JP2009280709A - Resin composition for water-based stainproofing one-package coating and coating film prepared from the coating resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-based coating usable as a one-package coating and giving a coating film exhibiting excellent stainproofing property from an early stage after application. <P>SOLUTION: The resin composition for a water-based stainproofing one-package coating contains (A) a synthetic resin emulsion, (B) an organosilicate compound expressed by general formula (1) Si-(OR<SP>1</SP>)<SB>4</SB>(in the formula, R<SP>1</SP>groups may be the same or different and are each a univalent hydrocarbon group selected from a 1-10C alkyl group, an aryl group and an aralkyl group, provided that at least one of the R<SP>1</SP>groups is a 1-4C alkyl group) or its partial hydrolytic condensation product, and (C) an inclusion compound of a compound accelerating the hydrolysis and condensation of an alkoxysilyl group and a cyclodextrin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an aqueous one-component antifouling coating resin composition that exhibits sufficient stain resistance while being a one-component type, and a coating film obtained from the coating resin composition.

  In recent years, in the field of paints, from the viewpoint of pollution control or resource saving, attempts have been made to switch from using organic solvents to water-soluble or water-dispersed resins. However, water-based paints tended to be inferior in coating film performance compared to solvent-based paints. Under such circumstances, water-based paints are also required to have the same coating film properties as solvent-based paints, and in particular, it is required to provide high performance such as stain resistance.

  As a method for imparting stain resistance to a paint, a method of blending an organosilicate in the paint is known (Patent Document 1).

  By this method, the hydrophilicity of the formed coating film is improved, which is effective in preventing the adhesion of oily contaminants, and the adhered contaminants can be washed away with water droplets such as rain. However, when the above method is applied to an aqueous paint, there is a problem that the miscibility of the organosilicate into the aqueous paint is poor and the surface gloss is lowered.

  On the other hand, a method of adding a mixture of an organosilicate and an emulsifier is disclosed as a method for improving the miscibility of an organosilicate in an aqueous paint (Patent Document 2).

  By this method, the miscibility with water-based paints was improved, and the extreme reduction in surface gloss was solved. However, since it does not contain a catalyst component, it takes a considerable amount of time to obtain the hydrophilicity of the coating film. Therefore, it takes time to develop the desired low contamination, and there is a problem that the initial contamination cannot be obtained. It was.

On the other hand, although the technique which mix | blended the catalyst is also disclosed (patent document 3), this presupposes the use by a two-pack type.
Although the present application is a one-pack type water-based paint, a coating film having excellent stain resistance can be obtained from the initial stage of coating, and the performance can be maintained for a period worth using as a one-pack type. It is characterized by.
WO1994 / 06870 Publication Japanese Patent Laid-Open No. 10-17850 JP 2007-84777 A

  The problem to be solved by the present invention is to provide an aqueous coating material in which the obtained coating film has excellent stain resistance from the initial stage of coating, and the coating material can be used as a one-pack type.

  By adding an organosilicate compound or a partially hydrolyzed condensate thereof (hereinafter referred to as an organosilicate compound) or a compound that promotes hydrolysis / condensation of the alkoxysilyl group encapsulated in cyclodextrin to the aqueous paint, It has been found that the paint has excellent stain resistance and can be used as a one-pack type.

That is, this application
(I).
(A) Synthetic resin emulsion (B) Organosilicate compound represented by the general formula (1) or a partially hydrolyzed condensate thereof:
Si- (OR ¹ ) ₄ (1)
Wherein R ¹ is the same or different and is a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, at least one having 1 to 4 carbon atoms An alkyl group)
(C) An aqueous one-component antifouling coating resin composition containing an inclusion compound of cyclodextrin and a compound that promotes hydrolysis / condensation of alkoxysilyl groups,
(II).
(A) 0.1 to 100 parts by weight of component (B) and 0.05 to 50 parts by weight of component (C) are blended with respect to 100 parts by weight of component (I). Resin composition for paints,
(III).
(C) The coating composition according to (I) or (II), wherein the compound that promotes hydrolysis and condensation of the alkoxysilyl group in the component is an acidic phosphoric acid compound and / or an organic carboxylic acid compound Resin composition,
(IV).
(C) The compound that promotes hydrolysis / condensation of the alkoxysilyl group in the component is a neutralized salt of an acidic phosphoric acid compound and / or a neutralized salt of an organic carboxylic acid (I) or ( II) Resin composition for paints according to
(V).
(B) at least one of the alkyl groups of the component contains an alkyl group having 2 or more carbon atoms, (I) to (IV),
(VI).
(B) The resin composition for coatings according to any one of (I) to (V), wherein the component is blended in an emulsion state,
(VII).
(A) Component is an acrylic resin emulsion, The resin composition for coatings in any one of (I)-(VI) characterized by the above-mentioned,
(VIII).
(A) The resin composition for paints according to any one of (I) to (VII), wherein the component is an emulsion of an alkoxysilyl group-containing polymer,
(IX).
(A) The resin composition for coatings according to any one of (I) to (VIII), wherein the component is an emulsion of a polyoxyalkylene group-containing polymer,
(X).
A coating film obtained by applying the coating resin composition according to any one of (I) to (IX);
About.

The stain resistance-imparting composition of the present invention can be produced at a low cost with a simple operation. Moreover, the resin composition for aqueous | water-based one-pack type | mold stain resistance imparting coating material of this invention forms the coating film to which the outstanding stain resistance was provided from the coating initial stage. Furthermore, the performance can be maintained for a period worth using as a one-pack type.

  Hereinafter, the present invention will be described in detail based on an embodiment thereof.

(Synthetic resin emulsion (A))
Examples of the synthetic resin emulsion (A) that can be used in the present invention include various known synthetic resin emulsions, including acrylic resin emulsion, urethane resin emulsion, fluorine resin emulsion, epoxy resin emulsion, polyester resin emulsion, alkyd resin emulsion, Examples include, but are not limited to, melamine resin emulsions. These may be used alone or in combination of two or more. Among these, acrylic resin emulsion is advantageous because of its high cost and high degree of freedom in resin design.

  As the acrylic resin emulsion, those obtained by radical copolymerization of an acrylic monomer and a monomer copolymerizable with the acrylic monomer can be used.

