JP2509841B2 - Reactive coating agent - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a reactive coating agent. More specifically, it relates to a reactive coating agent in which a component composed of a vinyl copolymer having a hydrolyzable silyl group is dispersed in an aqueous medium.

[0002]

2. Description of the Related Art Coating agents such as paints are shifting from solvent-based to emulsion-based from the viewpoints of low pollution, resource saving, and safety and hygiene. Among them, reactive type that enables improvement of physical properties such as water resistance. Research on resin emulsions is active. A resin emulsion having a hydrolyzable silyl group is known as one of the reactive resin emulsions. For example, in JP-A-61-9463, an organosilicon monomer having a polymerizable unsaturated group and a hydrolyzable group directly bonded to a silicon atom in the molecule: 0.1 to 40% by weight, carbon number of 1 to 18 (Meth) acrylic acid alkyl ester having 4 alkyl groups:
50-99.9% by weight and other polymerizable monomers: 0
Proposed a resin emulsion having a hydrolyzable silyl group for use as a coating agent for inorganic building materials, which has as an essential component an aqueous copolymer obtained by emulsion polymerization of a monomer mixture consisting of 40% by weight. ing.

[0003]

However, this emulsion was not practically satisfactory because the storage stability was not sufficiently satisfied. Especially when this emulsion was stored for a long period of time, the emulsion gelled, and the quality of the coating film obtained using this emulsion was significantly different from the quality of the initial coating film, so a stable quality coating film was obtained. There was a problem that I could not do it.

[0004]

Means for Solving the Problems The present inventors have proposed a coating agent in which a vinyl-based polymer having a hydrolyzable silyl group is dispersed in an aqueous medium, which has good long-term storage stability and stable quality. The present invention has been achieved as a result of earnest studies to obtain a coating agent which gives a coating film and has a rapid curing property after coating even at room temperature and which can be actually used. That is, in the present invention, the following (a) to (e) are essential constituent units, the (a) unit is 0.5 to 50% on a weight basis, and the (b) unit is 0.5.
.About.50%, (c) unit is 1 to 40%, (d) unit is 0.
5 to 30%, (e) unit is 30 to 90% [however, (a)
The total of the units (e) does not exceed 100%] is a reactive coating agent in which a component composed of a vinyl-based copolymer is dispersed in an aqueous medium. (A): Hydrolyzable silyl group-containing vinyl monomer (a1) and / or hydrolyzable silyl group- and vinyl group-containing oligomer (a2) (b): Aminimide group-containing vinyl monomer (a) c): Vinyl-based monomer having hydroxyl group (d): Vinyl-based monomer having ionic group or ion-forming group (e): (meth) acrylic acid alkyl ester (alkyl group having 1 to 5 carbon atoms)

A constituent component of the vinyl polymer (a)
Examples of the hydrolyzable silyl group in 1) and / or (a2) include a halogenosilyl group, an acyloxysilyl group, an amidosilyl group, an aminoxysilyl group, an alkenyloxysilyl group, an aminosilyl group, an oximesilyl group, an alkoxysilyl group, and thioalkoxy. Although there is a silyl group and the like, an alkoxysilyl group is preferable. Specific examples of the vinyl-based monomer having an alkoxysilyl group include vinylsilane [vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, etc.]; and (meth) acryloxyalkyl. Silane (γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltriethoxysilane, etc.) Can be mentioned. Specific examples of the oligomer having an alkoxysilyl group and a vinyl group include 1
An oligomer having at least one vinyl group and at least one alkoxysilyl group and selected from polyurethane, polyether, polyamide, epoxy resin or polyester can be mentioned. More specifically, JP-A-60-02602
No. 2 discloses a polyurethane-based oligomer having a vinyl group and an alkoxysilyl group [polycaprolactone triol (MW; 2,000) with NCO compound (1 mol) terminated with isophorone diisocyanate and 2-hydroxyethyl methacrylate (1 mol). ) And γ-aminopropyltrimethoxysilane (2 mol) and the like]; polypropylene glycol (MW; 4,000)
Polyether oligomer having one end OH esterified with (meth) acrylic acid and another end OH having a hydrolyzable silyl group by reaction with isocyanate propyltriethoxysilane; also polycaprolactone One end OH of diol (MW; 5,000) is esterified with (meth) acrylic acid to another end O
Polyester oligomer in which H is provided with a hydrolyzable silyl group by reaction with isocyanatepropyltriethoxysilane; polyamide system obtained by reacting polyamide and amino group-containing resin with glycidyl methacrylate and epoxy silane coupling agent Oligomer: An epoxy-based oligomer obtained by reacting an addition condensation product of bisphenol A and epichlorohydrin with an acrylamide and an amine-based silane coupling agent, and the like. Particularly preferable among those exemplified as (a) are (meth) acryloxyalkylsilanes, and polyurethane-based oligomers having a vinyl group and an alkoxysilyl group.

