JP2005113030A - Aqueous pollution control coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce rain streak contamination or rain spot contamination when exposed outdoors in a paint film composed of a water-based paint, and in particular, to prevent dirt immediately after the paint film is formed and Disclosed is a water-based antifouling coating composition that is excellent in sustainability to prevent rain stains.
An aqueous contamination-preventing coating composition comprising an aqueous dispersion, colloidal silica, and a specific surfactant.
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Description

  The present invention relates to an aqueous coating composition having excellent antifouling properties. In particular, the present invention relates to a water-based antifouling coating composition useful as a paint, a building finish coating material, and the like, a paint containing the water-based antifouling coating composition, and a coating method using the paint. Further, the present invention relates to a stain-resistant composite including a coating formed using the paint.

  In recent years, rain streaks or raindrop contamination seen on the walls of buildings has occurred in places where rainwater flows down, and the difference in dirt from places without rain streaks can damage the aesthetics of buildings. Has been. Usually, this rain stripe contamination can be prevented by increasing the hydrophilicity of the coating surface. In solvent-based paints, a technique has been proposed in which alkoxysilane is coordinated to the surface of the coating film and hydrolyzed with time to render the coating film surface hydrophilic. The problem with this technology is that the degree of hydrolysis depends on the weather conditions for about one month immediately after the formation of the coating film, so that the hydrolysis is delayed especially when the dry condition continues, and the coating film becomes dirty. There were drawbacks.

As a method for preventing this rain streak contamination in water-based paints, Japanese Patent Application Laid-Open No. 9-52974 proposes that by adding a specific solvent to an aqueous emulsion, the water contact angle of the coating film can be reduced and rain streaks can be reduced. However, the effect is not sufficient, and it was difficult to maintain the effect for a long time.
Japanese Patent Laid-Open No. 10-46099 proposes that rain streaks can be reduced by emulsion polymerization with a specific unsaturated monomer and a polymerizable surfactant, but it has been difficult to maintain the effect over a long period of time. .
JP-A-10-298489 proposes that a specific block copolymer crosslinking agent and dihydrazide compound crosslinking agent can be used in combination, and rain stripes can be reduced by a crosslinked coating film with a polycarbonyl compound. It was not good, and its sustainability was inferior.

Japanese Patent Application Laid-Open No. 11-217480 discloses a method of using an oxyalkylene group as a polymerization emulsifier, but it is not sufficient for preventing contamination.
Japanese Patent Laid-Open No. 54-13938 proposes a method of applying a top coating of a mixture of an acrylic resin and colloidal silica onto a coating film of a colloidal silica aqueous dispersion inorganic coating containing an inorganic filler. However, sufficient surface hardness and contamination were not obtained with the top coating alone.
JP-A-7-26165 proposes blending colloidal silica into an emulsion obtained by emulsion polymerization using a reactive surfactant for the purpose of improving heat blocking resistance and coating solution storage stability. However, the amount of colloidal silica added was large, and the resulting coating film had poor water resistance.

JP-A-56-57860 discloses an ethylenic coating for the purpose of improving adhesion as an undercoat for inorganic building materials, and JP-A-11-116885 for the purpose of imparting stain resistance to a paint film. It has been proposed to blend an emulsion obtained by copolymerizing an alkoxysilane having a group during emulsion polymerization with colloidal silica. However, if the mixed coating solution is stored as the storage stability of the coating solution, it will cause agglomeration and the coating will be impossible. Rather, when a large amount of an emulsifier was added for stabilization, the water resistance of the coating film was very poor.
In Japanese Examined Patent Publication No. 3-47669, the amount of colloidal silica added is large relative to the emulsion, the water resistance of the resulting coating film is poor, and when the mixed coating solution is stored as the storage stability of the coating solution, it causes agglomeration and coating. It became impossible.

In JP-A-7-118573, it is proposed to coat a blend of colloidal silica-containing emulsion and colloidal silica for the purpose of anti-slip properties. However, when used in paints, sufficient gloss cannot be obtained. It was.
Japanese Patent Application Laid-Open No. 59-217702 proposes an aqueous dispersion resin composition obtained by emulsion polymerization in the presence of colloidal silica and a polymerizable monomer capable of emulsification. However, polymerization stability and water resistance are proposed. However, the content of colloidal silica was low and the low contamination was not achieved.
Japanese Patent Application Laid-Open No. 11-1893 proposes an aqueous coating composition obtained by emulsion polymerization of colloidal silica, an ethylenically unsaturated compound in the presence of an activator and water. Many have poor polymerization stability and water resistance.

JP-A-9-165554 discloses a composition comprising a latex containing a large amount of dimethylsiloxane units and containing a keto group, a hydrazide compound, and colloidal silica. Requires a large amount of colloidal silica in the coating liquid, so that the storage stability of the coating liquid is not sufficient.
Japanese Patent Application Laid-Open No. 10-168393 discloses a composition comprising a keto group and silanol group-containing emulsion, a hydrazide compound, and colloidal silica surface-treated with a hydrolyzable silane. Requires a large amount of surface-treated colloidal silica in the coating liquid, so that the storage stability of the coating liquid was not sufficient.

Japanese Patent Application Laid-Open No. 2001-335721 discloses a composition in which a colloidal silica whose surface is coated with a nonionic surfactant or a vinyl polymer and an emulsion are blended. In order to maintain stability, many surfactants are disclosed. As a result, the water resistance is poor. Also, the stability was not sufficient.
Japanese Patent Application Laid-Open No. 55-40717 proposes a blend of colloidal silica and a specific surfactant and emulsion, but the amount of colloidal silica added to the emulsion is large, and the resulting coating film has water resistance and weather resistance. Sex was not enough.
In JP-A-9-40912 and JP-A-9-40913, an aqueous resin composition for paint containing a water-dispersible polysiloxane that gives a coating film with good transparency is proposed. It was not enough.

JP-A-9-52974 Japanese Patent Laid-Open No. 10-46099 Japanese Patent Laid-Open No. 10-298489 Japanese Patent Laid-Open No. 11-217480 JP 54-139938 A JP-A-7-26165 JP-A-56-57860 Japanese Patent Application Laid-Open No. 11-116885 Japanese Patent Publication No. 3-47669 JP-A-7-118573 JP 59-217702 A JP-A-11-1893 JP-A-9-165554 Japanese Patent Laid-Open No. 10-168393 JP 2001-335721 A JP 55-40717 A Japanese Patent Laid-Open No. 9-40912 Japanese Patent Laid-Open No. 9-40913

  The object of the present invention is to reduce rain streak contamination or rain stain contamination when exposed to water outdoors in a paint film comprising a water-based paint, and in particular, to prevent dirt immediately after the paint film is formed, and It is an object of the present invention to provide a water-based antifouling coating composition that is excellent in sustainability to prevent soil contamination or rain stain contamination.

As a result of intensive studies to solve the above problems, the present inventors have found that a coating film obtained from a composition containing an aqueous dispersion, colloidal inorganic particles, and a specific surfactant is water-resistant. The present inventors have found that the contact angle can be reduced to 75 ° or less and the effect that the rain streaks of the coating film are not conspicuous is achieved, and the present invention has been completed.
That is, the first of the present invention is (A) a polymer block having dimethylsiloxane as a repeating unit, (B) a polymer block having a vinyl polymerizable monomer as a repeating unit, and (A) the polymer block ( B) A graft block copolymer composed of (C) a silicon-containing graft-crossing agent unit copolymerized with the polymer block is emulsified and dispersed in an aqueous medium containing a surfactant, and C) The content of the silicon-containing graft crossing agent unit is 0.5 mol% or more and 50 mol% based on the silicon atom with respect to the total amount of the above-mentioned (A) polymer block and (C) silicon-containing graft crossing agent unit. An aqueous contamination-preventing coating composition comprising the following (D) aqueous dispersion, (E) colloidal inorganic particles, and (F) a sulfosuccinic acid surfactant.

The second of the present invention is the first aqueous antifouling coating composition of the invention characterized in that it comprises (G) a surfactant containing an alkylene oxide group.
In the third aspect of the present invention, (D) 0.1 to 95 parts by mass of colloidal inorganic particles and (F) a sulfosuccinic acid-based surfactant is 0.1% with respect to 100 parts by mass of the resin solid content of the aqueous dispersion. It is 1-20 mass parts, It is an aqueous | water-based antifouling coating composition in any one of 1st and 2 of the invention characterized by the above-mentioned.
A fourth aspect of the present invention is the aqueous contamination-preventing coating composition according to any one of the first to third aspects of the invention, wherein the colloidal inorganic particles include colloidal inorganic particles coated with an organic polymer. .
A fifth aspect of the present invention is the aqueous contamination-preventing coating composition according to any one of the first to fourth aspects of the invention, wherein the colloidal inorganic particles (E) are colloidal silica.
A sixth aspect of the present invention is any one of the first to fifth aspects of the present invention, wherein (F) the sulfosuccinic acid-based surfactant is a sulfosuccinic acid-based surfactant having no radical polymerizable double bond. A water-based antifouling coating composition.
A seventh aspect of the present invention is that the surfactant (G) having an alkylene oxide group is a surfactant having a radical polymerizable double bond containing an alkylene oxide group. Any aqueous antifouling coating composition.