  The monomer that can be used is not particularly limited, but specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, and benzyl. (Meth) acrylate, cyclohexyl acrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, etc. (Meth) acrylate monomers; aromatic hydrocarbon vinyl monomers such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene Vinyl compounds such as vinyl acetate and vinyl propionate; nitrile group-containing vinyl monomers such as (meth) acrylonitrile; epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; 2-hydroxypropyl (meta) ) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, hydroxystyrene, Aronics 5700 (manufactured by Toa Gosei Co., Ltd.), packageFA-1, packageFA-4, packageFM-1, packageFM-4 (or more, Daicel Chemical Co., Ltd.), HE-10, HE-20, HP-10, HP-20 (above, Nippon Shokubai Co., Ltd.), Bremer PEP series, Bremmer NKH-5050, Bremer GLM (above NOF ( Co., Ltd.), hydroxyl group-containing Hydroxyl group-containing vinyl monomers such as vinyl-modified hydroxyalkyl vinyl monomers; AS-6, AN-6, AA-6, AB-6, AK-5, etc., which are macromonomers manufactured by Toa Gosei Co., Ltd. A compound, vinyl methyl ether, propylene, butadiene, etc. are mentioned. In the present invention, (meth) acrylate represents acrylate and / or methacrylate.

  Furthermore, a hydrophilic vinyl monomer capable of improving the stability of the emulsion can also be used. Examples of the vinyl monomer having a hydrophilic group that can be used include sodium styrenesulfonate, sodium 2-sulfoethyl methacrylate, 2-sulfoethyl methacrylate ammonium, and vinyl monomers having a polyoxyalkylene chain.

  Although there is no limitation in the vinyl-type monomer which has a polyoxyalkylene chain, the acrylic acid ester or methacrylic acid ester which has a polyoxyalkylene chain is preferable.

  Specific examples of vinyl monomers having a polyoxyalkylene chain include NOF Corporation Bremer PE-90, PE-200, PE-350, AE-90, AE-200, AE-350, PP- 500, PP-800, PP-1000, AP-400, AP-550, AP-800, 700PEP-350B, 10PEP-550B, 55PET-400, 30PET-800, 55PET-800, 30PPT-800, 50PPT-800, 70PPT-800, PME-100, PME-200, PME-400, PME-1000, PME-4000, AME-400, 50POEP-800B, 50AOEP-800B, AEP, AET, APT, PLE, ALE, PSE, ASE, PKE, AKE, PNE, ANE, PNP, ANP PNEP-600, Kyoeisha Chemical Co., Ltd. light ester 130MA, 041MA, MTG, light acrylate EC-A, MTG-A, 130A, DPM-A, P-200A, NP-4EA, NP-8EA, EHDG-A, MA-30, MA-50, MA-100, MA-150, RMA-1120, RMA-564, RMA-568, RMA-506, MPG130-MA, Antox MS-60, MPG-130MA manufactured by Nippon Emulsifier Co., Ltd. , RMA-150M, RMA-300M, RMA-450M, RA-1020, RA-1120, RA-1820, Shin-Nakamura Chemical Co., Ltd. NK-ESTER M-20G, M-40G, M-90G, M- 230G, AMP-10G, AMP-20G, AMP-60G, AM-90G, LA, Sanyo (Ltd.) ELEMINOL such as RS-30, and the like. If such a monomer is used, water resistance and coating strength can be improved. The vinyl monomer having a polyoxyalkylene chain is desirably copolymerized using 0.5 to 20 parts by weight in 100 parts by weight of all monomers. If it is less than 0.5 part by weight, the effect of imparting water resistance is low, and if it exceeds 20 parts by weight, the antifoaming property is lowered, which is not preferable.

  Uses a monomer having two or more polymerizable unsaturated bonds such as polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triallyl cyanurate, allyl (meth) acrylate, divinylbenzene, diallyl phthalate It is also possible to do. In this case, the generated particles have a structure having cross-linking, and the water resistance of the formed coating film is improved.

  Moreover, trifluoro (meth) acrylate, pentafluoro (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, β- (perfluorooctyl) ethyl (meth) acrylate, etc. Fluorine-containing acrylic resin emulsions having high water and oil repellency can be prepared by using the above-mentioned fluorine-containing vinyl monomers.

  Moreover, a crosslinked acrylic resin emulsion in which a carbonyl group-containing vinyl monomer is copolymerized with the above monomer and a compound containing a hydrazine and / or hydrazide group is blended can also be produced. The water resistance of the coating film obtained from such a crosslinked acrylic resin emulsion is very good.

  Furthermore, an acrylic resin emulsion containing a hydrolyzable silyl group can be prepared by copolymerizing the monomer and a monomer having a hydrolyzable silyl group. As the monomer containing a hydrolyzable silyl group, an alkoxysilyl group-containing vinyl monomer is preferable from the viewpoint of ease of handling, cost, and the difficulty of producing a reaction byproduct.

  Specific examples of the vinyl monomer containing an alkoxysilyl group include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyltris (2-methoxyethoxy) silane, and vinyltriisopropoxysilane. , Γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltri-n-propoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, vinyltriacetoxysilane, β- (meth) acryloxyethyltrimethoxysilane, etc.These hydrolyzable silyl group-containing vinyl monomers may be used alone or in combination of two or more.

  Γ- (Meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ from the viewpoint of storage stability in the case of water-based paint -(Meth) acryloxypropyltri-n-propoxysilane and γ- (meth) acryloxypropyltriisopropoxysilane are particularly preferred.

  The hydrolyzable silyl group-containing monomer is desirably copolymerized using 0.1 to 50 parts by weight in 100 parts by weight of all monomers. If it is less than 0.1 parts by weight, the water resistance and durability are lowered, and if it exceeds 50 parts by weight, the emulsion becomes unstable, and 0.5 to 20 parts by weight is more preferable.

  The alkoxysilyl group-containing acrylic emulsion obtained as described above has a crosslinking reaction when the inclusion compound (C) of cyclodextrin and the compound that promotes hydrolysis / condensation of the alkoxysilyl group of the present invention is mixed. Progresses to a coating film with good water resistance and weather resistance.

  The acrylic resin emulsion that can be used in the present invention can be obtained by adopting a usual method, but an emulsion polymerization method is preferred in consideration of the particle size and stability of the emulsion.

  The emulsion polymerization method is not particularly limited, and can be appropriately selected from various emulsion polymerization methods such as a batch polymerization method, a monomer dropping polymerization method, and an emulsion monomer dropping polymerization method. In particular, in order to ensure the stability of the emulsion at the time of production, a monomer dropping polymerization method and an emulsion monomer dropping polymerization method are preferred.

  In emulsion polymerization, commonly used ionic or nonionic surfactants can be used.

  Examples of the ionic surfactant include an anionic surfactant having a polyoxyethylene chain such as polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene allyl ether sulfate, octylphenoxyethoxyethyl sulfonate, polyoxyethylene tridecyl ether sulfate, and the like. Sulfonic acid salts such as sodium lauryl sulfonate, sodium dodecylbenzene sulfonate and sodium isooctylbenzene sulfonate; ammonium salts such as imidazoline laurate and ammonium hydroxide are typical examples. An anionic surfactant having an oxyethylene chain is preferred.