Examples of the vinyl monomer containing an amine imide group (b) include compounds represented by the following general formulas 1 and 2.

[0007]

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[In the formula, R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (methyl, ethyl, propyl, hexyl group, etc.), halogen (chloro, bromo, etc.) or cyano group,
R ₁ and R ₂ are a hydrogen atom, an alkyl group or an aryl group, R
₃ is an alkyl group or a hydroxyalkyl group, and X is an alkyl group, an aryl group or an aralkyl group. ]

[0009]

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[In the formula, R, R ₁ , R ₂ , R ₃ and X are the same as in the case of Chemical formula ₁ . m is 0 or 1. ]

Specific examples of the compound represented by the above general formula 1 include 1,1,1-trimethylamine methacrylimide, 1,1-dimethyl-1-ethylamine methacrylimide and 1,1-dimethyl-1- (2 -Hydroxypropyl) amine methacrylimide, 1,1-dimethyl-1
-(2'-phenyl-2'-hydroxyethyl) amine methacrylimide, 1,1-dimethyl-1- (2'-hydroxy-3'-phenoxypropyl) amine methacrylimide, 1,1,1-trimethylamine acrylimide Etc. Specific examples of the compound represented by the general formula 2 include compounds represented by the following chemical formulas 3 and 4, and the like.

[0012]

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[0013]

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The vinyl monomer having a hydroxyl group of (c) is not particularly limited as long as it is a vinyl monomer having a hydroxyl group, and specifically, for example, 2-hydroxyethyl (meth) acrylate, (meth) 2-hydroxypropyl acrylate,
Examples thereof include (meth) acrylic acid 3-hydroxypropyl and diethylene glycol (meth) acrylic acid monoester. Preferred is 2-hydroxyethyl (meth) acrylate.

Specific examples of the vinyl-based monomer having an ionic group or an ion-forming group (d) are those which impart cationicity: N, N-dimethylaminoethyl (meth) acrylate, ( Adds anionic properties such as N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium methosulfate. Materials: vinyl carboxylic acid [(meth) acrylic acid, ethacrylic acid, crotonic acid, sorbic acid, maleic acid, itaconic acid, cinnamic acid, etc.], vinyl sulfonic acid [vinyl sulfonic acid, allyl sulfonic acid, vinyl toluene sulfonic acid , Styrene sulfonic acid, etc.], ( ) Acrylic acid [(meth) sulfoethyl acrylate, (meth) acrylic acid sulfopropyl] include (meth) [such as 2-acrylamido-2-methylpropanesulfonic acid] acrylamide sulfonic acid. Preferred are N, N-dimethylaminoethyl (meth) acrylate and (meth) acrylic acid.

Specific examples of the (meth) acrylic acid ester having an alkyl group having 1 to 5 carbon atoms of (e) include methyl (meth) acrylate, ethyl (meth) acrylate, and n- (meth) acrylate. Examples include propyl, n-butyl (meth) acrylate, n-amyl (meth) acrylate and the like. Preferred are methyl (meth) acrylate and n-butyl (meth) acrylate.