8th of this invention is characterized by including the (meth) acrylic acid ester which has 5 mass% or more of cycloalkyl groups in the polymer block component which uses (B) vinyl polymerizable monomer as a repeating unit. It is the water-based antifouling coating composition according to any one of the first to seventh aspects of the invention.
The ninth of the present invention is (B) a monomer having a radical polymerizable double bond containing at least one aldo group or keto group in the molecule in the polymer block component having a vinyl polymerizable monomer as a repeating unit. A water-based antifouling coating composition according to any one of the first to eighth aspects of the invention, comprising a body.
A tenth aspect of the present invention is the aqueous contamination-preventing coating composition according to any one of the first to ninth aspects of the present invention, comprising an organic hydrazine compound having two or more hydrazine residues.
An eleventh aspect of the present invention is the aqueous contamination-preventing coating composition according to any one of the first to ninth aspects, which comprises a semicarbazide-based curing agent.
A twelfth aspect of the present invention is the aqueous contamination-preventing coating composition according to any one of the first to eleventh aspects of the invention, wherein the particle size of the graft block copolymer is 20 nm or more and 150 nm or less.

The thirteenth aspect of the present invention is the water-based antifouling coating composition according to any one of claims 1 to 12, which is used for paints.
14th of this invention is the coating material containing the 13th aqueous | water-based antifouling coating composition of this invention.
A fourteenth aspect of the present invention is a stain resistant composite comprising a coating formed using the paint of claim 13.
A fifteenth aspect of the present invention is a coated article using the paint according to claim 13.
A sixteenth aspect of the present invention is an outer wall material characterized by using the paint according to claim 13.
A seventeenth aspect of the present invention is a building characterized by using the paint according to claim 13.
The eighteenth aspect of the present invention is a coating method using the paint according to claim 13.

  The water-based antifouling coating composition of the present invention is used in water-based paints, and can reduce rain streak-like contamination when a coating film made of the composition is exposed to the outdoors, and in particular, can prevent contamination immediately after the coating film is formed. , And the reduction of rain streak contamination can be maintained over a long period of time.

Hereinafter, the present invention will be described in detail. The aqueous dispersion (D) of the present invention comprises a graft block copolymer emulsified and dispersed in an aqueous medium in which a surfactant is present.
The graft block copolymer constituting the resin composition of the present invention includes (A) a polymer block having dimethylsiloxane as a repeating unit (hereinafter referred to as (A) polymer block), and (B) a vinyl polymerizable monomer. A polymer block (hereinafter referred to as (B) polymer block) and (C) a silicon-containing graft crossing agent unit (hereinafter referred to as (C) graft crossing agent unit), and (C) graft crossing The agent unit is composed of (A) a polymer block copolymerized via at least one siloxane bond, and (B) a copolymer block.

In the graft block copolymer, (C) the graft crossing agent unit and (B) the polymer block are copolymerized with (C) the vinyl polymerizable functional group in the graft crossing agent used as a raw material for the graft crossing agent unit (B) ) It can be carried out by radical copolymerization with a vinyl polymerizable monomer which is a raw material for the polymer block.
The polymer block (A) in the graft block copolymer of the present invention is composed of dimethyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopenta. Obtained by condensing dimethylsiloxane cyclic oligomers such as siloxane, dodecamethylcyclohexasiloxane, tetradecamethylcycloheptasiloxane, dimethylcyclics (dimethylsiloxane cyclic oligomer 3-7 mer mixture) and two or more types of alkoxysilanes Can be synthesized using raw materials such as alkoxysilane oligomers and dimethyldichlorosilane. Considering performance such as thermal stability of the obtained resin and cost, the most suitable raw material for the polymer block (A) is a dimethylsiloxane cyclic oligomer.

Moreover, it is preferable that the weight average molecular weight of the polymer block (A) of this invention is 10,000 or more. This is because if the weight average molecular weight is less than 10,000, the durability of the resulting coating film tends to decrease. More preferably, it is 50,000 or more.
(B) As an example of the vinyl polymerizable monomer used for constituting the polymer block, first, acrylic acid ester, methacrylic acid ester (in this application, acrylic acid and / or methacrylic acid are collectively expressed as (meth) acrylic acid. ). Specific examples of the monomer copolymerizable with the (meth) acrylic ester include monomers having a carboxylic acid group, methacrylamide monomers, vinyl cyanides and the like.

Examples of the monomer having a carboxylic acid group include itaconic acid, fumaric acid, maleic acid, maleic anhydride, maleic acid and monoesters thereof, acrylic acid, methacrylic acid, and crotonic acid.
Examples of (meth) acrylic acid esters include (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms in the alkyl part, (meth) acrylic acid hydroxyalkyl esters and ethylene oxide having 1 to 18 carbon atoms in the alkyl part. (Poly) oxyethylene (meth) acrylate having 1 to 100 groups, (poly) oxypropylene (meth) acrylate having 1 to 100 propylene oxide groups, and 1 to 100 ethylene oxide groups (Poly) oxyethylene di (meth) acrylate and the like.

Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acrylic acid. Examples include cyclohexyl, methyl cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, and the like.
Specific examples of the (meth) acrylic acid hydroxyalkyl ester include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxycyclohexyl (meth) acrylate, and dodecyl (meth) acrylate. Etc.
Specific examples of (poly) oxyethylene (meth) acrylate include ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate, (meth) Examples include tetraethylene glycol acrylate and tetraethylene glycol methoxy (meth) acrylate.

Specific examples of (poly) oxypropylene (meth) acrylate include propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, dipropylene glycol (meth) acrylate, dipropylene glycol methoxy (meth) acrylate , (Meth) acrylic acid tetrapropylene glycol, methoxy (meth) acrylic acid tetrapropylene glycol, and the like.
Specific examples of (poly) oxyethylene di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol methoxy (meth) acrylate, tetraethylene glycol di (meth) acrylate Etc. The (meth) acrylic acid ester is preferably used in an amount of 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, based on the total mass of the (E) ethylenically unsaturated monomer.

In the present invention, it is preferable to include (E) a (meth) acrylic acid ester having a cycloalkyl group as the ethylenically unsaturated monomer because it is particularly excellent in durability. (E) 5% by mass or more, more preferably 5% by mass or more and 99% by mass or less, and more preferably 5% by mass or more and 80% by mass or less of the ethylenically unsaturated monomer has a cycloalkyl group. An acid ester or a mixture thereof is preferred. When (meth) acrylic acid having a cycloalkyl group is 5% by mass or more, the durability is excellent, and when it is 80% or less, the film formability is good.
Examples of (meth) acrylamide monomers include (meth) acrylamide, N-methylol (meth) acrylamide, and N-butoxymethyl (meth) acrylamide. Examples of vinyl cyanides include (meth) acrylonitrile. and so on.

Examples of the ethylenically unsaturated monomer having an aldo group or keto group include acrolein, diacetone acrylamide, diacetone methacrylamide, vinyl methyl ketone, vinyl ethyl ketone, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, formylstyrol, and the like. And the combination thereof.
Specific examples of (E) ethylenically unsaturated monomers other than the above include olefins such as ethylene, propylene and isobutylene, dienes such as butadiene, haloolefins such as vinyl chloride and vinylidene chloride, acetic acid, and the like. Carboxylic acid vinyl esters such as vinyl, vinyl propionate, n-vinyl butyrate, vinyl benzoate, vinyl pt-butylbenzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate, vinyl laurate, Carboxylic acid isopropenyl esters such as isopropenyl acetate and isopropenyl propionate, vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether, aromatic vinyl compounds such as styrene and vinyl toluene, allyl acetate, and allyl benzoate Esters, allyl ethers such as allyl ethyl ether, allyl glycidyl ether, allyl phenyl ether, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy- 1,2,2,6,6-pentamethylpiperidine, perfluoromethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluoropropylmethyl (meth) acrylate, vinylpyrrolidone, trimethylolpropane tri (meth) Examples thereof include acrylate, glycidyl (meth) acrylate, 2,3-cyclohexene oxide (meth) acrylate, allyl (meth) acrylate, and the like and combinations thereof.

(B) Among vinyl polymerizable monomers constituting the polymer block, monomers having a highly polar functional group such as a carboxyl group, an amide group, and a hydroxyl group are adhesive to the base material of the coating film. Therefore, it is preferable to contain 0.5% by mass or more in the vinyl polymerizable monomer constituting the polymer block (B), particularly 0.5% by mass of the carboxyl group-containing monomer. It is preferable to contain above.
(C) The grafting agent used to constitute the grafting agent unit includes (A) one or more silanol groups, alkoxysilyl groups or chlorosilyl groups in the molecule for copolymerization with the polymer block. Examples thereof include those having a functional group and a polymerizable group such as vinyl group, allyl group, (meth) acryloyloxy group, and p-vinylphenyl group for copolymerization with the polymer block (B). In the invention, a vinyl polymerizable functional group-containing alkoxysilane compound is preferably used in consideration of polymerization reactivity and cost.

  Examples of vinyl polymerizable functional group-containing alkoxysilane compounds include, for example, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropyldiethoxydiethyl. Examples include silane, γ-methacryloyloxypropyldiethoxymethylsilane, and γ-methacryloyloxytriethoxysilane.

  The content of (C) graft crossing agent unit in the graft block copolymer is 0.5 mol% or more based on silicon atoms with respect to the total amount of (A) polymer block and (C) graft crossing agent unit. If it is less than 0.5 mol%, the transparency of the resulting resin coating film is lowered. On the other hand, if it exceeds 50 mol%, it is disadvantageous in terms of raw material costs. In addition, by-products such as alcohol desorbed at the time of condensation impair the stability and handleability of the latex, and further impair the performance of the coating film. The content of the (C) graft-crossing agent unit is preferably 0.5 mol% or more and 40 mol% or less, more preferably 0.5 mol% or more and 20 mol% or less based on the above criteria. (C) When the content of the graft crossing agent unit is 20 mol% or less, a latex can be stably obtained by emulsion polymerization.