  Examples of the nonionic surfactant include polyethylene glycol nonylphenyl ether; polyoxyethylenes such as polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl ether; L-77, L-720, L-5410, L Representative examples include nonionic surfactants containing silicone such as −7602 and L-7607 (manufactured by Union Carbide).

  In the present invention, it is preferable to use a reactive surfactant having a polymerizable double bond in one molecule as the surfactant in terms of water resistance and weather resistance. In particular, when a reactive surfactant having a polyoxyalkylene group in the molecule is used, the mechanical stability can be improved.

  Specific examples of such reactive surfactants include, for example, Adeka Soap ER-10, ER-20, ER-30, ER-40, SR-10, SR-20, SR-1025 manufactured by ADEKA Corporation, NE-10, NE-20, NE-30, NE-40, SE-10N), Nippon Emulsifier Co., Ltd. Antox-MS-60, RMA-1120, RMA-564, RMA-568, RMA-506, No. Aqualon KH-05, KH-10, RN-20, RN-30, RN-50, RN-2025, HS-10, HS-20, HS-1025, BC05, BC10, BC0515, manufactured by Ichi Kogyo Seiyaku Co., Ltd. BC1025, Sanyo Chemical Industries Co., Ltd. Eleminol JS-2, Eleminol RS-30, Kao Co., Ltd. Latemul S-180, S-180A, PD-104, PD 420, such as PD-430 and the like.

  Of these, non-alkylphenol-based ones are desirable in consideration of the environment.

  The surfactants can be used alone or in admixture of two or more, and the amount used is 10 parts by weight or less, preferably 0.5 to 8 parts by weight based on 100 parts by weight of the total amount of monomers. is there.

  The aqueous medium used for the emulsion polymerization only needs to contain water as an essential component, and may contain other organic solvents. Other organic solvents include water-soluble solvents such as alcohol solvents, ether solvents, ester solvents and ketone solvents, but it is better not to contain organic solvents from the viewpoint of emulsion stability and environment. preferable.

  Although there is no limitation in particular as a polymerization initiator, In order to perform superposition | polymerization more stably, it is desirable to use a redox system as a polymerization initiator. Further, in order to maintain the stability of the mixed solution during the polymerization and perform the polymerization stably, the temperature is 70 ° C. or lower, preferably 40 to 65 ° C., and the pH is preferably adjusted to 5 to 9.

  Examples of the initiator used in the redox system include potassium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, and the like. Examples thereof include acidic sodium sulfite, Rongalite, Bruggolite FF-6 (manufactured by Bruggamann Chemical US), thiourea dioxide, L-ascorbic acid and the like. In particular, a combination of an organic peroxide such as t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide and the like and Rongalite, Bruggolite FF-6 or thiourea dioxide is preferable.

  Note that the reducing agent is particularly preferably Bruggolite FF-6 or thiourea dioxide which does not generate formaldehyde in consideration of the environment.

  The amount of the polymerization initiator used is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomers. When the amount of the polymerization initiator used is less than 0.01 parts by weight, the polymerization may be difficult to proceed. When the amount exceeds 10 parts by weight, the molecular weight of the produced polymer tends to decrease. is there.

  In order to stably impart the catalytic activity of the polymerization initiator, a compound containing a divalent iron ion such as iron sulfate and a chelating agent such as disodium ethylenediaminetetraacetate may be used. The amount of the chelating agent used is 0.0001 to 1 part by weight, preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the total amount of monomers.

  Chain transfer agents can be added to control the molecular weight of the polymer. Known chain transfer agents such as n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, Examples include mercaptan compounds such as γ-mercaptopropylmethyldiethoxysilane, organic halides such as chloroform and carbon tetrachloride, sulfide benzene, isopropylbenzene, and ferric chloride.

  The resin solid content concentration in the acrylic resin emulsion is preferably 20 to 70% by weight, and more preferably 30 to 60% by weight. When the resin solid content concentration exceeds 70% by weight, the concentration of the system increases remarkably, making it difficult to remove the heat generated by the polymerization reaction or taking a long time to remove from the polymerization vessel. There is a tendency to become necessary. Further, when the resin solid content concentration is less than 20% by weight, there is no problem in terms of polymerization operation, but the amount of resin produced by one polymerization operation is small, which is disadvantageous in terms of economy.

  The acrylic resin emulsion used in the present invention preferably has an average particle size of about 0.02 to 1.0 μm. The average particle size can be adjusted by the amount of the emulsifier charged in the initial stage of polymerization.

  These acrylic resin emulsions are commercially available from various companies, for example, Dainippon Ink & Chemicals Co., Ltd. Boncoat, Watersol, Nippon Shokubai Co., Ltd. Acre Reset, Udouble, Showa High Polymer Co., Ltd. Polysol, Japan NS Co., Ltd. Yodosol, Kanebinol, Asahi Kasei Kogyo Co., Ltd. Polytron, Polydurex, Chuo Rika Kogyo Co., Ltd. Rikabond, Nippon Acrylic Co., Ltd. Primal, BASF Dispersion Co., Ltd., Acronal, Clariant Polymer ( Movinyl, Inc., Kaneka Zemrak, Kanevirak, Inc.

  Urethane resin emulsions include those in which urethane resin is dispersed in water, and those in which urethane resin is given a hydrophilic group and made self-dispersing, and those in which hydrophobic urethane resin is forcibly emulsified with an emulsifier, etc. Any of them can be used.

  These are commercially available from various companies. For example, Superflex 90, 107M, 110, 126, 130, 150, 150HS, 160, 300, 361, 370, 410, 420, 460, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 460S, 500, 600, E-2000, E-2500, E-4000, E-4500, E-4700, R-5000, Elastron BN-08, BN-11, BN-50D, NeoRez R-960 made by Avecia KK R-972, R-9637, R-9679, AX-311, R-966, R-967, R-9603, R-600, R-9320, R-9617, R-9621, NeoPac R-9000, R-9699, Takelac W-615, W-6010, W-6020, W-6 manufactured by Mitsui Takeda Chemical Co., Ltd. 061, W-511, W-405, W-7004, W-605, W-512A6, W-635, W-635C, WS-7000, WS-5000, WS-5070X, WS-4000, XW-75- Adekabon titer HUX-290H, HUX-290K, HUX-290N, HUX-395D, HUX-394, HUX-232, HUX-240, HUX-320, HUX-350, HUX-380, manufactured by ADEKA Corporation HUX-381, HUX-388, HUX-380A, HUX-386, HUX-401, HUX-750, HUX-670, HUX-680, HUX-575, HUX-580, and the like.

