JP2010106120A - Resin dispersion for water-based coating material and production method of the same, and water-based coating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-based coating material for forming a coating film excellent in blocking resistance, water resistance and weatherability, and to provide a resin dispersion for a water-based coating material for obtaining the above water-based coating material, and a production method of the resin dispersion for a water-based coating material. <P>SOLUTION: Provided is the resin dispersion for a water-based coating material having a silicon-containing water-based vinyl resin dispersed in an aqueous medium, the vinyl resin containing a silicon component and a polymer component that is obtained by polymerizing a radical polymerizable monomer composition containing a monomer having at least two allyl groups. The water-based coating material contains the above resin dispersion for a water-based coating material. The production method of the resin dispersion for a water-based coating material includes polymerizing a radical polymerizable monomer composition containing a monomer having at least two allyl groups in an aqueous medium in the presence of a silicon component to form the silicon-containing water-based vinyl resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin dispersion for an aqueous coating material, a method for producing the same, and an aqueous coating material.

  In recent years, in the field of paints used for buildings and civil engineering structures, a solvent using a volatile organic compound (hereinafter referred to as “VOC”) as a solvent in consideration of the health and environmental protection of the painter and surrounding residents. Conversion from water-based paints to water-based paints using water as a dispersion medium has been attempted. However, emulsion resins used in water-based emulsion paints, which are representative of water-based paints, have an inherent minimum film-forming temperature (hereinafter referred to as “MFT”), and are produced at temperatures below MFT to form a coating film. When the film was formed, it was necessary to add VOC as a film forming aid.

  On the other hand, in order to prevent blocking that tends to occur when the coated plates are stacked, it is necessary to use a high-hardness resin as the binder, but the coating film of the coating material using the high-hardness resin is resistant to frost damage. It is necessary to add a large amount of a film-forming aid because it decreases and MFT is high. Therefore, even if it is a water-based emulsion paint, it contains a considerable amount of VOC. If the drying after painting is insufficient, the remaining VOC reduces the blocking resistance, water resistance and weather resistance of the coating film. It was. Then, development of the aqueous coating material which has a blocking resistance and forms the coating film excellent in water resistance and a weather resistance is tried.

  For example, Patent Document 1 discloses an acrylic copolymer obtained by copolymerizing a polyfunctional monomer having at least one allyl group as a resin composition that forms a coating film excellent in dispersion stability, alcohol shock resistance, and water resistance. A resin composition is shown. However, since the acrylic resin composition has a very high acid value, the water resistance and weather resistance of the coating film may not be sufficient when used for exterior applications.

  Patent Document 2 discloses that a resin that forms a coating film excellent in blocking resistance, water resistance, smoothness, and weather resistance is obtained by copolymerizing an ethylenically unsaturated monomer having a carbonyl group, and a molecule. It has a core / shell structure composed of a shell layer containing a compound having two or more hydrazide groups therein and a core layer obtained by copolymerizing an ethylenically unsaturated monomer having an internal cross-linking structure such as divinylbenzene. An acrylic resin composition is shown. However, since the coating film formed from the acrylic resin composition has high hydrophilicity, the water resistance and weather resistance of the coating film may not be sufficient when used for exterior applications.

  Patent Document 3 discloses an acrylic resin composition obtained by copolymerizing a 1,3,5-triazine derivative such as triallyl cyanurate as a resin composition that forms a molding material having excellent flame retardancy. Yes. However, since the acrylic resin composition is used for a molding material, it is not suitable for a coating application.

  Patent Document 4 discloses a resin composition that forms a coating film excellent in flexibility, melt flowability, and transparency, and has a core / shell structure and graft bonding properties such as triallyl isocyanurate and allyl methacrylate. An acrylic resin composition obtained by copolymerizing a polyfunctional vinyl monomer is shown. However, since the acrylic resin composition does not contain a silicon component, the blocking resistance, water resistance and weather resistance of the coating film may not be sufficient when used for exterior applications.

Furthermore, Patent Document 5 discloses an acrylic graft silicone resin composite having a core / shell structure as a resin composite that forms a coating film excellent in weather resistance, water resistance and flexibility. However, since the resin composite has a Tg of the core layer as low as −60 to 20 ° C., the coating film may not have sufficient blocking resistance.
For these reasons, an aqueous coating material capable of forming a coating film having blocking resistance, water resistance and weather resistance is desired.
JP 2006-316185 A Japanese Patent Laid-Open No. 2002-3778 Japanese Patent Laid-Open No. 4-214009 Japanese Patent Laid-Open No. 7-10937 JP 2004-137374 A

  Therefore, in the present invention, an aqueous coating material capable of forming a coating film excellent in blocking resistance, water resistance and weather resistance, a resin dispersion for an aqueous coating material for obtaining the aqueous coating material, and the aqueous coating It aims at the manufacturing method of the resin dispersion liquid for materials.

The resin dispersion for an aqueous coating material of the present invention is a silicon-containing aqueous solution containing a polymer component obtained by polymerizing a radical polymerizable monomer composition containing a monomer having two or more allyl groups and a silicon component. A vinyl resin is a dispersion liquid dispersed in an aqueous medium.
Moreover, the aqueous coating material of this invention is an aqueous coating material containing the said resin dispersion liquid for aqueous coating materials.

The method for producing a resin dispersion for an aqueous coating material according to the present invention is a method for producing a dispersion in which a silicon-containing aqueous vinyl resin is dispersed in an aqueous medium, the monomer having two or more allyl groups. In the presence of a silicon component in an aqueous medium to form the silicon-containing aqueous vinyl resin.
The method for producing a resin dispersion for an aqueous coating material according to the present invention includes a polymer block (X) having a repeating unit of organosiloxane as the silicon-containing aqueous vinyl resin, and a single amount having at least two allyl groups. A polymer block (Y) obtained by polymerizing a radical polymerizable monomer composition containing a polymer, a silicon-containing graft crossing agent (Z) copolymerized with the polymer block (X) and the polymer block (Y), A method of forming a graft block copolymer comprising: reacting an organosiloxane with a silicon-containing graft crossing agent (Z) to produce a polymer block (X) incorporating the silicon-containing graft crossing agent (Z). After the formation, the polymer block (Y) may be formed by polymerizing the radical polymerizable monomer composition in an aqueous medium in the presence of the polymer block (X). Masui.

The aqueous coating material of the present invention can form a coating film excellent in blocking resistance, water resistance and weather resistance.
Moreover, according to the resin dispersion for aqueous coating materials of this invention, the aqueous coating material which forms the coating film excellent in blocking resistance, water resistance, and a weather resistance can be obtained. Moreover, according to the manufacturing method of this invention, the said resin dispersion for aqueous coating materials contained in the aqueous coating material which forms the coating film excellent in blocking resistance, water resistance, and a weather resistance can be obtained.

[Resin dispersion for aqueous coating materials]
The resin dispersion for aqueous coating materials of the present invention (hereinafter referred to as “resin dispersion”) is a polymer obtained by polymerizing a radical polymerizable monomer composition containing a monomer having two or more allyl groups. A silicon-containing aqueous vinyl resin (hereinafter referred to as “vinyl resin”) containing a component and a silicon component is a dispersion liquid dispersed in an aqueous medium.

The radical polymerizable monomer composition contains at least a monomer having two or more allyl groups (hereinafter referred to as “allyl group-containing monomer”).
An allyl group-containing monomer is a component that forms a crosslinked structure to improve the blocking resistance, water resistance, and weather resistance of the coating film. For example, triallyl cyanurate, triallyl isocyanurate, iso (tere) phthalic acid Examples include diallyl, diallyl isocyanurate, and diallyl maleate. Of these, triallyl cyanurate and triallyl isocyanurate having three allyl groups are preferred from the viewpoint of water resistance and weather resistance.
Since these allyl group-containing monomers have two or more allyl groups with relatively slow radical polymerizability, ethylene glycol dimethacrylate, allyl (meth) acrylate, divinylbenzene, tris (2-acryloyloxyethylene) isocyanurate Sufficient blocking resistance, water resistance and weather resistance can be obtained as compared with a monomer having two or more radical polymerizable groups other than allyl groups such as.

  The content of the allyl group-containing monomer in the radical polymerizable monomer composition (100% by mass) is preferably 0.1 to 10% by mass, and more preferably 0.2 to 8% by mass. Preferably, it is 0.5-8 mass%. If content of an allyl group containing monomer is 0.1 mass% or more, it will be easy to improve the blocking resistance of the formed coating film, water resistance, and a weather resistance. Moreover, if content of an allyl group containing monomer is 10 mass% or less, it will be easy to suppress the film formability of an aqueous coating material, and the fall of a coating-film elongation.

The radical polymerizable monomer other than the allyl group-containing monomer contained in the radical polymerizable monomer composition is not particularly limited, and one or more monomers including an ethylenically unsaturated monomer are copolymerized. be able to.
Specifically, it is preferable that t-butyl methacrylate and / or cyclohexyl methacrylate are contained from the viewpoint of excellent weather resistance and water resistance of the formed coating film. The content of these monomers in the radical polymerizable monomer composition (100% by mass) is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass. If the said content is 5 mass% or more, it will be easy to improve the weather resistance and water resistance of the coating film formed. Moreover, if the said content is 70 mass% or less, it will be easy to suppress the fall of the frost damage resistance of the coating film formed.

