JP5205006B2 - COATING METHOD AND COATED PRODUCT USING CURABLE COMPOSITION - Google Patents

Description

  The present invention relates to various coatings for interior and exterior of buildings, roofs, ceramic building materials, automobiles, household appliances, plastics, etc., especially coatings composed of inorganic base materials, organic-inorganic composite coatings, ceramic-modified coatings and low-contamination coatings. The present invention relates to a curable composition used for coating a film, glass, ceramics, and tile, a paint using the same, and a coating method thereof.

  In recent years, paints characterized by high weather resistance and low contamination have been developed and are used in various places including building exterior materials. These paints use reactive silicon compounds or silicon resins as binders and modifiers to improve weather resistance and stain resistance, and include inorganic paints, organic-inorganic composite paints, ceramic-modified paints, low-contamination paints, etc. is called.

  Coating films formed from paints using these reactive silicon compounds and silicon resins (hereinafter referred to as inorganic paints) are generally hard, and when exposed outdoors for long periods of time, sunlight, rainfall, Or a crack may arise in a coating film by influences, such as a change of temperature or humidity, and repainting may be required.

  In addition to such long-term changes over time, repainting may be required due to problems such as dust, blisters, scratches, and color differences during painting.

  However, the paint used for repainting does not adhere to the coating film obtained from the inorganic paint, and repainting is very difficult.

  As means for solving these problems, solvent-based primer coatings having excellent adhesion to inorganic coating materials have been developed and are currently commercially available. However, from the viewpoint of toxicity, danger, odor, etc. possessed by organic solvents, it is strongly desired to make the undercoat paint water-based.

  In response to this requirement, an epoxy group-containing organosilane as a curing agent is added to a main agent composed of a self-emulsifying cationic aqueous dispersion having a hydroxyl group and an amino group, and an amino group of the cationic aqueous dispersion and an epoxy of the organosilane. There has been proposed an aqueous primer composition added so that the equivalent ratio of groups (amino group / epoxy group) is in the range of 0.5 to 2.0 (see Patent Document 1).

  However, since the aqueous dispersion obtained by the method described in the literature is cationic, there is a problem that there is a great restriction on the formulation of the paint.

Further, the obtained coating film has a high degree of yellowing, and there is a problem that a transparent coating (clear) specification is not possible.
JP 2002-256221 A

  The problem to be solved by the present invention is a curable composition showing sufficient adhesion to inorganic base materials such as glass, ceramics, tiles, etc., including coating films obtained from inorganic paints, and using the same It is to provide a paint and a method for painting the same.

  Furthermore, it is to provide a coating method using a curable composition that can be anionic or nonionic in an aqueous system and has a low degree of yellowing.

  The present inventors have good adhesion to an inorganic base material by using a curable composition comprising an alkoxysilyl group-containing synthetic resin emulsion, a substance that promotes hydrolysis / condensation of alkoxysilyl groups and an organosilicate. It was found that a simple paint can be produced. The present inventors also found out a coating method using this paint.

That is, the present invention includes (I) an alkoxysilyl group-containing synthetic resin emulsion, (II) a substance that promotes hydrolysis / condensation of alkoxysilyl groups, and (III) an organosilicate (a compound represented by the following general formula (1) and / Or its partially hydrolyzed condensate) and / or its modified product (RO) ₄ Si (general formula 1)
The present invention relates to a coating method in which a curable composition containing (wherein R is the same or different and an alkyl group having 1 to 4 carbon atoms) is applied to an inorganic substrate (claim 1).

  The curable composition further comprises (IV) a water-soluble and / or water-dispersible curing agent having a reactive functional group and a hydrophilic group in the molecule, (V) a secondary amino group-containing alkoxysilane compound, and a ketoimino group-containing alkoxy. The curable composition comprising one or more compounds selected from a reaction product of a silane compound, a primary amino group-containing alkoxysilane compound and an epoxy group-containing compound. The present invention relates to a coating method (claim 2).

  The said (I) alkoxysilyl group containing synthetic resin emulsion is an alkoxysilyl group containing acrylic emulsion, It is related with the coating method of any one of Claims 1-2 (Claim 3).

  (I) The alkoxysilyl group-containing synthetic resin emulsion is an emulsion containing 60% by weight or more of (meth) acrylic acid ester having an alkyl group and / or a cycloalkyl group having 4 or more carbon atoms in 100% by weight of the emulsion resin solid content. The present invention relates to the coating method according to any one of claims 1 to 3 (claim 4).

  The (I) alkoxysilyl group-containing synthetic resin emulsion is an emulsion containing 0.5 to 20% by weight of a vinyl monomer having a polyoxyalkylene unit in 100% by weight of the emulsion resin solid content. It is related with the coating method of any one (Claim 5).

The (I) alkoxysilyl group-containing synthetic resin emulsion has a core / shell structure, and R ¹ R ² _(3-n) SiX _n (general formula 2) in 100 parts by weight of the resin component constituting the shell part
(Wherein R ¹ is a monovalent organic group having a polymerizable double bond, R ² is an alkyl group having 1 to 4 carbon atoms, X is an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 2 or 3) 0.5-30 parts by weight of an organosilicon compound represented by
R ³ R ⁴ _(3-a) SiY _a (general formula 3) in 100 parts by weight of the resin component constituting the core part
(In the formula, R ³ is a monovalent organic group having a polymerizable double bond, R ⁴ is an alkyl group having 1 to 4 carbon atoms, Y is an alkoxy group having 1 to 4 carbon atoms, and a is a relationship of a <n. The present invention relates to a coating method according to any one of claims 1 to 5, characterized in that it contains 0 to 20 parts by weight of an organosilicon compound represented by the following formula:

  (II) The coating method according to any one of claims 1 to 6, wherein the substance that promotes hydrolysis / condensation of the alkoxysilyl group is an organotin compound (claim 7).

  The inorganic base material is at least one base material selected from the group consisting of inorganic paints, organic-inorganic composite paints, ceramic-modified paints, low-contamination paints, glass, ceramics, and tiles. The coating method according to any one of (1) to (8).

  The said curable composition is a water-based coating material, It is related with the coating method of any one of Claims 1-8 (Claim 9).

  The coating method according to any one of claims 1 to 9, wherein after the curable composition is applied to an inorganic base material, an intermediate coating and / or a top coating is further applied. 10).

  It is related with the coating material obtained by the coating method of any one of Claims 1-10 (Claim 11).