  The urethane resin emulsion can be used alone or in a mixed system with other resin emulsions. In particular, a mixed system with an acrylic resin emulsion is useful in terms of ease of coating design and cost.

  As the fluororesin emulsion, a dispersion of a fluoroolefin polymer and / or a copolymer of a monomer copolymerizable with the fluoroolefin in water can be used.

  Examples of the fluoroolefin include vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, pentafluoropropylene, hexafluoropropylene and the like.

  Monomers that can be copolymerized with fluoroolefins include olefins such as ethylene and propylene, vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether, butyl vinyl ester, octyl vinyl ester, vinyl acetate, and versatic acid. Vinyl esters such as vinyl (Japan Epoxy Resin Co., Ltd. Veova 10, Veova 9, Veova 11), aromatic vinyl compounds such as styrene and vinyl toluene, allyl ethers such as ethyl allyl ether, and allyl such as butyl allyl ester Examples thereof include compounds and (meth) acrylic acid esters.

  These are commercially available from various companies, and examples thereof include Lumiflon manufactured by Asahi Glass Co., Ltd., Zaffle manufactured by Daikin Industries, Ltd., Cefral Coat manufactured by Central Glass Co., Ltd., and Fluonate manufactured by Dainippon Ink & Chemicals, Inc.

  Among the synthetic resin emulsions described above, when the inclusion compound (C) of cyclodextrin and a compound that promotes hydrolysis / condensation of alkoxysilyl groups are mixed, the crosslinking reaction proceeds and the water resistance and weather resistance are improved. Since a good coating film is obtained, an alkoxysilyl group-containing acrylic emulsion is the best.

(Organosilicate compound (B))
The organosilicate compound (B) that can be used in the present invention is a compound containing a hydrolyzable silicon group, and is a compound represented by the following general formula (1) or a partially decomposed condensate thereof.

Si- (OR ¹ ) ₄ (1)
Wherein R ¹ is the same or different and is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, at least one of which is an alkyl group having 1 to 4 carbon atoms )

  Specific compounds include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane and the like The partial hydrolysis-condensation product can be illustrated.

  In the case where it is composed only of an alkyl group having 5 or more carbon atoms, the hydrolysis rate is extremely slow, and the desired hydrophilicity, that is, contamination resistance cannot be obtained, so that it has an alkyl group having 1 to 4 carbon atoms. Among them, ethyl silicate 45, ethyl silicate 40, ethyl silicate 48 (manufactured by Colcoat Co., Ltd.), silicate 45, and silicate 40 (manufactured by Tama Chemical Co., Ltd.) are preferable. The said compound may be single 1 type, and may use 2 or more types together.

  Organosilicates containing different alkoxysilyl groups in the same molecule can also be used. For example, methyl ethyl silicate, methyl propyl silicate, methyl butyl silicate, ethyl propyl silicate, propyl butyl silicate and the like. The ratio of these substituents can be arbitrarily changed between 0 to 100%. Moreover, although it described that the partial hydrolysis and condensate of these silicates can also be used, about 1-20 are preferable for a condensation degree. A more preferable range of the condensation degree is 3-15.

  In the organosilicate compound, compounds having 1 to 4 carbon atoms in the alkoxysilyl group are exemplified, but it is generally known that the reactivity improves as the carbon number decreases. When added to a water-based paint, when an organosilicate having a small carbon number, for example, methyl silicate, is used, the reactivity is high and the storage stability tends not to be sufficiently secured. For this reason, it is preferable that at least one carbon number of the alkyl group of the organosilicate compound to be used is 2 or more.

  The amount of the organosilicate compound (B) used is 0.1 to 100 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the synthetic resin emulsion (A). If it is less than 0.1 part by weight, the resulting coating film tends to have insufficient stain resistance, and if it exceeds 100 parts by weight, problems such as coating film appearance and cracks tend to occur.

(Emulsion of organosilicate compound (B))
The emulsion of the organosilicate compound (B) according to the present invention is obtained by emulsifying the organosilicate compound (B) in an aqueous medium using a surfactant. Examples of the emulsifier include commonly used anionic surfactants, nonionic surfactants, and cationic surfactants. Among them, in the present invention, it is preferable to use an anionic surfactant that is an alkali metal salt as an essential component because stability is further improved.

  Examples of the anionic surfactant include polyoxyethylene aryl ether sulfate such as polyoxyethylene nonyl phenyl ether sulfate, polyoxyethylene polycyclic phenyl ether sulfate, and polyoxyethylene alkyl ether sulfate such as polyoxyethylene tridecyl ether sulfate. Sulfate ester having polyoxyethylene chain; Sulfate ester such as lauryl sulfate; Sulfonic acid such as lauryl sulfonic acid, dodecylbenzene sulfonic acid, alkylnaphthalene sulfonic acid, alkyldiphenyl ether disulfonic acid; Di (2-ethylhexyl) sulfosuccinic acid, etc. Alkylsulfosuccinic acid; alkyl phosphate ester, polyoxyethylene alkyl ether phosphate ester, etc. Such as esters and salts thereof.

  Various neutralizing cationic species of the anionic surfactant can be selected. In the present invention, a surfactant using an alkali metal, preferably sodium or potassium ion is used. By selecting this neutralized cation species, the stability of the emulsion of the organosilicate compound can be improved.

  Among the above anionic surfactants, when an alkylsulfosuccinic acid type surfactant is used, the emulsion stability is improved, and both the storage stability of the composition and the appearance of the resulting coating film are improved. preferable. Specific examples of the alkylsulfosuccinic acid surfactants include New Emuls 290, 291 and 293 manufactured by Nippon Emulsifier Co., Ltd., Neocor SW-C, YSK, P manufactured by Daiichi Kogyo Seiyaku Co., Ltd., PELEX manufactured by Kao Corporation. CS and OT-P.

  Further, when an alkylsulfosuccinic acid surfactant is used in combination with a sulfate ester surfactant having a polyoxyethylene chain, the emulsion stability is further improved, which is preferable.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, etc. Those having a polyoxyethylene chain; those having a hydroxyl group such as sorbitan fatty acid ester and glycerin fatty acid ester; KF-351, KF-352, KF-353, KF-354, KF-355, manufactured by Shin-Etsu Chemical Co., Ltd. KF-615, KF-618, KF-945, KF-907, X-22-6008, X-22-811, X-22-812, SH3748, SH3749, SH3771, SH8400, SF manufactured by Toray Dow Corning 410, SF8700 and other silicone-based surfactants that are polyorganosiloxanes modified at one and / or both ends and / or side chains with polyalkylene oxide; acetylene glycol surfactants, polyvinyl alcohol, hydroxyethyl cellulose, acrylamide Examples thereof include water-soluble polymer systems such as polymers.