In addition to (a) to (e), if necessary, other polymerizable monomers or oligomers exemplified in the following (a) to (l) may be used in combination. (A) alkyl (meth) acrylate (wherein the alkyl group has 6 to 30 carbon atoms) ester [2-ethylhexyl (meth) acrylate, n-lauryl (meth) acrylate, n-cetyl (meth) acrylate, ( (Meth) acrylic acid n-stearyl, (meth) acrylic acid n-oleyl, (meth)
Behenyl acrylate, etc.], etc.]; (b) Aromatic vinyl monomers (styrene, α-methylstyrene, α-chlorostyrene, etc.); (c) Halogenated vinyl monomers (vinyl chloride, etc.); (d) Alkyl or cycloalkyl vinyl ether (methyl vinyl ether, cyclohexyl vinyl ether, etc.); (e) vinyl ester (vinyl acetate, etc.); (f) nitrile group-containing monomer (acrylonitrile, etc.); (to) amide group-containing monomer [( (Meth) acrylamide,
Crotonamide, N-methylol acrylamide, fumaric acid diamide, etc.]; (H) Epoxy group-containing vinyl monomer [(meth) glycidyl acrylate, etc.]; (Re) Polysiloxane group-containing vinyl monomer {CH ₂ = CHCOO (CH ₂ ) ₃ [Si (CH ₃ ) ₂ O] _n Si (CH ₃ ) ₃ , CH ₂ = C (C
H ₃ ) COOC ₆ H ₄ [Si (CH ₃ ) ₂ O] _n Si (CH ₃ ) ₃ , CH ₂ = C (CH ₃ ) COO (CH
₂ ) ₃ [Si (CH ₃ ) ₂ O] _n Si (CH ₃ ) ₃ , CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ [Si
(CH ₃ ) (C ₆ H ₅ ) O] _n Si (CH ₃ ) ₃ , CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ [Si (C
₆ H ₅ ) ₂ O] _n Si (CH ₃ ) ₃ (n = 0 to 130 in each formula), etc .; (nu) a vinyl-based monomer having a perfluoroalkyl group having 3 to 30 carbon atoms [per (Meth) acrylic acid ester having a fluoroalkyl group: CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ OCOC (Me) = CH ₂ , CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ OCOCH =
CH ₂ , HCF ₂ (CF ₂ ) ₉ (CH ₂ ) ₂ OCOC (Me) = CH ₂ , H ₂ CF (CF ₂ ) ₉ (CH ₂ ) ₂ OCOCH = CH ₂ , C ₇ F ₁₅ CON (Et) (CH ₂ ) ₂ OCOC
(Me) = CH ₂ , C ₈ F ₁₇ SO ₂ N (Me) (CH ₂ ) ₂ OCOC (Me) = CH ₂ , C ₈ F _{17
SO 2 N (CH 2 CH 2} OCOCH = CH 2) 2 C 8 F 17 (CH 2) 11 OCOC (Me) = CH 2,
C ₈ F ₁₇ (CH ₂ ) ₁₁ OCOC (Me) = CH _{2 and the} like (in the above formula, Me represents a methyl group and Et represents an ethyl group); maleic acid mono- or diester having a perfluoroalkyl group: C ₈ F ₁₇ (CH ₂ )
₁₁ OCOCH = CHCOOMe, C ₈ F ₁₇ (CH ₂ ) ₁₁ OCOCH = CHCOOCH ₂ C ₇ F _15, etc .; vinyl ether or allyl ether having a perfluoroalkyl group: C ₇ F ₁₅ CH ₂ OCH = CH ₂ , C ₇ F ₁₅ CH ₂ OCH ₂
CH = CH ₂ etc .; vinyl sulfonic acid having a perfluoroalkyl group: C ₈ F ₁₇ SO ₂ NHCH ₂ SO ₂ CH = CH ₂ etc. (L) Polymerizable oligomer having vinyl group (Polyurethane, polyether, polyamide, epoxy resin, polyester, etc., in which one or more polymerizable double bonds are introduced, polycaprolactone diol and (meth) acrylic acid With ester, eg Praxel F
M-1, FM-5, FA-5 (manufactured by NOF CORPORATION), etc .: an ester of polyethylene glycol and (meth) acrylic acid,
For example, Bremmer PE-200, PE-350, PP-
300, PP-800 (manufactured by NOF CORPORATION): Reaction product of prepolymer of polytetramethylene glycol and isophorone diisocyanate (terminal OH) (1 mol) and isocyanate ethyl acrylate (1 mol): polyamide and (meth) acrylic Reaction product with acid ester: reaction product of epoxy resin and acrylic acid, etc.}.