Hereinafter, the present invention will be described in detail based on an embodiment thereof.
(I) Alkoxysilyl group-containing synthetic resin emulsion As the alkoxysilyl group-containing synthetic resin emulsion usable in the present invention, an alkoxysilyl group-containing acrylic resin emulsion, an alkoxysilyl group-containing urethane resin emulsion, an alkoxysilyl group-containing fluorine resin emulsion, Examples thereof include, but are not limited to, an alkoxysilyl group-containing epoxy resin emulsion, an alkoxysilyl group-containing polyester resin emulsion, an alkoxysilyl group-containing alkyd resin emulsion, and an alkoxysilyl group-containing melamine resin emulsion. These may be used alone or in combination of two or more. Among these, an alkoxysilyl group-containing acrylic resin emulsion is advantageous because of its high cost and high degree of freedom in resin design.

  The alkoxysilyl group-containing acrylic resin emulsion is obtained by radical copolymerization of (A) an acrylic monomer, (B) an alkoxysilyl group-containing monomer, and (C) a monomer copolymerizable therewith. Can be used.

  (A) Specific examples of the acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) methacrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) Acrylate, isobonyl (meth) acrylate, etc. are raised.

  In particular, when a methacrylic acid ester having an alkyl group having 4 or more carbon atoms and / or a cycloalkyl group is used in an amount of 60% by weight or more in 100% by weight of the emulsion resin solid content, the storage stability of the emulsion is greatly improved.

(B) The alkoxysilyl group-containing monomer is
(B1) Formula R ¹ R ² _(3-n) SiX _n (wherein R ¹ is a monovalent organic group having a polymerizable double bond, R ² is an alkyl group having 1 to 4 carbon atoms, and X is a carbon number) 1 to 4 alkoxyl groups, n is an organosilicon compound represented by 2 or 3), which has 2 or 3 alkoxyl groups and has a reactive double bond. Specific examples thereof include vinyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, vinyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxy. Silane, γ- (meth) acryloxypropyltributoxysilane, vinylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (Meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxypropylmethyldibutoxysilane, and the like can be used, and these can be used alone or in combination of two or more. Among these, X has particularly preferably 2 to 4 carbon atoms from the viewpoint of the storage stability of the emulsion.

  By using these in an amount of 0.5 to 30 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the shell part in the core / shell type emulsion, the shell part is highly crosslinked, and the weather resistance and water resistance are While improving, the adhesiveness to an inorganic type base material also improves.

In addition, (b2) Formula R ³ R ⁴ _(3-a) SiY _a (wherein R ³ is a monovalent organic group having a polymerizable double bond, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms, and Y is An organosilicon compound represented by an alkoxyl group having 1 to 4 carbon atoms, a is an integer of 1 or 2 having a relationship of a <n) has 1 or 2 alkoxyl groups, and has a reactive double bond. It is a compound that has. Specific examples thereof include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyl. Methyldipropoxysilane, γ- (meth) acryloxypropylmethyldibutoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, γ- (meth) acryloxypropyldimethylmethoxy Silane, γ- (meth) acryloxypropyldimethylpropoxysilane, γ- (meth) acryloxypropyldimethylbutoxysilane, and the like can be used, and these can be used alone or in combination of two or more.

  By using these in an amount of 0 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the core part in the core / shell type emulsion, a mild cross-linked structure is introduced into the core part, and flexibility is improved. Water resistance and coating strength can be improved without loss.

  It is preferable in terms of adhesion, tackiness, flexibility, and storage stability that the carbon numbers X and Y of the alkoxyl groups of (b1) and (b2) have a relationship of X> Y.

  The component (C) is not particularly limited as long as it is copolymerizable with the components (A) and (B). Specific examples thereof include aromatic hydrocarbon vinyl monomers such as styrene, α-methylstyrene, chlorostyrene, 4-hydroxystyrene, and vinyl toluene; vinyl acetate, vinyl propionate, vinyl versatate, diallyl phthalate, and the like. Vinyl esters and allyl compounds; Nitrile group-containing vinyl monomers such as (meth) acrylonitrile; Epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 2-hydroxyethyl vinyl ether, hydroxystyrene, Aronics 5700 (manufactured by Toa Gosei Chemical Co., Ltd.), packageFA-1, packageFA-4, packageFM-1, packageFM-4 (above, da Cell Chemical Co., Ltd.), HE-10, HE-20, HP-10, HP-20 (manufactured by Nippon Shokubai Chemical Co., Ltd.), Blemmer PEP series, Blemmer NKH-5050, Blemmer GLM (Nippon Oil and Fat (above) Co., Ltd.), hydroxyl-containing vinyl monomers such as hydroxyl-containing vinyl-modified hydroxyalkyl vinyl monomers; AS-6, AN-6, AA-6, AB which are macromonomers manufactured by Toa Synthetic Chemical Co., Ltd. -6, compounds such as AK-5, vinyl methyl ether, propylene, butadiene and the like.

  Furthermore, hydrophilic vinyl monomers 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, and as a specific example, Nippon Oil & Fats Co., Ltd. Blemmer 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, AE , 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 manufactured by Nippon Emulsifier Co., Ltd., MA-50, MA-100, MA-150, RMA-1120 , RMA-564, RMA-568, RMA-506, MPG130-MA, Antox MS-60, MPG-130MA, RMA-150M, RMA-300M, RMA-450M, RA-1020, RA-1120, RA-1820, NK-ESTER M-20G, M-40G, M manufactured by Shin-Nakamura Chemical Co., Ltd. 90G, M-230G, AMP-10G, AMP-20G, AMP-60G, AM-90G, LA, and the like.

  In addition, 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 or the like is used. It is also possible. In this case, the generated particles have a structure having cross-linking, and water resistance of the formed coating film is improved.

  Further, trifluoro (meth) acrylate, pentafluoro (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, β- (perfluorooctyl) ethyl (meth) acrylate, etc. It is also possible to impart high water and oil repellency by using a fluorine-containing vinyl monomer.

  It is also possible to impart crosslinkability by using a carbonyl group-containing vinyl monomer such as diacetone acrylamide or methyl vinyl ketone and blending a compound containing hydrazine and / or hydrazide group. The water resistance of the coated film is improved.

In particular, the use of a hydroxyl group-containing vinyl monomer and / or a vinyl monomer having a polyoxyalkylene chain in an amount corresponding to 0.5 to 20% by weight of the emulsion particles impairs the stability of the alkoxysilyl group. Therefore, the adhesion to the inorganic base material can be improved, and the mechanical stability and chemical stability of the emulsion can be further improved. Of these, vinyl monomers having a polyoxyalkylene chain having a hydroxyl group at the terminal are particularly effective.
If the amount used is less than 0.5% by weight, the mechanical stability and chemical stability are poor, and if it exceeds 20% by weight, the water resistance is lowered. Especially preferably, it is 1 to 5 weight%.

  Next, the manufacturing method of an emulsion is demonstrated.

  It can be obtained by emulsion polymerization of a mixture comprising the components (A), (B) and (C) by a known emulsion polymerization method.

