JP4889244B2 - Aqueous coating composition for pollution control - Google Patents

Description

  The present invention relates to an aqueous coating composition having excellent antifouling properties. In particular, the present invention relates to a pollution-preventing aqueous coating composition useful as a paint, a building finish coating material, and the like, a coating composition containing the pollution-preventing aqueous coating composition, and a coating method using the paint.

In recent years, contamination of rain lines or raindrops found on the walls of buildings has occurred in places where rainwater flows down, and it has been regarded as a problem that the difference in dirt from places where rain lines are not attached impairs the aesthetics of the building. ing.
Patent Document 1 discloses a composition comprising a solubilized latex containing a keto group, a hydrazide compound, and colloidal silica as an undercoat for inorganic building materials, but requires a large amount of colloidal silica in the coating liquid. The water resistance and storage stability of the coating film were not sufficient.
Patent Document 2 discloses a composition comprising a latex containing a keto group comprising two or more resin particles containing a keto group in the outermost layer and a hydrazide compound, but the stain resistance is not sufficient.
Patent Document 3 discloses a composition comprising a latex containing a keto group, a hydrazide compound, and colloidal silica. However, since a large amount of colloidal silica in the coating liquid is required to exhibit stain resistance, the coating composition is not disclosed. The water resistance and storage stability of the membrane were not sufficient.

Patent Document 4 discloses a composition comprising a latex containing a keto group, a hydrazide compound, and colloidal silica surface-treated with a hydrolyzable silane. In order to develop stain resistance, the surface treatment in the coating solution is performed. Since a large amount of colloidal silica is required, the water resistance and storage stability of the coating film were not sufficient.
Patent Document 5 discloses a composition comprising a keto group-containing latex containing at least two kinds of polymers in one particle and a hydrazide compound, but the stain resistance is not sufficient.
Patent Document 6 discloses a copolymer obtained by copolymerizing a cycloalkyl group-containing monomer, an alkoxysilyl group-containing monomer, and an anion group-containing monomer mixture in an organic solvent, and then substituting the organic solvent with an aqueous medium. An aqueous resin composition obtained by a production method comprising a step of obtaining an acrylic copolymer in the presence of a copolymer has been proposed. However, this method requires a complicated process of polymerizing the copolymer in the previous stage in an organic solvent, and then adding water and an alkaline substance to remove the organic solvent by vacuum distillation to make it aqueous.

JP-A-6-279707 Japanese Patent No. 3100792 Japanese Patent No. 3605458 Japanese Patent Laid-Open No. 10-168380 Japanese Patent Laid-Open No. 10-195313 JP 2002-88126 A

  The present invention can reduce rain streak-like contamination or rain stain contamination when exposed to the outdoors in a paint film comprising a water-based paint, and can prevent contamination immediately after formation of the paint film. It is an object of the present invention to provide an aqueous coating composition for preventing pollution, which is excellent in sustaining the effect of preventing soil contamination or rain stain contamination and has good storage stability of the coating liquid.

As a result of intensive studies to solve the above problems, the present inventors have obtained an aqueous dispersion obtained by emulsion polymerization of an ethylenically unsaturated monomer having an aldo group or a keto group, and a colloid The coating film obtained from the composition containing the fine inorganic particles and the specific surfactant has been found to exhibit the effect that the rain stripes of the coating film are not noticeable, and the present invention has been completed.
That is, the present invention
1. 5 to 15% by mass of the ethylenically unsaturated monomer (c1) having an aldo group or keto group, a (meth) acrylate monomer, and an ethylenically unsaturated monomer having a carboxyl group (in the polymer (C)) in the presence of against it) containing (ethylenically unsaturated monomer c1) other than (c2) from become polymer (C) and hydrolyzable silane (a), and (meth) acrylate monomer An aqueous dispersion (B) containing a polymer comprising a polymer (D) obtained by copolymerizing an ethylenically unsaturated monomer (c3) other than (c1) containing an ethylenically unsaturated monomer having a carboxyl group pollution aqueous coating composition containing,
2. The aqueous coating composition for preventing pollution according to the above 1, comprising an aqueous dispersion (B), colloidal inorganic particles (E), and a sulfosuccinic acid surfactant (F) ,

3. The glass transition temperature Tg _C of the polymer (C) comprising the ethylenically unsaturated monomer (c1) having an aldo group or keto group and another ethylenically unsaturated monomer (c2) is 80 ° C. or higher, Hydrolyzable polymer (C) composed of ethylenically unsaturated monomer (c1) having aldo group or keto group and other ethylenically unsaturated monomer (c2) in aqueous dispersion (B) The contamination according to 1 or 2 above , wherein the average Tg _{C + D of the} polymer comprising the polymer (D) obtained by copolymerizing another ethylenically unsaturated monomer (c3 ) in the presence of silane (A) is 60 ° C. or less. An aqueous coating composition for prevention ,
4). Polymer obtained by emulsion polymerization of ethylenically unsaturated monomer mixture containing 0.1 to 50% by mass of ethylenically unsaturated monomer (c1) having aldo group or keto group as polymer (C) The aqueous coating composition for preventing pollution according to any one of the above 1 to 3 ,
5. The aqueous coating composition for preventing contamination according to any one of 1 to 4 above, which comprises a surfactant (G) containing an alkylene oxide group ,

6). The aqueous dispersion (B) is an acrylic emulsion obtained by emulsion polymerization in the presence of a sulfosuccinic acid surfactant (F) and / or a surfactant (G) containing an alkylene oxide group. The aqueous coating composition for preventing contamination according to any one of 1 to 5 above ,
7). 0.1 to 95 parts by mass of colloidal inorganic particles (E) and 0.1 to 20 parts by mass of a sulfosuccinic surfactant (F) with respect to 100 parts by mass of the resin solid content of the aqueous dispersion (B). The aqueous coating composition for preventing contamination according to any one of 1 to 6 above, wherein the surfactant (G) containing an alkylene oxide group is 0.1 to 5 parts by mass ,

8). Hydrolyzable silane (A) contains the silane which has a structure represented by the following general formula (a), The aqueous | water-based coating composition for pollution prevention in any one of said 1-7 characterized by the above-mentioned .
_{^{(R 1) n -Si- (R}} 2) 4-n (a)
(Wherein n is an integer of 0 to 3, R ¹ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms,
It is selected from an aryl group having 5 to 10 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a vinyl group, an alkyl acrylate group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. The n R ¹ may be the same or different. R ² is selected from an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group. 4-n R ² may be the same or different. ).

9. The aqueous coating composition for preventing pollution according to any one of 2 to 8 above, wherein the colloidal inorganic particles (E) comprise colloidal inorganic particles coated with an organic polymer ,
10. The coating composition for preventing contamination according to any one of 2 to 9 above , wherein the colloidal inorganic particles (E) contain colloidal silica ,
11. The aqueous coating composition for preventing pollution according to any one of the above 2 to 10, wherein the sulfosuccinic acid-based surfactant (F) is a sulfosuccinic acid-based surfactant having no radical polymerizable double bond ,
12 The aqueous dispersion (B) is an acrylic emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer mixture containing 5% by mass or more of a (meth) acrylic acid ester having a cycloalkyl group. The aqueous coating composition for preventing pollution according to any one of 1 to 11 above ,

13. Pollution Aqueous coating composition according to any one of the above 1 to 12, characterized in that it comprises an organic hydrazine compound having two or more hydrazine residues,
14 The aqueous coating composition for preventing pollution according to any one of 1 to 13 above , comprising a semicarbazide-based curing agent ,
15. A paint comprising the contamination-preventing aqueous coating composition according to any one of 1 to 14 above ,
16. A coated article including a coating formed using the paint according to 15 above ,
17. A coating method using the paint according to 15 above ,
It is.

  The aqueous coating composition for preventing pollution 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, particularly preventing stains immediately after the coating film is formed. And a reduction in rain streak contamination can be maintained over time. The storage stability of the coating liquid is good.

The present invention will be specifically described below. In the present invention, the hydrolyzable silane (A) preferably includes at least one having a structure represented by the following formula (a).
_{^{(R 1) n -Si- (R}} 2) 4-n (a)
(In the formula, n is an integer of 0 to 3, and R ¹ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 5 to 10 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, It is selected from a vinyl group, an alkyl acrylate group having 1 to 10 carbon atoms, or an alkyl methacrylate group having 1 to 10 carbon atoms, n R ¹ may be the same or different, and R ² is carbon. It is selected from an alkoxy group, an acetoxy group or a hydroxyl group of formulas 1 to 8. 4-n R ² may be the same or different.
In particular, it is preferable that the hydrolyzable silane (A) contains at least one of silane (I) in which n = 0 in formula (a) and / or silane (II) in which n = 1. In order to obtain good polymerization stability of the aqueous dispersion and antifouling effect, silane (II) with n = 1 is more preferable.
R ² of silane (I) is preferably each independently a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, or a hydroxyl group. Preferable specific examples of silane (I) include tetramethoxysilane and tetraethoxysilane.

As R ¹ of silane (II), a methyl group, a phenyl group, a vinyl group, and a γ- (meth) acryloxypropyl group are preferable, and R ² each independently represents a methoxy group, an ethoxy group,
Propoxy, butoxy, methoxyethoxy and hydroxyl groups are preferred. Preferable specific examples of silane (II) include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane and the like. Moreover, as a hydrolyzable silane having a radically polymerizable double bond of silane (II), vinylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane and the like. These may be contained alone or in combination of two or more. Preferably, a hydrolyzable silane having a radical polymerizable double bond and a hydrolyzable silane not having a radical polymerizable double bond can be used in combination.

  When flexibility is required, the hydrolyzable silane (A) is at least one selected from the group consisting of cyclic silane and silane (III) obtained by setting n = 2 in the formula (a). Is preferably used. This lowers the crosslinking density of the silicone polymer formed by the hydrolyzable silane (A) by using at least one selected from the group consisting of silane (II), cyclic silane and silane (III), This is because the structure of the polymer can be prevented from becoming complicated, and thereby, flexibility can be imparted to a coating film provided from an aqueous emulsion or an acrylic emulsion, and is used in combination with silane (II). Particularly preferred in some cases.

