, and the like. In addition, the amount of water is arbitrarily determined in consideration of the workability of coating and the like. However, the amount of water is generally appropriate such that the solid content of the coating composition becomes 10 to 50% by weight. In the organic-inorganic composite resin aqueous emulsion thus obtained, an alcohol component is generated by the above-mentioned hydrolysis-condensation reaction, and this remains in the emulsion. Therefore, when the emulsion is used as it is as a coating composition, the volatile organic component (VOC) increases, so that the alcohol content may be removed under reduced pressure according to a conventional method. Next, the coating composition of the second invention will be described. The coating composition has the above-mentioned organic-inorganic composite resin as a binder, and water or an organic solvent and a filler for improving the storage stability and coating workability of the coating composition, if necessary, in the emulsion, a filler, a dye, Further, it is constituted by blending various additives such as a curing accelerator, a thickener, and a pigment dispersant.

Examples of the organic solvent include hydrophilic organic solvents such as alcohols such as methanol, ethanol, propanol and butanol, alcohol ethers such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, and ketones such as acetone and methyl ethyl ketone. It is possible to use a solvent or a mixed organic solvent thereof with various hydrophobic organic solvents for coating such as toluene, xylene, ethyl acetate and butyl acetate. In addition, these organic solvents can be blended as a solvent in the above-mentioned step (i) so that the reaction occurs uniformly. As the filler, for example, extenders and coloring pigments for various paints such as talc, barium carbonate, calcium carbonate, bentonite, titanium oxide, carbon black, red iron, lithopone and the like can be used. As the curing accelerator, for example, tin octylate, dibutyltin dilaurate, dibutyltin dimaleate, organic tin compounds such as tributyltin laurate, ethylenediamine, diethylenetriamine,
Examples of amine compounds such as piperidine, phenylenediamine, and triethylamine are typical examples,
Particularly, an organotin compound is effective. The coating composition of the present invention is applied to the surface of the object to be coated by coating means such as brush, spray, roll, dipping, etc.
By baking at a temperature of 00 ° C. or less, a cured coating film can be formed. In addition, as an object to be coated, an inorganic ceramic substrate, various metal substrates such as stainless steel and aluminum,
The present invention can be applied to various substrates such as a glass substrate, a plastic substrate, and a paper substrate.

[0021]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “parts” and “%” are shown on a mass basis unless otherwise specified. <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 stirred.
Warmed to ° C. Next, isobutyl methacrylate 50
Parts, 2-ethylhexyl methacrylate 31.5 parts, γ
-10 parts of methacryloxypropyltrimethoxysilane,
8.5 parts of acrylic acid and t-butylperoxy-2-
A mixed solution of 2.5 parts of ethyl hexanoate was heated at 100 ° C.
, And the temperature was raised to 105 ° C and maintained for 2 hours to terminate the reaction. The resulting silyl group-containing vinyl resin solution (a) had a solid content of 50%, an acid value of 65 mg KOH / g, and a number average molecular weight of 100.
00, and had an average of about 7 silyl groups per polymer molecule.

<Preparation of Silyl Group-Containing Vinyl Resin Solution (B)> 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. with stirring. Next, 50 parts of isobutyl methacrylate, 2-ethylhexyl methacrylate 3
A mixed solution of 1.5 parts, 8.5 parts of γ-methacryloxypropyltrimethoxysilane, 10.5 parts of acrylic acid, and 2.5 parts of t-butylperoxy-2-ethylhexanoate at 100 ° C. Dropping over 3 hours, then 105
C. and maintained for 2 hours to terminate the reaction. The resulting silyl group-containing vinyl resin solution (b) had a solid content of 50%, an acid value of the resin of 80 mgKOH / g, a number average molecular weight of 10,000, and an average of about 6 polymers per molecule. It had a silyl group.

Example 1 In a reactor equipped with a reflux condenser and a stirrer, (a) a partially hydrolyzed condensate of methyltrimethoxysilane (SR2402 manufactured by Dow Corning Toray Co., Ltd .; solid content: 100%)
65 parts, 29 parts of methyltrimethoxysilane and 6 parts of dimethyldimethoxysilane, (b) 18 parts of 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate, and (c) vinyl containing a silyl group After adding 58 parts of the system resin solution (a) and 6 parts of isopropanol and stirring, 10 parts of ion-exchanged water and 0.1 N hydrochloric acid were added.
The mixture was added so that the pH became 4, and reacted at 60 ° C. for 3 hours.
Further, 0.3 parts of triethoxyborane and 1 part of ion-exchanged water
5 parts and reacted at 60 ° C. for 3 hours. In the obtained reaction product, 75% of the hydrolyzable functional groups had undergone a hydrolytic condensation reaction (measured by gas chromatography). Then N,
After adding 22 parts of N-dimethylethanolamine and 100 parts of water and stirring at 50 ° C. for 1 hour, the mixture was cooled to obtain an aqueous emulsion of an organic-inorganic composite resin having a solid content of 35%.