  The core / shell type emulsion is produced by first subjecting a mixture comprising the components (A), (b2), and (C) to emulsion polymerization by a known emulsion polymerization method as the first stage, and obtaining the core component. In the presence, the mixture comprising (A), (b1) and (C) is emulsion polymerized to introduce the shell component. In addition, you may divide | segment several times and superpose | polymerize in each component of a core part and a shell part.

  When the core component is sufficiently hydrophobic with respect to the shell component, the target composition can be obtained even if the shell component is polymerized first.

  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 a reactive surfactant include, for example, Adeka Soap ER-10, ER-20, ER-30, ER-40, SR-05, SR-10, SR-20, manufactured by ADEKA Corporation. SR-1025, SR-2025, SR-3025, 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, Aqualon KH-05, KH-10, RN-20, RN-30, RN-50, RN-2025, HS-10, HS- from Daiichi Kogyo Seiyaku Co., Ltd. 20, HS-1025, BC05, BC10, BC0515, BC1025, Sanyo Chemical Industries Co., Ltd. Eleminor JS-2, JS-20, RS-30, Kao Corporation Latemuru S 180, S-180A, and the like PD-104, PD-420, PD-430.

  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.

  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, preferably 0.05 to 5 parts by weight based on 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 alkoxysilyl-containing 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 viscosity of the system is remarkably increased, so that it becomes difficult to remove heat generated by the polymerization reaction, or it takes a long time to take out 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 alkoxysilyl-containing 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.

  In the obtained emulsion composition, pigments (titanium dioxide, calcium carbonate, kaolin clay, talc, barium sulfate, white carbon, carbon, petal, ocher, cyanine blue, etc.) and components that are usually used in paints are optionally added. Additives commonly used in paints such as film aids, colloidal silica, plasticizers, solvents, dispersants, wetting agents, preservatives, antifreeze agents, light stabilizers, UV absorbers, antifoaming agents, etc. it can.

  Specific examples of the alkoxysilyl group-containing urethane resin emulsion include Takelac WS-7000, WS-5000, WS-5070X, WS-5100, WS-4000 and the like manufactured by Mitsui Chemicals Polyurethanes.

  Specific examples of the alkoxysilyl group-containing epoxy resin emulsion include Adeka Resins EM-0477 and EM-0487 manufactured by ADEKA Corporation.

  In other resin systems, it can be obtained by reacting various functional groups with a silane coupling agent.

  For example, glycidyl group-containing resin, carboxyl group-containing resin, method of reacting isocyanate group-containing resin with amino silane coupling agent, hydroxyl group-containing resin, amino group-containing resin, carboxyl group-containing resin with epoxy silane coupling agent, isocyanate And a method of reacting a silane coupling agent. These may be reacted with a pre-emulsified resin, or may be emulsified after completion of the reaction.

(II) Substance that promotes hydrolysis / condensation of alkoxysilyl groups The substance (hereinafter referred to as curing catalyst) that promotes hydrolysis / condensation of alkoxysilyl groups as component (II) in the present invention includes organometallic compounds and acidic catalysts. Basic catalysts are used. In particular, an organic tin compound is preferable.

  Specific examples of the organic tin compound include dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin dioleyl malate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dimethoxide, dibutyltin thioglycolate, dibutyltin bisisononyl 3-mercaptopro Pionate, dibutyltin bisisooctyl thioglycolate, dibutyltin bis-2-ethylhexyl thioglycolate, dimethyltin bisdodecyl mercaptide, dibutyltin bisdodecyl mercaptide, dioctyltin bisdodecyl mercaptide, dimethyltin bis (octylthiogl Cholic acid ester) salt, tin octylate and the like.

  Among them, dibutyltin thioglycolate, dibutyltin bisisononyl 3-mercaptopropionate, dibutyltin bisisooctylthioglycolate, dibutyltin bis2-ethylhexylthioglycolate, dimethyltin bisdodecyl from the viewpoint of stability in water Mercaptides such as mercaptides, dibutyltin bisdodecyl mercaptides, dioctyltin bisdodecyl mercaptides, and dimethyltin bis (octylthioglycolate) salts are preferred.

  The addition method is not particularly limited, but a method of adding after mixing with a surface active substance in advance is preferable from the viewpoint of miscibility in the emulsion and expression of gloss of the coating film.

  The addition amount of the curing catalyst is preferably 0.01 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the solid content of the emulsion. If it is less than 0.01 parts by weight, the curing activity is low, and if it exceeds 10 parts by weight, the pot life is shortened, and the water resistance and weather resistance of the coating film are lowered.

(III) Organosilicate and Modified Product thereof Organosilicate is a compound containing a hydrolyzable silicon group, and is a compound represented by the general formula 1 and / or a hydrolysis condensate thereof. By adding this to the emulsion, the adhesion of the obtained coating film to the inorganic base material and the stain resistance are greatly improved.

(RO) ₄ Si (General Formula 1)
(Wherein R is the same or different and has 1 to 4 carbon atoms).

  Specific examples of the compound include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, and These partial hydrolysis and condensates can be exemplified.

  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%. By adjusting the ratio, the pot life after addition to the emulsion can be adjusted.

  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.

  Since the organosilicate has low miscibility with the emulsion, a method of emulsifying in advance with a surface active substance in water or adding a mixture of a surface active substance and an organosilicate directly is preferable.

  The surface active substance is a substance having a hydrophilic group and a hydrophobic group in the molecule, and is capable of emulsifying and dispersing the organosilicate and the curing catalyst in water. Specific examples include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

  Examples of the anionic surfactants include higher alcohol sulfates, alkyl (benzene) sulfonates, alkyl sulfate salts, polyoxyethylene alkylphenyl sulfonates, alkyl diphenyl ether sulfonates, and polyoxyethylene alkylphenol sulfate salts. , Selected from the group consisting of styrene sulfonate or vinyl sulfate, alkyl sulfosuccinate, alkyl naphthalene sulfonate, alkyl phosphate, polyoxyethylene alkyl phosphate, polyacrylic acid (salt) and sulfonate These are various water-soluble oligomers, and various compounds such as water-soluble acrylic resins or derivatives thereof. These may be used alone or in combination of two or more. .

  Further, only typical examples of the above-mentioned nonionic surfactants will be exemplified. Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene higher fatty acid ester, sorbitan fatty acid ester, polyoxyethylene With various water-soluble polymer nonionic activators such as ethylene sorbitan fatty acid ester, polyoxyethylene-polyoxypropylene block copolymer, acetylene glycol surfactant, polyvinyl alcohol or hydroxyethyl cellulose. Yes, these may be used alone or in combination of two or more.

