JP5955526B2 - Water-based resin composition for paint - Google Patents

Description

  The present invention relates to an aqueous resin composition for paints. More specifically, for example, the present invention relates to an aqueous resin composition for paints useful for topcoat paints for inorganic building materials such as ceramic building materials, and an inorganic building material on which a coating film made of the aqueous resin composition for paints is formed. The aqueous resin composition for paints of the present invention can be suitably used, for example, when coating the outer wall of a building including inorganic building materials.

  In recent years, an aqueous resin composition has been used as a coating resin composition from the viewpoint of environmental protection. As an aqueous resin composition excellent in curability, durability and stain resistance among aqueous resin compositions, an acrylic resin emulsion including emulsion particles containing a curable monomer and / or oligomer is an essential component. An aqueous curable resin composition has been proposed (see, for example, Patent Document 1).

  The water-based curable resin composition is excellent in curability, durability, and stain resistance, but recently it is excellent in blocking resistance, weather resistance, frost damage resistance, and the like, and is an aqueous resin for paints that does not adversely affect the base. Development of the composition is awaited.

Special table 2009-510179 gazette

  The present invention has been made in view of the above prior art, and is excellent in blocking resistance, weather resistance and frost damage resistance, and does not adversely affect the base, and the aqueous resin composition for paints It aims at providing the inorganic building material in which the coating film which consists of was formed.

The present invention
(1) An aqueous resin composition used for coatings, comprising a hydrophobic resin emulsion, a polyfunctional monomer and a rheology control agent, wherein the hydrophobic resin emulsion contains 50% by mass or more of the hydrophobic monomer. It is a hydrophobic resin emulsion obtained by emulsion polymerization of the contained hydrophobic monomer component, and the hydrophobic monomer is alkyl (meth) acrylate, fluorine atom-containing alkyl (meth) acrylate, epoxy group-containing (meth) acrylate And a hydrophobic monomer selected from aromatic monomers, wherein the polyfunctional monomer is a polyfunctional monomer containing 1,4-butanediol di (meth) acrylate, and the rheology The control agent is made of a polymer obtained by polymerizing a monomer component containing (meth) acrylic acid alkyl ester and (meth) acrylic acid. An aqueous resin composition for coatings, which is a potash-soluble rheology control agent ;
(2) The aqueous resin composition for paints according to (1), wherein the glass transition temperature of the emulsion particles of the hydrophobic resin emulsion is 60 ° C. or higher,
(3) Furthermore, the aqueous resin composition for paints according to the above (1) or (2), which has a photopolymerization initiator as a painter,
(4) The coating material for inorganic building materials containing the aqueous resin composition for coating materials according to any one of (1) to (3), and (5) the coating material according to any one of (1) to (3). The present invention relates to an inorganic building material in which a coating film made of an aqueous resin composition is formed.

  The aqueous resin composition for coatings of the present invention is excellent in blocking resistance, weather resistance and frost damage resistance, and has an excellent effect of not adversely affecting the base.

  The hydrophobic resin emulsion used in the aqueous resin composition for paints of the present invention is a hydrophobic resin emulsion obtained by emulsion polymerization of a hydrophobic monomer component containing 50% by mass or more of a hydrophobic monomer. In such a case, the blocking resistance, weather resistance and frost damage resistance are further improved, and the excellent effect of not adversely affecting the groundwork is exhibited.

  In the aqueous resin composition for coatings of the present invention, the rheology control agent used in the hydrophobic resin emulsion is selected from the group consisting of an alkali-soluble rheology control agent, a urethane-associated rheology control agent, and a cellulose derivative-based rheology control agent. In the case of at least one rheology control agent, an excellent effect of having a viscosity suitable for coating with a spray or a roller is exhibited.

  When the aqueous resin composition for paints of the present invention contains a photopolymerization initiator, it can improve the blocking resistance of the aqueous resin composition for paints and is a coating film comprising the aqueous resin composition for paints. The excellent effect that the inorganic building material in which this is formed can be manufactured efficiently is exhibited.

  The coating material for inorganic building materials comprising the aqueous resin composition for coating materials of the present invention has excellent blocking resistance, and by using the coating material, an inorganic building material having a coating film excellent in weather resistance and frost damage resistance can be efficiently obtained. The excellent effect that it can be manufactured is produced.

  Since the inorganic building material of this invention has the coating film which consists of the said aqueous resin composition for coating materials, there exists the outstanding effect based on the said aqueous resin composition for coating materials.

  The aqueous resin composition for paints of the present invention is an aqueous resin composition used for paints as described above, and contains a hydrophobic resin emulsion, a polyfunctional monomer, and a rheology control agent. . Therefore, the aqueous resin composition for coatings of the present invention is excellent in blocking resistance, weather resistance and frost damage resistance, and has an excellent effect of not adversely affecting the base.

  In the present specification, the property that does not adversely affect the background, that is, the property that the color tone of the background does not change before and after application to the background is referred to as color tone retention.

  The hydrophobic resin emulsion used in the aqueous resin composition for paints of the present invention can be prepared by emulsion polymerization of a hydrophobic monomer component.

  In the present specification, the “hydrophobic monomer component” means a monomer component having a hydrophobic monomer content of 50% by mass or more. The hydrophobic monomer component may contain a hydrophilic monomer in addition to the hydrophobic monomer.

  Examples of the hydrophobic monomer include alkyl (meth) acrylates, fluorine atom-containing alkyl (meth) acrylates, epoxy group-containing (meth) acrylates, and aromatic monomers. It is not limited to illustration only.

  In the present specification, “(meth) acrylate” means “acrylate” or “methacrylate”, and “(meth) acryl” means “acryl” or “methacryl”.

  Examples of the alkyl (meth) acrylate include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, sec. -Butyl acrylate, sec-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, tridecyl acrylate, tridecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-lauryl acrylate, n- Lauryl methacrylate, 2- (acetoacetoxy) ethyla Examples thereof include alkyl (meth) acrylates having 1 to 18 carbon atoms in ester groups such as relate, 2- (acetoacetoxy) ethyl methacrylate, isobornyl acrylate, and isobornyl methacrylate. It is not limited to. These monomers may be used alone or in combination of two or more.

  Examples of the fluorine atom-containing alkyl (meth) acrylate include fluorine having 2 to 6 carbon atoms in an ester group such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl acrylate, tetrafluoropropyl methacrylate, and octafluoropentyl acrylate. Although an atom containing alkyl methacrylate etc. are mentioned, this invention is not limited only to this illustration. These monomers may be used alone or in combination of two or more.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl acrylate and glycidyl methacrylate, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of the aromatic monomer include styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, aralkyl (meth) acrylate, vinyltoluene, and the like. It is not limited to illustration only. Examples of the aralkyl (meth) acrylate include aralkyl groups having 7 to 18 carbon atoms such as benzyl acrylate, benzyl methacrylate, phenylethyl acrylate, phenylethyl methacrylate, methylbenzyl acrylate, methylbenzyl methacrylate, naphthylmethyl acrylate, and naphthylmethyl methacrylate. Although aralkyl (meth) acrylate etc. which have these are mentioned, this invention is not limited only to this illustration. These aromatic monomers may be used alone or in combination of two or more.