  In addition, an ethylenically unsaturated monomer containing a carbonyl group and / or an aldehyde group (hereinafter referred to as “carbonyl group-containing monomer”) is contained in the radical polymerizable monomer composition, and an aqueous coating material is obtained. In the preparation of the above, it is preferable to blend an organic hydrazine compound having at least two hydrazino groups in the molecule (hereinafter referred to as “hydrazine compound”) in the resin dispersion. As a result, a crosslinking reaction proceeds between the carbonyl group of the vinyl resin and the hydrazino group of the blended hydrazine compound at the time of drying after the coating of the water-based coating material, and the formed coating film has a blocking resistance and anti-resistance property. Frost damage, water resistance, weather resistance, stain resistance, solvent resistance and adhesion to various substrates are improved.

  Examples of carbonyl group-containing monomers include vinyl alkyl ketones having 4 to 7 carbon atoms such as acrolein, diacetone acrylamide, formyl styrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, and (meth) acryloxyalkyl. In addition to propanal, (meth) acrylamide, pivalinaldehyde, diacetone (meth) acrylate, acetonyl acrylate, acetoacetoxyethyl (meth) acrylate and the like can be mentioned. Of these, acrolein, diacetone acrylamide, and vinyl methyl ketone are particularly preferable. One or more of these can be selected and used as necessary. In the present specification, (meth) acrylate is a general term for acrylate and methacrylate.

  The content of the carbonyl group-containing monomer in the radical polymerizable monomer composition (100% by mass) is preferably 0.2 to 10% by mass, and more preferably 0.5 to 8% by mass. preferable. If the content is 0.2% by mass or more, it is easy to improve blocking resistance, frost damage resistance, water resistance, weather resistance, stain resistance, solvent resistance and adhesion to various bases of the formed coating film. . Moreover, if content is 10 mass% or less, it will be easy to suppress superposition | polymerization stability and the fall of the water resistance of a coating film.

  Specific examples of the hydrazine compound include ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, and glutaric acid dihydrazide. Adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, isophthalic acid dihydrazide, itaconic acid dihydrazide and the like, and dicarboxylic acid dihydrazides and 1,3-bis (hydrazinocarboethyl)- 5-isopropylhydantoin, 1,3-bis (hydrazinocarboethyl) -5- (2-methylmercaptoethyl) hydantoin, 1-hydrazinocarboethyl-3-hydrazinocarboisopropyl-5- (2-methylmercaptoeth ) Include compounds having the hydantoin skeleton such as hydantoin. One or more of these can be selected and used as necessary.

  The amount of the hydrazine compound used is that when the total number of carbonyl groups and aldehyde groups in the vinyl resin is (P), and the number of hydrazino groups in the hydrazine compound blended in the resin dispersion is (Q). The ratio (P) / (Q) is preferably 0.1 to 10, and more preferably 0.8 to 2. If the ratio (P) / (Q) is 0.1 or more, it is easy to suppress a decrease in water resistance of the coating film due to an excessively existing hydrazine compound without causing a crosslinking reaction with a carbonyl group or an aldehyde group. If the ratio (P) / (Q) is 10 or less, it is easy to obtain a sufficient degree of crosslinking and maintain the effect.

In addition, the radically polymerizable monomer composition has a hydroxy group in terms of blending stability when producing an aqueous coating material, stain resistance of the coating film, weather resistance, water resistance, and adhesion to various substrates. Alkyl (meth) acrylate is preferably contained.
Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2- (3-) hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth) acrylate. Can be mentioned. One or more of these can be selected and used as necessary.

  The content of hydroxyalkyl (meth) acrylate in the radical polymerizable monomer composition (100% by mass) is preferably 0.1 to 15% by mass, and preferably 0.5 to 12% by mass. . If content is 0.1 mass% or more, the said effect by hydroxyalkyl (meth) acrylate will be easy to be acquired. Moreover, if content is 15 mass% or less, it will be easy to suppress the fall of the water resistance of the coating film formed, and a weather resistance.

In addition, from the viewpoint of blocking resistance, stain resistance, weather resistance, water resistance, and adhesion to various bases of the formed coating film, the radical polymerizable monomer composition has a self-crosslinkable functional group-containing ethylenic property. It is preferable that an unsaturated monomer is included. Self-crosslinkable functional group-containing ethylenically unsaturated monomer means that the self-crosslinkable functional group remaining in the vinyl resin is chemically stable while the resin dispersion is stored at room temperature, A monomer that reacts with side-chain functional groups by drying, heating, or other external factors to form chemical bonds between the side-chain groups.
Examples of the self-crosslinkable functional group-containing ethylenically unsaturated monomer include oxirane group-containing ethylenically unsaturated monomers such as glycidyl (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, N Examples include alkylols or alkoxyalkyl compounds of ethylenically unsaturated amides such as butoxymethyl (meth) acrylamide and N-methoxymethyl (meth) acrylamide. One or more of these can be selected and used as necessary.

  The content of the self-crosslinkable functional group-containing ethylenically unsaturated monomer in the radical polymerizable monomer composition (100% by mass) is preferably 0.1 to 15% by mass, and 0.5 to 12%. More preferably, it is mass%. If content is 0.1 mass% or more, the said effect by a self-crosslinkable functional group containing ethylenically unsaturated monomer will be easy to be acquired. Moreover, if content is 15 mass% or less, it will be easy to suppress the fall of the water resistance of the coating film formed, and a weather resistance.

In addition, the radically polymerizable monomer composition contains an ethylenically unsaturated carboxylic acid from the viewpoint of storage stability of the resin dispersion and blending stability when a pigment or additive is added to form a paint. It is preferable.
Examples of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, citraconic acid, maleic acid, monomethyl maleate, monobutyl maleate, monomethyl itaconate, monobutyl itaconate, vinylbenzoic acid, monohydroxy oxalate Ethyl (meth) acrylate, tetrahydrophthalic acid monohydroxyethyl (meth) acrylate, tetrahydrophthalic acid monohydroxypropyl (meth) acrylate, 5-methyl-1,2-cyclohexanedicarboxylic acid monohydroxyethyl (meth) acrylate, phthalic acid mono Hydroxyethyl (meth) acrylate, monohydroxypropyl (meth) acrylate phthalate, monohydroxyethyl (meth) acrylate maleate, hydroxypropyl (meth) acrylate maleate Over DOO, tetrahydrophthalic acid mono-hydroxybutyl (meth) acrylate. One or more of these can be selected and used as necessary.

  The content of the ethylenically unsaturated carboxylic acid in the radical polymerizable monomer composition (100% by mass) is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass. preferable. When the content is 0.1% by mass or more, the above-described effect due to the ethylenically unsaturated carboxylic acid is easily obtained. Moreover, if the said content is 10 mass% or less, it will be easy to suppress the fall of the water resistance of the coating film formed, and a weather resistance.

In addition, the radically polymerizable monomer composition has a polyoxyalkylene from the viewpoint of blending stability of the resin dispersion, stain resistance of the formed coating film, weather resistance, water resistance, and adhesion to various bases. It is preferable that group-containing (meth) acrylate is contained.
Examples of polyoxyalkylene group-containing (meth) acrylates include hydroxypolyethylene oxide mono (meth) acrylate, hydroxypolypropyleneoxide mono (meth) acrylate, hydroxy (polyethyleneoxide-polypropyleneoxide) mono (meth) acrylate, and hydroxypoly (ethyleneoxide) / Propylene oxide) mono (meth) acrylate, hydroxy (polyethylene oxide-polytetramethylene oxide) mono (meth) acrylate, hydroxy poly (ethylene oxide / tetramethylene oxide) mono (meth) acrylate, hydroxy (polypropylene oxide-polytetramethylene oxide) ) Mono (meth) acrylate, hydroxypoly (propylene oxide / tetramethylene oxide) Terminal hydroxy type polyalkylene oxide group-containing ethylenically unsaturated monomers such as (meth) acrylate, methoxypolyethylene oxide mono (meth) acrylate, lauroxypolyethylene oxide mono (meth) acrylate, stearoxypolyethylene oxide mono (meth) Acrylate, allyloxypolyethylene oxide mono (meth) acrylate, nonylphenoxypolyethyleneoxide mono (meth) acrylate, nonylphenoxypolypropyleneoxide mono (meth) acrylate, octoxy (polyethyleneoxide-polypropyleneoxide) mono (meth) acrylate, nonylphenoxy (poly (Ethylene oxide-propylene oxide) mono (meth) acrylate and other alkyl group end-capped polyalkylene oxide groups Ethylenic unsaturated monomers. One or more of these can be selected and used as necessary.

  The content of the polyoxyalkylene group-containing (meth) acrylate in the radical polymerizable monomer composition (100% by mass) is preferably 0.1 to 15% by mass, and 0.5 to 12% by mass. It is more preferable. When the content is 0.1% by mass or more, the above-described effect due to the polyoxyalkylene group-containing (meth) acrylate is easily obtained. Moreover, if the said content is 15 mass% or less, it will be easy to suppress the fall of the water resistance of the coating film formed, and a weather resistance.