  Furthermore, only typical examples of the above-mentioned cationic surfactants include quaternary ammonium salts such as alkylamine salts and alkyltrialkylammonium chlorides, alkylbetaines, and amine oxides. These may be used alone or in combination of two or more.

  Each of the anionic surfactants, nonionic surfactants or cationic surfactants as listed above may be used singly or in combination of two or more, and among these, it can be particularly preferably used. As the surfactant, it is more preferable to use a nonionic surfactant having no ionic group.

  A particularly preferred nonionic surfactant is an acetylene glycol surfactant. The acetylene glycol surfactant can improve the dispersibility and reduce the surface tack. Specific examples of the acetylene glycol surfactant include Surfhinol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE manufactured by Nissin Chemical Industry Co., Ltd. , SE-F, 504, 61, 2502, 82, DF110D, DF37, CT111, CT121, CT131, CT136, TG, GA, FS-85, Dinol 604, Environment Gem AD-01, Olphine STG, SPC, E1004, E1010 AK-02, PD-001, PD-002W, PD-004, PD-301, WE-001, WE-002, WE-003, AF-103, AF-104, and the like. Of these, Surfynol 104 series, Surfynol 2502, and Envigem AD-01, to which ethylene oxide is not added, are preferable for reducing surface tack.

  As another method for improving the miscibility, a hydrophilic group such as a polyoxyalkylene chain or an amino group can be introduced and modified so that the organosilicate becomes water-soluble or self-water-dispersible.

  The addition amount of these organosilicates and / or modified products thereof is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the emulsion resin solid content. If it is less than 0.1 part by weight, sufficient adhesion cannot be ensured, and if it exceeds 50 parts by weight, the coating tends to be brittle. Further, the addition amount of the organosilicate and / or its modified product is 1 to 40 parts by weight, and the particularly preferable addition amount is 5 to 30 parts by weight.

(IV) Water-soluble and / or water-dispersible curing agent having a reactive functional group and a hydrophilic group in the molecule Water-soluble and / or water-dispersible curing agent having a reactive functional group and a hydrophilic group in the molecule Is a surface active substance having a reactive functional group. Due to its surface activity, the organosilicate and the curing catalyst are emulsified and dispersed in the emulsion, and the reactive functional group reacts with the resin component and / or other compounding agent incorporated in the emulsion, as well as the reactive functional group itself. This improves adhesion and water resistance. The reactive functional group may be the same as the hydrophilic group or the hydrophobic group. Specific reactive functional groups include (block) isocyanate groups, epoxy groups, carbodiimide groups, alkoxysilyl groups, oxazoline groups, hydrazide groups, allyl groups, propenyl groups, (meth) acryloyl groups, vinyl groups, and the like.

  Among these, (block) isocyanate groups, epoxy groups, carbodiimide groups, and alkoxysilyl groups are particularly desirable because they are effective for adhesion to inorganic base materials.

  Examples of the (block) isocyanate group-containing compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate ( MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), methylcyclohexyl diisocyanate (H6TDI), 4,4′-dicyclohexylmethane diisocyanate (H12MDI), 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI), Tetramethylxylylene diisocyanate (TMXDI), 2,2,4-trimethylhexamethylene diisocyanate (TMHDI), hexamethylene diisocyanate (HDI), norbornene diisocyanate ( NBDI), 2,4,6-triisopropylphenyl diisocyanate (TIDI), 1,12-diisocyanatododecane (DDI), 2,4, -bis- (8-isocyanate octyl) -1,3-dioctylcyclobutane (OCDI) N-pentane-1,4-diisocyanate and their isocyanurate-modified products, adduct-modified products, burette-modified products, allophanate-modified products, those having one or more isocyanate groups in these polymers, polyalkylene oxide groups, It is modified with a carboxyl group to make it water-soluble and / or water-dispersible. Further, these isocyanate groups may be masked with a blocking agent (phenol, ε-caprolactam, etc.). Among these, those using a non-yellowing or hardly yellowing isocyanate are preferable from the viewpoint of weather resistance.

  These are generally commercially available as crosslinking agents. For example, Bihydur 3100, Bihydur 2336, Bihydur LS2150 / 1, manufactured by Sumika Bayer Urethane Co., Ltd. Takenate WD-220, Takenate WD-240, Takenate WD-720, Takenate WD-725, Takenate WD-726, Takenate WD-730, Takenate WB-700, Takenate WB-720, Takenate WB-730, Takenate WB -920, Nippon Polyurethane Industry Co., Ltd. Aquanate 100, Aquanate 110, Aquanate 200, Aquane 210, Aquanate 120, manufactured by Asahi Kasei Corporation DURANATE WB40-100, Duranate WB40-80D, Duranate WT20-100, such as Duranate WT30-100 the like.

  Further, a vinyl monomer having a (block) isocyanate group, a hydrophilic group-containing vinyl monomer, and a copolymer with other vinyl monomers may be used.

  Examples of the vinyl monomer having a (block) isocyanate group include 2-methacryloyloxyethyl isocyanate, methacrylic acid-2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl, and m-iso. And propenyl-α and α-dimethylbenzyl isocyanate.

  Examples of the hydrophilic group-containing vinyl monomer include α, β-ethylenically unsaturated carboxylic acid, styrene sulfonic acid, vinyl sulfonic acid, sodium styrene sulfonate, sodium 2-sulfoethyl (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, dialkylaminoalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylate hydrochloride, 2-aminoethyl (meth) acrylate hydrochloride, vinyl monomer having a polyoxyalkylene chain, etc. can give.

  Examples of the α, β-ethylenically unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, maleic acid, crotonic acid, phthalic acid, citraconic acid and the like.

  Examples of the dialkylaminoalkyl (meth) acrylate and dialkylaminoalkyl (meth) acrylate hydrochloride include dimethylaminoethyl (meth) acrylate, diethylamineethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and hydrochloride thereof.

  The vinyl monomer having a polyoxyalkylene chain is not particularly limited, but an acrylic acid ester or a methacrylic acid ester having a polyoxyalkylene chain is preferred, and specific examples include Bremer PE-90 manufactured by NOF Corporation. 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-80 B, 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, manufactured by Nippon Emulsifier Co., Ltd. RMA-1120, RMA-564, RMA-568, RMA-506, MPG130-MA, Antox MS-60, MPG-130MA, RMA-150M, RMA-300M, RMA-450M, RA-1020, RA-1120, RA -1820, Shin-Nakamura Chemical Co., Ltd. NK-ESTER M-20G, M- 0G, M-90G, M-230G, AMP-10G, AMP-20G, AMP-60G, AM-90G, LA, Sanyo Chemical Industries Co., Ltd. ELEMINOL RS-30 and the like.