The content of each structural unit in the vinyl copolymer is (a) usually 0.5 to 50% by weight, preferably 3 to
30% by weight, (b) is usually 0.5 to 50% by weight, preferably 1 to 30% by weight, particularly preferably 1.5 to 10% by weight, and (c) is usually 1 to 40% by weight, preferably 3 ~ 30
%, (D) is usually 0.5 to 30% by weight, preferably 1 to 20% by weight, and (e) is usually 30 to 90% by weight, preferably 50 to 80% by weight. However, (a) to (e)
The total unit does not exceed 100% by weight. (A)
If less than 0.5% by weight, the curability of the coating film becomes insufficient and the coating film performance such as water resistance becomes poor. If it exceeds 50% by weight, the storage stability of the aqueous dispersion becomes poor. (B) is 0.
If it is less than 5% by weight or less than 1% by weight of (c), the storage stability of the aqueous dispersion becomes poor and gelation occurs.
When (b) exceeds 50% by weight or (c) exceeds 40% by weight, there is no further effect of improving the storage stability, and since expensive chemicals such as amine imide are used, it is not practical in terms of price. Become. When the content of (d) is less than 0.5% by weight, the dispersibility of the water dispersion is insufficient and a good water dispersion cannot be obtained. If it exceeds 30% by weight, the performance of the coating film such as water resistance becomes poor. If (e) is less than 30% by weight, the performance of the coating film such as water resistance becomes poor, and if it exceeds 90% by weight, a stable aqueous dispersion cannot be obtained.

The method for producing the reactive coating agent of the present invention includes a method of solution polymerization to obtain the vinyl-based copolymer, followed by emulsion dispersion, and a method of emulsion polymerization to obtain the coating agent of the present invention. In the case of solution polymerization, there are a method of irradiating with an electron beam or an ultraviolet ray, a method of heating, and a method of using an initiator. A preferred polymerization method is a method using an initiator in an organic solvent. As the organic solvent used, alcohol (ethanol, isopropanol, n-butanol, etc.), aromatic hydrocarbon (toluene, xylene, etc.),
Aliphatic hydrocarbons (hexane, cyclohexane, etc.), aliphatic esters (ethyl acetate, n-butyl acetate, etc.), aliphatic ketones (acetone, methyl ethyl ketone, etc.), aliphatic ethers (dioxane, tetrahydrofuran, etc.)
Etc. and mixtures of two or more thereof. Preferred are isopropanol, toluene, methyl ethyl ketone alone or as a mixture of two or more thereof. A solvent having a lower boiling point is more preferable when the solvent is topping afterwards, and a water-soluble solvent is preferable when emulsifying and dispersing in the solution during the solution polymerization. The ratio of the organic solvent and the total weight of the monomers (a) to (e) can be arbitrarily selected, but the total amount of the organic solvent: monomers is usually 0.2: 2 to 2: 1 by weight ratio,
It is preferably 0.5: 1 to 5: 1.