In addition, from the viewpoint of the weather resistance of the coating film to be formed, the radical polymerizable monomer composition preferably contains an ultraviolet resistant ethylenically unsaturated monomer.
Examples of the ultraviolet resistant ethylenically unsaturated monomer include (meth) acrylate having a light stabilizing action and (meth) acrylate having an ultraviolet absorbing component.
Examples of the (meth) acrylate having a light stabilizing action include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6. -Tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4 -Cyano-4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine and the like.
Examples of the (meth) acrylate having an ultraviolet absorbing component include 2- [2-hydroxy-5- (meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2-hydroxy-3-t-butyl. -5- (meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2-hydroxy-3-t-amyl-5- (meth) acryloyloxyethylphenyl] -2H-benzotriazole, and the like.
One or more of these can be selected and used as necessary.

  The content of the ultraviolet-resistant ethylenically unsaturated monomer in the radical polymerizable monomer composition (100% by mass) is preferably 0.1 to 20% by mass, and is 0.2 to 15% by mass. It is more preferable. When the content is 0.1% by mass or more, the above-described effect due to the ultraviolet-resistant ethylenically unsaturated monomer is easily obtained. Moreover, if the said content is 20 mass% or less, it will be easy to suppress the fall of polymerization stability.

In addition, when high contamination resistance is required for the coating film, or when there is a possibility that the contamination resistance of the coating film may be reduced due to bleed-out of the plasticizer, the radical-polymerizable monomer composition contains metal-containing ethylene. An unsaturated monomer may be contained.
Examples of metal-containing ethylenically unsaturated monomers include monochloroacetic acid metal (meth) acrylate, monofluoroacetic acid metal (meth) acrylate, propionic acid metal (meth) acrylate, octylic acid metal (meth) acrylate, and versatic acid metal. (Meth) acrylate, metal isostearate (meth) acrylate, metal palmitate (meth) acrylate, metal cresotate (meth) acrylate, metal α-naphthoate (meth) acrylate, metal β-naphthoate (meth) acrylate, benzoic acid Acid metal (meth) acrylate, 2,4,5-trichlorophenoxyacetic acid metal (meth) acrylate, 2,4-dichlorophenoxyacetic acid metal (meth) acrylate, quinolinecarboxylic acid metal (meth) acrylate, nitrobenzoic acid metal (meta Acu Relates, nitronaphthalenecarboxylic acid metal (meth) acrylates, puruvate metal (meth) acrylates, and the like, and the metals include magnesium, calcium, iron, copper, zinc, and zirconium. Of these, a zinc-containing ethylenically unsaturated monomer is preferable. One or more of these can be selected and used as necessary.

  The content of the metal-containing ethylenically unsaturated monomer in the radical polymerizable monomer composition (100% by mass) is preferably 0.1 to 10% by mass, and is 0.5 to 8% by mass. It is preferable. If the said content is 0.1 mass% or more, it will be easy to improve the stain resistance of the coating film formed. Moreover, if the said content is 10 mass% or less, it will be easy to suppress the fall of the water resistance of the coating film formed, and a weather resistance.

  Other usable radical polymerizable monomers include, for example, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polypropylene. Glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy-1,3-di ( (Meth) acryloxypropane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy)・ Polyethoxy) phenyl Propane, 2,2-bis [4- (methacryloxy polyethoxy) phenyl] propane, 2-hydroxy-1-acryloxy-3-methacryloxypropane, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (Meth) acrylate, ethylene oxide-modified hydrogenated bisphenol A di (meth) acrylate, propylene oxide-modified hydrogenated bisphenol A di (meth) acrylate, diglycidyl ether of bisphenol A and hydroxyalkyl (meth) such as hydroxy (meth) acrylate Diester compound of (meth) acrylic acid with diol such as epoxy (meth) acrylate with added acrylate, polyoxyalkylenated bisphenol A di (meth) acrylate, etc. A monomer having two radical polymerizable groups: trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Radical polymerization that is a polyester compound of (meth) acrylic acid and a compound having three or more hydroxyl groups per molecule, such as erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Monomers having two or more functional groups: triethylene glycol dimethacrylate, allyl (meth) acrylate, divinylbenzene, tris (2-acryloyloxyethylene) isocyanurate, ε-capro Monomers having two or more radical polymerizable groups such as kuton-modified tris (acryloxyethyl) isocyanurate; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) ) Acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, n- Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) Acrylate Alkyl (meth) acrylates having an alkyl group of 1 to 18 carbon atoms; cycloalkyl (meth) acrylates such as cyclohexyl acrylate and pt-butylcyclohexyl (meth) acrylate; 2-aminoethyl (meth) acrylate, Aminoalkyl (meth) acrylates such as 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-butylaminoethyl (meth) acrylate; dimethylaminoethyl (meth) acrylate methyl chloride salt, (Meth) acrylonitrile, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl Other (meth) acrylic monomers such as meth) acrylate; aromatic vinyl monomers such as styrene, methylstyrene, chlorostyrene, methoxystyrene; 1,3-butadiene, isoprene, 2-chloro-1, Examples include conjugated diene monomers such as 3-butadiene; radical polymerizable monomers such as vinyl acetate, vinyl chloride, ethylene, and vinyl propionate.

Of these, methyl methacrylate is preferred from the viewpoint of blocking resistance of the coating film.
The content of methyl methacrylate in the radical polymerizable monomer composition (100% by mass) is preferably 25% by mass or more, more preferably 30% by mass or more, and 65% by mass or less from the viewpoint of frost damage resistance of the coating film. Is preferred.
The radical polymerizable monomer is not limited to these as long as radical polymerization is possible.

Moreover, it is essential that the vinyl resin in the resin dispersion of the present invention has a silicon component, which further improves the weather resistance and water resistance of the coating film formed. As a form in which the silicon component is introduced into the vinyl resin, for example,
Form (1): Form introduced by polymerizing the radical polymerizable monomer composition in the presence of polysiloxane particles,
Form (2): Form introduced by radical polymerization of radically polymerizable monomer composition and hydrolyzable silane,
Form (3): The form introduce | transduced by radical-polymerizing a radically polymerizable monomer composition and a silicone type macromonomer is mentioned.
Among these, the form (1) is preferable, and the vinyl resin includes a polymer block (X) having an organosiloxane as a repeating unit, and a polymer block (Y) obtained by polymerizing a radical polymerizable monomer composition. More preferred is a graft block copolymer comprising a polymer block (X) and a silicon-containing graft crossing agent (Z) copolymerized with the polymer block (Y).

  Polymer block (X) includes dimethyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetra It can be synthesized using dimethylsiloxane cyclic oligomers such as decamethylcycloheptasiloxane and dimethylcyclics (dimethylsiloxane cyclic oligomer 3-7 mer mixture), dimethyldichlorosilane and the like as raw materials. Considering the price of the raw material and the performance such as the thermal stability of the resulting resin, a dimethylsiloxane cyclic oligomer is particularly preferable as the raw material for the polymer block (X).

The silicon-containing graft crossing agent (Z) is a component that bonds the polymer block (X) and the polymer block (Y) to ensure the transparency of the formed coating film.
Examples of the silicon-containing graft crossing agent (Z) include compounds containing one or more hydrolyzable silyl groups and one or more vinyl polymerizable functional groups or mercapto groups in the molecule. The hydrolyzable silyl group is preferably an alkoxysilyl group in view of polymerization reactivity, ease of handling, cost, and the like.
Specific examples of the silicon-containing graft crossing agent (Z) include vinyl silanes such as vinylmethyldimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane; γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyl Methacryloxyalkylsilanes such as dimethoxysilane and γ-methacryloxypropyltriethoxysilane; acryloxyalkyl such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, and γ-acryloxypropyltriethoxysilane Silanes; mercaptoalkylsilanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; It is. Of these, methacryloxyalkylsilanes, acryloxyalkylsilanes, and mercaptoalkylsilanes are particularly preferable from the viewpoint of vinyl polymerization reactivity, cost, and the like. One or more of these can be selected and used as necessary.

  The total content of the polymer block (X) and the silicon-containing graft crossing agent (Z) in the graft block copolymer is 0.2 to 50% by mass with respect to 100% by mass of the graft block copolymer. Is preferable, it is more preferable that it is 0.2-40 mass%, and it is further more preferable that it is 0.2-10 mass%. When the content is 0.2% by mass or more, it is easy to improve flexibility, water resistance, weather resistance, frost damage resistance, and smoothness of the coating film to be formed. Moreover, if the said content is 50 mass% or less, it will be easy to suppress the fall of the hardness of a coating film formed, intensity | strength, blocking resistance, and stain resistance.

The polymer block (Y) is formed by polymerizing the radical polymerizable monomer composition described above.
The content of the polymer block (Y) in the graft block copolymer is preferably 50 to 99.8% by mass, and 60 to 99.8% by mass with respect to 100% by mass of the graft block copolymer. More preferably, it is more preferably 90-99.8% by mass. If content of a polymer block (Y) is 50 mass% or more, it will be easy to improve the hardness of a coating film formed, intensity | strength, blocking resistance, and stain resistance. Moreover, if content of a polymer block (Y) is 99.8 mass% or less, it will be easy to suppress the fall of the flexibility of the formed coating film, water resistance, and weather resistance.