  These surfactants may be used alone or in combination of two or more. The usage-amount of an emulsifier is 0.05-100 weight part with respect to 100 weight part of organosilicate compounds (B), Preferably, it is 0.1-80 weight part. If it is less than 0.05 part by weight, a stable emulsion cannot be obtained, and the storage stability is also lowered. If it exceeds 100 parts by weight, the appearance and water resistance of the resulting coating film tend to decrease.

  The aqueous medium used for the emulsion of the organosilicate compound (B) only needs to contain water as an essential component, and may contain other organic solvents. Other organic solvents include water-soluble solvents such as alcohol solvents, ether solvents, ester solvents, and ketone solvents, but those that do not contain organic solvents from the viewpoint of emulsion stability and environment. Is preferred.

  The emulsion of the organosilicate compound (B) preferably has a pH of 6-10. Outside this range, the silicon compound tends to hydrolyze. At pH 6 or lower, hydrolysis is promoted, so that the subsequent condensation reaction also proceeds gradually, and the storage stability tends not to be maintained. Moreover, when pH10 is exceeded, not only an emulsion will become unstable, but the problem on operation will also arise.

  The method or order for adjusting and maintaining the pH is not particularly limited, but it is preferably performed from the time of preparation of the emulsion. The acid used to adjust the pH, the base, and the buffer used to maintain the pH are not particularly limited as long as they are generally used. Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; Examples of buffers such as ammonia and organic amines include carbonates such as sodium hydrogen carbonate and disodium hydrogen phosphate, phosphates, and carboxylates. Among these pH adjusters and buffering agents, those containing an alkali metal are preferred, and the use of sodium bicarbonate is more preferred.

  The solid content concentration of the organosilicate compound in the emulsion is preferably 5 to 60% by weight, more preferably 10 to 40% by weight. If the solid content concentration exceeds 60% by weight, the viscosity of the emulsion may increase, and problems such as impaired emulsion stability may occur. If it is less than 5% by weight, the resulting coating film This is disadvantageous in terms of coating workability and coating film performance degradation, such as a reduced thickness.

  Preparation of the emulsion of the organosilicate compound is carried out by emulsifying the above components and the aqueous medium by a general emulsification method. As an emulsification method, an organosilicate compound and a surfactant are mixed, water is slowly added thereto, and the water-in-oil emulsion is phase-inverted from an oil-in-water emulsion, so-called phase inversion emulsification method; Examples thereof include a method of mechanically finely dispersing with a disper, a high-pressure homogenizer or the like after mixing or after preliminary emulsification.

(Compound (C) that promotes hydrolysis and condensation of alkoxysilyl group)
In the present invention, a compound that promotes hydrolysis and condensation of an alkoxysilyl group is used as an inclusion compound (C) with cyclodextrin. It is known that cyclodextrins have a cyclic structure, and there are pores in the cyclic structure that do not have a hydroxyl group and can include small compounds, and therefore can include lipophilic compounds. Also, it is known that the compound encapsulated in cyclodextrin remains encapsulated in cyclodextrin when the system is hydrophilic, but is gradually encapsulated and released from cyclodextrin when the system becomes lipophilic. Yes. A compound that promotes hydrolysis / condensation of alkoxysilyl groups is included in cyclodextrin, so that when the system is hydrophilic (during storage and before coating), it does not accelerate the reaction. However, when the system becomes lipophilic (after coating), it is gradually wrapped to promote the reaction. For this reason, the reaction of the coating composition of the present invention does not proceed during storage and before coating, but the reaction proceeds after coating and can provide an excellent coating film derived from organosilicate.

  The inclusion compound (C) of the cyclodextrin and the compound that promotes hydrolysis / condensation of alkoxysilyl groups may be obtained as an aqueous solution or as a crystalline product. It doesn't matter.

  Component (C) can be blended in an amount of 0.05 to 50 parts by weight, preferably 0.05 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, per 100 parts by weight of organosilicate compound (B). It is. When the blending amount is less than 0.05 parts by weight, the effect of imparting stain resistance is low, and when it exceeds 50 parts by weight, the stability of the blend decreases. Further, when added to an aqueous paint, the amount of cyclodextrin increases, and the water resistance and weather resistance of the coating film tend to decrease.

  Cyclodextrins are available in α-type, β-type, γ-type, δ-type, and ε-type depending on the number of cyclized glucose, and those that are substituted with hydroxypropyl group, methyl group, acetyl group, etc. are also commercially available. ing. Although there is no restriction | limiting in the cyclodextrin which can be used this time, α-type, β-type, γ-type cyclodextrin, hydroxypropyl-β-cyclodextrin, and methyl-β-cyclodextrin are preferable from the viewpoint of availability and price. In addition, α-type and γ-type cyclodextrins are preferable because of their high solubility in water and easy synthesis of clathrate compounds.

  Examples of the compound that promotes hydrolysis / condensation of alkoxysilyl groups usable in the present invention include acidic phosphoric acid compounds, organic carboxylic acid compounds, organic sulfonic acid compounds, amine compounds, titanium compounds such as tetrapropyl titanate, and dibutyltin dilaurate. Organic tin compounds such as aluminum tris (acetylacetonate), zirconium compounds such as zirconium tetrakis (acetylacetonate), metal alkoxides such as tetrabutoxyhafnium, and the above acidic phosphate compounds, organic carboxylic acids And neutralized salts of acidic compounds such as compounds and organic sulfonic acid compounds. Among these, acidic phosphoric acid compounds, organic carboxylic acid compounds, neutralized salts of acidic phosphoric acid compounds, and neutralized salts of organic carboxylic acid compounds are preferable. In general, an organotin compound known as a compound that promotes hydrolysis / condensation of the alkoxysilyl group is not preferable because it is often difficult to ensure storage stability while providing sufficient functionality even after inclusion. .

  Examples of the acidic phosphorus compound include phosphorus-containing acidic compounds that do not have a polyoxyalkylene structure. Examples of such acidic phosphorus compounds include phosphoric acid, acidic phosphoric acid ester, phosphonic acid or acidic phosphonic acid ester represented by the general formula (2), acidic phosphoric acid group-containing polymers, condensates thereof, these Partially neutralized salts, completely neutralized salts and the like can be mentioned.

Q
‖
R ² _m (R ³ Q) _n P (QH) _3-mn (2)

(In the above formula, R ² and R ³ are an alkyl group having 12 or less carbon atoms, an alkylene group or an aralkyl group, Q represents an oxygen or sulfur atom, m and n are 0 to 2 and m + n is 2 or less. R ² or R ³ may be the same or different when m or n is 2. The preferred lower limit of the number of carbon atoms of R ² and R ³ is 4, more preferably 6, more preferably 8, and a preferable upper limit value is 12, more preferably 10, and most preferably 8 to 10 carbon atoms.