The content of the (B) polymer block in the graft block copolymer is 50% by mass or more and 95% by mass with respect to the total amount of the (A) polymer block, (B) polymer block and (C) graft crossing agent unit. % Or less is preferable. (B) The coating film formed from the resin composition having a polymer block content of less than 50% by mass tends to decrease in strength, and the content of (B) polymer block exceeds 95% by mass. In some cases, the water resistance and blocking resistance of the coating film tend to decrease. More preferably, it is 70 mass% or more and 95 mass% or less.
The aqueous dispersion (D) of the present invention is provided in the form of an emulsion in which the resin component having the above characteristics is emulsified and dispersed in water in the presence of a surfactant. The particle size of the emulsion is a weight average particle size. Therefore, it is preferably 20 nm or more and 150 nm or less. The emulsion particle diameter is 150 nm or less, and the transparency and appearance of the coating film are good. On the other hand, the particle diameter is 20 nm or more, the amount of surfactant used is not large, and the coating film performance such as coating film appearance and water resistance is good. good. A more preferable particle diameter of the emulsion is 120 nm or less. When the particle diameter is 120 nm or less, the transparency of the coating film is improved even when the amount of the grafting agent used is 1 mol% or less (about 3 mass% or less).

  The resin component content in the emulsion can usually be arbitrarily selected within a range of 50% by mass or less, but can be further increased by concentration. In the case of subjecting to normal spray coating, a content of 15 to 45% by mass is preferable in consideration of coating properties and coating film performance.

  As (E) colloidal inorganic particles in the present invention, colloidal silica is easily available, inexpensive and preferable. Colloidal silica can be prepared and used by a sol-gel method, and a commercially available product can also be used. When colloidal silica is prepared by the sol-gel method, Werner Stober et al; J. Colloid and Interface Sci., 26, 62-69 (1968), Rickey D. Badley et al; Lang muir 6, 792- 801 (1990), Color Material Association Journal, 61 [9] 488-493 (1988), and the like. Colloidal silica is a dispersion of water or a water-soluble solvent of silica having silicon dioxide as a basic unit, and the average particle diameter is preferably 5 to 120 nm, more preferably 10 to 80 nm. When the particle diameter is 5 nm or more, the storage stability of the coating liquid is good, and when it is 120 nm or less, the water whitening resistance is good. Colloidal silica having a particle size in the above range can be used in the state of an aqueous dispersion, whether acidic or basic, and is appropriately selected according to the stable region of the aqueous dispersion to be mixed (A). be able to. Examples of acidic colloidal silica using water as a dispersion medium include, as commercial products, Snowtex (trademark) -O manufactured by Nissan Chemical Industries, Ltd., Snowtex-OL, Adelite (trademark) AT- manufactured by Asahi Denka Kogyo Co., Ltd. 20Q, Clariant Japan Co., Ltd. clebosol (trademark) 20H12, clebosol 30CAL25, etc. can be used.

  Examples of basic colloidal silica include silica stabilized by addition of alkali metal ions, ammonium ions, and amines. For example, SNOWTEX-20, SNOWTEX-30, SNOWTEX-C, and SNOWTEX-C manufactured by Nissan Chemical Industries, Ltd. Tex-C30, Snowtex-CM40, Snowtex-N, Snowtex-N30, Snowtex-K, Snowtex-XL, Snowtex-YL, Snowtex-ZL, Snowtex PS-M, Snowtex PS-L Adelite AT-20, Adelite AT-30, Adelite AT-20N, Adelite AT-30N, Adelite AT-20A, Adelite AT-30A, Adelite AT-40, Adelite AT-50, etc. manufactured by Asahi Denka Kogyo Co., Ltd. Clariant Japan Co., Ltd. Kurebozoru 30R9, Kurebozoru 30R50, such Kurebozoru 50R50, DuPont Ludox (TM) HS-40, Ludox HS-30, Ludox LS, and the like Ludox SM-30.

Examples of colloidal silica using a water-soluble solvent as a dispersion medium include MA-ST-M (methanol dispersion type having a particle size of 20 to 25 nm), IPA-ST (particle size of 10) manufactured by Nissan Chemical Industries, Ltd. ˜15 nm isopropyl alcohol dispersion type), EG-ST (ethylene glycol dispersion type with particle diameter of 10 to 15 nm), EG-ST-ZL (ethylene glycol dispersion type with particle diameter of 70 to 100 nm), NPC-ST (particles) And ethylene glycol monopropyl ether dispersion type having a diameter of 10 to 15 nm).
These colloidal silicas may be used alone or in combination. As a minor component, alumina, sodium aluminate or the like may be contained. Colloidal silica may contain an inorganic base (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia) or an organic base (such as tetramethylammonium) as a stabilizer.

(E) As the colloidal inorganic particles, inorganic compounds that give colloidal particles other than silica may be used. Specific examples of the inorganic compounds include TiO ₂ , TiO ₃ , SrTiO ₃ , FeTiO ₃ , _{WO 3, SnO 2, Bi 2} O 3, In 2 O 3, ZnO, Fe 2 O 3, RuO 2, CdO, CdS, CdSe, GaP, GaAs, CdFeO 3, MoS 2, LaRhO 3, GaN, CdP, ZnS , ZnSe, ZnTe, Nb ₂ O ₅ , ZrO ₂ , InP, GaAsP, InGaAlP, AlGaAs, PbS, InAs, PbSe, InSb, and other semiconductors having photocatalytic activity, Al ₂ O ₃ , AlGa, As, Al (OH _{) 3, Sb 2 O 5,} Si 3 N 4, Sn-In 2 O 3, Sb-In 2 O 3, _{gF, CeF 3, CeO 2,} 3Al 2 O 3 · 2SiO 2, BeO, SiC, AlN, Fe, Co, Co-FeO X, CrO 2, Fe 4 N, BaTiO 3, BaO-Al 2 O 3 -SiO 2 , Ba ferrite, SmCO ₅ , YCO ₅ , CeCO ₅ PrCO ₅ , Sm ₂ CO ₁₇ , Nd ₂ Fe ₁₄ B, Al ₄ O ₃ , α-Si, SiN ₄ , CoO, Sb—SnO ₂ , Sb ₂ O ₅ , _{MnO 2, MnB, Co 3 O} 4, Co 3 B, LiTaO 3, MgO, MgAl 2 O 4, BeAl 2 O 4, ZrSiO 4, ZnSb, PbTe, GeSi, FeSi 2, CrSi 2, CoSi 2, MnSi 1. _{73, Mg 2 Si, β-} B, BaC, BP, BaC, BP, TiB 2, ZrB 2, HfB 2, Ru 2 i _3, TiO _{2 (rutile), TiO 3, PbTiO 3,} Al 2 TiO 5, Zn 2 SiO 4, Zr 2 SiO 4, 2MgO 2 -Al 2 O 2 -5SiO 2, Nb 2 O 5, Li 2 O -Al ₂ O ₃ -4SiO _2, Mg ferrite, Ni ferrite, Ni-Zn ferrite, Li ferrite, and the like Sr ferrite. These colloidal inorganic particles can be used alone or in admixture of two or more.

  As colloidal inorganic particles coated with an organic polymer, for example, particles obtained by emulsion polymerization of colloidal silica with hydrolyzable silane having an ethylenically unsaturated monomer and a radically polymerizable double bond (for example, Disclosed in JP-A-59-71316), particles obtained by emulsion polymerization of an ethylenically unsaturated monomer and an anionic polymerizable monomer in the presence of colloidal silica (for example, JP-A-59-71). (Disclosed in No. 217702), particles obtained by a method in which a water-soluble polymer compound is adsorbed on inorganic particles and then coated with a polymer of a radical polymerizable monomer (for example, disclosed in JP-A-60-58237), ethylene Particles obtained by emulsion polymerization of an ethylenically unsaturated monomer and an ethylenically unsaturated monomer having a hydroxyl group in the presence of colloidal silica (for example, (Disclosed in JP-A-6-199917), having a core / shell structure, an organic polymer and silica and / or colloidal silica not covalently bonded to the organic polymer in the core, By arranging molecules and forming a three-dimensional cross-linked network structure and / or IPN structure between the core organic polymer / shell organic polymer, the silica and / or colloidal silica in the core is physicochemically bonded without being covalently bonded. Particles obtained by a method of emulsion polymerization of an ethylenically unsaturated compound in the presence of particles (for example, disclosed in JP-A-8-290912), colloidal silica, an activator and water. (Disclosed in Kaihei 11-1893), particles in which a vinyl polymer is bonded to the surface of colloidal silica particles via a cationic residue (for example, Disclosed in JP-A-11-209622), particles in which a vinyl polymer is bonded to the surface of inorganic or organic particles directly or via a nonionic surfactant (for example, disclosed in JP-A-2000-290464), inorganic or It is preferably a colloidal fine particle (for example, disclosed in JP-A-2001-335721) in which nonionic surfactants are aggregated or aggregated and deposited on the surface of organic particles.

In the present invention, (E) the colloidal inorganic particles are preferably used in an amount of 0.1 to 95 parts by weight, more preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the resin solid content of the (D) aqueous dispersion. Parts, more preferably 0.5 to 20 parts by mass.
In the present invention, examples of the (S) sulfosuccinic acid surfactant include a sulfosuccinic acid compound represented by the following formula (1).