Example 2 In a reactor equipped with a reflux condenser and a stirrer, 57 parts of (a) a partially hydrolyzed condensate of methyltrimethoxysilane (SR2402 manufactured by Dow Corning Toray), methyltrimethoxy 35 parts of silane and dimethyldimethoxysilane 8
And (b) 44 parts of 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate, and (c)
After adding and mixing 110 parts of the silyl group-containing vinyl resin solution (b) and 10 parts of isopropanol, 15 parts of ion-exchanged water and 0.1 N hydrochloric acid are added so that the pH becomes 4, and 60 parts are added. The reaction was carried out at 3 ° C. for 3 hours. Further, 0.5 parts of triethoxyborane and 15 parts of ion-exchanged water were added,
The reaction was performed at 60 ° C. for 3 hours. In the obtained reaction product, 75% of the hydrolyzable functional groups had undergone a hydrolytic condensation reaction. Next, 4.5 parts of N, N-dimethylethanolamine and 110 parts of water were added, and the mixture was stirred at 50 ° C. for 1 hour and then cooled to obtain an organic-inorganic composite resin aqueous emulsion having a solid content of 35%.

COMPARATIVE EXAMPLE 1 In a reactor equipped with a reflux condenser and a stirrer, (a) 65 parts of a partially hydrolyzed condensate of methyltrimethoxysilane (SR2402 manufactured by Dow Corning Toray Co., Ltd.), 65 parts of methyltrimethoxysilane 29 parts and dimethyldimethoxysilane 6
And (c) a silyl group-containing vinyl resin solution (a) 80
And 6 parts of isopropanol, and after stirring, 10 parts of ion-exchanged water and 0.1 N hydrochloric acid are added to a pH of 4
And reacted at 60 ° C. for 3 hours. Further, 0.3 parts of triethoxyborane and 10 parts of ion-exchanged water were added and reacted at 60 ° C. for 3 hours. The resulting reactant is
75% of the hydrolyzable functional groups had undergone a hydrolytic condensation reaction. Next, 3 parts of N, N-dimethylethanolamine and 100 parts of water were added, and the mixture was stirred at 50 ° C. for 1 hour.
After cooling, an organic-inorganic composite resin aqueous emulsion having a solid content of 35% was obtained.

Comparative Example 2 In a reactor equipped with a reflux condenser and a stirrer, 57 parts of (a) a partially hydrolyzed condensate of methyltrimethoxysilane (SR2402 manufactured by Dow Corning Toray Co., Ltd.) were added. 35 parts of silane and 8 parts of dimethyldimethoxysilane, and (c) a silyl group-containing vinyl resin solution (b) 110
And 10 parts of isopropanol were added and mixed. Then, 10 parts of ion-exchanged water and 0.1 N hydrochloric acid were added so that the pH became 4, and the mixture was reacted at 60 ° C. for 3 hours. Further, 0.5 parts of triethoxyborane and 10 parts of ion-exchanged water
And reacted at 60 ° C. for 3 hours. In the obtained reaction product, 75% of the hydrolyzable functional groups had undergone a hydrolytic condensation reaction. Next, 4.5 parts of N, N-dimethylethanolamine and 100 parts of water were added, and the mixture was stirred at 50 ° C. for 1 hour, and then cooled to obtain an organic-inorganic composite resin aqueous emulsion having a solid content of 35%. Examples 1-2 and Comparative Examples 1
Organic-inorganic composite resin aqueous emulsion 100 obtained in 2
For each coating composition obtained by adding 5 parts of an aqueous dispersion of dibutyltin dilaurate to parts, the obtained coating film was tested for appearance, hardness, frost resistance, hot water resistance, stain resistance, weather resistance, and alkali resistance, The results are shown in Table 1. In addition, the test method was performed according to the following method.

<Coating Film Performance Test> A gypsum slag perlite plate (thickness: 12 mm) was used as a material, and a polyisocyanate prepolymer solution sealer "V-Seran."
100 Sealer "(trade name, manufactured by Dainippon Paint Co., Ltd.) (diluted 100% with a solution of butyl acetate: xylene = 1: 1) by spray coating so that the coating amount becomes 90 to 100 g / m ² (wet mass). did. This was dried at 100 ° C. for 5 minutes. Next, as a base paint, an acrylic silicone resin-based paint "V-Seran 500 enamel" (trade name, manufactured by Dainippon Paint Co., Ltd.) (butyl acetate: xylene = 1: 1 solution 40)
% Dilution) is 80 to 90 g / m ² (wet mass)
It was spray painted so that This was dried at 120 ° C. for 15 minutes. Next, each of the above-mentioned coating compositions was spray-coated so that the coating amount was 130 ± 10 g / m ² (wet mass). This was dried at 120 ° C. for 15 minutes and then at room temperature for 3 days.