  As an epoxy group containing compound, many things are marketed, for example, Nagase Chemtech Co., Ltd. Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-301, EX-313, EX-314, EX-321, EX-211, EX-810, EX-811, EX-851, EX-821, EX- 830, EX-832, EX-841, EX-861, EX-911, EX-941, EX-920, EX-921, EX-931, EX-145, EX-171, EX-701, Kyoeisha Chemical Co., Ltd. ) Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 00P, Epolite 1500NP, Epolite 80MF, Epolite 100MF, Sakamoto Pharmaceutical Co., Ltd. SR-NPG, SR-16H, SR-TMP, SR-TPG, SR-4PG, SR-2EG, SR-8EG, SR-8EGS, SR-GLG, SR-DGE, SR-4GL, SR-4GLS, Nippon Oil & Fats' Epiol BE-200, G-100, E-100, E-400, E-1000, P-200, NPG-100 , TMP-100, epiol OH and the like.

  Moreover, the copolymer with the vinyl monomer which has an epoxy group, a hydrophilic group containing vinyl monomer, and another vinyl monomer may be sufficient.

  Examples of vinyl monomers having an epoxy group include glycidyl (meth) acrylate, Daicel Chemical Industries, Ltd. M-GMA, Cycler M-100, Cycler A-200, Cycler M-101, Celoxide 2000, and the like. can give.

  Examples of the carbodiimide group-containing compound include water-soluble or self-emulsifying carbodiimide compounds described in JP-A-8-59303.

  This includes 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI) , Isophorone diisocyanate (IPDI), methylcyclohexyl diisocyanate (H6TDI), 4,4′-dicyclohexylmethane diisocyanate (H12MDI), 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI), tetramethylxylylene diisocyanate (TMXDI), 2,2,4-trimethylhexamethylene diisocyanate (TMHDI), hexamethylene diisocyanate (HDI), norbornene diisocyanate (NBDI), 2,4,6-triisopropylphenyl Diisocyanate (TIDI), 1,12-diisocyanate dodecane (DDI), 2,4, -bis- (8-isocyanate octyl) -1,3-dioctylcyclobutane (OCDI), n-pentane-1,4-diisocyanate, etc. One type or two or more types of polyfunctional isocyanates are subjected to a carbon dioxide decondensation reaction to carbodiimidize, and the residual isocyanate groups at the ends are sealed with hydrophilic groups.

  Examples of the hydrophilic group to be sealed include a residue of an alkyl sulfonate, a quaternary salt of a residue of a dialkylamino alcohol, a residue of a polyoxyalkylene whose end is blocked with an alkoxy group.

  These are commercially available as aqueous resin crosslinking agents. For example, Nisshinbo Carbodilite V-02, V-04, V-06, V-02-L2, E-01, E-02, E-03, E-04, E-05, and the like.

  Examples of water-free materials include V-02B, V-04B, V-04K, and Elastostab H01.

  Examples of the alkoxysilyl group-containing compound include A-1230, MAC-2101, and MAC-2301 manufactured by Momentive Performance Materials Japan GK.

  It can also be obtained by reacting an isocyanate-based silane coupling agent with the terminal hydroxy group of polyoxyalkylene.

  The polyoxyalkylene is not particularly limited as long as it has one or more hydroxy groups at the terminal.

  Examples of the isocyanate-based silane coupling agent include SILQUES A-1310 and Y-5187 manufactured by Momentive Performance Materials Japan GK, and KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.

  It can also be obtained by reacting the compound having an epoxy group with an amino silane coupling agent.

  Examples of the amino silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β- Aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, and commercially available products are Shin-Etsu Chemical Co., Ltd. Examples include KBE-9103, KBM-575, KBM-6123, SILQUEST A-1120, A-1122, A-1170, A-1110, Y-9669, and the like manufactured by Momentive Performance Materials Japan GK.

  Furthermore, it may be a copolymer with an alkoxysilyl group-containing vinyl monomer, a hydrophilic group-containing vinyl monomer, and other vinyl monomers.

  Specific examples of vinyl monomers containing alkoxysilyl groups include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrimethyl. Isopropoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldi Ethoxysilane, γ- (meth) acryloyloxypropyltri-n-propoxysilane, γ- (meth) acryloyloxypropyltriisopropoxysilane, vinyltriacetoxysilane, β- (meth) acryl Yl oxy ethyltrimethoxysilane, and the like.

  The oxazoline group-containing compound is commercially available as an aqueous crosslinking agent. For example, Nippon Curing Catalyst Co., Ltd. Epocross WS-500, K-2010E, K-2020E, K-2030E, K-1010E, K-1020E, K -1030E.

  Examples of the hydrazide group-containing compound include carbohydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanediohydrazide, aminopolyacrylamide, and the like.

If a water-soluble and / or water-dispersible curing agent having a reactive functional group and a hydrophilic group in these molecules is mixed in advance with an organosilicate and a curing catalyst and mixed in an emulsion immediately before coating, very good dispersion And a coating film exhibiting excellent stain resistance can be obtained.
The amount of the water-soluble and / or water-dispersible curing agent having a reactive functional group and a hydrophilic group in the molecule is 5 to 200 parts per 100 parts by weight of (III) organosilicate and / or a modified product thereof. It is preferable that If it is less than 5 parts by weight, the organosilicate and / or the modified product thereof is not uniformly dispersed in the aqueous paint, and the gloss value of the formed coating film is lowered. Moreover, when 200 weight part or more is used, the initial stage tack of the formed coating film arises or hardness falls. More preferably, it is 10 to 100 parts.

(V) One or more compounds selected from secondary amino group-containing alkoxysilane compounds, ketoimino group-containing alkoxysilane compounds, and reaction products of primary amino group-containing alkoxysilane compounds and epoxy group-containing compounds Secondary amino group-containing The alkoxysilane compound is a compound having a secondary amino group and an alkoxysilyl group in the molecule. For example, N-phenyl γ-aminepropyltrimethoxysilane, bis (γ-triethoxysilylpropyl) amine, N-ethyl γ-aminopropylsilane, N, N′-bis [3- (trimethoxysilyl) propyl] And ethylenediamine. As these commercial products, Shin-Etsu Chemical Co., Ltd. KBM-573, Momentive Performance Materials Japan GK SILQUEST A-1170, Y-9669, Toray Dow Corning Co., Ltd. Z-683, Chisso For example, Saraace XS1003 manufactured by Co., Ltd.

  A ketoimino group-containing alkoxysilane compound is a compound having a ketoimino group and an alkoxysilyl group obtained by reacting a ketone with a primary amino group in a molecule. Examples include 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine. Examples of these commercially available products include KBE-9103 manufactured by Shin-Etsu Chemical Co., Ltd., Sara Ace S340 manufactured by Chisso Corporation, and Z-6860 manufactured by Toray Dow Corning Corporation.