In the method using an initiator, an azo compound [azobisisobutyronitrile, 2,
2'-azobis (2,4-dimethylvaleronitrile),
Azobiscyanovaleric acid, 2,2-azobis (2-amidinopropane) hydrochloride, 2,2-azobis (2-amidinopropane) acetate, etc.], inorganic peroxides [hydrogen peroxide, ammonium persulfate, potassium persulfate, persulfate] Sodium sulfate, etc., organic peroxides [benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide acid peroxide, di (2-ethoxyethyl) peroxydicarbonate] and redox catalysts [alkali metal sulfites] Salt or bisulfite, ammonium sulfite, L-ascorbic acid, erythorbic acid and other reducing agents and alkali metal persulfates, ammonium persulfate, peroxides and other oxidizing agents] and two or more thereof Can be given. The amount of the initiator added is usually 0.001 to 20%, preferably 0.1 to 10%, based on the total solid weight of the monomers (a) to (d).

In some cases, a chain transfer agent (n-lauryl mercaptan, n-dodecyl mercaptan, t-
Dodecyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.) can be added to control the molecular weight.

The reaction temperature of the polymerization reaction is usually 50 to 150.
C., preferably 70 to 130.degree. The reaction time is usually 1 to 10 hours, preferably 2 to 7 hours. The end point of the polymerization is the double bond absorption (16
It can be confirmed by the disappearance of 48 cm ⁻¹ ) or the reduction of unreacted monomer by using gas chromatography.

When the vinyl copolymer is obtained by solution polymerization, it is then emulsified to obtain the reactive coating agent of the present invention. Examples of this emulsification method include a method in which the solution is polymerized and then the solution is topped to emulsify the remaining resin, and a method in which water is added as it is to emulsify and then the solvent is topped. The solvent may or may not remain after the emulsification. It is preferable to emulsify in a solution state if possible. In this case, an emulsifier or a pH adjuster may be added to emulsify.
As the emulsifier, for example, an alkyl sulfate ester salt,
Anionic surfactants such as alkyl aryl sulfonates, alkyl phosphate ester salts or fatty acid salts, cationic surfactants such as alkyl amine salts, alkyl quaternary ammonium salts, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, Alternatively, a nonionic surfactant such as a pluronic type, an amphoteric surfactant such as a carboxylate type (amino acid type, betaine type) or a sulfonate type can be used in combination.

It is well known that when a cation-forming group is present, the addition of an acid improves the hydrophilicity and helps emulsification of the resin. Examples of the acid include organic or inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, lactic acid, (meth) acrylic acid, oxalic acid, citric acid, maleic acid, itaconic acid, and adipic acid. Can be
When an anion-forming group is present, addition of amine (ammonia, methylamine, dimethylamine, diethanolamine, dimethylaminoethanol, triethylamine, etc.) or alkali (KOH, NaOH, etc.) improves hydrophilicity and assists emulsification. The amine imide group is amphoteric and the hydrophilicity is improved by adding either acid or base. The amount of the acid or base added is usually 0.3 to 1.5 times the mol of the total mol of the amine imide group and the ion-forming group.

Further, in order to improve the cross-linking density of the coating film after curing and the adhesion to the substrate, silanes may be blended before emulsification and put into the micelle during emulsification. Specific examples of such silanes include methyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-butoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxy. Propyltrimethoxysilane, γ
-Aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, silicate and the like.

When emulsifying the resin solution as it is, these additives are added to the resin solution, and then water is gradually added to emulsify.
The lower the emulsification temperature, the better, but usually 70 ° C or lower, preferably 5
It is 0 ° C or lower. After that, it may be diluted with water as it is, or may be topped with a solvent. 8 toppings
It is preferably carried out under reduced pressure of 0 ° C. or lower. In this way, a water-dispersed resin composition is obtained.