{In the formula, R ^a and R ^b may be the same or different, and hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, carbon A hydrocarbon group such as an aryl group of 5 to 10 carbon atoms, a C 6-19 aralkyl group or the like, or a part of which is substituted with a hydroxyl group, a carboxylic acid group, or the like, or a polyoxyalkylene alkyl ether group (carbon in the alkyl moiety) An organic group or an alkali metal having a number of 2 to 4, an alkylene oxide compound such as a polyoxyalkylene alkylphenyl ether group (wherein the alkyl portion has 0 to 20 carbon atoms, and the alkylene portion has 2 to 4 carbon atoms), ammonium, An organic amine base or an organic quaternary ammonium base, and M is an alkali metal, ammonium, organic amine base or organic quaternary base. Shows the ammonium salt.)

More specifically, in R ^a and R ^b of the compound represented by the above formula (1), R ^a and / or R ^b are represented by the following formulas (2), (3), and (4). It is done.

{In each of the formulas (2), (3), (4), R ²¹ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, carbon A hydrocarbon group such as an aryl group of 5 to 10 carbon atoms, a C 6-19 aralkyl group or the like, or a part of which is substituted with a hydroxyl group, a carboxylic acid group, or the like, or a polyoxyalkylene alkyl ether group (carbon in the alkyl moiety) An organic group containing an alkylene oxide compound such as a number of 2 to 4 and a polyoxyalkylene alkylphenyl ether group (wherein the alkyl portion has 0 to 20 carbon atoms and the alkylene portion has 2 to 4 carbon atoms), and A is carbon 2 to 4 alkylene groups or substituted alkylene groups, n is an integer of 0 to 200, and R ²² is hydrogen or a methyl group.)}

  In the present invention, as represented by the general formulas (1) to (4), for example, as a sulfosuccinic acid-based surfactant having no radical polymerizable double bond, dioctyl sodium sulfosuccinate {Perex manufactured by Kao Corporation (Trademark) OT-P or aerosol (trademark) OT-75 manufactured by Mitsui Cytec Co., Ltd.}, dihexyl sodium sulfosuccinate {Aerosol (trademark) MA-80 manufactured by Mitsui Cytech Co., Ltd.)}, Mitsui Cytec Co., Ltd. Aerosol (trademark) TR-70, A-196-85, AY-100, IB-45, A-102, A-103, 501 etc. are available. As sulfosuccinic acid type surfactants having a radically polymerizable double bond, Sanyo Chemical Co., Ltd. Eleminol (trademark) JS-2, JS-5, Kao Co., Ltd. latemuru (trademark) S-120, S-180 And S-180A. Among them, a sulfosuccinic acid-based surfactant having no radical polymerizable double bond is preferable in terms of lowering the water contact angle of the coating film.

In the present invention, (F) the sulfosuccinic acid type surfactant is used in an amount of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts per 100 parts by mass of the resin solid content of (D) the aqueous dispersion. Part by mass, more preferably 1.0 to 5 parts by mass is used. When used in this range, a film with good water resistance is formed.
In the present invention, (G) a surfactant containing an alkylene oxide group does not contain (F) in the structure, and an anionic surfactant having a radical polymerizable double bond containing an alkylene oxide group, An anionic surfactant having no radical polymerizable double bond containing an alkylene oxide group, a nonionic surfactant having a radical polymerizable double bond containing an alkylene oxide group, a radical polymerizable double containing an alkylene oxide group Nonionic surfactants having no bonds are included.

  In the present invention, examples of the anionic surfactant (G) containing an alkylene oxide group include compounds represented by the following formulas (5) and (6).

(In the formula ^{(5), (6),} R 51 represents an alkyl group having 1 to 20 carbon atoms, C20 alkenyl carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, aralkyl of 6 to 19 carbon atoms A hydrocarbon group such as a group, or a part of which is substituted with a hydroxyl group, a carboxylic acid group, or the like, or a polyoxyethylene alkyl ether group (wherein the alkyl moiety has 0 to 20 carbon atoms and the alkylene moiety has 2 carbon atoms) -4), an organic group containing an alkylene oxide compound such as a polyoxyalkylene alkylphenyl ether group (wherein the alkyl moiety has 0 to 20 carbon atoms and the alkylene moiety has 2 to 4 carbon atoms) A is 2 carbon atoms. -4 alkylene group or a partially substituted alkylene group, n is an integer of 0-200, and M is ammonium, sodium, potassium.)

  In the present invention, examples of the anionic surfactant (G) having a radical polymerizable double bond containing an alkylene oxide group include compounds represented by the following formulas (7), (8) and (9).

(Wherein R ⁷¹ is an alkyl group, alkenyl group or aralkyl group having 6 to 18 carbon atoms, R ⁷² is hydrogen, an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, and R ⁷³ is hydrogen or A propenyl group, A is an alkylene group having 2 to 4 carbon atoms or a partially substituted alkylene group, n is an integer of 1 to 200, and M is ammonium, sodium, or potassium.)

Wherein R ⁸¹ is hydrogen or a methyl group, R ⁸² is an alkyl group or acyl group having 8 to 24 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 0 to 50, and m is 0 to 0. An integer of 20, M is ammonium, sodium, potassium.)

Wherein R ⁹¹ is an alkyl group having 8 to 30 carbon atoms, R ⁹² is hydrogen or a methyl group, A is an alkylene group or substituted alkylene group having 2 to 4 carbon atoms, and n is 0 or an integer of 1 to 200. , M is an ammonium, sodium, potassium or alkanolamine residue.)
Examples of the alkylphenol ether compound represented by the formula (7) include Aqualon (trademark) HS-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and examples of the compound represented by the formula (8) include Asahi Denka. There are Adekaria Soap (trademark) SE-1025A, SR-1025A, SR-10N, SR-20N, etc. manufactured by Kogyo Co., Ltd., and examples of the compound represented by the above formula (9) include Daiichi Kogyo Seiyaku Co., Ltd. Examples include Aqualon (trademark) KH-5 and KH-10. Other examples of the anionic surfactant having a radically polymerizable double bond containing an alkylene oxide group include, for example, Antox (trademark) -MS-60 manufactured by Nippon Emulsifier Co., Ltd., Latemul PD-101 manufactured by Kao Corporation, PD-104, etc., and Sanyo Chemical Co., Ltd. Eleminor (trademark) RS-30, etc. are available.

  In the present invention, examples of the nonionic surfactant (G) containing an alkylene oxide group include compounds represented by the following formulas (10) and (11).

(In the formula ^{(10), (11),} R 101 represents an alkyl group having 1 to 20 carbon atoms, C20 alkenyl carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, aralkyl of 6 to 19 carbon atoms A hydrocarbon group such as a group, or a part of which is substituted with a hydroxyl group, a carboxylic acid group, or the like, or a polyoxyethylene alkyl ether group (wherein the alkyl moiety has 0 to 20 carbon atoms and the alkylene moiety has 2 carbon atoms) -4), an organic group containing an alkylene oxide compound such as a polyoxyalkylene alkylphenyl ether group (wherein the alkyl moiety has 0 to 20 carbon atoms and the alkylene moiety has 2 to 4 carbon atoms) A is 2 carbon atoms. An alkylene group of ˜4 or a partially substituted alkylene group, n is an integer of 0 to 200, and R ¹⁰² is hydrogen or a methyl group.)

  In the present invention, examples of the nonionic surfactant (G) having a radical polymerizable double bond containing an alkylene oxide group include compounds represented by the following formulas (12), (13) and (14).

(Wherein R ¹²¹ is an alkyl group having 6 to 18 carbon atoms, an alkenyl group, or an aralkyl group, R ¹²² is hydrogen, an alkyl group having 6 to 18 carbon atoms, an alkenyl group, or an aralkyl group, and R ¹²³ is hydrogen or A propenyl group, A is an alkylene group having 2 to 4 carbon atoms or a partially substituted alkylene group, and n is an integer of 1 to 200.)

(Wherein R ¹³¹ is hydrogen or a methyl group, R ¹³² is an alkyl group or acyl group having 8 to 24 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 0 to 100, and m is 0 to 0) It is an integer of 50.)

Wherein R ¹⁴¹ is an alkyl group having 8 to 30 carbon atoms, R ¹⁴² is hydrogen or a methyl group, A is an alkylene group or substituted alkylene group having 2 to 4 carbon atoms, and n is 0 or an integer of 1 to 200. .)
Examples of the compound represented by the above formula (12) include Aqualon (trademark) RN-10, RN-20, RN-30, and RN-50 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. As the compound represented by the above formula (13), for example, Adeka Soap (trademark) NE-20, NE-30, NE-40, ER-10, ER-20, ER-30, manufactured by Asahi Denka Kogyo Co., Ltd., ER-40 etc. are mentioned.

In the present invention, (G) a surfactant containing an alkylene oxide group has a radically polymerizable double bond containing an alkylene oxide group in order to obtain a film having good polymerization stability and good water resistance. A surfactant is preferable, and an anionic surfactant having a radical polymerizable double bond containing an alkylene oxide group is more preferable.
In the present invention, the amount of (G) the surfactant containing an alkylene oxide group is preferably small in order to obtain a film having good water resistance, and (D) the resin solid content of the aqueous dispersion is 100. 0.1-5 mass% can be used with respect to a mass part.

  In addition to (F) a sulfosuccinic acid type surfactant and (G) a surfactant containing an alkylene oxide group as surfactants used for emulsion polymerization in the present invention, sodium p-styrenesulfonate, p-styrenesulfonic acid Potassium, acrylic acid- (2-sulfoethyl) ester sodium, acrylic acid- (2-sulfoethyl) ester potassium, methacrylic acid- (2-sulfoethyl) ester sodium, acrylic acid- (3-sulfopropyl) ester potassium, methacrylic acid- (3-sulfopropyl) ester sodium, fatty acid soap, alkyl sulfonate, alkyl sulfosuccinate, polyoxyethylene sorbitan fatty acid ester, oxyethylene oxypropylene block copolymer and the like.