  Commercial products of the reaction product of the primary amino group-containing alkoxysilane compound and the epoxy group-containing compound include Sarace XS1104 manufactured by Chisso Corporation, Kanekazemulac Z-901, Z-902 manufactured by Kaneka Corporation, and the like.

  By adding the reaction product of these secondary amino group-containing alkoxysilane compounds, ketoimino group-containing alkoxysilane compounds, primary amino group-containing alkoxysilane compounds and epoxy group-containing compounds, adhesion to inorganic substrates is further improved. In addition, when different types of paint are applied on top of each other (so-called undercoat paint), the adhesion of the paint applied on top (so-called intermediate paint or topcoat paint) can be improved, and paint selectivity (application) Tend to limit the types of paint that can be produced).

  The added amount of these secondary amino group-containing alkoxysilane compounds, ketoimino group-containing alkoxysilane compounds, primary amino group-containing alkoxysilane compounds and epoxy group-containing compounds is 0 with respect to 100 parts by weight of the emulsion resin solid content. It is preferable to add 1 to 20 parts by weight. When the amount is 0.1 parts by weight or less, sufficient adhesion cannot be secured, and when the amount is 20 parts by weight or more, coloring is severe and the appearance of the obtained coating film may be deteriorated. More preferably, it is 0.5 to 10 parts by weight.

(Inorganic base material)
The inorganic base material is a coating film or article coated with a coating using a reactive silicon compound or silicon resin as a binder or modifier, glass, ceramics, tiles, and the like.

  Paints that use reactive silicon compounds or silicon resins as binders and modifiers are called inorganic paints, organic-inorganic composite paints, ceramic-modified paints, low-contamination paints, and the like.

  Among these, inorganic paints and organic-inorganic composite paints are mainly composed of reactive silicon compounds or silicon resins, and are characterized by high weather resistance, flame retardancy, high hardness, and the like.

  These are commercially available from various companies, for example, Matsushita Electric Works Co., Ltd. Fressera, Tsunewa Chemical Industry Co., Ltd. Serasex, Super Seran, China Paint Co., Ltd. Kaysor, Kikusui Chemical Co., Ltd. KS Seraton, Examples include Neo Cera Top manufactured by Asia Industries.

In addition, examples of products coated with these include KUBOTA Matsushita Electric Works Co., Ltd. exterior material Hikari Cera, Ceramic Coat, Nichiha Co., Ltd. exterior material Moen Xcellade, PanaHome Co., Ltd. exterior material Hi-Cera Coat Wall, etc. The ceramic-modified paint and the low-contamination paint are obtained by modifying a paint having an organic resin as a main binder with a reactive silicon compound or a silicon resin, and is mainly characterized by stain resistance.

  Many of these are commercially available from various companies. For example, SK Kaken Co., Ltd. Seratite Series, Clean Mild Series, Kansai Paint Co., Ltd. Cera Series, Sera Tect Series, Isamu Paint Co., Ltd. Neo Silica 21C Series Ecosilica 21C series, Hycera series manufactured by Hengwa Chemical Industry Co., Ltd., and natural series.

  Many of these are on-site enforcement paints for building exteriors, and the inorganic base materials that are the subject of the present invention are walls and roofs coated with these.

  Examples of the inorganic base material other than the coating film include glass, ceramics, tile, cement, mortar, concrete, slate, and flexible plate.

  In the present invention, the method for applying the curable composition to the inorganic base material is not particularly limited, and a known method can be used. Examples thereof include a method of applying with a brush, a method of applying with a roller, and a method of spraying. It is done. After applying the curable composition to the inorganic base material, a paint may be further applied. By such a coating method, (I) an alkoxysilyl group-containing synthetic resin emulsion, (II) a substance that promotes hydrolysis / condensation of alkoxysilyl groups, and (III) a curing containing an organosilicate and / or a modified product thereof The coating material in which the coating film obtained from an adhesive composition was formed on the inorganic type base material can be obtained.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto.
(Synthesis Example 1)
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen gas inlet tube and dropping funnel, 160 parts by weight of deionized water, 1.4 parts by weight of Newcol-707SF (manufactured by Nippon Emulsifier Co., Ltd.), 5% sodium hydrogen carbonate 1.0 part by weight of the aqueous solution was charged, and the temperature was raised to 50 ° C. while introducing nitrogen gas. After heating, 2.0 parts by weight of 7% t-butyl hydroperoxide aqueous solution, 1.1 parts by weight of 20% Bruggolite FF-6 aqueous solution, ferrous sulfate heptahydrate (0.10%) / ethylenediamine tetra 1.4 parts of a mixed aqueous solution of disodium acetate (0.40%) was added, and 200 parts by weight of the monomer mixture shown in the core part of Table 1 (E-1) was added to Adeka Soap SR-1025 (manufactured by ADEKA Corporation): Active ingredient 25%) 12 parts by weight, ADEKA rear soap ER-20 (manufactured by ADEKA: Active ingredient 75%) 1.9 parts by weight, and deionized water 71 parts by weight emulsified monomer emulsion for 200 minutes Added constant speed over time. Meanwhile, 2.2 parts by weight of 7% t-butyl hydroperoxide aqueous solution and 1.8 parts by weight of 2.5% Bruggolite FF aqueous solution were added in three portions. Polymerization was performed after 1 hour after the addition of the monomer emulsion was completed. Further, 0.6 parts by weight of 7% t-butyl hydroperoxide aqueous solution, 2.2 parts by weight of 2.5% Bruggolite FF aqueous solution and ferrous sulfate heptahydrate (0.10%) / ethylenediaminetetraacetic acid After adding 1.4 parts of a disodium (0.40%) mixed aqueous solution, 200 parts by weight of the monomer mixture shown in the shell part of Table 1 (E-1), 12 parts by weight of Adeka Soap SR-1025, and Adeka Soap A monomer emulsion obtained by adding 1.9 parts by weight of ER-20 and 71 parts by weight of deionized water and emulsifying the mixture was added at a constant rate over 200 minutes. Meanwhile, 2.4 parts by weight of 7% t-butyl hydroperoxide aqueous solution and 3.4 parts 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 22 parts of 5% aqueous sodium hydrogen carbonate solution to the resulting synthetic resin emulsion, the solid part was adjusted to 50% with deionized water (E-1).

(Preparation of main material paint)
Using the synthesized resin emulsion (E-1), a main material paint was prepared with the formulation shown in Table 2.

(Example of production of curing agent)
In a vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube and a dropping funnel, the components shown in Table 3 were added in the order of (VII), (VI), (IV), (III), (II), (V) Was added while stirring. After completion of the addition, the mixture was stirred at room temperature for 60 minutes to obtain a curing agent (curing agents 1 to 5).