Specific examples of the cyclic silane include octamethylcyclotetrasiloxane, octaphenylcyclosiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, and tetramethyltetravinylcyclotetrasiloxane.
Specific examples of silane (III) include dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, methylphenylsilane, and γ-methacryloxypropylmethyldimethoxysilane.
When the hydrolyzable silane (A) contains at least one selected from the group consisting of silane (I) and / or silane (II) and cyclic silane and silane (III), silane (I) And / or the molar ratio of silane (II) to at least one selected from the group consisting of the above-mentioned cyclic silane and silane (III) is preferably 10/100 or more in order to obtain a good antifouling effect, 100 or more is more preferable, and 100/100 or more is more preferable. When flexibility is required, 100/1 or less can be used.

Furthermore, the hydrolyzable silane (A) includes at least one selected from the group consisting of a linear siloxane having a hydrolyzable group, an alkoxysilane oligomer, and silane (IV) obtained by setting n = 3 in the formula (a). May contain seeds.
Specific examples of silane (IV) include triphenylethoxysilane and trimethylmethoxysilane.
Examples of the linear siloxane having a hydrolyzable group include compounds represented by the following formulas (1), (2) and (3).

（上記式（１）、（２）、（３）中、各Ｒ^１ は水素、炭素数１〜１６の脂肪族炭化水素基、炭素数５〜１０のアリール基、炭素数５〜６のシクロアルキル基、ビニル基、炭素数１〜１０のアクリル酸アルキル基又は炭素数１〜１０のメタクリル酸アルキル基から選ばれ、各Ｒ^２ はそれぞれ、独立して炭素数１〜８のアルコキシ基、アセトキシ基、水酸基、エポキシ基、アルキレンオキサイド基又はポリアルキレンオキサイド基から選ばれ、ｍは１〜９９９の正の整数を表す。）

(In the above formulas (1), (2) and (3), each R ¹ is hydrogen, an aliphatic hydrocarbon group having ^{1 to} 16 carbon atoms, an aryl group having 5 to 10 carbon atoms, or a cyclohexane having 5 to 6 carbon atoms. It is selected from an alkyl group, a vinyl group, an alkyl acrylate group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, and each R ² is independently an alkoxy group having 1 to 8 carbon atoms, acetoxy A group, a hydroxyl group, an epoxy group, an alkylene oxide group or a polyalkylene oxide group, and m represents a positive integer of 1 to 999.)

  Examples of the linear siloxane and alkoxysilane oligomer compounds represented by the above formulas (1), (2), and (3) include, for example, KC-89S, KR-500, X-40-9225, manufactured by Shin-Etsu Chemical Co., Ltd. KR-217, KR-9218, KR-213, KR-510, X-40-9227, X-40-9247, X-41-1053, X-41-1056, X-41-1805, X-41- 1810, X-40-2308, X-22-164A, X-22-164B, X-22-164C, X-22-174DX, X-24-8201, X-22-2426, Chissa Corporation Sila Plane FM-2231, FM-4411, FM-4421, FM-4425, FM-5511, FM-5521, FM-5525, FM-7711, FM-7721, M-7725, FM-0411, FM-0421, FM-0425, FM-0511, FM-0521, FM-0525, FM-0711, FM-0721, FM-0725, MAC-2101 manufactured by Nihon Unicar Co., Ltd. MAC-2301, FZ-3704, AZ-6200, Toray Dow Corning Silicone, Inc. SF8427, SF8428, Asahi Kasei Wacker Silicone, Inc. SILRES MSE100, and the like.

When the hydrolyzable silane (A) contains both silane (I) and / or silane (II) and at least one selected from the group consisting of a linear siloxane having a hydrolyzable group and silane (IV) The molar ratio of silane (I) and / or silane (II) to at least one selected from the group consisting of a linear siloxane having a hydrolyzable group and silane (IV) has a good antifouling effect. Is preferably 10/100 or more, more preferably 35/100 or more, and even more preferably 100/100 or more. When flexibility is required, 100/1 or less can be used.
In silane (III) or silane (IV), R ¹ is particularly preferably a methyl group or a phenyl group, and R ² is particularly preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group or a hydroxyl group.

  Hydrolyzable silane (A) is chlorosilane, for example, in addition to silane (II) and at least one selected from the group consisting of cyclic silane, silane (III), linear siloxane, alkoxysilane oligomer, silane (IV) Containing methylchlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenylchlorosilane, vinylchlorosilane, γ- (meth) acryloxypropyltrichlorosilane, γ- (meth) acryloxypropyldichloromethylsilane Can do.

The presence of the above-mentioned silane condensate can be known by ²⁹ SiNMR ( ²⁹ Si nuclear magnetic resonance spectrum) or ¹ HNMR (proton nuclear magnetic resonance spectrum). For example, a condensate of silane (II) can be identified by ²⁹ SiNMR chemical shift showing a peak at −40 to −80 PPM. Silane (IV) or condensate of cyclic silane can be identified by the ²⁹ Si NMR chemical shift showing a peak at -16 to -26 PPM.
In the present invention, the hydrolyzable silane (A) can be used in an amount of 0.01% by mass to 300% by mass with respect to the total mass of the ethylenically unsaturated monomer.
In the present invention, the hydrolyzable silane (A) is preferably added simultaneously with the emulsion polymerization of the polymer (D) copolymerized with the ethylenically unsaturated monomer. Examples of the method of addition include the following two methods, but are not limited thereto.

The first addition method is to add a hydrolyzable silane compound to a mixture of another ethylenically unsaturated monomer, a surfactant, a radical polymerization initiator and water when emulsion polymerizing the polymer (D). Then, a pre-emulsion is prepared using a homogenizer or the like, and successively or intermittently supplied to a reaction system polymerized in an aqueous medium.
In the second addition method, when the polymer (D) is subjected to emulsion polymerization, a hydrolyzable silane compound is added separately from a mixture of other ethylenically unsaturated monomer, surfactant, radical polymerization initiator, and water. Continuously or intermittently fed to the reaction system polymerized in the aqueous medium.
In the silicone modification with hydrolyzable silane in the present invention, after completion of emulsion polymerization, as a curing initiator at the time of film formation, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, tin octylate, tin laurate, octylic acid Metal salts of organic acids such as iron, lead octylate and tetrabutyl titanate, and amine compounds such as n-hexylamine and 1,8-diazabicyclo [5,4,0] -7-undecene are used as the aqueous acrylic emulsion of the present invention. It can be added to the composition. If these curing initiators are not water-soluble, they are preferably emulsified with a surfactant and water before use.

Examples of the ethylenically unsaturated monomer having an aldo group or keto group in the present invention include acrolein, diacetone acrylamide, formyl styrene, a vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone). Ketone, vinyl butyl ketone, etc.), acrylic (or methacrylic) oxyalkyl propenal, diacetone acrylate, acetonyl acrylate, diacetone methacrylate, 2-hydroxypropyl acrylate acetyl acetate, butanediol-1,4-acrylate acetyl acrylate-acrylate Examples include acetyl acrylate. Particularly preferred monomers are diacetone acrylamide, acrolein and vinyl methyl ketone, and these monomers may be used in combination of two or more.
Use of ethylenically unsaturated monomer having aldo group or keto group in polymer (C) comprising ethylenically unsaturated monomer having aldo group or keto group and other ethylenically unsaturated monomer The amount is preferably 0.1 to 50% by mass.
As another ethylenically unsaturated monomer in the present invention, radical polymerization represented by (meth) acrylic acid ester (in this application, acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid). (Meth) acrylate monomer, a carboxyl group-containing unsaturated monomer, and, if necessary, other monomers copolymerizable with these monomers.

Specific examples of (meth) acrylic acid esters include (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms in the alkyl moiety, and (poly) oxyethylene mono (meth) having 1 to 100 ethylene oxide groups. Acrylate, (poly) oxypropylene mono (meth) acrylate, (meth) acrylic acid hydroxyalkyl ester having 1 to 18 carbon atoms in the alkyl portion, and (poly) oxyethylene di (1) having 1 to 100 ethylene oxide groups And (meth) acrylate. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic acid t-. Examples include butyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, and (meth) acrylic acid cycloalkyl ester. Specific examples of (poly) oxyethylene mono (meth) acrylate include ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate, (meta ) Tetraethylene glycol acrylate, tetraethylene glycol methoxy (meth) acrylate, and the like. Specific examples of (poly) oxypropylene mono (meth) acrylate include propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, dipropylene glycol (meth) acrylate, dipropylene methoxy (meth) acrylate Examples include glycol, tetrapropylene glycol (meth) acrylate, and tetrapropylene glycol methoxy (meth) acrylate. Specific examples of the (meth) acrylic acid hydroxyalkyl ester include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Specific examples of (poly) oxyethylene di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and di (meth) acryl. Examples include acid tetraethylene glycol. Specific examples other than the above include glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like. 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 ethylenically unsaturated monomer.

In the present invention, it is preferable to include a (meth) acrylic acid ester having a cycloalkyl group as another ethylenically unsaturated monomer because it is particularly excellent in durability. (Meth) acrylic acid ester in which 5% by mass or more, more preferably 5% by mass or more and 99% by mass or less, more preferably 5% by mass or more and 80% by mass or less of the ethylenically unsaturated monomer has a cycloalkyl group, Alternatively, a mixture thereof is preferable. 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.
Specific examples of the carboxyl group-containing unsaturated monomer in the present invention include acrylic acid, methacrylic acid, itaconic acid and its monoester, fumaric acid and its monoester, and maleic acid and its monoester. In particular, the use of acrylic acid or methacrylic acid is preferred. These carboxyl group-containing unsaturated monomers may be used alone or in combination of a plurality of types.
The amount of the ethylenically unsaturated monomer having a carboxyl group in the polymer (C) comprising the ethylenically unsaturated monomer having an aldo group or keto group and another ethylenically unsaturated monomer is 1 -20 mass% is preferable and the usage-amount of 5-15 mass% is further more preferable. When the ethylenically unsaturated monomer having a carboxyl group is 1% by mass or more, the stain resistance is exhibited, and when it is 20% by mass or less, the water resistance is good.