  In the present invention, it contains (D) an aqueous dispersion, (E) colloidal inorganic particles and / or colloidal inorganic particles coated with an organic polymer, (F) a sulfosuccinic acid surfactant and (G) an alkylene oxide group. Specifically, the order of mixing the surfactants to be used is the method of mixing (D), (E), (F), (G), specifically (D) to (E), (F), (G). A method of mixing in the order of (D), a method of mixing in the order of (E), (G), (F), a method of mixing in the order of (F), (E), (G), (D ) To (F), (G), (E) in order, (D) to (G), (E), (F) in order, (D) to (G), (F ), A method of mixing in the order of (E), to (D), a mixture of (E) and (F), a method of mixing in the order of (G), to (D), (G), (E To (D), (E) and (G), (F), (F), (D), (F), (E) and (F) G) a method of mixing in the order of the mixture, to (D), a mixture of (F) and (G), a method of mixing in the order of (E), (D), (E), (F) and (G) And a method of mixing the mixture of (E), (F), and (G) into (D).

  Specific examples of using (F) and / or (G) when producing (D) include using (F) and / or (G) when producing (D), and then (E) A method of mixing (E) and / or (G) and then mixing (E) and (F) (in this case, (F) may be the same) May be different}, the method of using (F) and / or (G) in the production of (D) and then mixing (E) and (G) {in this case (G) is the same Or may be different}, a method of using (F) and / or (G) in the production of (D) and then mixing (E), (F), (G) {in this case ( F) and (G) may be the same or different}. When mixing, mixing at room temperature or heating and mixing up to 90 ° C. can be performed.

In the present invention, (D) the solid content of the colloidal inorganic particles is preferably 0.1 to 95 parts by mass, more preferably (D) aqueous, with respect to 100 parts by mass of the resin solid content of the aqueous dispersion. (E) The solid content of the colloidal inorganic particles is 0.1 to 50 parts by weight, more preferably (D) 100 parts by weight of the resin solids of the aqueous dispersion, with respect to 100 parts by weight of the resin solids of the dispersion. (E) The solid content of the colloidal inorganic particles is 0.5 to 20 parts by mass. (E) The water resistance of the coating film obtained when the colloidal inorganic particles are within this range is good, and the rain streaks of the coating film are inconspicuous.
In the present invention, the amount of (F) sulfosuccinic acid surfactant is preferably 0.1 to 20 parts by mass, more preferably (D) the aqueous dispersion with respect to 100 parts by mass of the resin solid content of (D) the aqueous dispersion. (F) Sulfosuccinic acid-based surfactant is 0.5 to 10 parts by mass with respect to 100 parts by mass of resin solid content of the body, and more preferably (D) with respect to 100 parts by mass of resin solid content of the aqueous dispersion. (F) The sulfosuccinic acid type surfactant is 1.0 to 5 parts by mass. (F) The water resistance of the coating film obtained when the sulfosuccinic acid surfactant is within this range is good, and the rain stripes of the coating film are not conspicuous. In addition, the storage stability of the coating liquid is improved.

  In the present invention, (F) a sulfosuccinic acid type surfactant during mixing or pre-dispersion of the paint pigment, (G) a surfactant containing an alkylene oxide group, other surfactants that can be added during polymerization, If necessary, the following surfactants can be used in combination. Specifically, for example, sodium salt, potassium salt or ammonium salt of hexametaphosphoric acid, sodium salt, potassium salt or ammonium salt of tripolyphosphoric acid, sodium salt or potassium salt of a polymer having a carboxylic acid group such as polyacrylic acid, Or ammonium salt. In addition, for example, anionic surfactants represented by salts of higher fatty acids, resin acids, acidic higher alcohols, sulfate esters, higher alkyl sulfonic acids, alkyl allyl sulfonates, sulfonated castor oil, etc., or ethylene oxide and long chain fats Nonionic surfactants represented by known reaction products with alcohol, phenols, and phosphoric acids, and cationic surfactants containing quaternary ammonium salts and the like can be mentioned.

The addition of the surfactant in the resin composition of the present invention is performed at the time of polymerization of the graft block copolymer, after completion of the polymerization, or at the time of blending the resin composition.
The method for producing the resin composition of the present invention is not particularly limited. For example, (A) a cyclic dimethylsiloxane oligomer that is a raw material of a polymer block and (C) a vinyl polymerizable functional group-containing alkoxysilane that is a raw material of a graft crossing agent unit. Can be produced by emulsion polymerization in the presence of an acidic emulsifier and neutralization, and (B) graft copolymerization in the presence of a radical polymerization initiator by adding a vinyl polymerizable monomer which is a raw material of the polymer block. .
The ratio between the total amount of the cyclic dimethylsiloxane oligomer and the vinyl polymerizable functional group-containing polyfunctional alkoxysilane and water can be arbitrarily selected, but the mass ratio is preferably in the range of 1: 1 to 1: 9.

The acidic emulsifier is not particularly limited as long as it can ring-open the cyclic dimethylsiloxane oligomer. Examples of the acidic emulsifier that can be easily obtained and are suitable for polymerization include dodecylbenzenesulfonic acid. The preferred amount of the acidic emulsifier varies depending on the particle size, solid content, polymerization temperature, and other surfactant used in the intended emulsion, but the siloxane polymerization proceeds rapidly and the particle size is easily reduced. Therefore, it is preferable to use 3% by mass or more based on the total amount of the cyclic dimethylsiloxane oligomer and the vinyl polymerizable functional group-containing polyfunctional alkoxysilane.
The polymerization temperature of the siloxane is preferably at least once subjected to a heat history of 60 ° C. or higher, more preferably 75 ° C. or higher.

The particle size of the siloxane polymer in the emulsion can be controlled by the degree of preliminary dispersion of the raw material, the amount of emulsifier, the polymerization temperature, and the raw material supply method. Emulsions with smaller particle sizes are pre-emulsified with a high shear generator such as a homogenizer in the presence of an emulsifier, and the raw material or water is dripped into the water, the emulsifier is increased, or polymerization is performed. It can be obtained by any method of raising the temperature or by appropriately combining these methods.
The time required for the polymerization of siloxane varies depending on the polymerization conditions, but is usually 0.5 hours or more and 1 month or less. In the siloxane polymer polymerized in the presence of the acidic emulsifier, substantially no unreacted alkoxysilane remains. The resulting siloxane polymer emulsion is strongly acidic and must be neutralized after the siloxane polymerization.

As the radical polymerization initiator used for the subsequent emulsion polymerization of the vinyl polymerizable monomer, known ones used for the emulsion radical polymerization can be used. Examples include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis. (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like can be mentioned.
The charging method of the vinyl polymerizable monomer is not particularly limited, and any method of batch charging or dropping may be used.

The aqueous contamination-preventing coating composition of the present invention may contain an auxiliary curing agent, a curing auxiliary, and the like, if necessary, and may be used by mixing with other emulsion resins and water-soluble resins.
In the present invention, specific examples of the organic hydrazine compound include dicarboxylic acid dihydrazides containing 2 to 10, particularly 4 to 6 carbon atoms, such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, and glutaric acid dihydrazide. Adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide and itaconic acid dihydrazide, and aliphatic water-soluble dihydrazines having 2 to 4 carbon atoms, such as ethylene-1,2-dihydrazine, Examples include propylene-1,3-dihydrazine and butylene-1,4-dihydrazine. Among these, adipic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide, and succinic acid dihydrazide are preferable. Moreover, these may use 2 or more types together.

In the present invention, the semicarbazide-based curing agent is obtained by reacting a polyisocyanate compound having three or more —NCO groups in one molecule with a hydrazine derivative.
In addition, the water-based antifouling coating composition of the present invention is usually added to and mixed with water-based paints, such as pigments, thickeners, film-forming aids, plasticizers, antifreezing agents, antifoaming agents, dyes, An antiseptic, an ultraviolet absorber, a light stabilizer and the like can be arbitrarily blended.
Specific examples of thickeners include polyvinyl alcohol (including partially saponified polyvinyl acetate), polymer dispersion stabilizers such as methylcellulose, hydroxyethylcellulose, and polyvinylpyrrolidone, and other polyether-based and polycarboxylic acid-based thickeners. Etc.

  Specific examples of film forming aids include diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol mono 2-ethylhexyl ether, 2,2,4-trimethyl-1,3-butanediol iso Examples include butyrate, diisopropyl glutarate, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol methyl ether, and tripropylene glycol methyl ether. These film-forming aids can be arbitrarily blended alone or in combination.

Specific examples of the plasticizer include dibutyl phthalate and dioctyl phthalate.
Specific examples of the antifreezing agent include propylene glycol and ethylene glycol.
There are benzophenone series, benzotriazole series, and triazine series as ultraviolet absorbers. Specific examples of benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4- Methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis (5-benzoyl-4- Hydroxy-2-methoxyphenyl) methane, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4 -Dodecyloxy-2-hi B carboxymethyl benzophenone, 2-hydroxy-4-methoxy-2'-carboxy benzophenone, and the like 2-hydroxy-4-stearyloxy benzophenone.