  Among the hydrophobic monomers, from the viewpoint of improving the weather resistance of the coating film, alkyl (meth) acrylate is preferable, and alkyl (meth) acrylate having 1 to 10 carbon atoms in the alkyl group is more preferable.

  Examples of the hydrophilic monomer include a carboxyl group-containing monomer, a hydroxyl group-containing (meth) acrylate, an oxo group-containing monomer, and a nitrogen atom-containing monomer. It is not limited to. These monomers may be used alone or in combination of two or more. Among the hydrophilic monomers, from the viewpoint of increasing the affinity between the emulsion particles contained in the hydrophobic resin emulsion and the rheology control agent, a carboxyl group-containing monomer and a hydroxyl group-containing (meth) acrylate are preferable. A group-containing monomer is more preferable.

  Examples of the carboxyl group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, maleic anhydride, and other carboxyl group-containing aliphatic monomers. The invention is not limited to such examples. These monomers may be used alone or in combination of two or more. Among these carboxyl group-containing monomers, acrylic acid, methacrylic acid and itaconic acid are preferable, and acrylic acid and methacrylic acid are more preferable from the viewpoint of improving the dispersion stability of the emulsion particles. In addition, the content of the carboxyl group-containing monomer in the hydrophobic monomer component is preferably 15% by mass or less, more preferably from the viewpoint of improving blocking resistance, weather resistance, frost damage resistance and color tone retention. It is 10 mass% or less, More preferably, it is 5 mass% or less. The lower limit of the content of the carboxyl group-containing monomer in the hydrophobic monomer component is 0% by mass, but preferably 0.5% by mass or more from the viewpoint of improving the dispersion stability of the emulsion particles. Preferably it is 1 mass% or more.

  Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Examples thereof include hydroxyl group-containing (meth) acrylates having 1 to 18 carbon atoms in ester groups such as butyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate. It is not limited to only. These monomers may be used alone or in combination of two or more.

  Examples of the oxo group-containing monomer include (di) ethylene glycols such as ethylene glycol acrylate, ethylene glycol methacrylate, ethylene glycol methoxy acrylate, ethylene glycol methoxy methacrylate, diethylene glycol acrylate, diethylene glycol methacrylate, diethylene glycol methoxy acrylate, and diethylene glycol methoxy methacrylate ( Although methoxy) (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These monomers may be used alone or in combination of two or more.

  Examples of the nitrogen atom-containing monomer include (meth) acrylamide compounds such as acrylamide, methacrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, diacetone acrylamide, and diacetone methacrylamide. , Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate and other nitrogen atom-containing (meth) acrylate compounds, N-vinylpyrrolidone, and the like, but the present invention is limited to such examples only. It is not a thing. These monomers may be used alone or in combination of two or more.

  In the hydrophobic monomer component, from the viewpoint of improving blocking resistance, weather resistance, frost damage resistance and color tone retention, the content of the hydrophobic monomer is 50% by mass or more, preferably 60% by mass or more, More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, The content rate of a hydrophilic monomer is 50 mass% or less, Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less, More preferably Is 20% by mass or less. In the hydrophobic monomer component, from the viewpoint of improving the affinity between the emulsion particles contained in the hydrophobic resin emulsion and the rheology control agent, the content of the hydrophobic monomer is 100% by mass or less, Preferably it is 99 mass% or less, and the content rate of a hydrophilic monomer is 0 mass% or more, Preferably it is 1 mass% or more.

  The emulsion particles contained in the hydrophobic resin emulsion may be composed of only one type of resin prepared by one-stage emulsion polymerization, and a plurality of emulsion particles prepared by multi-stage emulsion polymerization of hydrophobic monomer components. It may have a resin layer.

  Examples of a method for emulsion polymerization of a hydrophobic monomer component include, for example, an aqueous medium containing a water-soluble organic solvent such as methanol and a lower alcohol, and water, an emulsifier dissolved in a medium such as water, and the like. Examples of the method include dropping a water-soluble monomer component and a polymerization initiator, and a method of dropping a hydrophobic monomer component previously emulsified with an emulsifier and water into water or an aqueous medium. Is not limited to such a method. In addition, what is necessary is just to set the quantity of a medium suitably in consideration of the content rate of the non volatile matter contained in the resin emulsion obtained.

  Examples of the emulsifier include an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, an amphoteric emulsifier, and a polymer emulsifier. These emulsifiers may be used alone or in combination of two or more.

  Examples of the anionic emulsifier include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate and sodium dodecyl sulfonate; alkyl aryl sulfonate salts such as ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; Examples include polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts; dialkyl sulfosuccinates; aryl sulfonic acid-formalin condensates; fatty acid salts such as ammonium laurate and sodium stearate. It is not limited to illustration only.

  Nonionic emulsifiers include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, ethylene oxide and aliphatic Although the condensation product with an amine etc. are mentioned, this invention is not limited only to this illustration.

  Examples of the cationic emulsifier include alkylammonium salts such as dodecylammonium chloride, but the present invention is not limited to such examples.

  Examples of amphoteric emulsifiers include betaine ester type emulsifiers, but the present invention is not limited to such examples.

  Examples of the polymer emulsifier include poly (meth) acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinyl pyrrolidone; polyhydroxyalkyl (meth) acrylates such as polyhydroxyethyl acrylate; single polymers constituting these polymers. Although the copolymer etc. which use 1 or more types of a monomer as a copolymerization component are mentioned, this invention is not limited only to this illustration.

  Further, as the emulsifier, an emulsifier having a polymerizable group, that is, a so-called reactive emulsifier is preferable from the viewpoint of improving the weather resistance of the coating film, and a non-nonylphenyl emulsifier is preferable from the viewpoint of environmental protection.

  As the reactive emulsifier, for example, propenyl-alkylsulfosuccinic acid ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, (meth) acrylic acid polyoxyethylene phosphonate salt [for example, manufactured by Sanyo Chemical Industries, Ltd., Product name: Eleminol RS-30, etc.], polyoxyethylene alkylpropenyl phenyl ether sulfonate salt [for example, product name: Aqualon HS-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], allyloxymethylalkyloxypolyoxyethylene Sulfonate salt [eg, Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.], Sulphonate salt of allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene [eg, ADEKA Corporation, trade name: ADEKA Rear soap SE-10 Allyloxymethylalkoxyethylhydroxy polyoxyethylene sulfate ester salt [for example, manufactured by ADEKA, trade name: Adekaria soap SR-10, SR-30, etc.], bis (polyoxyethylene polycyclic phenyl ether) Methacrylated sulfonate salts [for example, manufactured by Nippon Emulsifier Co., Ltd., trade name: Antox MS-60, etc.], allyloxymethylalkoxyethylhydroxypolyoxyethylene [for example, manufactured by ADEKA Corporation, trade name: Adeka Soap ER -20, etc.], polyoxyethylene alkylpropenyl phenyl ether [for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon RN-20, etc.], allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene [for example, Co., Ltd. Made by ADEKA, quotient Name: Adekariasoap NE-10, etc.] Although the like, the present invention is not limited only to those exemplified.