Furthermore, if necessary, a polymerizable monomer copolymerizable with a (meth) acrylate monomer or a carboxyl group-containing unsaturated monomer can be used. These polymerizable monomers include acrylamide monomers or methacrylamide monomers such as (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, and N-butoxymethyl (meth) acrylamide. Examples of vinyl monomers include vinyl acetate, vinyl propionate, vinyl versatate, vinyl pyrrolidone, and methyl vinyl ketone. Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile. Can be mentioned. Furthermore, aromatic monomers such as vinyltoluene, styrene and α-methylstyrene, vinyl halides such as vinyl chloride and vinylidene chloride, butadiene, ethylene and the like can also be mentioned.
The Tg _C of the polymer (C) composed of an ethylenically unsaturated monomer having an aldo group or keto group and another ethylenically unsaturated monomer is 80 ° C. or higher and 120 ° C. or lower, and 85 ° C. or higher and 115 ° C. It is preferable that it is below, More preferably, it is 90 degreeC or more and 110 degrees C or less. When Tg _C is 80 ° C. or higher, high stain resistance is exhibited.
Here, Tg of the polymer is calculated from the monomer mixture constituting the polymer by the following Fox formula.

Fox formula: 1 / Tg = a1 / Tg1 + a2 / Tg2 + ... + an / Tgn
(A1, a2,..., An is the mass fraction of each monomer, and Tg1, Tg2,... Tgn is the Tg of each monomer homopolymer. Each monomer used in the calculation. The Tg of the homopolymer is described in, for example, Polymer Handbook (Jon Willy & Sons), Introduction to Synthetic Resins for Paints, etc. Specifically, methyl methacrylate 378K, cyclohexyl methacrylate 356K, n-butyl acrylate 228K, acrylic acid 2 -Ethylhexyl 218K, methacrylic acid 417K, acrylic acid 360K, diacetone acrylamide 338K.
Further, a polymer (C) comprising an ethylenically unsaturated monomer having an aldo group or keto group in the aqueous dispersion (B) and another ethylenically unsaturated monomer and a hydrolyzable silane (A) The average Tg _{C + D} of the polymer consisting of the polymer (D) copolymerized with other ethylenically unsaturated monomers in the presence of is 65 ° C. or more and 60 ° C. or less, and is flexible and stain resistant. A favorable balance is developed.
The polymer (D) obtained by copolymerizing another ethylenically unsaturated monomer in the presence of the hydrolyzable silane (A) may be polymerized in one stage or may be polymerized in multiple stages. . Further, when the polymerization is divided into a plurality of stages, the plurality of stages may be continuously polymerized, or from an ethylenically unsaturated monomer having an aldo group or a keto group and another ethylenically unsaturated monomer. A plurality of stages may be polymerized with the polymer (C) polymerized in between.

The mass ratio (C) / (D) of the polymers (C) and (D) constituting the contamination-preventing aqueous coating composition of the present invention is preferably 1/99 to 40/60, and 5/95 to 40/60. Is more preferable. When the polymer (C) is 1 mass ratio or more, stain resistance is exhibited, and when the polymer (C) is 40 mass ratio or less, the storage stability of the composition is good.
In the present invention, a chain transfer agent may be used if necessary. Examples of the chain transfer agent include mercaptans such as n-butyl mercaptan, t-butyl mercaptan, n-octyl mercaptan, and n-dodecyl mercaptan, disulfides such as tetramethylthuradium sulfide, halogenated derivatives such as carbon tetrachloride, α -A methyl styrene dimer etc. are mentioned, It can use individually or in combination of 2 or more types. N-dodecyl mercaptan is preferred.

As the colloidal inorganic particles (E) 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). 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 (B) to be mixed. 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, Snotex-CM40, Snotex-N, Snotex-N30, Snotex-K, Snotex-XL, Snotex-YL, Snotex-ZL, Snotex PS-M, Snotex 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.

In addition, as the colloidal inorganic particles (E), 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, Ce
F 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 Si 3, T O _{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 Examples thereof include O ₃ -4SiO ₂ , Mg ferrite, Ni ferrite, Ni-Zn ferrite, Li ferrite, and Sr ferrite. These colloidal inorganic particles can be used alone or in admixture of two or more.

  The colloidal inorganic particles coated with the organic polymer are not particularly limited. For example, an ethylenically unsaturated monomer, a hydrolyzable silane having a radical polymerizable double bond, and colloidal silica are used. By emulsion polymerization of particles obtained by emulsion polymerization (for example, disclosed in JP-A-59-71316), an ethylenically unsaturated monomer, and an anionic polymerizable monomer in the presence of colloidal silica Particles obtained (for example, disclosed in JP-A-59-217702), particles obtained by a method in which a water-soluble polymer compound is adsorbed onto inorganic particles and then coated with a polymer of a radical polymerizable monomer (for example, JP-A No. 60-58237), emulsifying ethylenically unsaturated monomer and ethylenically unsaturated monomer having a hydroxyl group in the presence of colloidal silica Particles obtained by combining methods (for example, disclosed in JP-A-6-199917), silica and / or colloidal having a core / shell structure, in which an organic polymer and an organic polymer are not covalently bonded in the core Silica in the core and / or colloidal by disposing silica, arranging an organic polymer in the shell, and forming a three-dimensional crosslinked network structure and / or IPN structure between the core organic polymer / shell organic polymer Emulsion polymerization of an ethylenically unsaturated compound in the presence of particles in which the silica is physicochemically held in the particles without being covalently bonded (for example, disclosed in JP-A-8-290912), colloidal silica, an activator and water. Particles obtained by the method (for example, disclosed in JP-A-11-1893), the surface of colloidal silica particles via a cationic residue Particles with vinyl polymer bonded (for example, disclosed in JP-A-11-209622), particles with vinyl polymer bonded to the surface of inorganic or organic particles directly or via a nonionic surfactant (for example, JP-A 2000-2000 290464), colloidal fine particles in which nonionic surfactants are aggregated or aggregated and deposited on the surface of inorganic or organic particles (for example, disclosed in JP 2001-335721 A).

In the present invention, the colloidal inorganic particles (E) are preferably used in an amount of 0.1 to 95 parts by mass, more preferably 0.1 to 50 parts by mass, with respect to 100 parts by mass of the resin solid content of the aqueous dispersion (B). Parts, more preferably 0.5 to 20 parts by mass.
In the present invention, the sulfosuccinic acid surfactant (F) includes a sulfosuccinic acid compound represented by the following formula (4).

｛式中、Ｒ^ａ，Ｒ^ｂは同一でも、異なっていてもよく、水素、炭素数１〜２０のアルキル基、炭素数１〜２０のアルケニル基、炭素数５〜１２のシクロアルキル基、炭素数５〜１０のアリール基、炭素数６〜１９アラルキル基等の炭化水素基、またはその一部が水酸基、カルボン酸基などで置換されたもの、もしくはポリオキシアルキレンアルキルエーテル基（アルキル部分の炭素数が２〜４、ポリオキシアルキレンアルキルフェニルエーテル基（アルキル部分の炭素数が０〜２０、およびアルキレン部分の炭素数が２〜４）などのアルキレンオキサイド化合物を含む有機基またはアルカリ金属、アンモニウム、有機アミン塩基または有機第四級アンモニウム塩基であり、Ｍはアルカリ金属、アンモニウム、有機アミン塩基または有機第四級アンモニウム塩基を示す。）
さらに詳しくは、上記式（４）で表される化合物のＲ^ａ，Ｒ^ｂにおいて、Ｒ^ａおよび／またはＲ^ｂが下記式（５）、（６）、（７）で表される化合物が挙げられる。

{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. It shows the ammonium salt.)
More specifically, in R ^a and R ^b of the compound represented by the above formula (4), compounds in which R ^a and / or R ^b are represented by the following formulas (5), (6), and (7) are exemplified. It is done.

{In each of the formulas (5), (6), (7), R ⁵¹ 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 ⁵² is hydrogen or a methyl group.)}

  In the present invention, as represented by the above formulas (4) to (7), for example, as a sulfosuccinic acid 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 the sulfosuccinic acid type surfactant having a radical polymerizable double bond, Sanyo Kasei Co., Ltd. Eleminol (trademark) JS-2, JS-5, Kao Co., Ltd. latemuru (trademark) S-120, S-180 , S-180A and the like. 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, the sulfosuccinic acid surfactant (F) 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 the aqueous dispersion (B). Part by mass, more preferably 1.0-5 parts by mass is used. When used in this range, a film with good water resistance is formed, and the rain streaks of the coating film are inconspicuous. In addition, the storage stability of the coating liquid is improved.
In the present invention, the surfactant (G) containing an alkylene oxide group does not contain (F) in the structure, and has 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 containing an alkylene oxide group include compounds represented by the following formulas (8) and (9).

(In the formula ^{(8), (9),} R 81 is 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 having a radical polymerizable double bond containing an alkylene oxide group include compounds represented by the following formulas (10), (11), and (12).

（式中、Ｒ^１０１は炭素数６〜１８のアルキル基、アルケニル基またはアラルキル基であり、Ｒ^１０２は水素、炭素数６〜１８のアルキル基、アルケニル基、またはアラルキル基、Ｒ^１０３は水素またはプロペニル基、Ａは炭素数２〜４のアルキレン基または一部が置換されたアルキレン基であり、ｎは１〜２００の整数、Ｍはアンモニウム、ナトリウム、カリウムである。）

(Wherein R ¹⁰¹ is an alkyl group, alkenyl group, or aralkyl group having 6 to 18 carbon atoms, R ¹⁰² is hydrogen, an alkyl group, alkenyl group, or aralkyl group having 6 to 18 carbon atoms, and R ¹⁰³ 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.)