Specific examples of radical polymerizable benzophenone-based UV absorbers include 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acryloxybenzophenone, and 2-hydroxy-5. -Methacryloxybenzophenone, 2-hydroxy-4- (acryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-diethoxy) benzophenone, 2-hydroxy-4- (Acryloxy-triethoxy) benzophenone.
Specific examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5- Di-tert-octylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenyl] benzotriazole), methyl-3- [3-tert-butyl -5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol (min 300) condensate (manufactured by Ciba Geigy Japan, product name: TINUVIN 1130), isooctyl-3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] Propionate (manufactured by Ciba Geigy Japan, product name: TINUVIN 384), 2- (3-dodecyl-5-methyl-2-hydroxyphenyl) benzotriazole (manufactured by Ciba Geigy Japan, product name: TINUVIN 571), 2- ( 2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, 2 -(2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- [2'-hydro Cis-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2-methylenebis [4- (1,1,3 , 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) ) Phenol (Nippon Ciba-Geigy Co., Ltd., product name: TINUVIN900).

  Specifically, as a radical polymerizable benzotriazole-based ultraviolet absorber, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., product name: RUVA-) 93), 2- (2′-hydroxy-5′-methacryloxyethyl-3-tert-butylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-methacrylyloxypropyl-3-tert) -Butylphenyl) -5-chloro-2H-benzotriazole, 3-methacryloyl-2-hydroxypropyl-3- [3 '-(2 "-benzotriazolyl) -4-hydroxy-5-tert-butyl] Phenyl propionate (manufactured by Nippon Ciba-Geigy Co., Ltd., product name: CGL-104).

Specific examples of triazine-based ultraviolet absorbers include TINUVIN400 (product name, manufactured by Ciba Geigy Japan).
As the light stabilizer, hindered amine light stabilizers are preferable, among them, those having low basicity are more preferable, and those having a base constant (pKb) of 8 or more are particularly preferable.
Specifically, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, 1- [2- [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propynyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyloxy] -2,2,6,6-tetramethylpiperidine, A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl-sebacate (Nippon Ciba Geigy ( ), Product name: TINUVIN292), bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, TINUVIN123 (product name, manufactured by Nihon Ciba-Geigy Corporation), and the like.

  Specific examples of the radical polymerizable hindered amine light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, 2, 2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidyl methacrylate, 2, 2,6,6, -tetramethyl-4-iminopiperidyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-cyano-1,2,2,6,6- Examples include pentamethyl-4-piperidyl methacrylate.

In the present invention, the ultraviolet absorber and / or light stabilizer is (D) a method of introducing the aqueous dispersion into the aqueous dispersion by being present during emulsion polymerization for producing the aqueous dispersion, the ultraviolet absorber and / or the light stabilizer. (D) a method of introducing an agent by mixing it with a film-forming auxiliary or the like, and adding it to the aqueous dispersion, mixing an ultraviolet absorber and / or a light stabilizer with the film-forming auxiliary, and adding a surfactant and water. After emulsification and addition, (D) a method of introducing by adding to an aqueous dispersion can be mentioned. In addition, when an ultraviolet absorber and a light stabilizer are used in combination, it exhibits excellent durability due to a synergistic effect.
The water-based antifouling coating composition of the present invention is useful as a paint, a building finish coating material, or the like. The coating formed using the coating material containing the aqueous pollution control coating composition of the present invention can reduce rain streak contamination or rain stain contamination when exposed to the outdoors in the coating film. The stain-resistant composite of the present invention, which can prevent contamination immediately after formation, has excellent durability to prevent rain streak contamination or rain stain contamination, has good storage stability of the coating liquid, and contains the coating. Has weather resistance and stain resistance.

  Examples of the base material include concrete boards / columns, cement mortar boards, slate boards, flexile boards, PC boards, ALC boards, calcium plates, gypsum boards, extruded boards, concrete blocks and other inorganic base materials, woven fabrics or non-woven fabrics. Building materials, metal plates, metal parts, wood, plastic products, stones, etc., which have been used as equipment, and those that have an old paint film surface that has deteriorated over time due to the coating of these base materials. It is mentioned as a suitable base material. For these article surfaces, primer, sealer coating, cement filler, or undercoating is preferably used as a base, and excellent anti-contamination properties can be obtained by using these bases as a coating for the article to be coated. The coated article shown in FIG. These include, for example, outer wall materials used for construction and the like. Examples of aggregates of these painted articles include buildings, automobiles, ships, and bridges.

Hereinafter, the present invention will be described in detail by way of examples and comparative examples. In addition, the part and% in an Example and a comparative example show a mass part and mass%, respectively. Moreover, about the physical-property test of the obtained aqueous | water-based antifouling coating composition, the coating material was adjusted with the compounding composition shown below using this aqueous | water-based antifouling coating composition, and the test was implemented according to the test method shown below.
<Test method>
-Solid content, such as water dispersion It is a dry mass after drying solid content measuring objects, such as an aqueous dispersion, at 105 degreeC for 3 hours.
-Resin solid content of aqueous dispersion The mass obtained by subtracting the dry mass of the surfactant, polymerization initiator, etc. from the dry mass of the aqueous dispersion after drying at 105 ° C for 3 hours.
・ Measurement of solid content such as water dispersion Precisely weigh about 1g of solid content measurement object such as water dispersion in an aluminum pan whose mass is known in advance, at 105 ° C for 3 hours with a constant temperature dryer After drying, the sample is allowed to cool for 30 minutes in a desiccator containing silica gel and then weighed accurately. The solid content was obtained by dividing the mass after drying of the substance by the mass before drying.

Measurement of particle diameter of aqueous dispersion The resin particle diameter (weight average particle diameter) of the aqueous dispersion was measured by a dynamic light scattering method.
Transparency of coating film, appearance of coating film 20% by weight of butyl cellosolve (solid content of the coating composition for water-based antifouling) was added to the water-based antifouling coating composition of each example and comparative example, and this was applied onto a glass plate. Then, the film was heated at 90 ° C. for 3 hours to form a coating film having a thickness of about 100 μm, and the transparency and the coating film appearance of the obtained coating film were visually evaluated. The evaluation of transparency was determined according to the following criteria.
Evaluation of transparency:
○: No cloudiness is observed Δ; Slight cloudiness is observed ×: Clear cloudiness is recognized

Rain stain contamination After coating a commercially available aqueous white enamel paint on the alumite plate shown in FIG. 1 and drying at room temperature for 7 days, 20% butyl cellosolve was added to each of the aqueous contamination prevention coating compositions of Examples and Comparative Examples. Apply clear paint with mass% (solid content of water-based antifouling coating composition) added, and heat at 90 ° C. for 3 hours to form a clear paint film with a thickness of about 100 μm on the paint film of commercially available aqueous white enamel paint. And dried for one week at room temperature to obtain a test specimen. The test specimen was fixed outdoors on the ground so that the coating surface was vertical and northward, and rain stain contamination was visually determined about 3 months after the start of exposure. Judgment criteria are as follows.
A: No rain streaks are seen.
〇: Although the whole is dirty, no rain streaks are seen.
Δ: Overall dirt and slight rain streaks are observed.
×: Rain streaks are noticeable.

[Production Example 1 of Aqueous Dispersion]
95 parts by mass of dimethyl cyclic (DMC. Cyclic dimethylsiloxane oligomer 3-7 mer mixture), 5 parts by mass of γ-methacryloyloxypropyltrimethoxysilane (graft cross-linking agent), 300 parts by mass of water and sodium dodecylbenzenesulfonate (DBSNa) ) (Surfactant) A composition consisting of 1 part by mass was premixed with a homomixer, sheared with a homogenizer at a pressure of 200 kg / cm @ 2, and forcedly emulsified to obtain a silicone raw material emulsion.

Next, 100 parts by mass of water and 20 parts by mass of dodecylbenzenesulfonic acid (DBSA) (acidic emulsifier) were charged into a flask equipped with a stirrer, a condenser, a heating jacket, and a dropping pump, and the temperature in the flask was maintained at 85 ° C. for 3 hours. The above silicone raw material emulsion was added dropwise. After completion of dropping, the mixture was further heated and stirred for 1 hour, and then the obtained emulsion was cooled to room temperature, and dodecylbenzenesulfonic acid was neutralized with sodium hydroxide to obtain a silicone polymer emulsion.
Next, the total amount of the obtained silicone polymer emulsion, 820 parts by mass of water and 5 parts by mass of potassium persulfate were charged into a flask equipped with a stirrer, a condenser, a heating jacket and an inert gas introduction hole, and the temperature was raised to 70 ° C. While stirring in a nitrogen atmosphere, a mixture of 342 parts by weight of methyl methacrylate (MMA), 540 parts by weight of n-butyl methacrylate (BMA) and 18 parts by weight of methacrylic acid (MAA) was dropped and polymerized over 4 hours. After completion of the dropping, the mixture was held at 70 ° C. for 1 hour, further heated to 80 ° C. and held for 1 hour. The reaction solution was cooled to room temperature and neutralized with aqueous ammonia to obtain an aqueous dispersion. The obtained aqueous dispersion had a solid content of 45.5%, a particle size of 55 nm, and a single distribution.

[Production Example 2 of Aqueous Dispersion]
95 parts by mass of dimethyl cyclic (DMC. Cyclic dimethylsiloxane oligomer 3-7 mer mixture), 5 parts by mass of γ-methacryloyloxypropyltrimethoxysilane (graft cross-linking agent), 300 parts by mass of water and sodium dodecylbenzenesulfonate (DBSNa) ) (Surfactant) A composition consisting of 1 part by mass was premixed with a homomixer, sheared with a homogenizer at a pressure of 200 kg / cm @ 2, and forcedly emulsified to obtain a silicone raw material emulsion.
Next, 100 parts by mass of water and 20 parts by mass of dodecylbenzenesulfonic acid (DBSA) (acidic emulsifier) were charged into a flask equipped with a stirrer, a condenser, a heating jacket, and a dropping pump, and the temperature in the flask was maintained at 85 ° C. for 3 hours. The above silicone raw material emulsion was added dropwise. After completion of dropping, the mixture was further heated and stirred for 1 hour, and then the obtained emulsion was cooled to room temperature, and dodecylbenzenesulfonic acid was neutralized with sodium hydroxide to obtain a silicone polymer emulsion.