  In addition, the content of silicon atoms contained in the silicon-containing graft crossing agent (Z) in the graft block copolymer is 0.5 to 50 based on 100 mol% of the total silicon atoms in the graft block copolymer. It is preferable that it is mol%, and it is more preferable that it is 1-15 mol%. If the said content is 0.5 mol% or more, it will be easy to improve the transparency of the coating film formed. Moreover, if the said content is 50 mol% or less, it will be easy to improve the performance of the coating film formed. Moreover, if the said content is 1 mol% or more, the transparency of the coating film formed will become very favorable. Moreover, if the said content is 15 mol% or less, the stability in the case of emulsion polymerization will become more favorable.

The vinyl resin may be in a form (2) in which a silicon component is introduced by radical polymerization of a radical polymerizable monomer composition and hydrolyzable silane.
The hydrolyzable silane is not particularly limited as long as it hydrolyzes and condenses with an acid catalyst or an alkali catalyst to form an organopolysiloxane. Specific examples of the hydrolyzable silane include organoalkoxysilanes represented by the following general formula (I).
(R ¹ ) _n Si (R ² ) _4-n (I)
(In the formula, R ¹ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an allyl group or a cycloalkyl group, and R ² represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group. N represents an integer of 1 to 3.)
In formula (I), if R ¹ is present two or three may be R ¹ are all the same group, may be a part or all different groups. R ¹ is particularly preferably a methyl group or a phenyl group. R ² is particularly preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, or a hydroxyl group.

  Examples of the organoalkoxysilanes represented by the formula (I) include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, and diphenyldioxysilane. Particularly preferred are ethoxysilane, isobutyltrimethoxysilane, methylphenyldimethoxysilane and the like.

Further, as alkoxysilanes other than the formula (I), vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ- (, which can be copolymerized with the radical polymerizable monomer composition. (Meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyldimethoxymethylsilane, γ-glycidoxypropyltrimethoxysilane, N-β- (aminoethyl) ) Γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane and the like can also be used.
And chlorosilanes such as methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenylchlorosilane, vinylchlorosilane, γ- (meth) acryloxypropyltrichlorosilane, γ- (meth) acryloxypropyldichloromethylsilane; Cyclic silanes such as octamethylcyclotetrasilane, octaphenylcyclosiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, tetramethyltetravinylcyclotetrasiloxane, and the like can also be used.
One or more of these hydrolyzable silanes can be selected and used as necessary. Further, it is particularly preferable to use a hydrolyzable silane copolymerizable with the radical polymerizable monomer composition and a hydrolyzable silane represented by the formula (I).

  Content of the polymer component obtained by superposing | polymerizing the radically polymerizable monomer composition in the vinyl resin of form (2) is 80- with respect to 100 mass% of solid content (vinyl resin) of a resin dispersion. It is preferable that it is 99.9 mass%. If content of a radically polymerizable monomer composition is 80 mass% or more, it will be easy to improve the hardness of a coating film formed, intensity | strength, blocking resistance, and stain resistance. Moreover, if content of a radically polymerizable monomer composition is 99.9 mass% or less, it will be easy to suppress the fall of the flexibility of the formed coating film, water resistance, and weather resistance.

  The content of the hydrolyzable silane in the vinyl resin of the form (2) is preferably 0.1 to 20% by mass with respect to 100% by mass of the solid content (vinyl resin) of the resin dispersion. When the content of the hydrolyzable silane is 0.1% by mass or more, the effect of improving the weather resistance and water resistance due to the use of the hydrolyzable silane as a constituent component is easily exhibited. Moreover, if content of hydrolysable silane is 20 mass% or less, it will be easy to suppress the fall of the flexibility of the coating film formed.

Next, the form (3) will be described.
The silicone-based macromonomer is a general term for high molecular weight monomers having a radical polymerizable group and having a polysiloxane structure. The molecular weight is generally about 1000 to 10,000. The radical polymerizable group of the silicone-based macromonomer is preferably an acryl group or a methacryl group from the viewpoint of ease of copolymerization with the ethylenically unsaturated monomer.
The silicone-based macromonomer can be obtained as a commercial product, for example. Specific examples include FM0711 and FM0721 manufactured by Chisso Corporation (in the following formula (II), m≈60, R ³ = E = methyl group, D = methacryloyloxypropyl group), FM0725 (in the following formula (II)) M≈130, R ³ = E = methyl group, D = methacryloyloxypropyl group), AK-5, AK-30, AK-32 manufactured by Toa Gosei Co., Ltd., X manufactured by Shin-Etsu Chemical Co., Ltd. -22-174DX (all are trade names). One or more of these can be selected and used as necessary.

  Content of the polymer component obtained by superposing | polymerizing the radically polymerizable monomer composition in the vinyl resin of form (3) is 90-99.5 mass% with respect to 100 mass% of vinyl resins. Is preferred. If content of a radically polymerizable monomer composition is 90 mass% or more, it will be easy to improve the hardness of a coating film formed, intensity | strength, blocking resistance, and stain resistance. Moreover, if content of a radically polymerizable monomer composition is 99.5 mass% or less, it will be easy to suppress the fall of the flexibility of the formed coating film, water resistance, and weather resistance.

The content of the silicone macromonomer in the vinyl resin of the form (3) is preferably 0.5 to 10% by mass with respect to 100% by mass of the vinyl resin. If content of a silicone type macromonomer is 0.5 mass% or more, an improvement effect of a weather resistance and water resistance will be easy to express. In addition, if the content of the silicone macromonomer is 10% by mass or less, a phenomenon occurs in which unreacted silicone macromonomer remains or the polymer component rich in the silicon component is separated from the resin dispersion. Easy to suppress.
When the above phenomenon occurs, the polymerization stability during production of the resin dispersion deteriorates, and the coating film formed with the paint (aqueous coating material) using the resin dispersion is not uniform. Become. In addition, the adhesive layer formed by the unreacted silicone-based macromonomer may cause contamination, and as a result, a strong coating film may not be formed in a portion where there is too much silicon component, resulting in a decrease in weather resistance and water resistance of the coating film Or

[Method for producing resin dispersion for aqueous coating material]
The method for producing a resin dispersion for an aqueous coating material according to the present invention is a method for producing a dispersion in which a silicon-containing aqueous vinyl resin is dispersed in an aqueous medium, and includes radical polymerization containing the above-mentioned allyl group-containing monomer. This is a method of polymerizing a polymerizable monomer composition in an aqueous medium in the presence of a silicon component to form a vinyl resin.

For the polymerization of the radical polymerizable monomer composition in the production method of the present invention, for example, a known polymerization method such as a suspension polymerization method or an emulsion polymerization method can be used. In particular, it is preferable to obtain a resin dispersion in the form of an emulsion by emulsion polymerization from the viewpoint of various physical properties such as storage stability of the aqueous coating material, blocking resistance of the coating film, water resistance, weather resistance, and stain resistance.
In the emulsion polymerization, for example, a known method in which a radical polymerizable monomer composition is supplied into a polymerization system in the presence of a surfactant and polymerization is performed with a radical polymerization initiator can be used.

  As the radical polymerization initiator, known ones usually used for radical polymerization can be used. Specific examples include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis ( 2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), oil-soluble azo compounds such as 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2 -(1-hydroxyethyl)] propionamide}, 2,2′-azobis {2-methyl-N- [2- (1-hydroxybutyl)] propionamide}, 2,2 ′ Azobis [2- (5-methyl-2-imidazolin-2-yl) propane] and salts thereof, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] and salts thereof, 2,2 '-Azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] and its salts, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazoline -2-yl] propane} and salts thereof, 2,2′-azobis (2-methylpropionamidine) and salts thereof, 2,2′-azobis (2-methylpropyneamidine) and salts thereof, 2,2 ′ -Water-soluble azo compounds such as azobis [N- (2-carboxyethyl) -2-methylpropionamidine] and salts thereof; benzoyl peroxide, cumene hydroperoxide, t-butyl Idro peroxide, t- butyl peroxy-2-ethylhexanoate, organic peroxides such as t-butyl peroxy isobutyrate and the like. These radical polymerization initiators may be used alone or in combination of two or more.

The use amount of the radical polymerization initiator is usually 0.01 to 10% by mass with respect to 100% by mass of the radical polymerizable monomer composition, but taking into consideration the progress of polymerization and control of the reaction, It is preferable that it is 0.05-5 mass%.
Moreover, when acceleration | stimulation of a polymerization rate and superposition | polymerization at the low temperature of 70 degrees C or less are desired, reducing agents, such as sodium bisulfite, ferrous sulfate, ascorbate, are used in combination with a radical polymerization initiator, for example. And is advantageous.

  In the case of adjusting the molecular weight of the vinyl resin, as a molecular weight modifier, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan, etc. Mercaptans, halogen compounds such as carbon tetrachloride and ethylene bromide, and known chain transfer agents such as α-methylstyrene dimer can be used. The amount of the chain transfer agent used is preferably 1% by mass or less with respect to 100% by mass of the radical polymerizable monomer composition from the viewpoint that the weather resistance is not lowered excessively.

Moreover, it is preferable to use a surfactant for the polymerization.
Examples of the surfactant include various anionic, cationic or nonionic surfactants, and polymer emulsifiers. A reactive surfactant having an ethylenically unsaturated bond in the surfactant component can also be used. Especially, it is preferable to use a reactive surfactant from the point of the weather resistance and water resistance of the coating film to be formed. Furthermore, from the viewpoint of improving the water resistance and weather resistance of the coating film to be formed, it is particularly preferable that 50% by mass or more of all the surfactant components to be used is a reactive surfactant.