（式中、Ｒ^１１１は水素またはメチル基、Ｒ^１１２は炭素数８〜２４のアルキル基またはアシル基、Ａは炭素数２〜４のアルキレン基、ｎは０〜５０の整数、ｍは０〜２０の整数、Ｍはアンモニウム、ナトリウム、カリウムである。）

(Wherein R ¹¹¹ is hydrogen or a methyl group, R ¹¹² 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.)

（式中、Ｒ^１２１は炭素数８〜３０のアルキル基、Ｒ^１２２は水素またはメチル基、Ａは炭素数２〜４のアルキレン基もしくは置換アルキレン基、ｎは０または１〜２００の整数であり、Ｍはアンモニウム、ナトリウム、カリウムもしくはアルカノールアミン残基である。）

Wherein R ¹²¹ is an alkyl group having 8 to 30 carbon atoms, R ¹²² 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 above formula (10) include Aqualon (trademark) HS-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and examples of the compound represented by the above formula (11) include Asahi Denka. There are Adeka 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 (12) 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 containing an alkylene oxide group include compounds represented by the following formulas (13) and (14).

（上記式（１３）、（１４）中、Ｒ^１３１は、炭素数１〜２０のアルキル基、炭素数１〜２０アルケニル基、炭素数５〜１２のシクロアルキル基、炭素数６〜１９のアラルキル基などの炭化水素基、またはその一部が水酸基、カルボン酸基などで置換されたもの、もしくはポリオキシエチレンアルキルエーテル基（アルキル部分の炭素数が０〜２０、およびアルキレン部分の炭素数が２〜４）、ポリオキシアルキレンアルキルフェニルエーテル基（アルキル部分の炭素数が０〜２０、およびアルキレン部分の炭素数が２〜４）などのアルキレンオキサイド化合物を含む有機基である。Ａは炭素数２〜４のアルキレン基または一部が置換されたアルキレン基であり、ｎは０〜２００の整数であり、Ｒ^１３２は水素またはメチル基である。）
本発明において、アルキレンオキサイド基を含むラジカル重合性二重結合を有するノニオン性界面活性剤は下記式（１５）、（１６）、（１７）で表される化合物が挙げられる。

(In the above formulas (13) and (14), R ¹³¹ 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, and an aralkyl having 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 R ¹³² is hydrogen or a methyl group.)
In the present invention, examples of the nonionic surfactant having a radical polymerizable double bond containing an alkylene oxide group include compounds represented by the following formulas (15), (16) and (17).

（式中、Ｒ^１５１は炭素数６〜１８のアルキル基、アルケニル基またはアラルキル基であり、Ｒ^１５２は水素、炭素数６〜１８のアルキル基、アルケニル基、またはアラルキル基、Ｒ^１５３は水素またはプロペニル基、Ａは炭素数２〜４のアルキレン基または一部が
置換されたアルキレン基であり、ｎは１〜２００の整数である。）

(Wherein R ¹⁵¹ is an alkyl group, alkenyl group or aralkyl group having 6 to 18 carbon atoms, R ¹⁵² is hydrogen, an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, and R ¹⁵³ 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.)

（式中、Ｒ^１６１は水素またはメチル基、Ｒ^１６２は炭素数８〜２４のアルキル基またはアシル基、Ａは炭素数２〜４のアルキレン基、ｎは０〜１００の整数、ｍは０〜５０の整数である。）

Wherein R ¹⁶¹ is hydrogen or a methyl group, R ¹⁶² 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.)

（式中、Ｒ^１７１は炭素数８〜３０のアルキル基、Ｒ^１７２は水素またはメチル基、Ａは炭素数２〜４のアルキレン基もしくは置換アルキレン基、ｎは０または１〜２００の整数である。）
上記式（１５）で表される化合物として例えば、第一工業製薬（株）製アクアロン（商標）ＲＮ−１０、ＲＮ−２０、ＲＮ−３０、ＲＮ−５０などが挙げられる。上記式（１６）で表される化合物として例えば、旭電化工業（株）製アデカリアソープ（商標）ＮＥ−２０、ＮＥ−３０、ＮＥ−４０、ＥＲ−１０、ＥＲ−２０、ＥＲ−３０、ＥＲ−４０などが挙げられる。

Wherein R ¹⁷¹ is an alkyl group having 8 to 30 carbon atoms, R ¹⁷² 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 formula (15) 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 (16), 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, the surfactant (G) 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 the surfactant (G) containing an alkylene oxide group is not particularly limited, but the amount used is preferably small in order to obtain a film having good water resistance, and the aqueous dispersion (B ) To 100 parts by mass of the resin solid content of 0.1 to 5% by mass.

In addition to the sulfosuccinic acid type surfactant (F) and the surfactant (G) containing an alkylene oxide group as surfactants used for emulsion polymerization in the present invention, p-styrenesulfonic acid sodium, p-styrenesulfonic acid Potassium, acrylic acid- (2-sulfoethyl)
Sodium ester, potassium acrylic acid- (2-sulfoethyl) ester, sodium methacrylic acid- (2-sulfoethyl) ester, potassium acrylic acid- (3-sulfopropyl) ester, sodium methacrylic acid- (3-sulfopropyl) ester, fatty acid Examples include soaps, alkyl sulfonates, alkyl sulfosuccinates, polyoxyethylene sorbitan fatty acid esters, and oxyethylene oxypropylene block copolymers.

  In the present invention, a sulfosuccinic acid type surfactant (F), a surfactant containing an alkylene oxide group (G) at the time of mixing or pre-dispersing the paint pigment, 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 emulsion polymerization in the present invention is a radical polymerization initiator that can be radically decomposed by heat or a reducing substance to cause addition polymerization of a radically polymerizable unsaturated monomer, and is water-soluble or oil-soluble persulfuric acid. Salts, peroxides, azobis compounds and the like can be advantageously 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) can be mentioned, but it is also effective as a catalyst for promoting the hydrolysis reaction and condensation reaction of hydrolyzable silane. It is preferable to use potassium persulfate, sodium persulfate, or ammonium persulfate. As a quantity of a radical polymerization initiator, 0.05 mass%-1 mass% can be normally used with respect to the mass of a radically polymerizable monomer.

At the time of polymerization, radically polymerizable monomer, surfactant, radical polymerization initiator, etc. may be supplied to the reaction system in a pre-emulsified state together with polymerization water, or various raw materials may be supplied separately to the reaction system. You may do it.
Usually, the polymerization reaction is preferably carried out under normal pressure and at a polymerization temperature of 65 to 90 ° C., but can also be carried out under high pressure in accordance with characteristics such as vapor pressure at the polymerization temperature of the radical polymerizable monomer. The polymerization time includes a supply time and a aging time after the supply. The supply time is usually several minutes when supplying various raw materials to the reaction system at the same time, and when sequentially supplying various raw materials to the reaction system, the heat generation due to polymerization is sequentially supplied to the reaction system within a range where heat can be removed. Although it depends on the polymer concentration in the finally obtained emulsion, it is usually 10 minutes or longer. The aging time after feeding is preferably at least 10 minutes or more. Below this polymerization time, part of each radical polymerizable monomer may be unreacted or the hydrolyzable silane may not be condensed and remain as a hydrolyzate. When acceleration of polymerization rate and polymerization at a low temperature of 70 ° C. or lower are desired, for example, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, Rongalite is used in combination with a radical polymerization initiator. And is advantageous.

The emulsion according to the present invention preferably has an average particle size of the dispersoid of 10 to 1000 nm.
In the present invention, when the aqueous dispersion (B) is subjected to emulsion polymerization, the pH of the reaction system is preferably 4.0 or less, more preferably from 1.5 to 3.0.
The aqueous coating composition for preventing contamination of the present invention is adjusted to a pH of 5 to 10 using amines such as ammonia, sodium hydroxide, potassium hydroxide and dimethylaminoethanol in order to maintain dispersion stability during long-term storage. It is preferable to do.

  In order to further improve the stain resistance and water resistance, the hydrazine derivative having at least two hydrazino groups in the molecule is added to the aqueous coating composition for preventing pollution of the present invention. Examples of the hydrazine derivative include succinic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide and the like, saturated aliphatic carboxylic acid dihydrazide having 2 to 18 carbon atoms; maleic acid dihydrazide Monoolefinic unsaturated dicarboxylic acid dihydrazide such as fumaric acid dihydrazide, itaconic acid dihydrazide; phthalic acid, terephthalic acid or isophthalic acid dihydrazide, and pyromellitic acid dihydrazide, trihydrazide or tetrahydrazide; nitrilotrihydrazide, citric acid trihydrazide, 1,2,4-benzenetrihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, low carboxylic acid Polyhydrazide obtained by reacting a low polymer having an alkyl ester group with hydrazine or hydrazine hydrate (hydrazine hydride) (see Japanese Patent Publication No. 52-22878); carbonic acid dihydrazide, bissemicarbazide; A polyfunctional semicarbazide obtained by excessively reacting a polyisocyanate compound having an allophanate group obtained by urethanization reaction of diisocyanate and alcohol or simultaneously with an allophanate group with a hydrazine compound or the above-mentioned dihydrazide, Examples of the isocyanate group in the reaction product of an isocyanate compound and an active hydrogen compound containing a hydrophilic group such as polyether polyols and polyethylene glycol monoalkyl ethers are shown above. An aqueous polyfunctional semicarbazide obtained by excessively reacting dihydrazide, or a mixture of the polyfunctional semicarbazide and aqueous polyfunctional semicarbazide (see JP-A-8-151358, JP-A-8-245878, Japanese Patent No. 312857) Etc.