  Next, the total amount of the obtained silicone polymer emulsion, 820 parts by mass of water and 5 parts by mass of potassium persulfate were charged into a flask equipped with a stirrer, a condenser, a heating jacket and an inert gas introduction hole, and the temperature was raised to 70 ° C. While stirring in a nitrogen atmosphere, a mixture of 142 parts by weight of methyl methacrylate (MMA), 200 parts by weight of cyclohexyl methacrylate, 540 parts by weight of n-butyl methacrylate (BMA) and 18 parts by weight of methacrylic acid (MAA) Drop polymerization was performed over time. After completion of the dropping, the mixture was held at 70 ° C. for 1 hour, further heated to 80 ° C. and held for 1 hour. The reaction solution was cooled to room temperature and neutralized with aqueous ammonia to obtain an aqueous dispersion. The obtained aqueous dispersion had a solid content of 45.5%, a particle size of 58 nm and a single distribution.

[Production Example 3 of Aqueous Dispersion]
95 parts by mass of dimethyl cyclic (DMC. Cyclic dimethylsiloxane oligomer 3-7 mer mixture), 5 parts by mass of γ-methacryloyloxypropyltrimethoxysilane (graft cross-linking agent), 300 parts by mass of water and sodium dodecylbenzenesulfonate (DBSNa) ) (Surfactant) A composition consisting of 1 part by mass was premixed with a homomixer, sheared with a homogenizer at a pressure of 200 kg / cm @ 2, and forcedly emulsified to obtain a silicone raw material emulsion.
Next, 100 parts by mass of water and 20 parts by mass of dodecylbenzenesulfonic acid (DBSA) (acidic emulsifier) were charged into a flask equipped with a stirrer, a condenser, a heating jacket, and a dropping pump, and the temperature in the flask was maintained at 85 ° C. for 3 hours. The above silicone raw material emulsion was added dropwise. After completion of dropping, the mixture was further heated and stirred for 1 hour, and then the obtained emulsion was cooled to room temperature, and dodecylbenzenesulfonic acid was neutralized with sodium hydroxide to obtain a silicone polymer emulsion.

  Next, the total amount of the obtained silicone polymer emulsion, 820 parts by mass of water and 5 parts by mass of potassium persulfate were charged into a flask equipped with a stirrer, a condenser, a heating jacket and an inert gas introduction hole, and the temperature was raised to 70 ° C. While stirring in a nitrogen atmosphere, 142 parts by weight of methyl methacrylate (MMA), 200 parts by weight of cyclohexyl methacrylate, 540 parts by weight of n-butyl methacrylate (BMA), 18 parts of methacrylic acid (MAA) and non-sulfosuccinic acid 30 parts by weight of a reactive surfactant (product name: Aerosol OT-75 (effective amount: about 75%), manufactured by Mitsui Cytec Co., Ltd.), an anionic reactive surfactant containing an alkylene oxide group (product name: Adekaria soap SR-10, manufactured by Asahi Denka Kogyo Co., Ltd. It was dropping polymerization Te. After completion of the dropping, the mixture was held at 70 ° C. for 1 hour, further heated to 80 ° C. and held for 1 hour. The reaction solution was cooled to room temperature and neutralized with aqueous ammonia to obtain an aqueous dispersion. The obtained aqueous dispersion had a solid content of 46.1%, a particle size of 60 nm, and a single distribution.

[Production Example 4 of Aqueous Dispersion]
95 parts by mass of dimethyl cyclic (DMC. Cyclic dimethylsiloxane oligomer 3-7 mer mixture), 5 parts by mass of γ-methacryloyloxypropyltrimethoxysilane (graft cross-linking agent), 300 parts by mass of water and sodium dodecylbenzenesulfonate (DBSNa) ) (Surfactant) A composition consisting of 1 part by mass was premixed with a homomixer, sheared with a homogenizer at a pressure of 200 kg / cm @ 2, and forcedly emulsified to obtain a silicone raw material emulsion.
Next, 100 parts by mass of water and 20 parts by mass of dodecylbenzenesulfonic acid (DBSA) (acidic emulsifier) were charged into a flask equipped with a stirrer, a condenser, a heating jacket, and a dropping pump, and the temperature in the flask was maintained at 85 ° C. for 3 hours. The above silicone raw material emulsion was added dropwise. After completion of dropping, the mixture was further heated and stirred for 1 hour, and then the obtained emulsion was cooled to room temperature, and dodecylbenzenesulfonic acid was neutralized with sodium hydroxide to obtain a silicone polymer emulsion.

  Next, the total amount of the obtained silicone polymer emulsion, 820 parts by mass of water and 5 parts by mass of potassium persulfate were charged into a flask equipped with a stirrer, a condenser, a heating jacket and an inert gas introduction hole, and the temperature was raised to 70 ° C. While stirring in a nitrogen atmosphere, 130 parts by weight of methyl methacrylate (MMA), 200 parts by weight of cyclohexyl methacrylate, 525 parts by weight of n-butyl methacrylate (BMA), 18 parts by weight of methacrylic acid (MAA), diacetone acrylamide (DAAm) 27 parts by mass and sulfosuccinic acid-based non-reactive surfactant (product name: Aerosol OT-75 (effective amount: about 75%), manufactured by Mitsui Cytec Co., Ltd.), 30 parts by mass, containing an alkylene oxide group Anionic Reactive Surfactant (Product name: Adeka Soap SR-1 Asahi Denka 9 parts by mass of Co.), was added dropwise the polymerization over a mixture of 4 hours. After completion of the dropping, the mixture was held at 70 ° C. for 1 hour, further heated to 80 ° C. and held for 1 hour. The reaction solution was cooled to room temperature and neutralized with aqueous ammonia to obtain an aqueous dispersion. The obtained aqueous dispersion had a solid content of 46.2%, a particle size of 63 nm, and a single distribution.

[Production Example 5 of aqueous dispersion]
90 parts by mass of dimethyl cyclic (cyclic dimethylsiloxane oligomer 3-7 mer mixture), 10 parts by mass of γ-methacryloyloxypropyldimethoxymethylsilane (graft cross-linking agent), 300 parts by mass of deionized water and sodium dodecylbenzenesulfonate (interface) Activator) A composition consisting of 0.5 parts by mass was premixed with a homomixer, then sheared at a pressure of 200 kg / cm ² by a homogenizer and forcedly emulsified to obtain a silicone raw material emulsion.
Next, 100 parts by mass of deionized water and 10 parts by mass of dodecylbenzenesulfonic acid (acidic emulsifier) were charged into a flask equipped with a stirrer, a condenser, a temperature controller and a dropping pump, and the temperature inside the flask was maintained at 85 ° C. The silicone raw material emulsion was dropped over time. After completion of dropping, the mixture was further heated and stirred for 1 hour, and then the obtained emulsion was cooled to room temperature, and dodecylbenzenesulfonic acid was neutralized with sodium hydroxide to obtain a silicone emulsion. The number average molecular weight (GPC measurement value) of the obtained silicone was about 100,000.

  500 parts of the obtained silicone emulsion, 164 parts of deionized water and 2.4 parts of potassium persulfate were charged into a flask equipped with a stirrer, condenser, temperature controller, dropping pump and nitrogen introduction tube, and the temperature was raised to 70 ° C. Then, with stirring in a nitrogen atmosphere, 168 parts by mass of methyl methacrylate (MMA), 168 parts by mass of n-butyl methacrylate (n-BMA), 44 parts by mass of 2-ethylhexyl acrylate (2-EHA), methacryl A mixture of 8 parts by weight of acid (MAA), 12 parts by weight of diacetone acrylamide (DAAm) and 1 part by weight of γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM503) is added dropwise over 4 hours. did. After completion of the dropping, the mixture was held at 70 ° C. for 1 hour, further heated to 80 ° C. and held for 1 hour. The reaction solution was cooled to room temperature and neutralized with aqueous ammonia to obtain an aqueous dispersion. Polymerization proceeded stably and no formation of aggregates was observed. The obtained aqueous dispersion had a solid content of 47.2%, a particle size of 61 nm, and a single distribution.

[Synthesis Example of Polyisocyanate Compound A]
222 parts by mass of isophorone diisocyanate, 168 parts of hexamethylene diisocyanate, and 2.4 parts by mass of water as a buret agent are dissolved in 130 parts by mass of a 1: 1 (weight ratio) mixed solvent of ethylene glycol methyl ether acetate and trimethyl phosphate. And reacted at a reaction temperature of 160 ° C. for 1.5 hours. Using the thin film distillation can, the obtained reaction solution was subjected to surplus isophorone diisocyanate by a two-step treatment under the condition of 1.0 mmHg / 160 ° C for the first time and 0.1 mmHg / 200 ° C for the second time. Hexamethylene diisocyanate and the solvent were recovered by distillation.