  Examples of such acidic phosphoric acid compounds include inorganic phosphoric acid compounds such as phosphoric acid, metaphosphoric acid, pyrophosphoric acid; monopropyl phosphate, mono-isopropyl phosphate, monobutyl phosphate, mono- (2-ethylhexyl) phosphate, mono Octyl phosphate, monodecyl phosphate, monoisodecyl phosphate, monolauryl phosphate, mono- (methacryloxyethyl) phosphate, mono- (acryloxyethyl) phosphate dimethyl phosphate, diethyl phosphate, dipropyl phosphate, di-isopropyl phosphate, dibutyl phosphate , Di- (2-ethylhexyl) phosphate, di- (2-ethylhexyl) dithiophosphate, dioctyl phosphate, didecyl phosphate, dii Acid phosphate esters such as decyl phosphate, dilauryl phosphate, di- (methacryloxyethyl) phosphate, di- (acryloxyethyl) phosphate; phosphones such as phenylphosphonic acid, 2-ethylhexylphosphonic acid mono (2-ethylhexyl) ester Acid or acidic phosphonic acid ester; reaction product of phosphoric acid or acidic phosphoric acid ester and polyvalent epoxide such as bisphenol A type epoxy resin, copolymer of mono- (methacryloxyethyl) phosphate and other vinyl monomers, etc. Examples thereof include an acidic phosphate group-containing polymer. Among these, phosphates having a medium-chain alkyl group are preferable, and specifically, di- (2-ethylhexyl) phosphate and mono- (2-ethylhexyl) phosphate are easily included and are preferable because they are economical. .

  On the other hand, specific examples of organic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, octylic acid, 2-ethylhexanoic acid, neodecanoic acid, decanoic acid, dodecanoic acid, benzoic acid, phthalic acid, There are fumaric acid, maleic acid, succinic acid, itaconic acid and their anhydrides. Among these, carboxylic acids having a medium-chain alkyl group are preferable. Specifically, 2-ethylhexanoic acid, neodecanoic acid, and decanoic acid have a high ability to promote hydrolysis and condensation, are easily included, and are economical. Therefore, it is preferable.

  The usage-amount of the compound which accelerates | stimulates hydrolysis / condensation of an alkoxy silyl group can be represented by the equivalent ratio at the time of manufacturing an inclusion compound (C) with a cyclodextrin. It is preferable to prepare a clathrate compound (C) by charging 0.2 mol equivalent or more and 1.5 mol equivalent or less of a compound that promotes hydrolysis / condensation with respect to 1 mol equivalent of cyclodextrin. If it is less than 0.2 molar equivalent, the amount of the compound that promotes hydrolysis / condensation is small, and a large amount of non-inclusion cyclodextrin remains, which is not economical. On the other hand, if it exceeds 1.5 molar equivalents, a compound that promotes hydrolysis / condensation that is not clathrated may be formed, which is not preferable because the storage stability of the coating composition decreases.

  In addition, as a basic compound for forming a neutralized salt, alkali metal hydroxides or carbonates such as lithium, sodium, potassium, cesium; alkaline earth metal hydroxides such as calcium, magnesium, barium , Oxides or carbonates; transition metal salts such as aluminum, zinc, titanium; ammonia; trimethylamine, diethylamine, triethylamine, propylamine, tripropylamine, dibutylamine, amylamine, 1-aminooctane, 2-aminoethanol, 2- Dimethylaminoethanol, ethylaminoethanol, 2-diethylaminoethanol, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, 1-dimethylamino-2-propanol, 3-dimethylamino 1-propanol, 2-propyl-aminoethanol, diethanolamine, ethoxy propylamine, aminobenzyl alcohol, morpholine, N- methylmorpholine, and organic amines DBU and the like. Among these, ammonia is preferable because it is easy to clean and economical.

  The usage-amount of the basic compound for forming a neutralization salt can be represented by the equivalent ratio at the time of manufacturing an inclusion compound (C) with a cyclodextrin. It is preferable to use 1 mol equivalent or less with respect to 1 mol equivalent of the charged amount of the compound that promotes hydrolysis / condensation of the alkoxysilyl group. If it exceeds 1 molar equivalent, a free basic compound will be present, which accelerates the reaction of the silicon compound (B) and makes it impossible to obtain the desired contamination resistance.

  The method for producing the inclusion compound (C) of a cyclodextrin with a compound that promotes hydrolysis / condensation of alkoxysilyl groups is not particularly limited. For example, hydrolysis / condensation is promoted in an aqueous solution in which cyclodextrin is dissolved. There is a method in which the compound to be added is added and stirred, and the resulting precipitate is washed by filtration and dried. Further, when no precipitate is formed, the aqueous solution may be used as it is without washing by filtration.

  Although said aqueous solvent is not specifically limited, What is necessary is just to contain water, and you may contain the other organic solvent. Other organic solvents include alcohols such as methanol, ethanol and isopropanol, ethers such as diethyl ether and diisopropyl ether, esters such as ethyl acetate and methyl acetate, halogenated hydrocarbons such as chloroform and methylene chloride, dimethyl Although amides such as formamide and dimethylacetamide can be mentioned, it is preferable not to contain them.

  The concentration of the aqueous solution of cyclodextrin is preferably set below the solubility at the target temperature because the solubility in water varies greatly depending on the ring structure such as α-type, β-type and γ-type and its substituents. Above the solubility, it is not economical because insoluble cyclodextrins that do not contribute to inclusion are present.

  The temperature and stirring conditions for preparing the aqueous solution of cyclodextrin are not particularly limited. The preparation temperature is preferably 0 ° C. or higher and 100 ° C. or lower, and more preferably 20 ° C. or higher and 60 ° C. or lower. Moreover, if an appropriate solvent and solvent amount are selected, it can be dissolved at room temperature, and room temperature is most preferred. The stirring speed and time are not particularly limited, and stirring is preferably performed at a stirring speed of 50 rpm to 1000 rpm. Stirring may be performed until the cyclodextrin is completely dissolved, and stirring is preferably performed for 3 minutes to 60 minutes.

  A method for adding a compound that promotes hydrolysis / condensation to an aqueous solution in which cyclodextrin is dissolved is not particularly limited. However, when the compound that promotes hydrolysis / condensation is liquid, it is preferably dropped as it is. If the compound that promotes hydrolysis / condensation is a solid, it may be added as it is, but it may be added to the cyclodextrin aqueous solution after dissolving the solid in a good solvent in advance. This is preferable because the amount of can be reduced.