In the aqueous coating composition for preventing contamination according to the present invention, components usually added and mixed in water-based paints, such as film forming aids, thickeners, antifoaming agents, pigments, dispersants, dyes, preservatives, etc. An ultraviolet absorber and a light stabilizer can be arbitrarily blended in
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 introduced into the aqueous dispersion (B) by being present during the emulsion polymerization for producing the aqueous dispersion (B), the ultraviolet absorber and / or the light stabilizer. A method of introducing an agent by mixing it with a film-forming auxiliary or the like and adding it to the aqueous dispersion (B), an ultraviolet absorber and / or a light stabilizer are mixed with the film-forming auxiliary, and a surfactant and water are added. After emulsification, the method of introducing by adding to the aqueous dispersion (B) 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 present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the part and% in an Example and a comparative example represent a mass part and the mass%, respectively. Moreover, about the physical-property test of the obtained aqueous coating composition, the coating material was adjusted with the compounding composition shown below using this aqueous coating composition, and the test was implemented according to the test method shown below.
<Coating composition>
・ Preparation of clear paint (except comparative example 3)
Each anti-fouling aqueous coating composition (solid content conversion) 50.00 parts 50 parts ethylene glycol monobutyl ether and 50 parts water
10.00 parts CS-12 (deposition aid: 2,2,4-trimethyl-1,3-butane
Diol isobutyrate) (Product name, manufactured by Chisso Corporation)
10.00 parts (for Comparative Example 3, ethylene glycol monobutyl ether and CS-12 were not blended)

-Preparation of pigment dispersion Dispersant: Pig. Disperser MD20
(Product name, manufactured by BASF Japan Ltd.) 5.35 parts Ammonia water 0.50 parts Propylene glycol 23.50 parts Water 147.50 parts Taipei CR-97 (trade name, manufactured by Ishihara Sangyo Co., Ltd.) 333.50 Part Antifoam: SN deformer 1310
(Trade name, manufactured by San Nopco Co., Ltd.) 2.85 parts The above-mentioned composition was dispersed for 20 minutes in a tabletop sand mill to obtain a pigment dispersion.

・ Production of enamel paint (except comparative example 3)
Each anti-fouling aqueous coating composition (solid content conversion) 50.00 parts 50 parts ethylene glycol monobutyl ether and 50 parts water
10.00 parts CS-12 (deposition aid: 2,2,4-trimethyl-1,3-butane
Diol isobutyrate) (Product name, manufactured by Chisso Corporation)
10.00 parts Pigment dispersion 51.32 parts Thickener: Adecanol UH-438 (Asahi Denka Kogyo Co., Ltd.)
(Comparative Example 3 was not blended with ethylene glycol monobutyl ether or CS-12)

<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 water dispersion The mass obtained by subtracting the dry weight of the surfactant, polymerization initiator, etc. from the dry weight of the water 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.
-Storage stability of coating liquid The enamel coating composition was placed in a sealed container, left in a 50 ° C constant temperature bath for 4 weeks, and the state after 4 weeks was visually determined. Judgment criteria are as follows.
A: No increase in viscosity and fluidity.
Δ: There is an increase in viscosity, but there is fluidity.
X: Gelled.

-Water resistance The above-mentioned enamel coating composition is applied to the wire coater No. 50 was applied to an alumite sulfate plate and dried at room temperature for 2 days. Furthermore, after drying at 50 degreeC for 2 days, it was immersed in 20 degreeC water for 30 days, and the state was determined visually. Judgment criteria are as follows.
A: No blistering or glossiness is seen.
○: Slightly blistering but no glossiness.
Δ: There is blistering and glossiness is also seen.
X: The whole surface is blistering and glossy.
· On the anodized aluminum plate shown in rain stains contaminating Figure 1, the enamel coating formulation was applied with a wire coater to a dry film thickness of 100 g / m ^2, the specimen was dried for four weeks at room temperature Obtained. 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.

-Weather resistance The above-mentioned enamel coating composition was applied to a wire coater No. 50 was applied to an alumite sulfate plate and dried at room temperature for 30 days. Subsequently, an exposure test (rain cycle; 18 minutes / 2 hours, black panel temperature 60 to 66 ° C.) was performed using a sunshine type weatherometer (Suga Test Instruments Co., Ltd., WEL-SUN-DC). Changes in appearance after 2000 hours of exposure were observed. Judgment criteria are as follows.
A: No change.
○;
Δ: Shiny and partially cracked.
X: Cracks are seen on the entire surface with glossiness.

[Production Example 1 of Water Dispersion]
Prepare a reaction vessel equipped with a stirrer, reflux condenser, two dripping tanks and a thermometer. The two dripping tanks are Y-tubes (100 mm metal mesh is packed at the outlet of the Y-tubes. Filled with molecular sieves 3A (product name: manufactured by Wako Pure Chemical Industries, Ltd.) to the point where the liquid is mixed, the pre-emulsified liquid containing the radical polymerizable monomer and the hydrolyzable silane can be gently mixed. It was assembled so that it could flow into the reaction system via 426 parts of water and 6 parts of an anionic reactive surfactant containing an alkylene oxide group (product name: Adekaria soap SR-1025, manufactured by Asahi Denka Kogyo Co., Ltd.) were raised to 80 ° C., and then ammonium persulfate 5 minutes after adding 15 parts of a 2% aqueous solution of methyl methacrylate, 244 parts of cyclohexyl methacrylate, 335 parts of n-butyl acrylate, 13 parts of methacrylic acid, 23 parts of Adecare Soap SR-1025, alkylsulfosucci 21.7 parts of an acid salt surfactant (product name: Aerosol OT-75, manufactured by Nippon Cytec Industries Co., Ltd.), 32.5 parts of a 2% aqueous solution of ammonium persulfate, and 262 parts of water were added to the mixture. And a pre-emulsion prepared by mixing 5 minutes with a homomixer and γ-methacryloxypropyltrimethoxysilane 6 , 66 parts of methyltrimethoxysilane was a mixture consisting of 16 parts of diphenyldimethoxysilane from different dropping tanks is flowed over 120 minutes through the Y-shaped tube. The pH during the silicone modification reaction was maintained at 4 or less. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.

  Next, 170 parts of methyl methacrylate, 20 parts of diacetone acrylamide, 10 parts of methacrylic acid, 2 parts of dodecyl mercaptan, 4 parts of Adecalia soap SR-1025, alkylsulfosuccinate surfactant (product name: Eleminol JS- 2, 8 parts of SANYO KASEI KOGYO CO., LTD., 20 parts of 2% aqueous solution of ammonium persulfate and 130 parts of water were added, and the pre-emulsified liquid prepared by mixing the mixed solution for 5 minutes with a homomixer was added to the reaction vessel. It was made to flow in from the dropping tank over 45 minutes. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.

Next, 69 parts of methyl methacrylate, 56 parts of cyclohexyl methacrylate, 22 parts of n-butyl acrylate, 3 parts of methacrylic acid, 3 parts of ADEKA rear soap SR-1025, 5 parts of Aerosol OT-75, ammonium persulfate A pre-emulsion prepared by adding 7.5 parts of a 2% aqueous solution and 163 parts of water and mixing the mixture for 5 minutes with a homomixer, 1.3 parts of γ-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane A mixed liquid consisting of 15 parts and 3.7 parts of diphenyldimethoxysilane was allowed to flow from a separate dropping tank through the Y-shaped tube over 30 minutes. The pH during the silicone modification reaction was maintained at 4 or less. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and maintained for 90 minutes.
After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.3. A 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100-mesh wire mesh. The dry mass of the filtered aggregate was as little as 20 ppm with respect to the obtained solid content mass. The solid content of the obtained emulsion was 47.6%.
Table 1 shows Tg _{C + D} and Tg _C of the obtained emulsion.

[Production Example 2 of Water Dispersion]
Prepare a reaction vessel equipped with a stirrer, reflux condenser, two dripping tanks and a thermometer. The two dripping tanks are Y-tubes (100 mm metal mesh is packed at the outlet of the Y-tubes. The molecular sieves 3A were filled up to the point where they were mixed, and adjusted so that the pre-emulsified liquid containing the radical polymerizable monomer and the hydrolyzable silane could be mixed gently.) It was assembled so that it could flow. 5 minutes after adding 426 parts of water and 6 parts of Adeka Soap SR-1025, raising the temperature to 80 ° C. and adding 15 parts of a 2% aqueous solution of ammonium persulfate, 102 parts of methyl methacrylate and 244 parts of cyclohexyl methacrylate , 291 parts of 2-hydroxyethyl acrylate, 13 parts of methacrylic acid, hindered amine light stabilizer (product name: TINUVIN123, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 23 parts of ADEKA rear soap SR-1025 A pre-emulsion prepared by mixing 21 parts of Aerosol OT-75, 32.5 parts of a 2% aqueous solution of ammonium persulfate and 262 parts of water and mixing for 5 minutes with a homomixer, and γ-methacrylate 6 parts roxypropyltrimethoxysilane, 66 parts methyltrimethoxysilane, diph And a mixture consisting of alkenyl silane 16 parts from different dropping tanks was flowed over 120 minutes through the Y-shaped tube. The pH during the silicone modification reaction was maintained at 4 or less. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.
Next, 170 parts of methyl methacrylate, 20 parts of diacetone acrylamide, 10 parts of methacrylic acid, 2 parts of dodecyl mercaptan, 4 parts of Adecalia Soap SR-1025, 8 parts of Eleminor JS-2, 2% aqueous solution of ammonium persulfate 20 And 130 parts of water were added, and the pre-emulsion prepared by mixing the mixed solution for 5 minutes with a homomixer was allowed to flow into the reaction vessel from the dropping tank over 45 minutes. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.

Next, 69 parts of methyl methacrylate, 56 parts of cyclohexyl methacrylate, 22 parts of n-butyl acrylate, 3 parts of methacrylic acid, 3 parts of ADEKA rear soap SR-1025, 5 parts of Aerosol OT-75, ammonium persulfate A pre-emulsion prepared by adding 7.5 parts of a 2% aqueous solution and 163 parts of water and mixing the mixture for 5 minutes with a homomixer, 1.3 parts of γ-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane A mixed liquid consisting of 15 parts and 3.7 parts of diphenyldimethoxysilane was allowed to flow from a separate dropping tank through the Y-shaped tube over 30 minutes. The pH during the silicone modification reaction was maintained at 4 or less. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and maintained for 90 minutes.
After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.3. A 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100-mesh wire mesh. The dry mass of the filtered aggregate was as little as 20 ppm with respect to the obtained solid content mass. The solid content of the obtained emulsion was 48.0%. Table 1 shows Tg _{C + D} and Tg _C of the obtained emulsion.