  The amount of the emulsifier is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, from the viewpoint of improving polymerization stability per 100 parts by mass of the hydrophobic monomer component. Particularly preferably 3 parts by mass or more, and from the viewpoint of improving the weather resistance of the coating film, it is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, still more preferably 6 parts by mass or less, and even more preferably 5 parts by mass. Part or less, particularly preferably 4 parts by weight or less.

  Examples of the polymerization initiator include azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 ′. -Azo compounds such as azobis (2-diaminopropane) hydrochloride, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-methylpropionamidine); ammonium persulfate, sodium persulfate, Examples include persulfates such as potassium persulfate; peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide. However, the present invention is limited to such examples. Is not to be done. These polymerization initiators may be used alone or in combination of two or more.

  The amount of the polymerization initiator is preferably 0.05 parts by mass or more, more preferably from the viewpoint of increasing the polymerization rate and reducing the residual amount of unreacted monomer per 100 parts by mass of the hydrophobic monomer component. From the viewpoint of improving the weather resistance of the coating film, it is preferably 1 part by mass or less, and more preferably 0.5 part by mass or less.

  The method for adding the polymerization initiator is not particularly limited. Examples of the addition method include batch charging, divided charging, and continuous dripping. From the viewpoint of advancing the completion time of the polymerization reaction, a part of the polymerization initiator may be added before or after the hydrophobic monomer component is added to the reaction system.

  In order to accelerate the decomposition of the polymerization initiator, for example, a reducing agent such as sodium bisulfite and a polymerization initiator decomposition agent such as transition metal salt such as ferrous sulfate are added in an appropriate amount to the reaction system. Also good.

  In addition, additives such as a chain transfer agent such as a compound having a thiol group such as tert-dodecyl mercaptan, a pH adjusting agent, a pH buffering agent, and a chelating agent may be added to the reaction system as necessary. . Since the amount of the additive varies depending on the type, it cannot be determined unconditionally. Therefore, it is preferable to adjust the amount to be an appropriate amount according to the type.

  The atmosphere for emulsion polymerization of the hydrophobic monomer component is not particularly limited, but is preferably an inert gas such as nitrogen gas from the viewpoint of enhancing the efficiency of the polymerization initiator.

  The polymerization temperature at the time of emulsion polymerization of the hydrophobic monomer component is not particularly limited, but is usually preferably 50 to 100 ° C, more preferably 60 to 95 ° C. The polymerization temperature may be constant or may be changed during the polymerization reaction.

  The polymerization time for emulsion polymerization of the hydrophobic monomer component is not particularly limited and may be appropriately set according to the progress of the polymerization reaction, but is usually about 2 to 9 hours.

  By hydrophobic polymerizing the hydrophobic monomer component as described above, a hydrophobic resin emulsion containing emulsion particles can be obtained.

  The glass transition temperature of the emulsion particles themselves (the glass transition temperature of the polymer constituting the emulsion particles) is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, from the viewpoint of improving blocking resistance. The glass transition temperature of the polymer is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, from the viewpoint of improving the weather resistance. The glass transition temperature of the polymer can be easily adjusted by adjusting the composition of the monomer used for the hydrophobic monomer component.

In the present specification, the glass transition temperature of the emulsion particles (the glass transition temperature of the polymer constituting the emulsion particles) is the monomer homopolymer used in the hydrophobic monomer component constituting the polymer. Using the glass transition temperature of
1 / Tg = Σ (Wm / Tgm) / 100
[Wm is the content (% by weight) of monomer m in the hydrophobic monomer component constituting the polymer, and Tgm is the glass transition temperature of the homopolymer of monomer m (absolute temperature: K). Indicates
The temperature calculated | required based on the Formula of Fox (Fox) represented by these.

  The glass transition temperature of the polymer is, for example, 105 ° C. for a homopolymer of methyl methacrylate, 66 ° C. for a homopolymer of cyclohexyl methacrylate, 180 ° C. for a homopolymer of isobornyl methacrylate, and a homopolymer of 2-ethylhexyl acrylate -70 ° C, n-butyl methacrylate homopolymer at -20 ° C, n-butyl acrylate homopolymer at -56 ° C, methacrylic acid homopolymer at 130 ° C, acrylic acid homopolymer at 95 ° C It is.

  The glass transition temperature of the polymer is a value obtained based on the Fox equation, but the measured value of the glass transition temperature of the polymer was obtained based on the Fox equation. The value is preferably the same. The actual measured value of the glass transition temperature of the polymer can be obtained, for example, by measuring the differential scanning calorific value.

  Examples of the differential scanning calorimeter measuring device include Seiko Instruments Inc., product number: DSC220C. Further, when measuring the differential scanning calorific value, a method of drawing a differential scanning calorific value (DSC) curve, a method of obtaining a first derivative curve from the differential scanning calorific value (DSC) curve, a method of performing a smoothing process, and a method of obtaining a target peak temperature There is no limitation in particular. For example, when the measuring device is used, the drawing may be performed from data obtained by using the measuring device. At that time, analysis software capable of performing mathematical processing can be used. Examples of the analysis software include analysis software [manufactured by Seiko Instruments Inc., product number: EXSTAR6000], but the present invention is not limited to such examples. In addition, the peak temperature obtained in this way may include an error due to plotting of about 5 ° C. up and down.

  The average particle diameter of the emulsion particles is not particularly limited, but from the viewpoint of improving the storage stability of the emulsion particles, it is preferably 30 nm or more, more preferably 50 nm or more, still more preferably 70 nm or more, particularly preferably 100 nm or more, From the viewpoint of improving the weather resistance of the coating film, it is preferably 400 nm or less, more preferably 300 nm or less, still more preferably 250 nm or less, and particularly preferably 200 nm or less.

  In the present specification, the average particle size of the emulsion particles is measured using a particle size distribution measuring instrument (manufactured by Particle Sizing Systems, trade name: NICOMP Model 380) by a dynamic light scattering method. It means the volume average particle diameter.

  The content of non-volatile components in the hydrophobic resin emulsion is preferably 20% by weight or more from the viewpoint of improving the film-forming property and frost damage resistance, and preferably 60% by weight or less from the viewpoint of improving the weather resistance. .

In the present specification, the content of non-volatile content in the resin emulsion is obtained by weighing 1 g of the resin emulsion and drying it at a temperature of 110 ° C. for 1 hour with a hot air dryer, and setting the resulting residue as non-volatile content.
[Nonvolatile content in resin emulsion (% by mass)]
= ([Residue mass] / [resin emulsion 1 g]) × 100
Means the value obtained based on

  The water-based resin composition for paints of the present invention also has one major feature in that it contains a polyfunctional monomer. Since the aqueous resin composition for paints of the present invention contains a polyfunctional monomer, it is excellent in blocking resistance. In addition, the polyfunctional monomer said to this specification is a thing of the concept including a polyfunctional oligomer.