When the aqueous dispersion of the present invention is obtained by emulsion polymerization, a method in which a polymerizable emulsifying agent is used and copolymerization is carried out together with the respective constituents in an aqueous medium is employed. As the initiator, the same one as in the case of solution polymerization can be used. During emulsion polymerization, other emulsifiers and pH adjusters may be used together. These may be the same as those in the emulsification described above. Further, for the purpose of stabilizing emulsion polymerization, a protective colloid agent such as partially saponified polyvinyl alcohol, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like can be used. As a polymerization method, any of a batch polymerization method and a continuous polymerization method can be used by a known polymerization method. Known polymerization methods include a batch charging method, a monomer addition method, and a monomer emulsion addition method. The polymerization temperature and the like may be the same as in the case of solution polymerization. As the polymerizable emulsifier used here, various conventionally known polymerizable emulsifiers can be used. Specifically, for example, a cationic group containing a (meth) allyl group or a (meth) acrylic group as a polymerizable group and a cationic group such as a quaternary ammonium salt, a tertiary amine salt or an amine imide group as an emulsifying functional group, or a sulfone Examples thereof include anionic salts such as acid salts and carboxylic acid salts, and nonionic salts such as ethylene oxide groups. The amount of polymerizable emulsifier is from (a) to
0.1 to 20% by weight of the total amount of (d), preferably 0.1.
It is 5 to 10% by weight.

The state of the aqueous dispersion thus obtained may be various states such as a solubilized state, an emulsion and a paste state, but any state may be used.

In the state of being dispersed in water, the silyl group is in the micelle and is blocked from water, so that the silyl group is stable. Condensation begins. The condensation mechanism of the hydrolyzable silyl group after the water has flown is as follows.

The reactive coating agent of the present invention may be the water dispersion thus obtained as it is, or various emulsions such as acrylic emulsion, urethane emulsion, epoxy emulsion and melamine or NCO group usually used as a curing agent. It may be a mixture of emulsions containing In addition, pigments usually added as paints, various additives (silyl group curing catalyst, ultraviolet absorber,
Antioxidant, heat resistance improver, leveling agent, anti-sagging agent, matting agent, etc.) may be contained. In this case, in order to improve the compatibility stability with the emulsion, it is desirable that it be in a water dispersion state.

As the pigment, an extender pigment (calcium carbonate,
Kaolin, talc, aluminum silicate, aerosil, etc.),
Inorganic pigments (titanium oxide, iron oxide, yellow lead, cadmium oxide, carbon black, aluminum flakes, etc.), organic pigments (azo, azo lake, phthalocyanine, quinacridone, isoindolinone organic pigments, etc.) To be It is desirable to use a pigment dispersed in water.

A curing catalyst may be used in combination to accelerate the curing of the hydrolyzable silyl group. As such a catalyst, those conventionally used can be used. Examples of such compounds include organic titanate-based compounds [isopropyl triisostearoyl titanate, isopropyl tri (dioctyl pyrophosphate) titanate, tetraisopropyl di (lauryl phosphite) titanate, etc.], organic aluminum-based compounds (acetoalkoxy aluminum diisopropyiate). ), Carboxylic acid-type tin compounds (tin dioctylate, dibutyltin dilaurate, dibutyltin malate, etc.), sulfide-type, mercaptide-type sulfur-containing organic tin compounds (dibutyltin sulfide, etc.), dialkyltin oxides (dibutyltin) Oxides, dioctyltin oxide, etc.) Other carboxylic acid metal salts (sodium acetate, zinc caproate, lead octylate, cobalt naphthenate, etc.), acid phosphates (monomethyl acidity) Acid ester, dimethyl acid phosphoric acid ester, diethyl acid phosphoric acid ester, monobutyl acid phosphoric acid ester, etc.), carboxylic acid and its acid anhydride (adipic acid, maleic acid, citric acid, itaconic acid, succinic acid, phthalic acid, Trimellitic acid, maleic anhydride,
Phthalic anhydride, etc.) Aminosilane (γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, etc.), amine and its salts (triethylamine,
Examples thereof include curing catalysts such as dibutylamine-2-hexoate, cyclic amidine and salts thereof, and quaternary ammonium salts (tetrabutylammonium hydroxide). Since an oily catalyst may destroy micelles, a water-soluble catalyst or a water-dispersed catalyst is preferable. These catalysts may be used alone or in combination of two or more. When using a catalyst, the amount added is usually based on the vinyl copolymer.
It is 0.001 to 20% by weight.