  The amount of the surfactant used is preferably 0.1 to 10 parts by mass and more preferably 0.5 to 8 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer composition. If the usage-amount of surfactant is 0.1 mass part or more, it will be easy to improve the polymerization stability and storage stability of emulsion particles. Further, if the amount of the surfactant used is 10 parts by mass or less, it is easy to maintain the stability at the time of coating, the stability over time of the coating, etc. without impairing the water resistance of the formed coating film. Become.

In addition, the coating film smoothness and emulsion obtained because the phenomenon called “more” that shrinks the coating film formed during drying after coating and the phenomenon called “mud crack” that cracks the coating film do not occur. From the viewpoint of low foaming property in the particle dispersion, it is preferable to use a phosphate ester type reactive surfactant in combination.
The phosphate ester type reactive surfactant can be obtained as a commercial product. Specific examples include FP-80, FP-100, FP-120, FP-160, FP-200, FP-125, and ADEKA rear manufactured by Adeka Co., Ltd., which are surfmer series manufactured by Toho Chemical Industry Co., Ltd. Examples of the soap series are PP-70 and PPE-710. One or more of these can be selected and used as necessary.

  The amount of the phosphate ester type reactive surfactant used is preferably 0.05 to 5 parts by mass, and 0.1 to 3 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer composition. More preferably. If the said usage-amount is 0.05 mass part or more, it will be easy to improve the smoothness of the coating film formed, and the low foaming property in the dispersion liquid of an emulsion particle. Moreover, if the said usage-amount is 5 mass parts or less, it will be easy to suppress the fall of the water resistance of the coating film formed, and a weather resistance.

  In the production method of the present invention, the method for introducing the silicon component is not particularly limited, and examples thereof include the following methods (a) to (c). By the methods (a) to (c), resin dispersions in which the vinyl resins of the above forms (1) to (3) are dispersed in an aqueous medium are obtained. Moreover, it can also implement combining 2 or more of method (a)-(c) as needed.

Method (a): A method of obtaining a resin dispersion by polymerizing the radical polymerizable monomer composition in the presence of polysiloxane particles dispersed in an aqueous medium.
Method (b): A method in which a radically polymerizable monomer composition and a hydrolyzable silane are radically polymerized in the presence of water, a surfactant and a radical polymerization initiator to obtain a resin dispersion.
Method (c): A method in which a radically polymerizable monomer composition and a silicone-based macromonomer are radically polymerized in the presence of water, a surfactant, and a radical polymerization initiator to obtain a resin dispersion.

  Among the methods (a) to (c), the method (a) is particularly preferable because the coating film to be formed can achieve the most balanced blocking resistance, water resistance, weather resistance, and flexibility. Representative examples of the method (a) include a polymer block (X) having an organosiloxane as a repeating unit, a polymer block (Y) obtained by polymerizing a radical polymerizable monomer composition, and a polymer block ( This is a method of obtaining a resin dispersion in which a graft block copolymer composed of a silicon-containing graft cross-linking agent (Z) copolymerized with X) and a polymer block (Y) is dispersed in an aqueous medium.

The method (a) will be described by taking as an example the case where the graft block copolymer is formed as a vinyl resin.
By reacting the organosiloxane with the silicon-containing graft crossing agent (Z), the hydrolyzable silyl group of the silicon-containing graft crossing agent (Z) participates in the polymerization, and the silicon-containing graft crossing agent (Z) is incorporated. Polymer block (X) (polysiloxane particles) is obtained. As a method for producing the polymer block (X), a known method can be used. For example, an organosiloxane and a silicon-containing graft crossing agent (Z) are forced into water with a homomixer, a pressure type homogenizer, or the like. A method in which an acid catalyst such as an alkylbenzene sulfonic acid is added as a polymerization initiator and polycondensed is added to the emulsion emulsified and dispersed.

  Next, the polymer block (Y) is formed by polymerizing the radical polymerizable monomer composition in an aqueous medium in the presence of the obtained polymer block (X). For the polymerization for forming the polymer block (Y), the above-described polymerization method can be used. In the polymerization, the vinyl polymerizable functional group or mercapto group in the silicon-containing graft crossing agent (Z) is involved in the polymerization. Thus, a polymer block (X), a polymer block (Y), and a graft block copolymer comprising a polymer block (X) and a silicon-containing graft crossing agent (Z) copolymerized with the polymer block (Y) Is obtained.

  In the method (b), the radical polymerizable monomer composition and the hydrolyzable silane are radically polymerized with water, a surfactant and a radical polymerization initiator as essential components. In the polymerization in the method (b), it is preferable to carry out emulsion polymerization in a dispersion form comprising, as basic components, a surfactant, a radical polymerization initiator, a hydrolyzable silane hydrolysis and condensation acid catalyst. In the emulsion polymerization, the radical polymerizable monomer composition and the hydrolyzable silane may be polymerized simultaneously in the same reaction system, or one of them may be polymerized first. It is preferable to polymerize simultaneously.

The acid catalyst for hydrolysis and condensation of the hydrolyzable silane is not particularly limited. For example, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, β-naphthalenesulfonic acid , Organic sulfonic acids such as 2-mesitylenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and alkylbenzenesulfonic acid, and fatty acids such as formic acid, acetic acid, maleic acid, fumaric acid and (meth) acrylic acid Can do.
The amount of the catalyst used is preferably 0.01 to 10 parts by mass and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the solid content of the resin dispersion.

  In the method (c), a radical polymerizable monomer composition and a silicone macromonomer are radically polymerized with water, a surfactant and a radical polymerization initiator as essential components. The radical polymerization can be performed by the method described above.

  In the production method of the present invention using the method for introducing a silicon component such as the methods (a) to (c), the polymerization of the radical polymerizable monomer composition may be a one-stage polymerization, or two or more stages. However, in order to improve the balance of blocking resistance, weather resistance, and water resistance, two-stage polymerization is preferred. In the case of multistage polymerization, the composition of the radical polymerizable monomer composition may be different in each stage of polymerization, if necessary. In addition, when the silicon component is introduced by multistage polymerization in the method (b) or method (c), the silicon component may be introduced by any stage of polymerization.

In the case of two-stage polymerization, the monomer composition of the first stage is used to improve the blocking resistance of the coating film by the following formula (1) (Fedors formula (RF Fedors, Polym. Eng. Sci. , 14, (2), 1974)), the monomer having an SP value of 20 to 30 is preferably 75% by mass or more in all monomers used in the first stage.
δj = (ΔE / V) ^1/2 = (ΣiΔei / ΣiΔvi) ^1/2 (1)
Here, the symbols in formula (1) have the following meanings.
δj (J / cm ³ ) ^1/2 : SP value of monomer (j) ΔE (J / mol): Aggregation energy density V (cm ³ / mol) of monomer (j): monomer ( j) molar volume Δei (J / mol): evaporation energy of atom or atomic group (i) Δvi (cm ³ / mol): molar volume of atom or atomic group (i)

Examples of monomers having an SP value of 20 to 30 include methyl (meth) acrylate, ethyl acrylate, propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl (meth). ) Ethylenically unsaturated monomers having an SP value of 20 to 25 such as acrylate, 4-hydroxybutyl (meth) acrylate, methoxyethyl acrylate, methacrylic acid, glycidyl (meth) acrylate, diacetone acrylamide, styrene, etc .; 2-hydroxy Examples thereof include ethylenically unsaturated monomers having an SP value exceeding 25, such as ethyl acrylate, acrylic acid, itaconic acid, acrylonitrile and the like.
Especially, it is more preferable to use an ethylenically unsaturated monomer having an SP value of 20 to 25 from the viewpoint of water resistance and weather resistance of the coating film.

The Tg of the polymer component obtained by polymerizing the first stage monomer is preferably 50 to 150 ° C, more preferably 70 to 110 ° C. If Tg is 50 degreeC or more, the blocking resistance of a coating film will improve. Moreover, if Tg is 150 degrees C or less, the frost damage resistance of a coating film will improve.
Here, Tg is a value obtained by the Fox equation shown in the following equation (2).
1 / (273 + Tg) = Σ (W _i / (273 + Tg _i )) (2)
In formula (2), W _i represents the mass fraction of monomer i, and Tg _i represents the Tg (° C.) of the homopolymer of monomer i.

  The amount of the first-stage monomer used is preferably 20 to 70% by mass and more preferably 25 to 65% by mass based on 100% by mass of the total radical polymerizable monomer composition. If the usage-amount is 20 mass% or more, the blocking resistance of a coating film will become higher. Moreover, if the usage-amount is 70 mass% or less, the frost damage resistance of a coating film will become higher.

The monomer composition in the second stage is not particularly limited as long as it is a radically polymerizable ethylenically unsaturated monomer, but the ethylenic unsaturation having an SP value of less than 20 (J / cm ³ ) ^1/2. It is preferable to contain a monomer. The content of such a monomer in all monomers used in the second stage is preferably 50 to 100% by mass, and more preferably 55 to 90% by mass. When the content is 50% by mass or more, the water absorption resistance is improved, so that the water resistance, weather resistance, and frost damage resistance of the coating film are improved, and the smoothness is further improved. In order to increase the smoothness of the coating film, it is more preferable to use a monomer having an SP value of 19.5 or less.