  Examples of the polyfunctional monomer include 4 to 8 carbon atoms of an alkyl group of a polyhydric alcohol residue such as 1,4-butanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate. 1,3-butylene glycol di (meth) acrylate, ethylene oxide modified 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, propylene oxide modified neo Alkyl di (meth) acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as pentyl glycol di (meth) acrylate and tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) having 1 to 50 moles of added ethylene oxide ) Acrylate and propylene oxide It has an alkylene oxide group having 2 to 4 carbon atoms such as polypropylene glycol di (meth) acrylate having 1 to 50 moles and tripropylene glycol di (meth) acrylate, and the number of added moles of alkylene oxide is 1 to 50. Alkyl di (meth) acrylate; ethoxylated glycerin tri (meth) acrylate, propylene oxide modified glycerol tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( Of polyhydric alcohols having 1 to 10 carbon atoms such as (meth) acrylate, pentaerythritol monohydroxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, etc. Poly (meth) acrylates; tetra (meth) acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate; pentaerythritol penta (meth) acrylate and dipenta Penta (meth) acrylate of polyhydric alcohols having 1 to 10 carbon atoms such as erythritol (monohydroxy) penta (meth) acrylate; Hexa (meta) of polyhydric alcohols having 1 to 10 carbon atoms such as pentaerythritol hexa (meth) acrylate ) Acrylates; polyfunctional (meth) acrylates such as bisphenol A di (meth) acrylate, 2- (2′-vinyloxyethoxyethyl) (meth) acrylate, urethane (meth) acrylate epoxy (meth) acrylate, etc. However, the present invention is not limited to such examples. These polyfunctional monomers may be used alone or in combination of two or more.

  Among the polyfunctional monomers, from the viewpoint of improving the water resistance of the aqueous resin composition for paints, an alkyl (meth) acrylate having 2 to 8 alkyl groups having 2 hydroxyl groups and an addition mole of ethylene oxide. Polyethylene glycol di (meth) acrylate having a number of 1 to 50, polypropylene glycol di (meth) acrylate having an addition mole number of propylene oxide of 1 to 50, tri (meth) acrylate of polyhydric alcohol, tetra (meth) of polyhydric alcohol ) Acrylate, polyhydric alcohol penta (meth) acrylate and polyhydric alcohol hexa (meth) acrylate are preferred, 1,4-butanediol di (meth) acrylate, 1.6-hexanediol di (meth) acrylate, ethylene Polyethylene rubber with 1-50 added moles of oxide Koruji (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate are more preferred.

  The amount of the polyfunctional monomer is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, from the viewpoint of improving the water resistance of the aqueous resin composition for coatings per 100 parts by mass of the nonvolatile content of the resin emulsion. From the viewpoint of improving resistance to freezing damage, it is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, and still more preferably 100 parts by mass or less.

  The water-based resin composition for coatings of the present invention also has one major feature in that it contains a rheology control agent. Since the aqueous resin composition for paints of the present invention contains a rheology control agent, the excellent effect of being excellent in frost damage resistance and color tone retention is exhibited.

  The rheology control agent is originally used when the viscosity is increased or decreased. However, surprisingly, the aqueous resin composition for paints of the present invention is excellent not only in frost damage resistance but also in color tone retention due to the use of a rheology control agent.

  Examples of the rheology control agent include alkali-soluble rheology control agents such as alkali-soluble poly (meth) acrylic acid- (meth) acrylic acid ester copolymers; urethane-associated types such as polyether urethane-associated group modified products Rheology control agent; Cellulose derivative-based rheology control agent such as carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose; inorganic rheology control agent such as silicate such as water-soluble aluminum silicate, montmorillonite, colloidal alumina; casein, sodium caseinate, Protein-based rheology control agents such as ammonium caseinate; Alginate-based rheology control agents such as sodium alginate; Polyvinyl alcohol, Polyvinyl Polypyrrole-based rheology control agents such as lupyrrolidone and polyvinyl-benzyl ether copolymer; Polyacrylic-based rheology such as sodium polyacrylate and alkali-soluble poly (meth) acrylic acid- (meth) acrylic ester copolymer Control agents; polyether rheology control agents such as pluronic polyethers, polyether dialkyl esters, polyether dialkyl ethers, polyether urethane-associated group modified products, polyether epoxy modified products; vinyl methyl ether-maleic anhydride copolymer Maleic anhydride copolymer-based rheology control agent such as partial ester, half ester of reaction product of drying oil fatty acid allyl alcohol ester and maleic anhydride; acetylene glycol, xanthan gum, Ntangamu, the like starch, the present invention is not limited only to those exemplified.

  Among the rheology control agents, an alkali-soluble rheology control agent, a urethane-associative rheology control agent, and cellulose from the viewpoint of imparting a viscosity suitable for application to the aqueous resin composition for coatings of the present invention by spraying or rollers. At least one rheology control agent selected from the group consisting of derivative rheology control agents is preferred, and at least one rheology control agent selected from the group consisting of alkali-soluble rheology control agents and cellulose derivative rheology control agents. Is more preferable, and an alkali-soluble rheology control agent is more preferable.

  The alkali-soluble rheology control agent referred to in the present specification means a rheology control agent in which 50% by mass or more is dissolved in an aqueous solvent having a pH of 8 or more at room temperature (for example, 25 ° C.).

  Examples of the alkali-soluble rheology control agent include an alkali-soluble rheology control agent obtained by polymerizing a monomer component containing (meth) acrylic acid alkyl ester and (meth) acrylic acid. However, the present invention is not limited to such examples.

Examples of (meth) acrylic acid alkyl esters include alkyl (meth) acrylates having 1 to 4 carbon atoms in alkyl groups such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. Although ester etc. are mentioned, this invention is not limited only to this illustration. These ( meth) acrylic acid alkyl esters may be used alone or in combination of two or more.

  The content of the (meth) acrylic acid alkyl ester in the monomer component is preferably 20 to 80% by mass, more preferably 40 to 70% by mass, from the viewpoint of improving weather resistance, frost resistance and color tone retention. is there. In addition, the content of (meth) acrylic acid in the monomer component is preferably 20 to 80% by mass, more preferably 30 to 60% by mass from the viewpoint of improving weather resistance, frost resistance and color tone retention. is there. The monomer component may contain other monomers as long as the object of the present invention is not inhibited.

  Examples of the method for polymerizing the monomer component include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method, but the present invention is not limited to such examples. Among these polymerization methods, the emulsion polymerization method is preferred from the viewpoint of increasing the affinity with the hydrophobic resin emulsion and improving the weather resistance, frost resistance and color tone retention. The polymerization conditions for the emulsion polymerization of the monomer component for hydrophilic resin may be the same as the method for emulsion polymerization of the hydrophobic monomer component.