  The resulting polyisocyanate compound A is a couburette type polyisocyanate of isophorone diisocyanate and hexamethylene diisocyanate, the residual isophorone diisocyanate is 0.7% by mass, the residual hexamethylene diisocyanate is 0.1% by mass, and the -NCO content is 19. 6 mass%, viscosity is 20000 (± 3000) mPa.s. s / 40 ° C., the number average molecular weight is about 800 (± 100), and the average —NCO functional group number is about 3. 7. Polyisocyanate compound A was made into a 79.6% solution with ethyl acetate.

[Synthesis example of semicarbazide curing agent]
In a reactor having a reflux condenser, a thermometer, and a stirring device, 22 parts by mass of tetrahydrofuran, 23 parts by mass of polyisocyanate A (79.6% ethyl acetate solution, NCO group content 15.6% by mass), “Uniox ( "Trademark) M1000" (manufactured by NOF Corporation, polyoxyethylene methyl ether having a hydroxyl value of 56.9) and 0.001 part by mass of dibutyltin dilaurate as a catalyst were added and reacted at 60 ° C for 4 hours. Next, 7.3 parts by mass of hydrazine monohydrate was added to 147 parts of tetrahydrofuran in a reactor equipped with a reflux condenser, a thermometer and a stirring device at room temperature over 30 minutes with stirring, and then for another 1 hour. Stir. The reaction product obtained previously was added to this reaction solution over 1 hour with stirring at 40 ° C., and then further stirred at 40 ° C. for 4 hours. Thereafter, 182 parts of water were added at 40 ° C. over 30 minutes and stirring was continued for another 30 minutes. Tetrahydrofuran, ethyl acetate, hydrazine, water and the like in the obtained reaction liquid were distilled off under reduced pressure by heating to obtain an aqueous dispersion of a semicarbazide-based curing agent having a solid content of 30%.

[Example 1]
To 219.8 parts by mass of the aqueous dispersion obtained in Production Example 1 of the aqueous dispersion, a sulfosuccinic acid-based non-reactive surfactant (product name: Aerosol OT-75 (effective amount: about 75%), Mitsui Cytec ( 2.7 parts by mass, nonionic surfactant containing an alkylene oxide group (product name: Emulgen 120, manufactured by Kao Corporation), 5 parts by mass, colloidal silica (product name: Adelite AT) -30A, manufactured by Asahi Denka Kogyo Co., Ltd.) was mixed uniformly in the order of 50.0 parts by mass to obtain an aqueous contamination-preventing coating composition having a solid content of 42.5%. Each test described above was performed on this water-based antifouling coating composition, and the results are shown in Table 1.

[Example 2]
To 219.8 parts by mass of the aqueous dispersion obtained in Production Example 2 of the aqueous dispersion, a sulfosuccinic acid-based non-reactive surfactant (product name: aerosol OT-75 (effective part: about 75%), Mitsui Cytec ( 2.7 parts by mass, nonionic surfactant containing an alkylene oxide group (product name: Emulgen 120, manufactured by Kao Corporation), 5 parts by mass, colloidal silica (product name: Snowtex) -C30, manufactured by Nissan Chemical Industries, Ltd.) was mixed uniformly in the order of 50.0 parts by mass to obtain an aqueous contamination-preventing coating composition having a solid content of 42.5%. Each test described above was performed on this water-based antifouling coating composition, and the results are shown in Table 1.

[Example 3]
Uniformly mixed with 216.9 parts by mass of the aqueous dispersion obtained in Production Example 3 of the aqueous dispersion in the order of 50.0 parts by mass of colloidal silica (product name: Adelite AT-30A, manufactured by Asahi Denka Kogyo Co., Ltd.). Thus, an aqueous contamination-preventing coating composition having a solid content of 43.1% was obtained. Each test described above was performed on this water-based antifouling coating composition, and the results are shown in Table 1.

[Example 4]
To 216.5 parts by mass of the aqueous dispersion obtained in Production Example 4 of the aqueous dispersion, 50.0 parts by mass of colloidal silica (product name: Adelite AT-30A, manufactured by Asahi Denka Kogyo Co., Ltd.), adipic acid dihydrazide 1 The mixture was uniformly mixed in the order of 7 parts by mass to obtain an aqueous antifouling coating composition having a solid content of 43.5%. Each test described above was performed on this water-based antifouling coating composition, and the results are shown in Table 1.

[Example 5]
To 216.5 parts by mass of the aqueous dispersion obtained in Production Example 4 of the aqueous dispersion, 50.0 parts by mass of colloidal silica (product name: Adelite AT-30A, manufactured by Asahi Denka Kogyo Co., Ltd.), semicarbazide-based curing agent The mixture was uniformly mixed in the order of 12.4 parts by mass to obtain an aqueous antifouling coating composition having a solid content of 42.6%. Each test described above was performed on this water-based antifouling coating composition, and the results are shown in Table 1.

[Comparative Example 1]
Each test described above was performed on the aqueous dispersion obtained in Production Example 1 of the aqueous dispersion, and the results are shown in Table 1.

[Comparative Example 2]
Uniformly mixed with 219.8 parts by mass of the aqueous dispersion obtained in Production Example 1 of the aqueous dispersion in the order of 50.0 parts by mass of colloidal silica (product name: Snowtex-30, manufactured by Nissan Chemical Industries, Ltd.). Thus, an aqueous contamination-preventing coating composition having a solid content of 42.6% was obtained. Each test described above was performed on this water-based antifouling coating composition, and the results are shown in Table 1.

[Comparative Example 3]
To 211.9 parts by mass of the aqueous dispersion obtained in Production Example 5 of the aqueous dispersion, 100.8 parts by mass of colloidal silica (product name: Snowtex-30, manufactured by Nissan Chemical Industries, Ltd.), adipic acid dihydrazide (ADH) The mixture was uniformly mixed in the order of 1.5 parts by mass to obtain an aqueous contamination prevention coating composition having a solid content of 41.9%. Each test described above was performed on this water-based antifouling coating composition, and the results are shown in Table 1.
Next, 504 parts of an aqueous colloidal silica dispersion having an average particle size of 10 to 20 nm (silica content: 30 wt%, manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex 30) was added with stirring at room temperature. Hold for 1 hour.
Thereafter, 7.6 parts of adipic acid dihydrazide (hereinafter ADH) and 100 parts of butyl cellosolve were added with stirring, and the mixture was further stirred for 30 minutes to obtain an aqueous coating composition.

  INDUSTRIAL APPLICABILITY The present invention can be suitably used as an aqueous coating composition having excellent antifouling properties, particularly in the field of aqueous antifouling coating compositions useful as paints, building finish coating materials and the like.

It is the schematic of the shape of the outdoor exposure board used by the Example and the comparative example.

Claims (19)

  (A) a polymer block having dimethylsiloxane as a repeating unit, (B) a polymer block having a vinyl polymerizable monomer as a repeating unit, and (A) the polymer block and (B) the polymer block. A graft block copolymer composed of copolymerized (C) silicon-containing graft crossover unit is emulsified and dispersed in an aqueous medium containing a surfactant, and (C) the silicon-containing graft crossover unit described above. (D) Aqueous dispersion with a content of 0.5 mol% or more and 50 mol% or less based on silicon atoms with respect to the total amount of (A) polymer block and (C) silicon-containing graft-crossing agent unit described above And (E) colloidal inorganic particles, and (F) a sulfosuccinic acid-based surfactant.   (G) The aqueous | water-based antifouling coating composition of Claim 1 containing the surfactant containing an alkylene oxide group.   (D) 0.1 to 95 parts by mass of colloidal inorganic particles and (F) 0.1 to 20 parts by mass of a sulfosuccinic surfactant based on 100 parts by mass of the resin solid content of the aqueous dispersion. The water-based antifouling coating composition according to any one of claims 1 and 2.   The aqueous contamination-preventing coating composition according to any one of claims 1 to 3, wherein (E) the colloidal inorganic particles include colloidal inorganic particles coated with an organic polymer.   (E) Colloidal inorganic particle is colloidal silica, The aqueous | water-based antifouling coating composition in any one of Claims 1-4 characterized by the above-mentioned.   6. The aqueous contamination-preventing coating composition according to claim 1, wherein the sulfosuccinic acid surfactant is a sulfosuccinic acid surfactant having no radical polymerizable double bond. Stuff.   (G) The surfactant containing an alkylene oxide group is a surfactant having a radically polymerizable double bond containing an alkylene oxide group, and the aqueous contamination prevention according to any one of claims 2 to 6 Coating composition.   (B) The (meth) acrylic acid ester which has 5 mass% or more of cycloalkyl groups in the polymer block component which makes a vinyl polymerizable monomer a repeating unit is included, The any of Claims 1-7 characterized by the above-mentioned. A water-based antifouling coating composition according to claim 1.   (B) A polymer block component having a vinyl polymerizable monomer as a repeating unit contains a monomer having a radical polymerizable double bond containing at least one aldo group or keto group in the molecule. The aqueous contamination-preventing coating composition according to any one of claims 1 to 8.   The water-based antifouling coating composition according to claim 1, comprising an organic hydrazine compound having two or more hydrazine residues.   The water-based antifouling coating composition according to claim 1, comprising a semicarbazide-based curing agent.   The aqueous stain-proof coating composition according to any one of claims 1 to 11, wherein the particle size of the graft block copolymer is 20 nm or more and 150 nm or less.   The water-based antifouling coating composition according to any one of claims 1 to 12, which is used for coatings.   A paint comprising the water-based antifouling coating composition according to claim 13.   A stain resistant composite comprising a coating formed using the paint of claim 14.   A coated article comprising the paint according to claim 14.   An outer wall material using the paint according to claim 14.   A building using the paint according to claim 14.   A coating method using the paint according to claim 14.

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