[Production Example 3 of Water Dispersion]
Prepare a reaction vessel equipped with a stirrer, reflux condenser, two dripping tanks and a thermometer. The two dripping tanks are Y-tubes (100 mm metal mesh is packed at the outlet of the Y-tubes. The molecular sieves 3A were filled up to the point where they were mixed, and adjusted so that the pre-emulsified liquid containing the radical polymerizable monomer and the hydrolyzable silane could be mixed gently.) It was assembled so that it could flow. 408 parts of water and 8 parts of Adeka Soap SR-1025 were added, the temperature was raised to 80 ° C., and 5 minutes after adding 15 parts of a 2% aqueous solution of ammonium persulfate, 170 parts of methyl methacrylate and 20 parts of diacetone acrylamide were added. , 10 parts of methacrylic acid, 2 parts of dodecyl mercaptan, 4.8 parts of Adecalia Soap SR-1025, 8 parts of Eleminol JS-2, 20 parts of 2% aqueous solution of ammonium persulfate and 167 parts of water, A pre-emulsion prepared by mixing for 5 minutes with a homomixer was allowed to flow into the reaction vessel from the dropping tank over 60 minutes. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.

Next, 125 parts of methyl methacrylate, 300 parts of cyclohexyl methacrylate, 359 parts of n-butyl acrylate, 16 parts of methacrylic acid, 38.4 parts of Adekalia Soap SR-1025, and 13.3 parts of Aerosol OT-75 40 parts of a 2% aqueous solution of ammonium persulfate and 410 parts of water were added, and the pre-emulsion prepared by mixing the mixture for 5 minutes with a homomixer, 7.2 parts of γ-methacryloxypropyltrimethoxysilane, A mixed liquid consisting of 81.2 parts of methoxysilane and 19.7 parts of diphenyldimethoxysilane was allowed to flow from a separate dropping tank through the Y-shaped tube over 150 minutes. The pH during the silicone modification reaction was maintained at 4 or less. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and maintained for 90 minutes.
After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.3. A 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100-mesh wire mesh. The dry mass of the filtered aggregate was as little as 20 ppm with respect to the obtained solid content mass. The solid content of the obtained emulsion was 47.2%. Table 1 shows Tg _{C + D} and Tg _C of the obtained emulsion.

[Production Example 4 of Water Dispersion]
Prepare a reaction vessel equipped with a stirrer, reflux condenser, two dripping tanks and a thermometer. The two dripping tanks are Y-tubes (100 mm metal mesh is packed at the outlet of the Y-tubes. The molecular sieves 3A were filled up to the point where they were mixed, and adjusted so that the pre-emulsified liquid containing the radical polymerizable monomer and the hydrolyzable silane could be mixed gently.) It was assembled so that it could flow. 510 parts of water and 8 parts of Adeka Soap SR-1025 were added, the temperature was raised to 80 ° C., and 5 minutes after adding 15 parts of a 2% aqueous solution of ammonium persulfate, 6 parts of methyl methacrylate and 160 parts of cyclohexyl methacrylate were added. , 324 parts of n-butyl acrylate, 10 parts of methacrylic acid, 24 parts of ADEKA rear soap SR-1025, 8.3 parts of aerosol OT-75, 25 parts of 2% aqueous solution of ammonium persulfate, 239 parts of water, A pre-emulsion prepared by mixing the mixed solution for 5 minutes with a homomixer, and 5.8 parts of γ-methacryloxypropyltrimethoxysilane, 50.7 parts of methyltrimethoxysilane, and 12.3 parts of diphenyldimethoxysilane The mixed solution was allowed to flow from a separate dropping tank through the Y-shaped tube over 90 minutes. The pH during the silicone modification reaction was maintained at 4 or less. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.

Next, 150 parts of methyl methacrylate, 40 parts of diacetone acrylamide, 10 parts of methacrylic acid, 2 parts of dodecyl mercaptan, 9.6 parts of Adecalia Soap SR-1025, 8 parts of Eleminol JS-2, 2% of ammonium persulfate A pre-emulsion prepared by adding 20 parts of an aqueous solution and 126 parts of water and mixing the mixed solution for 5 minutes with a homomixer was allowed to flow into the reaction vessel from the dropping tank over 45 minutes. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.

Next, 125 parts of methyl methacrylate, 140 parts of cyclohexyl methacrylate, 32 parts of n-butyl acrylate, 3 parts of methacrylic acid, 14.4 parts of ADEKA rear soap SR-1025, 5 parts of aerosol OT-75, A pre-emulsion prepared by adding 15 parts of a 2% aqueous solution of ammonium sulfate and 140 parts of water and mixing the mixture for 5 minutes with a homomixer, 1.4 parts of γ-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane A mixed liquid consisting of 30.5 parts and 7.4 parts of diphenyldimethoxysilane was allowed to flow in from a separate dropping tank through the Y-shaped tube over 60 minutes. The pH during the silicone modification reaction was maintained at 4 or less. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and maintained for 90 minutes.
After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.3. A 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100-mesh wire mesh. The dry mass of the filtered aggregate was as little as 20 ppm with respect to the obtained solid content mass. The solid content of the obtained emulsion was 46.6%. Table 1 shows Tg _{C + D} and Tg _C of the obtained emulsion.

[Production Example 5 of water dispersion]
Prepare a reaction vessel equipped with a stirrer, reflux condenser, two dripping tanks and a thermometer. The two dripping tanks are Y-tubes (100 mm metal mesh is packed at the outlet of the Y-tubes. The molecular sieves 3A were filled up to the point where they were mixed, and adjusted so that the pre-emulsified liquid containing the radical polymerizable monomer and the hydrolyzable silane could be mixed gently.) It was assembled so that it could flow. 5 minutes after adding 426 parts of water and 6 parts of Adeka Soap SR-1025 and raising the temperature to 80 ° C. and adding 15 parts of a 2% aqueous solution of ammonium persulfate, 58 parts of methyl methacrylate and 244 parts of cyclohexyl methacrylate , 335 parts of n-butyl acrylate, 13 parts of methacrylic acid, 23.4 parts of ADEKA rear soap SR-1025, 32.5 parts of 2% aqueous solution of ammonium persulfate and 268 parts of water were added, and the mixture was mixed with a homomixer. A pre-emulsion prepared by mixing for 5 minutes, and a mixed solution comprising 5.8 parts of γ-methacryloxypropyltrimethoxysilane, 66 parts of methyltrimethoxysilane, and 16 parts of diphenyldimethoxysilane are separated from the above dropping tanks. It was allowed to flow through the Y-shaped tube over 120 minutes. The pH during the silicone modification reaction was maintained at 4 or less. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.

  Next, 170 parts of methyl methacrylate, 20 parts of diacetone acrylamide, 10 parts of methacrylic acid, 2 parts of dodecyl mercaptan, 4 parts of Adecalia Soap SR-1025, 8 parts of Eleminor JS-2, 2% aqueous solution of ammonium persulfate 20 And 130 parts of water were added, and a pre-emulsion prepared by mixing the mixed solution for 5 minutes with a homomixer was allowed to flow into the reaction vessel from the dropping tank over 45 minutes. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.

Next, 69 parts of methyl methacrylate, 56 parts of cyclohexyl methacrylate, 22 parts of n-butyl acrylate, 3 parts of methacrylic acid, 3 parts of Adekari Soap SR-1025, 7.5 parts of 2% aqueous solution of ammonium persulfate, water 165 parts was added, and the pre-emulsion prepared by mixing the mixed solution for 5 minutes with a homomixer, 1.3 parts of γ-methacryloxypropyltrimethoxysilane, 15.2 parts of methyltrimethoxysilane, diphenyldimethoxysilane 3 And 7 parts of the mixed solution were allowed to flow from separate dropping tanks through the Y-shaped tube over 30 minutes. The pH during the silicone modification reaction was maintained at 4 or less. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and maintained for 90 minutes.
After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.3. A 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100-mesh wire mesh.
The dry mass of the filtered aggregate was as little as 20 ppm with respect to the obtained solid content mass. The resulting emulsion had a solid content of 47.1%. Table 1 shows Tg _{C + D} and Tg _C of the obtained emulsion.

[Production Example 6 of water dispersion]
Prepare a reaction vessel equipped with a stirrer, reflux condenser, two dripping tanks and a thermometer. The two dripping tanks are Y-tubes (100 mm metal mesh is packed at the outlet of the Y-tubes. The molecular sieves 3A were filled up to the point where they were mixed, and adjusted so that the pre-emulsified liquid containing the radical polymerizable monomer and the hydrolyzable silane could be mixed gently.) It was assembled so that it could flow. 408 parts of water and 8 parts of Adeka Soap SR-1025 were added, the temperature was raised to 80 ° C., 5 minutes after adding 15 parts of 2% aqueous solution of ammonium persulfate, 260 parts of methyl methacrylate, 30 parts of diacetone acrylamide , 10 parts of methacrylic acid, 3 parts of dodecyl mercaptan, 7.2 parts of Adecalia Soap SR-1025, 12 parts of Eleminol JS-2, 30 parts of 2% aqueous solution of ammonium persulfate and 153 parts of water, A pre-emulsion prepared by mixing for 5 minutes with a homomixer was poured into the reaction vessel from the dropping tank over 60 minutes. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.