  By polymerizing the monomer component as described above, an alkali-soluble rheology control agent is obtained. When the alkali-soluble rheology control agent is prepared by an emulsion polymerization method, the average particle size of the emulsion particles is not particularly limited, but is preferably 30 nm or more, more preferably from the viewpoint of improving the storage stability of the emulsion particles. From the viewpoint of improving the weather resistance of the coating film, is preferably 400 nm or less, more preferably 300 nm or less, still more preferably 250 nm or less, and particularly preferably 200 nm or less. The content of non-volatile components in the alkali-soluble rheology control agent is preferably 20% by weight or more from the viewpoint of improving the storage stability and economy of the emulsion particles, and from the viewpoint of improving the storage stability of the emulsion particles. It is preferably 50% by weight or less.

  Alkali-soluble rheology control agents can be easily obtained commercially, for example, Acryset WR-507, Acreset WR-650 [above, manufactured by Nippon Shokubai Co., Ltd., trade name], etc. However, the present invention is not limited to such examples.

  The urethane-associative rheology control agent referred to in the present specification means a rheology control agent in which urethane compounds are associated with each other by hydrophobic interaction.

  Urethane associative rheology control agents can be easily obtained commercially. For example, Adecanol UH-420, Adecanol UH-438, Adecanol UH-450VF, Adecanol UH-472 [above, ADEKA Corporation] Manufactured, trade name, etc.], but the present invention is not limited to such examples. These rheology control agents may be used alone or in combination of two or more.

  Cellulose derivative-based rheology control agents can be easily obtained commercially, for example, SP-600, SP-800, SP-850 [above, manufactured by Daicel Chemical Industries, Ltd., hydroxyethyl cellulose, commercial product The present invention is not limited to such examples.

  The amount of the active ingredient of the rheology control agent is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and further preferably from the viewpoint of improving the frost damage resistance of the aqueous resin composition for paints of the present invention. Is 0.5 parts by mass or more, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably from the viewpoint of improving the weather resistance of the coating film made of the aqueous resin composition for paints of the present invention. It is 10 parts by mass or less.

  The aqueous resin composition for coatings of the present invention preferably contains a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Among the polymerization initiators, a photopolymerization initiator is preferable from the viewpoint of improving blocking resistance and efficiently producing an inorganic building material on which a coating film made of the aqueous resin composition for coating is formed.

  Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2 -Propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butanone, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, 2-hydroxy-1- {4- [4- (2-hydroxy- Acetophenones such as 2-methylpionyl) benzyl] phenyl} -2-methylpropan-1-one; Benzoins such as in, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3, 3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2- Benzophenones such as propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-die Thioxanthones such as luthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride , Phenylglyoxylic methyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, etc., but the present invention is only such examples It is not limited to. These photopolymerization initiators may be used alone or in combination of two or more. Among these photopolymerization initiators, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide 1-hydroxycyclohexyl phenyl ketone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone are preferred.

  Examples of the thermal polymerization initiator include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (tert-hexylperoxy) -3, 3, 5-trimethylcyclohexane, 1,1-bis (tert-hexylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butyl) Peroxy) -2-methylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) cyclododecane, 1,1-bis (tert-butylperoxy) butane 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene Hydroperoxide, tert-hexyl hydroperoxide, tert-butyl hydroperoxide, α, α'-bis (tert-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (Tert-butylperoxy) hexane, tert-butylcumyl peroxide, ditert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyne-3, isobutyryl peroxide, 3, 5, 5- Limethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxide Carbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethoxyhexylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-s-butyl Peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, Luperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, tert-hexylperoxyneodecanoate, tert-butylperoxyneodecanoate, tert-hexylperoxypivalate, tert-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5 -Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, tert-hexylperoxy-2-ethylhexanoate, tert -Butylperoxy-2-ethylhexanoate, te t-hexyl peroxysopropyl monocarbonate, tert-butyl peroxysobutyrate, tert-butyl peroxymalate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaur Tert-butylperoxysopropyl monocarbonate, tert-butylperoxy-2-ethylhexyl monocarbonate, tert-butylperoxyacetate, tert-butylperoxy-m-toluylbenzoate, tert-butylperoxybenzoate, bis (Tert-butylperoxy) isophthalate, 2,5-dimethyl-2,5-bis (m-tolylperoxy) hexane, tert-hexylperoxybenzoate, 2,5-dimethyl-2,5-bi Sus (benzoylperoxy) hexane, tert-butylperoxyallyl monocarbonate, tert-butyltrimethylsilyl peroxide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,3-dimethyl Organic peroxide polymerization initiators such as -2,3-diphenylbutane;

2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl) azo] formamide, 1,1′-azobis (cyclohexane-1-carbonitrile), 2, 2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2, 4-dimethyl-4-methoxyvaleronitrile), 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2 , 2′-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [N- (4-hydrophenyl) -2-methyl Propionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (2-propenyl) propion Amidine] dihydrochloride, 2,2′-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazoline- 2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2 ″ -azobis [2- (4,5,6) , 7-Tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] Dihydrochloride, 2,2'- Azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azobis {2- [1- (2-hydroxyethyl) -2 -Imidazolin-2-yl] propane} dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis {2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2 ′ -Azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (2-methylpropionamide), 2,2'-azobis (2,4,4-trimethylpentane) 2,2′-azobis (2-methylpropane), 2,2′-azobis (2-methylpropionic acid) dimethyl, 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis [2 An azo polymerization initiator such as-(hydroxymethyl) propionitrile] may be mentioned, but the present invention is not limited to such examples. These thermal polymerization initiators may be used alone or in combination of two or more.

  Among the thermal polymerization initiators, 2,2′-azobis (2-methylbutyronitrile), methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, tert-butyl peroxybenzoate, benzoyl peroxide, 2,2 '-Azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) are preferred.

  The amount of the photopolymerization initiator per 100 parts by mass of the polyfunctional monomer is preferably 0.1 parts by mass or more, more preferably 0 from the viewpoint of improving the frost damage resistance and weather resistance of the aqueous resin composition for coatings. From the viewpoint of improving the blocking resistance, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.

  If necessary, the aqueous resin composition for paints of the present invention may contain a film forming aid. Examples of film forming assistants include 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, butyl cellosolve, butyl carbitol acetate, 2-ethylhexyl diglycol, propylene glycol methyl ether, propylene glycol, n -Propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, and the like. Is not limited to such examples. These film forming assistants may be used alone or in combination of two or more.

  The amount of the film forming auxiliary agent per 100 parts by mass of the nonvolatile content of the resin emulsion is preferably 1 part by mass or more, more preferably 5 parts by mass or more from the viewpoint of improving the film forming property, and improves the blocking resistance. From the viewpoint, it is preferably 100 parts by mass or less, more preferably 50 parts by mass or less.

  If necessary, the aqueous resin composition for paints of the present invention may contain a pigment. Examples of the pigment include organic pigments and inorganic pigments, and these may be used alone or in combination of two or more.