Examples of monomers having an SP value of less than 20 (J / cm ³ ) ^1/2 include, for example, ethyl methacrylate, i-propyl acrylate, n-butyl acrylate, cyclohexyl methacrylate, 2-methoxyethyl methacrylate, ethoxyethyl acrylate, n -An ethylenically unsaturated monomer having an SP value of 19.5 to 20 such as propoxyethyl acrylate, methoxyethoxyethyl acrylate, n-propyl methacrylate, i-butyl acrylate, n-butyl methacrylate, n-hexyl acrylate, isobol Nyl acrylate, α-methyl styrene, p-methyl styrene, 2-ethoxyethyl methacrylate, i-propoxyethyl acrylate, n-butoxyethyl acrylate, ethoxyethoxyethyl acrylate, dimethylamino Ethylenically unsaturated monomers having an SP value of 19.0 to 19.5 such as ethyl methacrylate, i-propyl methacrylate, t-butyl (meth) acrylate, i-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl ( Ethylenic unsaturation with SP value of 19.0 or less, such as meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl methacrylate, t-butoxyethyl acrylate, diethylaminoethyl methacrylate Monomer.

  The Tg of the polymer component obtained by polymerizing the second stage monomer is preferably −50 to 50 ° C., and more preferably −30 to 30 ° C. When Tg is −50 ° C. or higher, the blocking resistance and stain resistance of the coating film are improved. Moreover, if Tg is 50 ° C. or less, the film-forming property is improved, and even if the drying after coating is insufficient, the remaining VOC has an adverse effect on the blocking resistance, water resistance and frost resistance of the coating film. Less.

  The amount of the second-stage monomer used is preferably 30 to 80% by mass, more preferably 35 to 75% by mass in 100% by mass of the total radical polymerizable monomer composition. If the amount of the second-stage monomer used is 30% by mass or more, the frost damage resistance, smoothness, water resistance and weather resistance of the coating film will be higher. When the amount of the second-stage monomer used is 80% by mass or less, the blocking resistance of the coating film is improved.

  When the resin dispersion of the present invention is in the form of an emulsion, the particle size of the emulsion particles is preferably 30 to 300 nm, preferably 50 to 130 nm, considering the balance between particle stability and coating film performance. Is more preferable. If the particle diameter is 30 nm or more, aggregates are hardly generated during the polymerization, and a small amount of surfactant is used for the polymerization, so that it is easy to maintain the water resistance of the formed coating film. Moreover, if the particle diameter is 300 nm or less, a film-forming defect is unlikely to occur, and the film formability is improved, so that the formed coating film exhibits more excellent water resistance and weather resistance. The particle size can be controlled, for example, by changing the type and amount of surfactant used and the monomer composition.

[Water-based coating material]
The aqueous coating material of the present invention is an aqueous coating material containing the aforementioned resin dispersion.
The water-based coating material of the present invention includes various pigments, antifoaming agents, pigment dispersants, leveling agents, anti-sagging agents, matting agents, ultraviolet absorbers, antioxidants, heat resistance improvers, slip agents, as necessary. You may contain antiseptic | preservative etc. Moreover, you may mix and use hardening agents, such as another emulsion resin, water-soluble resin, a viscosity control agent, and melamines.
The aqueous coating material of the present invention forms a solid content with emulsion particles (vinyl resin) as a main component and the surfactant, additive and the like, and is usually used in a state of 20 to 80% by mass of the solid content. .

The aqueous coating material of the present invention is made of various materials such as cement mortar, slate board, gypsum board, extruded board, foamable concrete, metal, glass, porcelain tile, asphalt, wood, waterproof rubber material, plastic, calcium silicate base material, etc. It is useful as a surface finish coating material, and particularly useful as a water-based coating material for protecting buildings such as buildings and civil engineering structures.
Examples of methods for coating the aqueous coating material on the surface of various substrates include various coating methods such as spray coating, roller coating, bar coating, air knife coating, brush coating, dipping, and flow coating. Can be used. Moreover, the aqueous coating material of this invention can form the coating film fully formed into a film by drying at room temperature or 50-180 degreeC heat drying.

Examples of the curing catalyst during film formation include metal salts of organic acids such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, tin octylate, tin laurate, tin octylate, lead octylate, and tetrabutyltitanate. Can be used.
The amount of the curing catalyst used is preferably 0.0001 to 10 parts by mass and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the solid content of the aqueous coating material. In addition, the curing catalyst is preferably emulsified with a surfactant and water when used.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following description. In the following description, “part” means “part by mass”, and “%” means “% by mass”.
Evaluation of the aqueous coating material in the present Example was performed according to the following method.
[Production of water-based coating material for evaluation (clear paint)]
For emulsion particles (vinyl resin) having an MFT of more than 10 ° C., diethylene glycol monobutyl ether (hereinafter referred to as “BDG”) was added as a film-forming aid to the resin dispersion to bring the MFT to 10 ° C. or less. Next, 0.5 g of RHEOLATE350 (RHEOX Co., Ltd., thickener) and Surfynol DF-58 (Air Products Co., Ltd., defoaming agent) 0.5 g per 100 g of resin dispersion of emulsion particles The mixture was stirred well, deionized water was added, and the mixture was adjusted to about 30 seconds with Ford Cup # 4. Thereafter, filtration was carried out using a 100 mesh nylon bag to obtain an aqueous coating material for evaluation.

[Evaluation methods]
In this example, a coating film was formed from the obtained aqueous coating material, and the blocking resistance, water resistance and weather resistance of the coating film were evaluated. Moreover, the particle diameter of the emulsion particles in the obtained aqueous coating material was measured.
(1) Blocking resistance An aqueous coating material for evaluation was coated on a glass plate with a 4 mil applicator (length 80 mm × width 80 mm), and forcedly dried at 100 ° C. for 20 minutes. Next, after cooling to 50 ° C., place gauze on the surface of the coating film in an atmosphere of 50 ° C., and place a weight that has been heated to 50 ° C. in advance, and apply a load of 3 kg / cm ² for 30 minutes. did. Next, after cooling to room temperature, the glass plate was slowly turned upside down to peel off the gauze, and the difficulty of peeling at that time and the trace of the gauze were visually observed and evaluated according to the following criteria. When the gauze did not fall naturally, the gauze was peeled off by hand.
A: The gauze falls naturally and almost no trace of gauze remains on the coating film.
○: The gauze does not fall naturally, but there is almost no trace of gauze remaining on the coating film.
(Triangle | delta): Although gauze does not fall naturally, it can peel with a little force and the trace of gauze remains a little.
X: When peeling gauze, a part of coating film also peeled and the trace of gauze remains clearly.

(2) Water resistance An aqueous coating material for evaluation was applied to a zinc phosphate-treated steel plate (bonderite # 100-treated steel plate, plate thickness 0.8 mm, length 150 mm × width 70 mm) with a bar coater # 48 at 130 ° C. Force-dried for 20 minutes. Subsequently, it was left to cool to room temperature. Thereafter, the zinc phosphate-treated steel sheet was immersed in hot water at 50 ° C. for 100 hours, and the appearance of the coating film was visually observed immediately after being pulled up and after a predetermined time had elapsed, and evaluated according to the following criteria.
A: The painted surface was not whitened, and a clear coating film (transparent appearance) was obtained immediately after pulling up.
◯: Some whitening of the painted surface was observed, but after clearing, a clear coating film was obtained in about 2 to 3 hours.
Δ: Some whitening of the painted surface was observed, and it was slightly turbid even after 24 hours from lifting, and after 48 hours barely became a clear coating film.
X: The painted surface was considerably whitened and remained white even after being pulled up, and did not become a clear coating film until the end.

(3) Weather resistance Using the same test plate as that used for the water resistance evaluation, a weather resistance test was performed with a die plastic metal weatherer KU-R4-W type (manufactured by Daipura Wintes Co., Ltd.). At this time, the test cycle was irradiation 4 hours (spray 5 seconds / 15 minutes) / condensation 4 hours, UV intensity: 65 mW / cm ² , black panel temperature: 63 ° C. during irradiation / 30 ° C. during condensation, humidity: 50 during irradiation Under the conditions of% RH / 96% RH at the time of condensation, the 60 ° gloss retention after 1200 hours and the color difference were used as weather resistance indicators and evaluated according to the following criteria.
A: Gloss retention 80% or more and less than 2 color difference O: Gloss retention 70% or more and color difference 2 or more and less than 3 Δ: Gloss retention 60% or more and color difference 3 or more and less than 5 ×: Gloss retention 60% Less than or color difference 5 or more

(4) Particle size of emulsion particles Measured at room temperature using a dense particle size analyzer FPAR-1000 manufactured by Otsuka Electronics Co., Ltd. and calculated by cumulant analysis.

[Production Example 1] Preparation of polyorganosiloxane aqueous dispersion (SiEm) Dimethylsiloxane cyclic oligomer 3-7 mer mixture (98 parts), γ-methacryloxypropyltrimethoxysilane (2 parts), water (310 parts) and A composition comprising sodium dodecylbenzenesulfonate (1 part) was premixed with a homomixer and then forcedly emulsified with a pressure homogenizer at a pressure of 200 kg / cm ² to obtain a silicon raw material pre-emulsion.
Next, water (90 parts) and dodecylbenzenesulfonic acid (9 parts) were charged into a flask equipped with a stirrer, a reflux condenser, a temperature controller and a dropping pump, and the internal temperature of the flask was kept at 85 ° C. with stirring. The silicon raw material pre-emulsion was dropped over 4 hours. After completion of the dropwise addition, the polymerization was further allowed to proceed for 1 hour, followed by cooling and addition of dodecylbenzenesulfonic acid and an equimolar amount of sodium hydroxide to prepare a polyorganosiloxane aqueous dispersion (SiEm). The solid content was 18%.