  Next, 30 parts of methyl methacrylate, 300 parts of cyclohexyl methacrylate, 356 parts of n-butyl acrylate, 14 parts of methacrylic acid, 33.6 parts of Adekari Soap SR-1025, and 13.3 parts of Aerosol OT-75 35 parts of 2% aqueous solution of ammonium persulfate and 418 parts of water were added, and the pre-emulsion prepared by mixing the mixture for 5 minutes with a homomixer, 7.2 parts of γ-methacryloxypropyltrimethoxysilane, A mixed liquid consisting of 81.2 parts of methoxysilane and 19.7 parts of diphenyldimethoxysilane was allowed to flow from a separate dropping tank through the Y-shaped tube over 120 minutes. The pH during the silicone modification reaction was maintained at 4 or less. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and maintained for 90 minutes.

After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.3. A 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100-mesh wire mesh. The dry mass of the filtered aggregate was as little as 20 ppm with respect to the obtained solid content mass. The solid content of the obtained emulsion was 47.2%. Table 1 shows Tg _{C + D} and Tg _C of the obtained emulsion.

[Production Example 7 of water dispersion]
Prepare a reaction vessel equipped with a stirrer, reflux condenser, two dripping tanks and a thermometer. The two dripping tanks are Y-tubes (100 mm metal mesh is packed at the outlet of the Y-tubes. Filled with molecular sieves 3A (product name: manufactured by Wako Pure Chemical Industries, Ltd.) to the point where the liquid is mixed, the pre-emulsified liquid containing the radical polymerizable monomer and the hydrolyzable silane can be gently mixed. It was assembled so that it could flow into the reaction system via 422 parts of water, 13.3 parts of an anionic surfactant containing an alkylene oxide group (product name: New Coal 707SF, manufactured by Nippon Emulsifier Co., Ltd.), heated to 80 ° C., and 2% aqueous solution of ammonium persulfate 5 minutes after adding 15 parts of methyl methacrylate, 244 parts of cyclohexyl methacrylate, 335 parts of n-butyl acrylate, 13 parts of methacrylic acid, 28.3 parts of New Coal 707SF, 21 parts of Aerosol OT-75 7 parts, 32.5 parts of a 2% aqueous solution of ammonium persulfate and 341 parts of water, and a pre-emulsion prepared by mixing the mixed solution for 5 minutes with a homomixer, and 6 parts of γ-methacryloxypropyltrimethoxysilane , 66 parts of methyltrimethoxysilane, 16 parts of diphenyldimethoxysilane Through the Y-shaped tube was flowed over 120 minutes. The pH during the silicone modification reaction was maintained at 4 or less. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.

Next, 170 parts methyl methacrylate, 20 parts diacetone acrylamide, 10 parts methacrylic acid, 2 parts dodecyl mercaptan, 10 parts Newcor 707SF, 8 parts Eleminor JS-2, 20 parts 2% aqueous solution of ammonium persulfate, water 99 parts were added, and the pre-emulsion prepared by mixing the mixed solution for 5 minutes with a homomixer was allowed to flow into the reaction vessel from the dropping tank over 45 minutes. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.
Next, 69 parts methyl methacrylate, 56 parts cyclohexyl methacrylate, 22 parts n-butyl acrylate, 3 parts methacrylic acid, 6.7 parts Newcor 707SF, 5 parts Aerosol OT-75, 2 parts ammonium persulfate A pre-emulsion prepared by adding 7.5 parts of an aqueous solution and 129 parts of water and mixing the mixture for 5 minutes with a homomixer, 1.3 parts of γ-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane 15 Part and a mixed solution consisting of 3.7 parts of diphenyldimethoxysilane were allowed to flow from separate dropping tanks over 30 minutes through the Y-shaped tube. The pH during the silicone modification reaction was maintained at 4 or less. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and maintained for 90 minutes.

After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.3. A 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100-mesh wire mesh. The dry mass of the filtered aggregate was as little as 20 ppm with respect to the obtained solid content mass. The solid content of the obtained emulsion was 47.3%.
Table 1 shows Tg _{C + D} and Tg _C of the obtained emulsion.

[Production Example 8 of Water Dispersion]
Prepare a reaction vessel equipped with a stirrer, reflux condenser, two dripping tanks and a thermometer. The two dripping tanks are Y-tubes (100 mm metal mesh is packed at the outlet of the Y-tubes. The molecular sieves 3A were filled up to the point where they were mixed, and adjusted so that the pre-emulsified liquid containing the radical polymerizable monomer and the hydrolyzable silane could be mixed gently.) It was assembled so that it could flow. 435 parts of water and 8 parts of Adeka Soap SR-1025 were added, the temperature was raised to 80 ° C., and 5 minutes after adding 15 parts of a 2% aqueous solution of ammonium persulfate, 105 parts of methyl methacrylate and 150 parts of cyclohexyl methacrylate were added. 224 parts of n-butyl acrylate, 15 parts of diacetone acrylamide, 6 parts of methacrylic acid, 20 parts of ADEKA rear soap SR-1025, a nonionic surfactant containing an alkylene oxide group (product name: Emulgen 120, Kao Corporation )) 20% aqueous solution, ammonium persulfate 2% aqueous solution 25 parts, and water 333 parts, and a pre-emulsion prepared by mixing the mixture for 5 minutes with a homomixer, and γ-methacryloxypropyltri 5.8 parts of methoxysilane, 21 parts of methyltrimethoxysilane, 34 dimethyldimethoxysilane Through the Y-shaped tube the mixture and consisting of separate dropping funnel were introduced into it over 90 minutes. The pH during the silicone modification reaction was maintained at 4 or less. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.

Next, 94 parts of methyl methacrylate, 60 parts of cyclohexyl methacrylate, 30 parts of n-butyl acrylate, 6 parts of diacetone acrylamide, 10 parts of methacrylic acid, 2 parts of dodecyl mercaptan, 4 parts of adecalia soap SR-1025 A pre-emulsion prepared by adding 20 parts of a 2% aqueous solution of ammonium sulfate and 135 parts of water and mixing the mixture with a homomixer for 5 minutes was allowed to flow into the reaction vessel over 45 minutes. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and kept for 30 minutes.
Next, 96 parts of methyl methacrylate, 90 parts of cyclohexyl methacrylate, 102 parts of n-butyl acrylate, 9 parts of diacetone acrylamide, 3 parts of methacrylic acid, 6 parts of ADEKA rear soap SR-1025, 2% aqueous solution of ammonium persulfate 7.5 parts and 166 parts of water were added, and the pre-emulsion prepared by mixing the mixed solution for 5 minutes with a homomixer, 1.4 parts of γ-methacryloxypropyltrimethoxysilane, and 12.7 of methyltrimethoxysilane And a mixed liquid consisting of 20 parts of dimethyldimethoxysilane were allowed to flow in from a separate dropping tank over 60 minutes through the Y-shaped tube. The pH during the silicone modification reaction was maintained at 4 or less. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 80 ° C. and maintained for 90 minutes.

After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.5. A 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100-mesh wire mesh. The dry mass of the filtered aggregate was as little as 20 ppm with respect to the obtained solid content mass. The solid content of the obtained emulsion was 45.9%. Table 1 shows Tg _{C + D} and Tg _C of the obtained emulsion.

[Production Example 9 of water dispersion]
Into a reaction vessel equipped with a stirrer, reflux condenser, dripping tank and thermometer, 1166 parts of water and 5 parts of sodium dodecylbenzenesulfonate are added, the temperature is raised to 70 ° C., and then a 10% aqueous solution of potassium persulfate is added. 5 minutes after the addition, 420 parts of methyl methacrylate, 420 parts of n-butyl acrylate, 110 parts of 2-ethylhexyl acrylate, 30 parts of diacetone acrylamide, 20 parts of methacrylic acid, 10 parts of γ-methacryloxypropyltrimethoxysilane Was allowed to flow in over 240 minutes. During the inflow, the temperature in the reaction vessel was kept at 70 ° C. After completion of the inflow, the temperature in the reaction vessel was raised to 80 ° C. and kept for 60 minutes.
After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.5. A 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100-mesh wire mesh. The dry mass of the filtered agglomerate was a slight 30 ppm with respect to the obtained solid mass. The solid content of the obtained emulsion was 45.5%. Table 1 shows Tg _{C + D} and Tg _C of the obtained emulsion.

[Production Example 10 of water dispersion]
A reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 500 parts of water, 20 parts of an anionic surfactant containing an alkylene oxide group (product name: Emar NC, manufactured by Kao Corporation), Emulgen 20 parts of 20% aqueous solution of 120, 35 parts of methyl methacrylate, 32 parts of n-butyl acrylate, 12 parts of diacetone acrylamide, 0.5 part of acrylic acid, 4 parts of Emar NC, 4 parts of 20% aqueous solution of Emulgen 120 A mixture of 32.5 parts of water was added, heated to 90 ° C., and 25 parts of a 2% aqueous solution of potassium persulfate was added.
Next, a mixture of 315 parts of methyl methacrylate, 288 parts of n-butyl acrylate, 108 parts of diacetone acrylamide, 4.5 parts of acrylic acid, 36 parts of Emar NC, 36 parts of 20% aqueous solution of Emulgen 120, and 293 parts of water Was allowed to flow in over 60 minutes. During the inflow, the temperature in the reaction vessel was kept at 90 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 90 ° C. and kept for 60 minutes.

Next, 80 parts of methyl methacrylate, 80 parts of n-butyl acrylate, 30 parts of diacetone acrylamide, 15 parts of acrylic acid, 1.4 parts of t-dodecyl mercaptan, 8 parts of Emar NC, 10% 20% aqueous solution of Emulgen 120 And a mixture of 97 parts of water were allowed to flow in over 60 minutes.
225 parts of a 2% aqueous solution of potassium persulfate was added continuously.
During the inflow, the temperature in the reaction vessel was kept at 90 ° C. After the inflow was completed, the temperature in the reaction vessel was raised to 90 ° C. and maintained for 90 minutes.
After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.5. A 25% aqueous ammonia solution was added to adjust the pH to 8.5, followed by filtration through a 100-mesh wire mesh.
The dry mass of the filtered agglomerate was a slight 30 ppm with respect to the obtained solid mass. The solid content of the obtained emulsion was 42.0%. Table 1 shows Tg _{C + D} and Tg _C of the obtained emulsion.