  Compound that promotes hydrolysis / condensation in cyclodextrin solution when neutralization salt of acidic phosphoric acid compound and / or neutralization salt of organic carboxylic acid is used as compound that promotes hydrolysis / condensation of alkoxysilyl group It is preferable to add a basic compound for forming a neutralized salt and to stir after the inclusion compound is prepared. It is not preferable to add a basic compound before adding a compound that promotes hydrolysis / condensation, because the inclusion of the compound that promotes hydrolysis / condensation is hindered and affects the storage stability of the coating composition.

  Stirring conditions after adding the compound that promotes hydrolysis / condensation of the alkoxysilyl group or the compound that promotes hydrolysis / condensation of the alkoxysilyl group and the basic compound are not particularly limited, but are 0 ° C. or more and 100 ° C. The following is preferable, 20 ° C to 60 ° C is more preferable, and room temperature is most preferable. Further, the stirring speed and time are not particularly limited, and it is preferable to stir for 3 minutes to 60 minutes at a stirring speed of 50 rpm to 1000 rpm.

  A method for filtering and washing the produced precipitate is not particularly limited, and may be performed by a known method. For example, a method of filtering using a filter paper or a suction funnel and washing the precipitate with water, a method of centrifuging, discarding the supernatant, adding new water, centrifuging and washing, and the like can be mentioned.

  A method for drying the washed precipitate is not particularly limited, and may be a known drying method, and examples thereof include a method using a normal dryer or a vacuum dryer. Since the clathrate compound (C) may be decomposed when heated, it is preferably dried under reduced pressure at room temperature.

  Regarding the blending form of the resin composition for aqueous one-component paints of the present invention, it is not necessary to separate the main agent and the curing agent, the emulsion of the synthetic resin emulsion (A) and the organosilicate compound (B), the hydrolysis of the alkoxysilyl group. A one-pack type blending form in which an inclusion compound (C) of a compound that promotes decomposition / condensation and cyclodextrin is mixed is possible. The storage stability of the resin composition for aqueous one-component paints of the present invention is good, and it is stable at 40 ° C. for one month in a state where the component (A), the emulsion of the component (B), and the component (C) are mixed. The physical properties of the coating film do not deteriorate.

  If necessary, pigments that are usually used in paints (white pigments such as titanium dioxide, calcium carbonate, barium carbonate, kaolin, and colored pigments such as carbon, bengara, and cyanine blue) are used in the synthetic resin emulsion that can be used in the present invention. Can be used. Titanium dioxide is the most used and important among the pigments. Gloss and weather resistance are improved by using titanium dioxide surface-treated with alumina or zirconia. Also for ordinary coatings such as film-forming aids, colloidal silica, plasticizers, solvents, dispersants, thickeners, antifoaming agents, antiseptics, fungicides, algaeproofing agents, ultraviolet absorbers, light stabilizers, etc. Additives used as ingredients can also be blended.

  The water-based paint imparted with stain resistance of the present invention is, for example, for interior and exterior of buildings, for direct coating of metals such as aluminum and stainless steel, slate, concrete, roof tile, mortar, gypsum board, asbestos slate, asbestos board, precast concrete, lightweight It is used as a paint or top treatment for ceramic materials such as cellular concrete, calcium oxalate plates, tiles and bricks, glass, natural marble, granite and other stone materials.

  In addition to direct coating, water-based or solvent-based primer, acrylic rubber, multi-layer finishing top coat, flexible top finishing coating, concrete-based inorganic base materials such as concrete Alternatively, it can be used for coating on a solvent-based permeable water absorption preventing material.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto.

(Production Example 1 of Acrylic Resin Emulsion)
Into a reaction vessel equipped with a stirrer, reflux condenser, nitrogen gas introduction tube and dropping funnel, 41.7 parts by weight of deionized water as an initial charge, Neocor P (Daiichi Kogyo Seiyaku Co., Ltd .: 75% active ingredient) 0.08 weight part, 0.25 weight part of 5% sodium hydrogencarbonate aqueous solution was prepared, and it heated up at 50 degreeC, introduce | transducing nitrogen gas. After the temperature rise, 0.5 parts by weight of 7% t-butyl hydroperoxide aqueous solution, 0.27 parts by weight of 20% Bruggolite FF-6 aqueous solution, 0.10% ferrous sulfate and heptahydrate and 0.40% Add 0.35 parts of a mixed aqueous solution of ethylenediaminetetraacetic acid disodium and add 1.0 part by weight of Neocor P as the first part and 50 parts by weight of the monomer mixture shown in the (Em-1) core part of Table 1 as the first stage. A monomer emulsion obtained by adding 0.8 parts by weight of ER-20 (manufactured by ADEKA: 75% active ingredient) and 20.0 parts by weight of deionized water and emulsifying the mixture was added at a constant rate over 260 minutes. Meanwhile, 0.55 parts by weight of 7% t-butyl hydroperoxide aqueous solution and 0.43 parts by weight of 2.5% Bruggolite FF-6 aqueous solution were added in three portions. Polymerization was performed after 1 hour after the addition of the monomer emulsion was completed.

  Further, 0.15 parts by weight of 7% t-butyl hydroperoxide aqueous solution, 0.55 parts by weight of 2.5% Bruggolite FF-6 aqueous solution, and 0.40% with 0.10% ferrous sulfate heptahydrate. Add 0.35 parts of a mixed aqueous solution of ethylenediaminetetraacetic acid disodium, and in the second stage, add 50 parts by weight of the monomer mixture shown in the shell part of Table 1 (Em-1) to 1.0 part by weight of Neocol P -20 0.2 parts by weight and deionized water 20.0 parts by weight were added and the emulsified monomer emulsion was added at a constant rate over 200 minutes. Meanwhile, 0.6 part by weight of 7% t-butyl hydroperoxide aqueous solution and 0.85 part by weight of 2.5% Bruggolite FF-6 aqueous solution were added in four portions. After completion of the addition of the monomer emulsion, polymerization was carried out 1.5 hours later. After adding 5.5 parts of 5% aqueous sodium hydrogen carbonate solution to the resulting emulsion, the solid part was adjusted to 50% with deionized water to obtain an acrylic resin emulsion (Em-1).

(Production Example 2 of Acrylic Resin Emulsion)
In the same manner as in Production Example 1 except that each monomer in the core part and shell part in Production Example 1 is changed to (Em-2) in Table 1, the initial charge surfactant and the surfactant for monomer emulsification are active ingredients. The surfactant was changed to the surfactant shown in Table 1 so as to have the same weight, and the amount of deionized water used was adjusted to obtain an acrylic resin emulsion (Em-2) having a resin solid content of 50% by weight.