When the coating agent of the present invention is made into a paint, the method for making it into a paint is to add the components used for making the above-mentioned paints to the resin emulsion consisting of the vinyl copolymer in the usual manner. Mixing by stirring alone may be used, or a paint can be obtained by dispersing and mixing using a mixing device (ball mill, kneader, sand grinder, roll mill, flatstone mill, etc.).

Examples of the coating method of the coating agent of the present invention include brush coating, roll coating, spray coating, flow coating and dipping, and are not particularly limited.
After the application, the composition is left standing at room temperature or heated at 60 to 200 ° C. to be cured. Also, by heating above 130 ° C, the amine imide group is decomposed into amine and isocyanate,
The generated isocyanate reacts with active hydrogen to further improve the crosslink density and improve the physical properties of the coating film such as water resistance.

[0035]

The present invention will be further described with reference to the following examples.
The present invention is not limited to this.

Example 1 80 g of isopropanol was charged into a 300 ml four-necked Kolben and heated to 80 ° C. with stirring. Then, a mixed solution containing the components of the following formulation was added dropwise over 3 hours. [Formulation] γ-methacryloxypropyltrimethoxysilane (hereinafter MP silane) 15 g 1,1-dimethyl-1- (2-hydroxypropyl) amine methacrylimide (hereinafter AI) 3 g 2-hydroxyethyl acrylate (hereinafter HEA) 10 g Acrylic acid (AA) 7 g Methyl methacrylate (MMA) 40 g n-Butyl acrylate (BA) 25 g n-lauryl mercaptan (LM) 2 g Azobisisovaleronitrile (AIVN) 2 g Isopropanol (IPA) 20 g After the dropping was completed, the reaction was carried out at the same temperature for 2 hours, and then AIVN0.
An additional 3 g was added and the reaction was continued for another 2 hours. I like this
A 50% PA solution copolymer was obtained. In addition to this solution 20
After adding 3.2 g of ammonia water (28%) at -40 ° C and mixing well, 250 g of water is gradually added to form an aqueous dispersion. This aqueous dispersion was topped with IPA at 50 ° C. or lower under reduced pressure and finally prepared with water to obtain a coating agent [1] of the present invention having a solid content of 30%.

Production Example 1 100 ml of polycaprolactone triol (MW 2,000), 100 g of polycaprolactone diol (MW 1,000), 6.5 g of 2-hydroxyethyl methacrylate, and 121 g of n-propyl acetate were added to 500 ml of Kolben.
Was charged, and the atmosphere was replaced with nitrogen, and the temperature was raised to 80 ° C. to uniformly dissolve it.
After dropping 56 g of isophorone diisocyanate, 0.01 g of dioctyltin mercaptide was added and the reaction was carried out at the same temperature for 6 hours. After that, the temperature was lowered to 50 ° C. or lower, and then 17.9 g of γ-aminopropyltrimethoxysilane was added and reacted with the remaining NCO. NC at 2250 cm ^-1 of IR
After confirming that there is no O absorption, a urethane oligomer having an alkoxysilyl group and a vinyl group (solid content 70%, U
(Abbreviated as OG) was manufactured.

Examples 2 to 6 and Comparative Examples 1 and 2 Coating agents [2] to [6] of the present invention and comparative coating agents were prepared in the same manner as in Example 1 except that the formulations shown in Table 1 below were used. [7] to [9] were obtained.