[Example 1]
To 105 parts of the aqueous dispersion obtained in Production Example 1 of the aqueous dispersion, 25 parts of colloidal silica (product name: Adelite AT-30A, manufactured by Asahi Denka Kogyo Co., Ltd.), Hardener SC (manufactured by Asahi Kasei Chemicals Co., Ltd.) 2 parts of a polyfunctional semicarbazide aqueous solution) was added to obtain an aqueous coating composition for preventing contamination. The coating composition described above was blended with respect to this anti-fouling aqueous coating composition, and each test was performed. The results are shown in Table 2.
[Example 2]
2 parts of Hardener SC was added to 105 parts of the aqueous dispersion obtained in Production Example 1 of the aqueous dispersion to obtain an aqueous coating composition for preventing contamination. The coating composition described above was blended with respect to this anti-fouling aqueous coating composition, and each test was performed. The results are shown in Table 2.
Example 3
25 parts of Adelite AT-30A and 2 parts of hardener SC were added to 104 parts of the aqueous dispersion obtained in Production Example 2 of the aqueous dispersion to obtain an aqueous coating composition for preventing contamination. The coating composition described above was blended with respect to this anti-fouling aqueous coating composition, and each test was performed. The results are shown in Table 2.

Example 4
To 106 parts of the aqueous dispersion obtained in Production Example 3 of the aqueous dispersion, 25 parts of colloidal silica (product name: Snowtex C-30, manufactured by Nissan Chemical Industries, Ltd.), 1.2 parts of Hardener SC, adipine An aqueous coating composition for preventing contamination was obtained by adding 2.3 parts of a 10% aqueous solution of acid dihydrazide. The coating composition described above was blended with respect to this anti-fouling aqueous coating composition, and each test was performed. The results are shown in Table 2.
Example 5
25 parts of Adelite AT-30A and 2.4 parts of Hardener SC were added to 107 parts of the aqueous dispersion obtained in Production Example 4 of the aqueous dispersion to obtain an aqueous coating composition for preventing contamination. The coating composition described above was blended with respect to this anti-fouling aqueous coating composition, and each test was performed. The results are shown in Table 2.

Example 6
To 106 parts of the aqueous dispersion obtained in Production Example 5 of the aqueous dispersion, 1.3 parts of a sulfosuccinic acid surfactant (product name: Aerosol OT-75, manufactured by Nippon Cytec Industries Co., Ltd.), Adelite AT-30A 16.7 parts and 2 parts Hardener SC were added to obtain an aqueous coating composition for preventing contamination. The coating composition described above was blended with respect to this anti-fouling aqueous coating composition, and each test was performed. The results are shown in Table 2.
Example 7
Contamination prevention by adding 25 parts of Snowtex C-30 and 1.2 parts of Hardener SC to 3.5 parts of 10% aqueous solution of adipic dihydrazide to 106 parts of the aqueous dispersion obtained in Production Example 6 of the aqueous dispersion An aqueous coating composition was obtained. The coating composition described above was blended with respect to this anti-fouling aqueous coating composition, and each test was performed. The results are shown in Table 2.

Example 8
An aqueous coating composition for preventing contamination was obtained by adding 16.7 parts of Adelite AT-30A and 2 parts of hardener SC to 106 parts of the aqueous dispersion obtained in Production Example 7 of the aqueous dispersion. The coating composition described above was blended with respect to this anti-fouling aqueous coating composition, and each test was performed. The results are shown in Table 2.

Comparative example

[Comparative Example 1]
2.8 parts of hardener SC was added to 109 parts of the aqueous dispersion obtained in Production Example 8 of the aqueous dispersion to obtain an aqueous coating composition for preventing contamination. The coating composition described above was blended with respect to this anti-fouling aqueous coating composition, and each test was performed. The results are shown in Table 2.
[Comparative Example 2]
To 109 parts of the aqueous dispersion obtained in Production Example 8 of the aqueous dispersion, 16.7 parts of Adelite AT-30A and 3.5 parts of a 10% aqueous solution of adipic acid dihydrazide were added to prepare an aqueous coating composition for preventing pollution. Obtained. The coating composition described above was blended with respect to this anti-fouling aqueous coating composition, and each test was performed. The results are shown in Table 2.

[Comparative Example 3]
To 110 parts of the aqueous dispersion obtained in Production Example 9 of the aqueous dispersion, 50 parts of colloidal silica (product name: Snowtex 30, manufactured by Nissan Chemical Industries, Ltd.) and a 10% aqueous solution of adipic acid dihydrazide were 2.3. In addition, an aqueous coating composition for preventing contamination was obtained. The coating composition described above was blended with respect to this anti-fouling aqueous coating composition, and each test was performed. The results are shown in Table 2.
[Comparative Example 4]
An aqueous coating composition for preventing pollution by adding 33.3 parts of Snowtex C-30 and 3.7 parts of a 10% aqueous solution of adipic acid dihydrazide to 119 parts of the aqueous dispersion obtained in Production Example 10 of the aqueous dispersion. Got. The coating composition described above was blended with respect to this anti-fouling aqueous coating composition, and each test was performed. The results are shown in Table 2.

  The present invention is an aqueous coating composition for preventing pollution that can form a coating film excellent in rain streak stain resistance, flexibility, water resistance, weather resistance, and durability. Synthetic resin emulsion paints such as main materials and top coats for layer finish paints, thin finish paints, thick finish paints, stone finishes, gloss paints, metal paints, wood paints, tile paints It can be suitably used in the field.

It is the schematic of the alumite board used for judging rain-stain stain | pollution | contamination stain resistance.

Claims (17)

5 to 15% by mass of the ethylenically unsaturated monomer (c1) having an aldo group or keto group, a (meth) acrylate monomer, and an ethylenically unsaturated monomer having a carboxyl group (in the polymer (C)) in the presence of against it) containing (ethylenically unsaturated monomer c1) other than (c2) from become polymer (C) and hydrolyzable silane (a), and (meth) acrylate monomer An aqueous dispersion (B) containing a polymer comprising a polymer (D) obtained by copolymerizing an ethylenically unsaturated monomer (c3) other than (c1) containing an ethylenically unsaturated monomer having a carboxyl group An aqueous coating composition for pollution control containing   The aqueous coating composition for preventing pollution according to claim 1, comprising an aqueous dispersion (B), colloidal inorganic particles (E), and a sulfosuccinic acid surfactant (F). The glass transition temperature Tg _C of the polymer (C) comprising the ethylenically unsaturated monomer (c1) having an aldo group or keto group and another ethylenically unsaturated monomer (c2) is 80 ° C. or higher, Hydrolyzable polymer (C) composed of ethylenically unsaturated monomer (c1) having aldo group or keto group and other ethylenically unsaturated monomer (c2) in aqueous dispersion (B) The average Tg _{C + D of} a polymer comprising a polymer (D) obtained by copolymerizing another ethylenically unsaturated monomer (c3 ) in the presence of silane (A) is 60 ° C or less. An aqueous coating composition for preventing contamination. Polymer obtained by emulsion polymerization of ethylenically unsaturated monomer mixture containing 0.1 to 50% by mass of ethylenically unsaturated monomer (c1) having polymer (C) having aldo group or keto group The aqueous coating composition for preventing contamination according to any one of claims 1 to 3, wherein   The aqueous coating composition for preventing pollution according to any one of claims 1 to 4, comprising a surfactant (G) containing an alkylene oxide group.   The aqueous dispersion (B) is an acrylic emulsion obtained by emulsion polymerization in the presence of a sulfosuccinic acid surfactant (F) and / or a surfactant (G) containing an alkylene oxide group. An aqueous coating composition for preventing contamination according to any one of claims 1 to 5. The colloidal inorganic particles (E) are 0 with respect to 100 parts by mass of the resin solid content of the aqueous dispersion (B).
. 1 to 95 parts by mass, 0.1 to 20 parts by mass of the sulfosuccinic acid surfactant (F), and 0.1 to 5 parts by mass of the surfactant (G) containing an alkylene oxide group. The aqueous | water-based coating composition for pollution prevention in any one of Claims 1-6. The aqueous coating composition for preventing pollution according to any one of claims 1 to 7, wherein the hydrolyzable silane (A) contains a silane having a structure represented by the following general formula (a).
^{_{(R 1) n -Si- (R}} 2) 4-n (a)
(In the formula, n is an integer of 0 to 3, and R ¹ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 5 to 10 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, It is selected from a vinyl group, an alkyl acrylate group having 1 to 10 carbon atoms, or an alkyl methacrylate group having 1 to 10 carbon atoms, n R ¹ may be the same or different, and R ² is carbon. It is selected from an alkoxy group, an acetoxy group or a hydroxyl group of formulas 1 to 8. 4-n R ² may be the same or different.   The aqueous coating composition for preventing contamination according to any one of claims 2 to 8, wherein the colloidal inorganic particles (E) include colloidal inorganic particles coated with an organic polymer.   The coating composition for preventing contamination according to any one of claims 2 to 9, wherein the colloidal inorganic particles (E) contain colloidal silica.   The aqueous coating composition for preventing pollution according to any one of claims 2 to 10, wherein the sulfosuccinic acid-based surfactant (F) is a sulfosuccinic acid-based surfactant having no radical polymerizable double bond.   The aqueous dispersion (B) is an acrylic emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer mixture containing 5% by mass or more of a (meth) acrylic acid ester having a cycloalkyl group. The aqueous | water-based coating composition for pollution prevention in any one of Claims 1-11. Pollution Aqueous coating composition according to any one of claims 1 to 12, characterized in that it comprises an organic hydrazine compound having two or more hydrazine residues.   The aqueous coating composition for preventing contamination according to any one of claims 1 to 13, comprising a semicarbazide-based curing agent.   The coating material containing the aqueous | water-based coating composition for pollution prevention in any one of Claims 1-14.   A coated article comprising a coating formed using the paint according to claim 15.   The coating method using the coating material of Claim 15.

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