  Examples of organic pigments include azo pigments, azomethine pigments, methine pigments, anthraquinone pigments, phthalocyanine pigments, perinone pigments, perylene pigments, diketopyrrolopyrrole pigments, thioindigo pigments, iminoisoindoline pigments, iminoisoindolinone pigments, and quinacridone red. And quinacridone pigments such as quinacridone violet, flavanthrone pigment, indanthrone pigment, anthrapyrimidine pigment, carbazole pigment, monoarylide yellow, diarylide yellow, benzoimidazolone yellow, tolyl orange, naphthol orange, quinophthalone pigment, etc. However, the present invention is not limited to such examples. These organic pigments may be used alone or in combination of two or more.

  Examples of inorganic pigments include titanium dioxide, red iron oxide, black iron oxide, iron oxide, chromium oxide green, carbon black, ferric ferrocyanide (Prussian blue), ultramarine, lead chromate, and mica. (Mica), clay, aluminum powder, pigment having a flat shape such as talc, aluminum silicate, and extender pigments such as calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, magnesium carbonate, etc. Is not limited to such examples. These inorganic pigments may be used alone or in combination of two or more. Among the pigments, titanium dioxide is more preferable from the viewpoint of improving the weather resistance.

  The amount of the pigment per 100 parts by mass of the nonvolatile content of the resin emulsion is preferably 5 parts by mass or more, more preferably 10 parts by mass or more from the viewpoint of sufficiently imparting a coloring effect, and from the viewpoint of improving film formability. The amount is preferably 400 parts by mass or less.

  The aqueous resin composition for paints of the present invention can be easily prepared by mixing a resin emulsion, a polyfunctional monomer, a rheology control agent, and, if necessary, a polymerization initiator, a film forming aid, and a pigment. it can.

  The nonvolatile content in the aqueous resin composition for paints of the present invention is preferably 20% by weight or more from the viewpoint of improving the film-forming property and frost damage resistance, and preferably 60% from the viewpoint of improving the weather resistance. % By weight or less.

In addition, in this specification, the content rate of the non volatile matter in the aqueous resin composition for paints of the present invention is determined by weighing 1 g of the resin emulsion and drying it with a hot air dryer at a temperature of 110 ° C. for 1 hour. Non-volatile content, formula:
[Non-volatile content (% by mass) in aqueous resin composition for paints]
= ([Residue mass] / [resin emulsion 1 g]) × 100
Means the value obtained based on

  The aqueous resin composition for paints of the present invention obtained as described above is generally excellent in blocking resistance, color tone retention, weather resistance and frost damage resistance, so that it is an undercoat paint for substrates such as inorganic building materials In addition, it can be suitably used for various paints such as an intermediate paint and a top paint, and in particular, a paint applied to a top coat (outermost surface) of a substrate can be suitably used. Therefore, the aqueous resin composition for paints of the present invention is useful for topcoat paints for inorganic building materials such as ceramic building materials.

  Examples of the inorganic building material include a ceramic base material and a metal base material. Ceramic base materials are used for applications such as tiles and outer wall materials, for example. Ceramic base materials are the addition of inorganic fillers, fibrous materials, etc. to the hydraulic glue used as the raw material for inorganic hardened bodies, molding the resulting mixture, curing the resulting molded body, and curing it. Obtained by. Examples of the inorganic building material include slate board, flexible board, siding board, calcium silicate board, gypsum slag perlite board, wood chip cement board, precast concrete board, ALC board, gypsum board, etc. It is not limited to only.

  Such an inorganic building material generally has a property of being easily deteriorated because water is easily permeable to the inside thereof. Therefore, the aqueous resin composition for paint is generally applied to the surface and the back surface of the inorganic building material, and the top coating material is usually applied to the surface of the inorganic building material in order to impart a desired design.

  The inorganic building material of this invention is obtained by apply | coating the aqueous resin composition for coatings to the surface and back surface, and has a coating film which consists of the said aqueous resin composition for coatings.

  Examples of the method for applying the aqueous resin composition for coating on the front and back surfaces of inorganic building materials include application methods using brushes, bar coaters, applicators, air sprays, airless sprays, roll coaters, flow coaters, and the like. The present invention is not limited to such examples.

  The amount of the aqueous resin composition for paint applied to the inorganic building material is not particularly limited, and the thickness at the time of application is usually 5 to 500 μm, and a thickness suitable for the application is selected from this thickness range. It is preferable to do.

  The coating film formed by applying the aqueous resin composition for paint to an inorganic building material can be cured by, for example, irradiating with ultraviolet rays, electron beams, or heating. At this time, when using a photopolymerization initiator as a polymerization initiator, it is preferable to cure by irradiating ultraviolet rays, near infrared rays, etc., and when using a thermal polymerization initiator as a polymerization initiator, It is preferable to cure by heating.

  As described above, the aqueous resin composition for paints of the present invention is generally excellent in blocking resistance, color tone retention, weather resistance, and frost damage resistance, and is therefore preferably used for, for example, inorganic building materials. It is something that can be done.

  EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to this Example. In the following examples, “part” means “part by mass” and “%” means “% by weight” unless otherwise specified.

Production Example 1
802 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser. In a dropping funnel, 250 parts of deionized water, 105 parts of a 15% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Hytenol N-08], an emulsifier [manufactured by Sanyo Chemical Industries, Ltd., trade name: Nonipol 200] was prepared as a pre-emulsion for dripping consisting of 81 parts of a 20% aqueous solution, 300 parts of ethyl acrylate, 200 parts of methyl methacrylate and 500 parts of methacrylic acid, of which 86 parts corresponding to 6% of the total amount of all monomer components were flasked. Then, the temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 23 parts of a 5% aqueous solution of ammonium persulfate was added to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping and 23 parts of a 5% aqueous solution of ammonium persulfate were uniformly dropped into the flask over 240 minutes. After completion of the dropping, the polymerization temperature was maintained at the same temperature for 60 minutes to complete the polymerization reaction. 1140 parts of deionized water was added to the resulting reaction mixture, cooled to room temperature, and then filtered through a 300-mesh wire mesh to obtain an alkali-soluble rheology control agent.

Example 1
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged.

  In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10], 800 parts of methyl methacrylate, 90 parts of 2-ethylhexyl acrylate, n- A pre-emulsion for dropping comprising 90 parts of butyl methacrylate, 10 parts of methacrylic acid and 10 parts of acrylic acid was prepared.

  Of the obtained pre-emulsion for dripping, 85 parts corresponding to 6% of the total amount of the monomer components were added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 3.5% ammonium persulfate. 43 parts of an aqueous solution was added into the flask to initiate the polymerization reaction.

  Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were added dropwise into the flask over 240 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 25% aqueous ammonia was added to the flask, and the pH (measured at 23 ° C. using Horiba, Ltd., product number: F-23, the same shall apply hereinafter) was adjusted to 9 to complete the polymerization reaction. After cooling the obtained resin emulsion to room temperature, 25 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and a polyfunctional monomer A mixed solution with 500 parts of 1,4-butanediol diacrylate, 1260 parts of deionized water, and 5 parts of a defoaming agent (manufactured by San Nopco Co., Ltd., trade name: SN deformer 777) are added to the flask and left as it is. For 120 minutes.