[0039]

[Table 1]

The abbreviations used in Table 1 above represent the following compounds. BMA; n-butyl methacrylate CMA; n-cetyl methacrylate DMAPMA; N, N-dimethylaminoethyl methacrylamide UOG; polyurethane having hydrolyzable silyl groups and vinyl groups produced in Reference Production Example 1 (solid content 70% )

Test Examples 1 to 6 and Comparative Test Examples 1 and 2 The coating agents [1] to [6] of the present invention and the comparative coating agents [7] to [9] were dried on a glass plate or a slate plate to give a dry film of 20 μm. A test piece was prepared by applying the coating solution as described above and leaving it at room temperature for 1 week.Evaluation results of various physical properties immediately after the preparation are shown in Table 2. Also, each coating agent was stored at 50 ° C. for 1 month, and similarly. Table 3 below shows the results of physical property evaluation
Shown in

[0042]

[Table 2]

[0043]

[Table 3]

Note) The method of testing each evaluation item shown in Tables 2 and 3 above is shown below. Emulsion state: Observed with the naked eye. The state of sedimentation of particles was evaluated by ◯ Δ ×. Adhesion: Goto method, 2 mm square, 25 pieces of cellophane tape peeled. (Glass plate, slate plate) Hardness: Pencil hardness Uses Mitsubishi Uni-Pencil. (Glass plate) Water resistance: The state of the coating film (blister, whitening, etc.) after immersion in tap water at 25 ° C. for 1 week was visually observed. (Glass plate, slate plate) Solvent resistance: Spot test with toluene, the state of peeling was evaluated by ◯ Δx. (Glass plate)

[0045]

The reactive coating agent of the present invention has the following effects. (1) It can be put to practical use by forming a coating film by evaporating water and moisture-curing at room temperature. Curing can be accelerated by heating. (2) Despite being a moisture-curable resin, it has good storage stability in a water-dispersed state and can be used for a long period of time. Also, stable physical properties can be obtained even after long-term storage. (3) A film in which silyl groups are condensed and cured has excellent water resistance,
It exhibits physical properties such as heat resistance, acid resistance, solvent resistance, stain resistance, and weather resistance. (4) Good adhesion to various inorganic / organic substrates. By exhibiting the above effects, the reactive coating agent of the present invention is a coating agent at room temperature to under heating, for example, a paint,
It is useful in various applications such as coating agents, adhesives, primers and binders in a narrow sense. Specifically, for example, weather-resistant paints for building materials (for example, inorganic materials such as glass, slate, ceramics, metals such as aluminum, woodworking, plastics, etc.), acid rain resistant paints, antifouling paints, anticorrosion paints, etc. Water repellent for building materials (water absorption inhibitor), primer for inorganic building materials, electrodeposition paint, vehicle topcoat paint, vehicle repair paint, vehicle parts paint, hard coat agent, can coating agent, water-based rust preventive coating, water-based Release agent, coating agent for plastics (for example, coating agent for PVC sheet such as PVC desk mat and wallpaper coating for PVC), moisture-proof coating agent for electric and electronic parts,
Insulation coating agents, back coating agents for ink ribbons and magnetic tapes, binders for inks, release agents for information paper (for example, sublimation type thermal transfer paper), hard finishing agents / water repellents for fibers,
It is suitable as a treating agent for paper. Since it is water-based, it can be used in other fields where solvents cannot be used.

Claims (1)

(57) [Claims] 1. The following (a) to (e) are essential constitutional units, the (a) unit is 0.5 to 50%, the (b) unit is 0.5 to 50%, and the (c) unit is on a weight basis. Is 1 to 40%, (d)
A component composed of a vinyl-based copolymer having units of 0.5 to 30% and (e) units of 30 to 90% (however, the total of (a) to (e) units does not exceed 100%). A reactive coating agent in which is dispersed in an aqueous medium. (A): Hydrolyzable silyl group-containing vinyl monomer (a1) and / or hydrolyzable silyl group- and vinyl group-containing oligomer (a2) (b): Aminimide group-containing vinyl monomer (a) c): Vinyl-based monomer having hydroxyl group (d): Vinyl-based monomer having ionic group or ion-forming group (e): (meth) acrylic acid alkyl ester (alkyl group having 1 to 5 carbon atoms)