Methacrylate 100: Polyoxyethylene chain-containing hydrophilic vinyl monomer (Nippon Emulsifier Co., Ltd.)
BLEMMER PE200: Polyoxyethylene chain-containing hydrophilic vinyl monomer (manufactured by NOF Corporation)
(Creation of paint)
Using the synthesized resin emulsion, paints were prepared using the pigment paste of Table 2 with the formulation (parts by weight) shown in Table 3 (AS-1 and 2).

(Method for producing organosilicate emulsion: Production Examples 1 to 3)
In a container equipped with a stirrer, a reflux condenser, and a dropping funnel, 30 parts by weight of an organosilicate compound shown in Table 4 and Neocor SW-C (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient 70%, sodium dialkylsulfosuccinate) ) 10 parts by weight, Hytenol XJ-630S (Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient 30%, polyoxyalkylene decyl ether sulfate sodium salt) is mixed and mixed with deionized water while stirring. 55 parts by weight were dropped to obtain an emulsion (B-1) of an organosilicate compound having an effective solid content concentration of 30%. It was confirmed visually that there was no separation / sedimentation.

  Similarly, emulsions (B-2 and 3) of organosilicate compounds having an effective solid content concentration of 30% were obtained.

Silicate 40: Ethyl silicate partially hydrolyzed condensate (silica residual ratio 40%) (manufactured by Tama Chemical Co., Ltd.)
Silicate 45: ethyl silicate partial hydrolysis condensate (silica residual ratio 45%) (manufactured by Tama Chemical Co., Ltd.)
Neugen GIS320: PEG-20 glycerin triisostearate (active ingredient 100%) (Daiichi Kogyo Seiyaku Co., Ltd.)

(Method for producing cyclodextrin inclusion compound: Production Examples 1 to 3)
As shown in Table 5, cyclodextrin was weighed in a container equipped with a stirrer, a reflux condenser, and a dropping funnel, and pure water was added and stirred to obtain a solution. Furthermore, the compound which accelerates | stimulates hydrolysis and condensation of an alkoxy silyl group was dripped and stirred, and the precipitation product was obtained. The resulting precipitated product was filtered off, the remaining cyclodextrin was removed by washing with water, and further dried under reduced pressure to obtain the desired clathrate compounds (C-1 and 3) in respective yields.

  In addition, 0.3 g of 28% aqueous ammonia was added to the clathrate compound (C-1) before filtration and stirred. After thorough stirring, a milky white solution was obtained. The obtained milky white clathrate-containing aqueous solution was defined as (C-2).

A-208: Di- (2-ethylhexyl) phosphate (manufactured by Sakai Chemical Co., Ltd.)

(Evaluation of the physical properties)
-Coating-film preparation Each component shown in Table 6 was mix | blended in order, and it stirred for 5 minutes at 1000 rpm, and created the composition for one-pack type stain resistance imparting coating materials. One-component paint after 3 hours of preparation and after storage for 1 month at 40 ° C. in a sealed state was applied to a glass plate with a 6 mil applicator and cured at room temperature for 7 days. Then, the water contact angle of the coating film was measured after being immersed in water for 14 days and dried at room temperature. The results are shown in Table 6.

  In addition, after the storage of the comparative example 1, the viscosity increase of the coating material was not large and it did not come to paint.

-Measurement of water contact angle of coating film Using Kyowa Interface Science Co., Ltd. contact angle measuring machine CA-S150, the contact angle of pure water was measured. The lower the value, the higher the surface hydrophilicity and the better the stain resistance. If it is 70 ° or less, the effect of the stain resistance in the actual outdoor exposure test tends to be remarkable. In particular, the value after water immersion assumes the state after rain, and this low value tends to have a high durability and long-lasting surface hydrophilic property, and a long-term antifouling effect tends to be prominent. is there.

  In Examples 1 to 5, the water contact angle after water immersion in a white enamel coating film after storing the one-pack type aqueous coating composition at 40 ° C. for 1 month is 66 ° to 70 °, and an actual outdoor exposure test In this case, the surface hydrophilicity value, which is considered to have a stain resistance effect, was satisfied even after storage.

  On the other hand, in Comparative Example 1, although the initial contact angle was as good as 63 °, the viscosity of the paint increased during storage, and sufficient storage stability was not obtained.

  In Comparative Example 2, the initial contact angle was as good as 59 °, and the paint did not significantly thicken even after storage, but the water contact angle was 85 ° and sufficient hydrophilicity was not exhibited. .

As described above, the one-component aqueous coating composition of the present invention is confirmed to have good surface hydrophilicity and its storage stability, and provides a one-component aqueous coating that provides a coating film with excellent stain resistance. It was confirmed to be useful as a coating composition.

Claims (10)

(A) Synthetic resin emulsion (B) Organosilicate compound represented by the general formula (1) or a partially hydrolyzed condensate thereof:
Si- (OR ¹ ) ₄ (1)
Wherein R ¹ is the same or different and is a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, at least one having 1 to 4 carbon atoms An alkyl group)
(C) An aqueous one-component antifouling coating resin composition containing an inclusion compound of cyclodextrin and a compound that promotes hydrolysis / condensation of alkoxysilyl groups.   The component (B) is 0.1 to 100 parts by weight and the component (C) is 0.05 to 50 parts by weight with respect to 100 parts by weight of the component (A). Resin composition for paints.   The resin composition for paint according to claim 1 or 2, wherein the compound that promotes hydrolysis and condensation of the alkoxysilyl group in component (C) is an acidic phosphoric acid compound and / or an organic carboxylic acid compound. object.   3. The compound that promotes hydrolysis / condensation of alkoxysilyl groups in component (C) is a neutralized salt of an acidic phosphoric acid compound and / or a neutralized salt of an organic carboxylic acid. The resin composition for coatings according to 1.   (B) At least 1 of the alkyl group of a component contains a C2 or more alkyl group, The resin composition for coating materials in any one of Claim 1 to 4 characterized by the above-mentioned.   (B) Component is mix | blended in the state of an emulsion, The resin composition for coating materials in any one of Claim 1 to 5 characterized by the above-mentioned.   (A) Component is an acrylic resin emulsion, The resin composition for coating materials in any one of Claim 1 to 6 characterized by the above-mentioned.   (A) Component is the emulsion of an alkoxysilyl group containing polymer, The resin composition for coating materials in any one of Claim 1 to 7 characterized by the above-mentioned.   The resin composition for paints according to any one of claims 1 to 8, wherein the component (A) is an emulsion of a polyoxyalkylene group-containing polymer. The coating film obtained by apply | coating the resin composition for coating materials in any one of Claim 1 to 9.