Hereinafter, examples and comparative examples will be described.
[Example 1] Silicon component introduction method:
In a flask equipped with a stirrer, reflux condenser, temperature controller, and dropping pump, deionized water (110 parts), New Coal 707SF (manufactured by Nippon Emulsifier Co., Ltd., solid content 30%) (5 parts), SiEm (5 Part, solid content: 0.9 part), and a mixture of radical polymerizable monomer compositions having the composition shown in “First stage” of Table 1, perbutyl H69 (manufactured by NOF Corporation) (0.02 Part). After raising the internal temperature of the flask to 40 ° C., from ferrous sulfate (0.0002 parts) / EDTA (0.0005 parts) / sodium ascorbate (0.12 parts) / deionized water (6 parts) An aqueous reducing agent solution was added. After confirming the peak top temperature due to the polymerization exotherm, the internal temperature of the flask was maintained at 75 ° C.
0.5 hours after addition of the reducing agent aqueous solution, the radical polymerizable monomer composition having the composition shown in “Second stage” in Table 1, deionized water (25 parts), New Coal 707SF (2.5 parts) ), Surfmer FP-120 (manufactured by Toho Chemical Co., Ltd.) (0.5 part) and a pre-emulsion liquid in which a 28% aqueous ammonia solution (0.17 part) is pre-emulsified and dispersed, and perbutyl H69 (0.03 part) ) Was dissolved in deionized water (5 parts) dropwise over 2 hours. During the dropping, the internal temperature of the flask was maintained at 75 ° C., and the temperature was further maintained at 75 ° C. for 1.5 hours after the dropping was completed. Next, after adding 28% aqueous ammonia (1.25 parts), the mixture was cooled to room temperature, and a mixture of adipic acid dihydrazide (0.7 parts) and deionized water (1.5 parts) was added to the emulsion particles. A resin dispersion was obtained.
Using this resin dispersion of emulsion particles, 8 parts of a film-forming aid BDG was added to 100 parts of the emulsion particles to prepare an aqueous coating material for evaluation.

[Examples 2 to 12] Silicon component introduction method:
Except for changing the composition of the radical polymerizable monomer composition ("first stage" and "second stage"), the surfactant, and the organic hydrazine compound as shown in Table 1, it was the same as in Example 1. A resin dispersion of emulsion particles was obtained.
Using this resin dispersion of emulsion particles, 8 parts of a film-forming aid BDG was added to 100 parts of emulsion particles to prepare an aqueous coating material for evaluation.

[Example 13] Silicon component introduction method:
In a flask equipped with a stirrer, reflux condenser, temperature controller, and dropping pump, deionized water (100 parts), New Coal 707SF (manufactured by Nippon Emulsifier Co., Ltd., solid content 30%) (4 parts), SiEm (5 parts, solid content 0.9 parts) and a radical polymerizable monomer composition having the composition shown in “first stage” of Table 1, deionized water (35 parts), New Coal 707SF (3.5 parts) ), Surfmer FP-120 (0.5 part) and a 28% aqueous ammonia solution (0.17 part) were pre-emulsified and dispersed for 10% and perbutyl H69 (0.02 part). . After raising the internal temperature of the flask to 40 ° C., from ferrous sulfate (0.0002 parts) / EDTA (0.0005 parts) / sodium ascorbate (0.12 parts) / deionized water (6 parts) An aqueous reducing agent solution was added. After confirming the peak top temperature due to the polymerization exotherm, the internal temperature of the flask was maintained at 75 ° C.
0.5 hours after adding the reducing agent aqueous solution, a polymerization initiator solution in which the remaining pre-emulsion liquid (90%) and perbutyl H69 (0.03 parts) were dissolved in deionized water (5 parts) was added for 2 hours. It was dripped over. During the dropping, the internal temperature of the flask was maintained at 75 ° C., and the temperature was further maintained at 75 ° C. for 1.5 hours after the dropping was completed. Next, after adding 28% aqueous ammonia (1.25 parts), the mixture was cooled to room temperature, and a mixture of adipic acid dihydrazide (0.7 parts) and deionized water (1.5 parts) was added to the emulsion particles. A resin dispersion was obtained.
Using this resin dispersion of emulsion particles, 8 parts of a film-forming aid BDG was added to 100 parts of emulsion particles to prepare an aqueous coating material for evaluation.

[Example 14] Silicon component introduction method:
In a flask equipped with a stirrer, reflux condenser, temperature controller, and dropping pump, deionized water (109 parts), Adeka Soap SR-1025 (Adeka Co., Ltd., solid content 25%) (6 parts), SiEm (5 parts, solid content 0.9 parts) and a mixture of radically polymerizable monomer compositions having the composition shown in “First stage” of Table 1 and perbutyl H69 (0.02 parts) were charged. After raising the internal temperature of the flask to 40 ° C., from ferrous sulfate (0.0002 parts) / EDTA (0.0005 parts) / sodium ascorbate (0.12 parts) / deionized water (6 parts) An aqueous reducing agent solution was added. After confirming the peak top temperature due to the polymerization exotherm, the internal temperature of the flask was maintained at 75 ° C.
0.5 hours after the addition of the reducing agent aqueous solution, the radical polymerizable monomer composition having the composition shown in “Second stage” in Table 1, deionized water (25 parts), Adekari Soap SR-1025 (3 Part), Surfmer FP-120 (0.5 part) and a pre-emulsion liquid in which a 28% aqueous ammonia solution (0.17 part) is pre-emulsified and dispersed, and perbutyl H69 (0.03 part) in deionized water (5 parts) The polymerization initiator solution dissolved in (2) was added dropwise over 2 hours. During the dropping, the internal temperature of the flask was maintained at 75 ° C., and the temperature was further maintained at 75 ° C. for 1.5 hours after the dropping was completed. Next, after adding 28% aqueous ammonia (1.25 parts), the mixture was cooled to room temperature, and a mixture of adipic acid dihydrazide (0.7 parts) and deionized water (1.5 parts) was added to the emulsion particles. A resin dispersion was obtained.
Using this resin dispersion of emulsion particles, 8 parts of a film-forming aid BDG was added to 100 parts of emulsion particles to prepare an aqueous coating material for evaluation.

[Example 15] Silicon component introduction method:
In a flask equipped with a stirrer, a reflux condenser, a temperature controller, and a dropping pump, deionized water (100 parts), SiEm (56 parts, solid content 10 parts), a radical having the composition shown in “First stage” in Table 1 A mixture of polymerizable monomer compositions and perbutyl H69 (0.02 parts) were charged. After raising the internal temperature of the flask to 40 ° C., from ferrous sulfate (0.0002 parts) / EDTA (0.0005 parts) / sodium ascorbate (0.12 parts) / deionized water (6 parts) An aqueous reducing agent solution was added. After confirming the peak top temperature due to the polymerization exotherm, the internal temperature of the flask was maintained at 75 ° C.
0.5 hours after the addition of the reducing agent aqueous solution, the radical polymerizable monomer composition having the composition shown in “Second stage” in Table 1, deionized water (25 parts), Adekari Soap SR-1025 (3 Part), Surfmer FP-120 (0.5 part) and a pre-emulsion liquid in which a 28% aqueous ammonia solution (0.17 part) is pre-emulsified and dispersed, and perbutyl H69 (0.03 part) in deionized water (5 parts) The polymerization initiator solution dissolved in (2) was added dropwise over 2 hours. During the dropping, the internal temperature of the flask was maintained at 75 ° C., and further maintained at 75 ° C. after the dropping was completed. Next, 28% aqueous ammonia (1.25 parts) was added, then cooled to room temperature for 1.5 hours, and a mixture of adipic acid dihydrazide (0.7 parts) and deionized water (1.5 parts) was added. Thus, a resin dispersion of emulsion particles was obtained.
Using this resin dispersion of emulsion particles, 8 parts of a film-forming auxiliary BDG was added to 100 parts of emulsion particles to prepare an aqueous coating material for evaluation.

[Example 16] Silicon component introduction method: (b)
In a flask equipped with a stirrer, a reflux condenser, a temperature controller, and a dropping pump, deionized water (110 parts), New Coal 707SF (5 parts), a radically polymerizable monomer having the composition shown in “First stage” in Table 1 A mixture of the monomer composition and perbutyl H69 (0.02 part) were charged. After raising the internal temperature of the flask to 40 ° C., from ferrous sulfate (0.0002 parts) / EDTA (0.0005 parts) / sodium ascorbate (0.12 parts) / deionized water (6 parts) An aqueous reducing agent solution was added. After confirming the peak top temperature due to the polymerization exotherm, the internal temperature of the flask was maintained at 75 ° C.
0.5 hours after adding the reducing agent aqueous solution, the radical polymerizable monomer composition having the composition shown in “second stage” of Table 1, hydrolyzable silane having the composition shown in Table 1, deionized water (25 Part), New Coal 707SF (2.5 parts), Surfmer FP-120 (0.5 parts) and 28% aqueous ammonia solution (0.17 parts) were pre-emulsified and dispersed, and perbutyl H69 (0. (03 parts) in a deionized water (5 parts) solution was added dropwise over 2 hours. During the dropping, the internal temperature of the flask was maintained at 75 ° C., and the temperature was further maintained at 75 ° C. for 1.5 hours after the dropping was completed. Next, after adding 28% aqueous ammonia (1.25 parts), the mixture was cooled to room temperature, and a mixture of adipic acid dihydrazide (0.7 parts) and deionized water (1.5 parts) was added to the emulsion particles. A resin dispersion was obtained.
Using this resin dispersion of emulsion particles, 8 parts of a film-forming aid BDG was added to 100 parts of emulsion particles to prepare an aqueous coating material for evaluation.