Silicate 40 (manufactured by Tama Chemical Industry Co., Ltd .: tetraethoxysilane partial hydrolysis condensate (silica residual ratio 40%))
Carbodilite V-04B (Nisshinbo: Polycarbodiimide)
SR-TPG (manufactured by Sakamoto Pharmaceutical Co., Ltd .: tripropylene glycol diglycidyl ether Surfynol 104 (manufactured by Nissin Chemical Industry Co., Ltd .: acetylene glycol surfactant)
Envirogem AD01 (Nissin Chemical Industry Co., Ltd .: acetylene glycol surfactant)
UNILOVE 70MO-10SB (Nippon Yushi Co., Ltd .: Nonionic surfactant)
Kanekazemulac Z-902 (manufactured by Kaneka Corporation: reaction product of primary amino group-containing alkoxysilane compound and epoxy group-containing compound, active ingredient 40%)
SILQUEST A-1170 (Momentive Performance Materials Japan GK: Bis (γ-triethoxysilylpropyl) amine)
SILQUEST Y-9669 (Momentive Performance Materials Japan GK: N-phenylγ-aminepropyltrimethoxysilane)
KBE-9103 (manufactured by Shin-Etsu Chemical Co., Ltd .: 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine)
CS-12 (manufactured by Chisso Corporation: 2,2,4-trimethylpentanediol 1,3-monoisobityrate)

(Preparation of inorganic substrate for evaluation)
Epomalin (solvent-based two-component epoxy resin paint) manufactured by Kansai Paint Co., Ltd. was applied as an undercoat paint to the flexible board and dried at room temperature for 24 hours. On top of that, Diamond Super Seran (solvent-based two-component organic / inorganic composite coating) manufactured by Hengwa Chemical Industry Co., Ltd. or Seratite Si (solvent-based two-component ceramic modified acrylic silicon-based low-contamination coating) manufactured by SK Kaken Co., Ltd. It was applied twice with an in-process interval of 3 hours. After leaving at room temperature for 24 hours, it was placed in a dryer at 50 ° C. for 7 days to be completely cured to obtain an inorganic base material for evaluation.

(Adhesion evaluation 1)
On the prepared inorganic base material for evaluation and a commercially available inorganic base material, the undercoat paint shown in Table 4 was applied and dried at room temperature for 16 hours. On top of this, Nippon Paint's water-based silicon sera (acrylic silicone emulsion-based enamel paint) was sprayed twice with an in-process interval of 16 hours. After drying at room temperature for 7 days, 25 notches of 2 mm square grids were put, and a cellophane tape was pasted thereon, and the state when peeled off was observed. Further, the test specimen was immersed in warm water at 40 ° C. for 7 days and dried at room temperature for 24 hours or more, and then the same adhesion test was performed.

The judgment criteria are as follows.
◎ There is no peeling of the paint film.
○ Part of the film is peeled off, and the state is cohesive failure of the inorganic base material.
Δ: A part of the coating film is peeled off, and the peeling site is the interface between the base coating and the top coating.
X The peeling of the coating film was observed in part, and the peeling location was the interface between the inorganic base material and the primer coating.
XX Completely peeled off at the interface between the inorganic base material and the primer coating.

Aqueous component primer: SK Kaken Co., Ltd. acrylic emulsion base coating (anionic)
Diamond wide sealer: Acrylic emulsion base coating (cationic) manufactured by Hengwa Chemical Industry Co., Ltd.
Water-based silicone sera: Nippon Paint Co., Ltd. acrylic silicon emulsion-based enamel paint Excelsiera Sera 15 Excellent pattern (REM733JK): Kubota Matsushita Electric Works Co., Ltd. inorganic paint (ceramic coat) coating siding board Diamond super seranium: HONWA CHEMICAL INDUSTRY CO., LTD. Solvent-based two-component organic / inorganic composite paint plate SERATITE Si: SK Kaken Co., Ltd. solvent-based two-component ceramic modified acrylic silicon-based low-contamination paint coating plate Flexible plate: Fiber reinforced cement plate

(Adhesion evaluation 2)
On the commercially available tiles (KTB-402 Koguchidaira white glossy made by Komori Tile), the base coat shown in Table 5 was applied and dried at room temperature for 24 hours. In addition, as needed, a diamond laurel PS-EM (acrylic emulsion-based waterproofing material for tile repair) manufactured by Hengwa Chemical Industry Co., Ltd. as an intermediate coating is used twice at an in-process interval of 16 hours (0.8 kg / m ² ) Painted. Furthermore, after drying at room temperature for 16 days, the top coat shown in Table 5 was spray-coated. After this test body was dried at room temperature for 7 days, 25 incisions of 2 mm square grids were put, a cellophane tape was stuck on it, and the state when peeled was observed. Further, the test specimen was immersed in warm water at 40 ° C. for 7 days and dried at room temperature for 24 hours or more, and then the same adhesion test was performed.

The judgment criteria are as follows.
◎ There is no peeling of the paint film.
○ Part of the coating film is peeled off, which is a cohesive failure of the intermediate coating or top coating.
Δ: A part of the coating film is peeled off, and the peeling site is the interface between the base coating and the intermediate coating or the top coating.
X The peeling of the coating film was observed in part, and the peeling location was the interface between the inorganic base material and the primer coating.
XX Completely peeled off at the interface between the inorganic base material and the primer coating.

(Contamination resistance)
On the commercially available tiles (KTB-402 Koguchidaira white glossy made by Komori Tile), the base coat shown in Table 5 was applied and dried at room temperature for 24 hours. In addition, as needed, a diamond laurel PS-EM (acrylic emulsion-based waterproofing material for tile repair) manufactured by Hengwa Chemical Industry Co., Ltd. as an intermediate coating is used twice at an in-process interval of 16 hours (0.8 kg / m ² ) Painted. Furthermore, after drying at room temperature for 16 days, the top coat shown in Table 5 was spray-coated. The specimen was dried at room temperature for 7 days and then exposed for 3 months at 45 ° south surface in Settsu City, Osaka Prefecture. Using a Minolta colorimeter CR-300, the color before the start of exposure and the color for 3 months of exposure were measured, and the lightness difference (ΔL) was calculated.

Aqueous component primer: SK Kaken Co., Ltd. acrylic emulsion base coating (anionic)
Diamond Laurel PS-EM: Acrylic emulsion waterproofing material for tile repair made by Hengwa Chemical Industry Co., Ltd. Diamond bi-fresh silicone clear: Acrylic silicon emulsion clear coating made by Hengwa Chemical Industry Co., Ltd. KTB-402: Tile made by Komori tile Koguchidaira white glossy

The evaluation results are shown in Tables 4 and 5.