Next, as a rheology control agent, 50 parts of a urethane-associative rheology control agent [manufactured by ADEKA, trade name: Adecanol UH-472, active ingredient content: 30%] is added to the flask, After maintaining for 30 minutes, the content in the flask was filtered through a 300-mesh wire mesh to obtain an aqueous resin composition for paint. The glass transition temperature of the emulsion particles contained in the obtained aqueous resin composition for coatings was 70 ° C., and the nonvolatile content of the aqueous resin composition for coatings was 40% by mass.
In addition, Example 1 is handled as a reference example.

Example 2
In Example 1, as the rheology control agent, the same operation as in Example 1 except that 50 parts of a cellulose-based thickener [manufactured by Daicel Chemical Industries, Ltd., product number: 3% aqueous solution of SP-600] was used. By carrying out the above, an aqueous resin composition for paints was obtained. The glass transition temperature of the emulsion particles contained in the obtained aqueous resin composition for coatings was 70 ° C., and the nonvolatile content of the aqueous resin composition for coatings was 40% by mass.
In addition, Example 2 is handled as a reference example.

Example 3
In Example 1, the aqueous resin composition for coating materials was obtained by performing the same operation as in Example 1 except that 25 parts of the alkali-soluble rheology control agent obtained in Production Example 1 was used. The glass transition temperature of the emulsion particles contained in the obtained aqueous resin composition for coatings was 70 ° C., and the nonvolatile content of the aqueous resin composition for coatings was 40% by mass.

Example 4
In Example 3, an aqueous resin composition for paints was obtained by performing the same operation as in Example 3 except that the amount of the alkali-soluble rheology control agent was changed from 25 parts to 50 parts. The glass transition temperature of the emulsion particles contained in the obtained aqueous resin composition for coatings was 70 ° C., and the nonvolatile content of the aqueous resin composition for coatings was 40% by mass.

Example 5
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged.

  In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10], 800 parts of methyl methacrylate, 90 parts of 2-ethylhexyl acrylate, n- A pre-emulsion for dropping comprising 90 parts of butyl methacrylate, 10 parts of methacrylic acid and 10 parts of acrylic acid was prepared.

  Of the obtained pre-emulsion for dripping, 85 parts corresponding to 6% of the total amount of the monomer components were added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 3.5% ammonium persulfate. 43 parts of an aqueous solution was added into the flask to initiate the polymerization reaction.

  Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were added dropwise into the flask over 240 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 25% aqueous ammonia was added to the flask, the pH was adjusted to 9, and the polymerization reaction was completed. After cooling the obtained resin emulsion to room temperature, 25 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and a polyfunctional monomer A mixed solution of 250 parts of 1,4-butanediol diacrylate and 250 parts of ditrimethylolpropane tetraacrylate, 1260 parts of deionized water and 5 parts of defoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) And maintained for 120 minutes.

  Next, 25 parts of the alkali-soluble rheology control agent obtained in Production Example 1 was added to the flask, and after maintaining that state for 30 minutes, the contents in the flask were filtered through a 300-mesh wire mesh. An aqueous resin composition for paint was obtained. The glass transition temperature of the emulsion particles contained in the obtained aqueous resin composition for coatings was 70 ° C., and the nonvolatile content of the aqueous resin composition for coatings was 40% by mass.

Example 6
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged.

  In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10], 900 parts of methyl methacrylate, 10 parts of 2-ethylhexyl acrylate, n- A pre-emulsion for dropping consisting of 70 parts of butyl methacrylate, 10 parts of methacrylic acid and 10 parts of acrylic acid was prepared.

  Of the obtained pre-emulsion for dripping, 85 parts corresponding to 6% of the total amount of the monomer components were added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 3.5% ammonium persulfate. 43 parts of an aqueous solution was added into the flask to initiate the polymerization reaction.

  Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were added dropwise into the flask over 240 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 25% aqueous ammonia was added to the flask, the pH was adjusted to 9, and the polymerization reaction was completed. After cooling the obtained resin emulsion to room temperature, 50 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and a polyfunctional monomer A mixed solution of 500 parts of 1,4-butanediol diacrylate and 500 parts of polyethylene glycol diacrylate (added mole number of ethylene oxide group: 9), 2,2,4-trimethyl-1,3- as a film forming aid 250 parts of pentanediol monoisobutyrate [manufactured by Chisso Co., Ltd., product number: CS-12], 2165 parts of deionized water and defoaming agent [manufactured by San Nopco Co., Ltd., trade name: SN deformer 777] in the flask And maintained as such for 120 minutes.

  Next, 25 parts of the alkali-soluble rheology control agent obtained in Production Example 1 was added to the flask, and after maintaining that state for 30 minutes, the contents in the flask were filtered through a 300-mesh wire mesh. An aqueous resin composition for paint was obtained. The glass transition temperature of the emulsion particles contained in the obtained aqueous resin composition for paint was 94 ° C., and the nonvolatile content of the aqueous resin composition for paint was 40% by mass.

Example 7
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged.

  In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10), 380 parts of methyl methacrylate, 450 parts of cyclohexyl methacrylate, 2-ethylhexyl acrylate A pre-emulsion for dropping consisting of 50 parts, 100 parts of n-butyl methacrylate, 10 parts of methacrylic acid and 10 parts of acrylic acid was prepared.

  Of the obtained pre-emulsion for dripping, 85 parts corresponding to 6% of the total amount of the monomer components were added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 3.5% ammonium persulfate. 43 parts of an aqueous solution was added into the flask to initiate the polymerization reaction.

  Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were added dropwise into the flask over 240 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 25% aqueous ammonia was added to the flask, the pH was adjusted to 9, and the polymerization reaction was completed. After cooling the obtained resin emulsion to room temperature, 25 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and a polyfunctional monomer A mixed solution with 500 parts of 1,4-butanediol diacrylate, 1260 parts of deionized water, and 5 parts of a defoaming agent (manufactured by San Nopco Co., Ltd., trade name: SN deformer 777) are added to the flask and left as it is. For 120 minutes.

  Next, 25 parts of the alkali-soluble rheology control agent obtained in Production Example 1 was added to the flask, and after maintaining that state for 30 minutes, the contents in the flask were filtered through a 300-mesh wire mesh. An aqueous resin composition for paint was obtained. The glass transition temperature of the emulsion particles contained in the obtained aqueous resin composition for coatings was 70 ° C., and the nonvolatile content of the aqueous resin composition for coatings was 40% by mass.

Example 8
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged.

  In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10], 800 parts of methyl methacrylate, 90 parts of 2-ethylhexyl acrylate, n- A pre-emulsion for dropping comprising 90 parts of butyl methacrylate, 10 parts of methacrylic acid and 10 parts of acrylic acid was prepared.