[Example 17] Silicon component introduction method: (c)
A resin dispersion of emulsion particles was obtained in the same manner as in Example 16 except that FM0725 (trade name, manufactured by Chisso Corporation), which is a silicone-based macromonomer, was used instead of the hydrolyzable silane mixture.
Using this resin dispersion of emulsion particles, 8 parts of a film-forming auxiliary BDG was added to 100 parts of emulsion particles to prepare an aqueous coating material for evaluation.

[Comparative Examples 1 to 6] Silicon component introduction method:
A resin dispersion of emulsion particles was obtained in the same manner as in Example 1 except that the radical polymerizable monomer composition, surfactant, and hydrazine compound having the composition shown in Table 2 were used.
Using this resin dispersion of emulsion particles, 8 parts of a film-forming auxiliary BDG was added to 100 parts of emulsion particles to prepare an aqueous coating material for evaluation.

[Comparative Example 7] Silicon component introduction method:
A resin dispersion of emulsion particles was obtained in the same manner as in Example 13 except that the radical polymerizable monomer composition, surfactant, and hydrazine compound having the composition shown in Table 2 were used.
Using this resin dispersion of emulsion particles, 8 parts of a film-forming auxiliary BDG was added to 100 parts of emulsion particles to prepare an aqueous coating material for evaluation.

[Comparative Example 8]
In a flask equipped with a stirrer, a reflux condenser, a temperature controller, and a dropping pump, deionized water (100 parts), New Coal 707SF (manufactured by Nippon Emulsifier Co., Ltd., solid content 30%) (4 parts), table 1 radical polymerization monomer composition having the composition shown in “first stage”, deionized water (35 parts), New Coal 707SF (3.5 parts), Surfmer FP-120 (0.5 parts) and 28 A 10% portion of a pre-emulsion liquid in which an aqueous ammonia solution (0.17 part) was previously emulsified and dispersed, and perbutyl H69 (0.02 part) were charged. After raising the internal temperature of the flask to 40 ° C., from ferrous sulfate (0.0002 parts) / EDTA (0.0005 parts) / sodium ascorbate (0.12 parts) / deionized water (6 parts) An aqueous reducing agent solution was added. After confirming the peak top temperature due to the polymerization exotherm, the internal temperature of the flask was maintained at 75 ° C.
0.5 hours after adding the reducing agent aqueous solution, the remaining pre-emulsion liquid (90%) and a polymerization initiator solution in which perbutyl H69 (0.03 parts) was dissolved in deionized water (5 parts) It was dripped over 2 hours. During the dropping, the internal temperature of the flask was maintained at 75 ° C., and the temperature was further maintained at 75 ° C. for 1.5 hours after the dropping was completed. Next, after adding 28% ammonia water (1.25 parts), the mixture was cooled to room temperature, and a mixture of adipic acid dihydrazide (0.7 parts) and deionized water (1.5 parts) was added to form emulsion particles. A resin dispersion was obtained.
Using this resin dispersion of emulsion particles, 8 parts of a film-forming auxiliary BDG was added to 100 parts of emulsion particles to prepare an aqueous coating material for evaluation.

ただし、表１及び表２における略号は以下の意味を示す。
ＭＭＡ：メチルメタクリレート
ＧＭＡ：グリシジルメタクリレート
２−ＨＥＭＡ：２−ヒドロキシエチルメタクリレート
ｎ−ＢＭＡ：ｎ−ブチルメタクリレート
２−ＥＨＡ：２−エチルヘキシルアクリレート
ＡＡ：アクリル酸
ＤＡＡｍ：ジアセトンアクリルアミド
ＴＡＣ：トリアリルシアヌレート
ＴＡＩＣ：トリアリルイソシアヌレート
ＣＨＭＡ：シクロヘキシルメタクリレート
ｔ−ＢＭＡ：ｔ−ブチルメタクリレート
ＥＤＭＡ：エチレングリコールジメタクリレート
ＴＭＰ−ＴＭＡ：トリメチロールプロパントリメタクリレート
ＦＡ−７３１Ａ：トリス（２−アクリロイルオキシエチル）イソシアヌレート（日立化成工業（株）製）
ＡＭＡ：アリルメタクリレート
ＤＶＢ：ジビニルベンゼン
ニューコール ７０７ＳＦ：非反応性アニオン性界面活性剤（日本乳化剤（株）製）
アデカリアソープ ＳＲ−１０２５：反応性アニオン性界面活性剤（商品名、アデカ（株）製）
サーフマーＦＰ−１２０：リン酸エステル型反応性界面活性剤（商品名、東邦化学工業（株）製）
ＡＤＨ：アジピン酸ジヒドラジド
ＦＭ０７２５：シリコーン系マクロモノマー（商品名、チッソ（株）製）

However, the abbreviations in Tables 1 and 2 have the following meanings.
MMA: methyl methacrylate GMA: glycidyl methacrylate 2-HEMA: 2-hydroxyethyl methacrylate n-BMA: n-butyl methacrylate 2-EHA: 2-ethylhexyl acrylate AA: acrylic acid DAAm: diacetone acrylamide TAC: triallyl cyanurate TAIC: Triallyl isocyanurate CHMA: cyclohexyl methacrylate t-BMA: t-butyl methacrylate EDMA: ethylene glycol dimethacrylate TMP-TMA: trimethylolpropane trimethacrylate FA-731A: tris (2-acryloyloxyethyl) isocyanurate (Hitachi Chemical Industries ( Made by Co., Ltd.)
AMA: Allyl methacrylate DVB: Divinylbenzene New Coal 707SF: Non-reactive anionic surfactant (Nippon Emulsifier Co., Ltd.)
ADEKA rear soap SR-1025: Reactive anionic surfactant (trade name, manufactured by ADEKA CORPORATION)
Surfmer FP-120: Phosphate ester type reactive surfactant (trade name, manufactured by Toho Chemical Industry Co., Ltd.)
ADH: Adipic acid dihydrazide FM0725: Silicone macromonomer (trade name, manufactured by Chisso Corporation)

About the aqueous coating material for evaluation obtained in Examples and Comparative Examples, the blocking resistance, water resistance and weather resistance of the formed coating film were evaluated, and the particle size of emulsion particles in the aqueous coating material for evaluation was measured. The results are shown in Tables 3 and 4.

As shown in Table 3, in Examples 1 to 17 which are the aqueous coating materials of the present invention, the formed coating film had excellent blocking resistance, water resistance and weather resistance.
On the other hand, as shown in Table 4, in Comparative Examples 1 to 7 using a monomer having two or more radical polymerizable groups other than the allyl group-containing monomer, the formed coating film has blocking resistance, Any one or more of water resistance and weather resistance was inferior to the examples, and the physical property balance was poor. Moreover, although the allyl group containing monomer is used, in the comparative example 8 in which the silicon component is not contained, the formed coating film was inferior in all of blocking resistance, water resistance and weather resistance.

  Since the water-based coating material of the present invention has excellent blocking resistance, water resistance and weather resistance, it is useful as a surface finishing coating material for various materials, and particularly for water protection for building bodies such as buildings and civil engineering structures. Useful as a coating material.

Claims (4)

  A silicon-containing aqueous vinyl resin containing a polymer component obtained by polymerizing a radical polymerizable monomer composition containing a monomer having two or more allyl groups and a silicon component was dispersed in an aqueous medium. Resin dispersion for aqueous coating materials.   An aqueous coating material comprising the resin dispersion for an aqueous coating material according to claim 1. A method for producing a dispersion in which a silicon-containing aqueous vinyl resin is dispersed in an aqueous medium,
For aqueous coating materials, wherein a radical polymerizable monomer composition containing a monomer having two or more allyl groups is polymerized in an aqueous medium in the presence of a silicon component to form the silicon-containing aqueous vinyl resin. A method for producing a resin dispersion. As the silicon-containing aqueous vinyl resin, a polymer block (X) having an organosiloxane as a repeating unit and a radical polymerizable monomer composition containing a monomer having two or more allyl groups are polymerized. A method of forming a graft block copolymer comprising a polymer block (Y), a polymer block (X) and a silicon-containing graft cross-linking agent (Z) copolymerized with the polymer block (Y),
An organosiloxane and a silicon-containing graft crossing agent (Z) are reacted to form a polymer block (X) in which the silicon-containing graft crossing agent (Z) is incorporated, and then in the presence of the polymer block (X). The method for producing a resin dispersion for an aqueous coating material according to claim 3, wherein the radically polymerizable monomer composition is polymerized in an aqueous medium to form a polymer block (Y).