Appearance: The appearance of the coating film was visually determined. Hardness: Pencil hardness determined according to JIS K 5400 Frost damage resistance: Measured by ASTM-C666A method (18
0 cycle) Evaluation criteria ◎ ・ ・ ・ No crack and no change in gloss ○ ・ ・ ・ No crack but slight decrease △ ・ ・ ・ Slight crack generation × ・ ・ ・ Significant crack generation Hot water resistance: Test piece at 80 ° C water It was immersed in water for 7 days, and the abnormality in the appearance of the coating film was visually determined. Evaluation criteria ○ ・ ・ ・ No change △ ・ ・ ・ Slight change such as gloss reduction, whitening etc. × ・ ・ ・ Large change such as gloss reduction, whitening etc.

Stain resistance: Twenty-four hours after the application of Red and Black Magic Ink (registered trademark), the stain was wiped off with a cloth wetted with n-butanol, and decontamination was visually evaluated. Evaluation criteria ◎ ・ ・ ・ Complete removal ○ ・ ・ ・ Extremely slight contamination △ ・ ・ ・ Contamination × ・ ・ ・ Remarkable contamination Weather resistance: Sunshine weather o-meter 3100 hours Evaluation criteria ○ ・ ・ ・ No change in coating film appearance , Gloss retention of 95% or more △: slight change in coating appearance, gloss retention of 80 to
94% ×: The coating film change is remarkable, the gloss retention is less than 80%

Solvent resistance: A rubbing test was carried out 50 times back and forth with a cloth wetted with xylene, and the coating film surface was visually evaluated. Evaluation criteria ○ ・ ・ ・ No change △ ・ ・ ・ Coating film surface turbidity × ・ ・ ・ Part of coating film surface dissolved Alkali resistance: 4 coated plates in saturated slaked lime alkaline aqueous solution
After immersion at 00 ° C. for 100 minutes, the coating film surface was visually evaluated. Evaluation criteria ○ ・ ・ ・ No change △ ・ ・ ・ Slight turbidity of film surface × ・ ・ ・ Paint turbidity of coating film As is clear from Table 1, coating composition using the aqueous organic composite resin emulsions of Examples 1 and 2 of the present invention. The product had excellent coating performance. On the other hand, Comparative Examples 1 and 2, which did not use the silyl group-containing organic compound as the component (b),
The frost resistance, hot water resistance, etc. were poor.

[0031]

[Table 1] Example 1 Comparative Example 1 2 1 2 Appearance Good Good Good Good Hardness 2H 2H 2H 2H Frost damage resistance ◎ ◎ × × Hot water resistance ○ ○ △ △ Stain resistance ◎ ◎ ◎ ◎ Weather resistance ○ ○ ○ ○ Solvent resistance ○ ○ ○ ○ Alkali resistance ○ ○ ○ △

The coating composition containing the aqueous organic-inorganic composite resin emulsion obtained by the method of the present invention forms a coating film having excellent frost damage resistance, hot water resistance, stain resistance, weather resistance and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 3/03 CFH C09D 183/14 3/075 CFH C08L 83:14 C09D 183/14 C08J 3/03 CFH / / C08L 83:14 (72) Inventor Hiroharu Sasaki 7-1414-46 Shimo-Nagata, Nishinasuno-machi, Nasu-gun, Tochigi Prefecture 4F075 CA18 CA32 CA44 EA13 EB42 4F070 AA60 AB08 AC12 AC46 CA03 CB01 CB13 4J035 GA02 HA03 LA08 LB01 4J038 CL001 DL031 DL081 DL111 GA01 GA03 GA06 GA08 GA15 HA156 KA02 NA03 NA04 NA05 NA11 NA12 NA14

Claims (2)

[Claims] (I) (a) Equation (1) (R ¹ ) _n Si
(OR ² ) _{4-n 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 one or both of the organosilane represented by the formula (1) and a partially hydrolyzed condensate thereof: (b) Formula (2): Wherein R ¹ and R ² have the same meaning as described above, and A is
(CH ₂ ) _m , where m is an integer of 1 to 8, and n is
0, 1 or 2. 1 to 240 parts by mass of a silyl group-containing organic compound represented by the formula: and (c) a hydrolyzable silyl group or a silyl group having a silicon atom bonded to a hydroxyl group, and an acid value of 20 to 150 mgKOH / g. A mixture comprising 5 to 200 parts by mass of a silyl group-containing vinyl resin of the formula (a), followed by a hydrolysis-condensation reaction, and then (ii)
A process for adding a neutralizing agent and water to the reaction product solution obtained in the step (i), wherein the method comprises the steps of: 2. A coating composition containing the organic-inorganic composite resin aqueous emulsion obtained in claim 1.