Reference Example 1 showed good adhesion to various inorganic base materials. However, (V) the secondary amino group-containing alkoxysilane compound, the ketoimino group-containing alkoxysilane compound, and the reaction product of the primary amino group-containing alkoxysilane compound and the epoxy group-containing compound are not included. There wasn't. When the curable composition of the present invention is used as a final (finished) paint, there is no problem, but when a different kind of paint is further coated thereon (so-called undercoat paint), the selectivity of the top coat is generated. There is.

Examples 1 to 2 and Reference Examples 2 to 3 showed good adhesion to various inorganic substrates. Also, there was no problem with the adhesion to the top coating material.

  In Comparative Example 1, (II) a substance that promotes hydrolysis / condensation of alkoxysilyl groups and (III) an organosilicate and / or a modified product thereof were not used, but only (I) an alkoxysilyl group-containing synthetic resin emulsion was used. Except for the flexible plate, sufficient adhesion could not be secured.

  Comparative Examples 2 and 3 were evaluated using a commercially available acrylic emulsion-based undercoating material that does not contain an alkoxysilyl group-containing synthetic resin emulsion instead of the curable composition of the present invention. Except for this, sufficient adhesion could not be secured.

  In Comparative Example 4, (I) a commercially available acrylic emulsion-based undercoat containing no alkoxysilyl group-containing synthetic resin emulsion, (II) a substance that promotes hydrolysis and condensation of alkoxysilyl groups, and (III) an organosilicate and / or its The modified product, (V) ketoimino group-containing alkoxysilane compound, and improved adhesion under standard conditions were observed, but the adhesion after immersion in hot water was not sufficient.

Example 3 and Reference Example 4 showed good adhesion to the tile. Moreover, the coating film showed favorable stain resistance.

In Example 4 , the adhesion to the tile was good, but the topcoat was not low-contamination, so the stain resistance was lower than Example 3 where the curable composition of the present invention was also used for the topcoat.

Examples 5 to 6 have coating specifications in which an acrylic emulsion waterproofing material is added as an intermediate coating, but all showed good adhesion. However, since the top coating material used in Example 6 is not a low contamination type, the stain resistance was lower than that in Example 5 in which the curable composition of the present invention was also used for the top coating material.

Reference Example 5 showed good adhesion to the tile. However, it does not include (V) secondary amino group-containing alkoxysilane compounds, ketoimino group-containing alkoxysilane compounds, and primary amino group-containing alkoxysilane compounds and epoxy group-containing compounds. There wasn't.

  Comparative Examples 5 to 6 were evaluated using (I) a commercially available acrylic emulsion-based undercoat containing no alkoxysilyl group-containing synthetic resin emulsion instead of the curable composition of the present invention. Regardless of the presence or absence, it did not adhere to the tile at all.

  As mentioned above, it was confirmed that the curable composition of this invention has favorable adhesiveness with respect to various inorganic type base materials. Furthermore, (V) a secondary amino group-containing alkoxysilane compound, a ketoimino group-containing alkoxysilane compound, a reaction product of a primary amino group-containing alkoxysilane compound and an epoxy group-containing compound is added thereto, so that various different kinds of paints can be formed thereon. It was confirmed that it was repeatedly applied, and it was confirmed that it was useful as a primer coating.

  In addition, (V) a secondary amino group-containing alkoxysilane compound, a ketoimino group-containing alkoxysilane compound, and a coating that does not contain a reaction product of a primary amino group-containing alkoxysilane compound and an epoxy group-containing compound, is applied over the coating. However, it has been confirmed that it is useful as a final (finished) coating because it has good adhesion to various inorganic substrates and is excellent in its own stain resistance.

Claims (11)

(I) alkoxysilyl group-containing synthetic resin emulsion,
(II) a substance that promotes hydrolysis / condensation of alkoxysilyl groups ,
( III) Organosilicate (a compound represented by the following general formula (1) and / or a partial hydrolysis condensate thereof) and / or a modified product (RO) ₄ Si (general formula 1)
Wherein R is the same or different and is an alkyl group having 1 to 4 carbon atoms , and
(V) a curable composition containing a ketoimino group-containing alkoxysilane compound and one or more compounds selected from a reaction product of a primary amino group-containing alkoxysilane compound and an epoxy group-containing compound; A coating method that is applied to the base material. The curable composition further comprises (IV) a curable composition containing a water-soluble and / or water-dispersible curing agent having a reactive functional group and a hydrophilic group in the molecule. Item 1. The coating method according to item 1. Wherein (I) alkoxy method paint according to any one of claims 1-2 silyl group-containing synthetic resin emulsion is an alkoxysilyl group-containing acrylic emulsion. (I) The alkoxysilyl group-containing synthetic resin emulsion is an emulsion containing 60% by weight or more of (meth) acrylic acid ester having an alkyl group and / or a cycloalkyl group having 4 or more carbon atoms in 100% by weight of the emulsion resin solid content. The coating method according to any one of claims 1 to 3. The (I) alkoxysilyl group-containing synthetic resin emulsion is an emulsion containing 0.5 to 20% by weight of a vinyl monomer having a polyoxyalkylene unit in 100% by weight of the emulsion resin solid content. The coating method according to any one of the above. The (I) alkoxysilyl group-containing synthetic resin emulsion has a core / shell structure, and R ¹ R ² _(3-n) SiX _n (general formula 2) in 100 parts by weight of the resin component constituting the shell portion.
(Wherein R ¹ is a monovalent organic group having a polymerizable double bond, R ² is an alkyl group having 1 to 4 carbon atoms, X is an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 2 or 3) 0.5-30 parts by weight of an organosilicon compound represented by
R ³ R ⁴ _(3-a) SiY _a (general formula 3) in 100 parts by weight of the resin component constituting the core part
(In the formula, R ³ is a monovalent organic group having a polymerizable double bond, R ⁴ is an alkyl group having 1 to 4 carbon atoms, Y is an alkoxy group having 1 to 4 carbon atoms, and a is a relationship of a <n. The coating method according to any one of claims 1 to 5, comprising 0 to 20 parts by weight of an organic silicon compound represented by 1 or 2 having an integer of 1 to 2. The coating method according to claim 1, wherein the substance that promotes hydrolysis and condensation of the (II) alkoxysilyl group is an organic tin compound. The inorganic base material is at least one base material selected from the group consisting of inorganic paints, organic-inorganic composite paints, ceramic-modified paints, low-contamination paints, glass, ceramics, and tiles. The coating method according to any one of the above. The coating method according to any one of claims 1 to 8, wherein the curable composition is a water-based paint. The coating method according to any one of claims 1 to 9, wherein after the curable composition is applied to the inorganic base material, an intermediate coating and / or a top coating is further applied. The coated object obtained by the coating method of any one of the said Claims 1-10.