  Of the obtained pre-emulsion for dripping, 85 parts corresponding to 6% of the total amount of the monomer components were added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 3.5% ammonium persulfate. 43 parts of an aqueous solution was added into the flask to initiate the polymerization reaction.

  Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were added dropwise into the flask over 240 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 25% aqueous ammonia was added to the flask, the pH was adjusted to 9, and the polymerization reaction was completed. After cooling the obtained resin emulsion to room temperature, 25 parts of 2,2′-azobis (2-methylbutyronitrile) as a thermal polymerization initiator and 500 parts of 1,4-butanediol diacrylate as a polyfunctional monomer are used. A mixed solution, 1260 parts of deionized water, and 5 parts of a defoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) were added to the flask and maintained for 120 minutes.

  Next, 25 parts of the alkali-soluble rheology control agent obtained in Production Example 1 was added to the flask, and after maintaining that state for 30 minutes, the contents in the flask were filtered through a 300-mesh wire mesh. An aqueous resin composition for paint was obtained. The glass transition temperature of the emulsion particles contained in the obtained aqueous resin composition for coatings was 70 ° C., and the nonvolatile content of the aqueous resin composition for coatings was 40% by mass.

Example 9
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged.

  In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10], 300 parts of methyl methacrylate, isobornyl methacrylate [Kyoeisha Chemical Co., Ltd. Product name: Light ester IB-X] A pre-emulsion for dripping comprising 640 parts, 40 parts of n-butyl acrylate, 10 parts of methacrylic acid and 10 parts of acrylic acid was prepared.

  Of the obtained pre-emulsion for dripping, 85 parts corresponding to 6% of the total amount of the monomer components were added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 3.5% ammonium persulfate. 43 parts of an aqueous solution was added into the flask to initiate the polymerization reaction.

  Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were added dropwise into the flask over 240 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 25% aqueous ammonia was added to the flask, the pH was adjusted to 9, and the polymerization reaction was completed. After cooling the obtained resin emulsion to room temperature, 25 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and a polyfunctional monomer A mixed solution with 500 parts of 1,4-butanediol diacrylate, 1260 parts of deionized water, and 5 parts of a defoaming agent (manufactured by San Nopco Co., Ltd., trade name: SN deformer 777) are added to the flask and left as it is. For 120 minutes.

  Next, 25 parts of the alkali-soluble rheology control agent obtained in Production Example 1 was added to the flask, and after maintaining that state for 30 minutes, the contents in the flask were filtered through a 300-mesh wire mesh. An aqueous resin composition for paint was obtained. The glass transition temperature of the emulsion particles contained in the obtained aqueous resin composition for paints was 136 ° C., and the nonvolatile content of the aqueous resin composition for paints was 40% by mass.

Example 10
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged.

  In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10], 800 parts of methyl methacrylate, 90 parts of 2-ethylhexyl acrylate, n- A pre-emulsion for dropping comprising 90 parts of butyl methacrylate, 10 parts of methacrylic acid and 10 parts of acrylic acid was prepared.

  Of the obtained pre-emulsion for dripping, 85 parts corresponding to 6% of the total amount of the monomer components were added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 3.5% ammonium persulfate. 43 parts of an aqueous solution was added into the flask to initiate the polymerization reaction.

  Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were added dropwise into the flask over 240 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 25% aqueous ammonia was added to the flask, the pH was adjusted to 9, and the polymerization reaction was completed. After cooling the obtained resin emulsion to room temperature, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 1-hydroxycyclohexyl phenyl ketone were mixed at a mass ratio of 1: 3 as a photopolymerization initiator. A mixed solution of 25 parts of a mixture and 250 parts of 1,4-butanediol diacrylate and 250 parts of ditrimethylolpropane tetraacrylate as a polyfunctional monomer, 1260 parts of deionized water and a defoaming agent [manufactured by San Nopco, [Product name: SN deformer 777] 5 parts were added to the flask and maintained for 120 minutes.

  Next, 50 parts of the alkali-soluble rheology control agent obtained in Production Example 1 was added to the flask, and after maintaining that state for 30 minutes, the contents in the flask were filtered through a 300-mesh wire mesh. An aqueous resin composition for paint was obtained. The glass transition temperature of the emulsion particles contained in the obtained aqueous resin composition for coatings was 70 ° C., and the nonvolatile content of the aqueous resin composition for coatings was 40% by mass.

While stirring 125 parts of the aqueous resin composition for paints obtained above with a homodisper at a rotation speed of 1500 min ^−1, 41 parts of deionized water was added to adjust the content of non-volatile content to 30%. 47 parts of enamel pigment paste was added to the aqueous resin composition for paints whose non-volatile content was adjusted to 30%, and further using a Krebs unit viscometer (manufactured by Brookfield, product number: KU-1). After adding a cellulose-based thickener [Daicel Chemical Industries, product number: SP-600, active ingredient content: 3%] so that the viscosity when measured at 25 ° C. is 65 ± 1 KU, The resulting mixture was stirred with a homodisper at a rotational speed of 1500 min ^{-1 for} 30 minutes to obtain a clear paint. The resulting clear paint was stabilized by allowing it to stand at room temperature for 1 day and then used.

The enamel pigment paste is composed of 60 parts of a dispersant (trade name: Demol EP, manufactured by Kao Corporation), 50 parts of a dispersant (trade name: DISCOAT N-14, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). , Wetting agent [Kao Co., Ltd., trade name: Emulgen LS-106] 10 parts, Propylene glycol 60 parts, Deionized water 210 parts, Titanium oxide [Ishihara Sangyo Co., Ltd., product number: CR-95] 1000 parts An antifoaming agent (manufactured by San Nopco Co., Ltd., trade name: Nopco 8034L) and 500 parts of glass beads (diameter: 1 mm) were dispersed with a homodisper at a rotational speed of 3000 min ^{-1 for} 60 minutes.

Comparative Example 1
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged.

  In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10], 800 parts of methyl methacrylate, 90 parts of 2-ethylhexyl acrylate, n- A pre-emulsion for dropping comprising 90 parts of butyl methacrylate, 10 parts of methacrylic acid and 10 parts of acrylic acid was prepared.

  Of the obtained pre-emulsion for dripping, 85 parts corresponding to 6% of the total amount of the monomer components were added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 3.5% ammonium persulfate. 43 parts of an aqueous solution was added into the flask to initiate the polymerization reaction.

  Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were added dropwise into the flask over 240 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 25% aqueous ammonia was added to the flask, the pH was adjusted to 9, and the polymerization reaction was completed. After cooling the obtained resin emulsion to room temperature, 25 parts of 2,2′-azobis (2-methylbutyronitrile) as a thermal polymerization initiator and 500 parts of 1,4-butanediol diacrylate as a polyfunctional monomer are used. 1260 parts of deionized water and 5 parts of a defoaming agent (manufactured by San Nopco Co., Ltd., trade name: SN deformer 777) were added to the flask and maintained as it was for 120 minutes.

  Next, the content in the flask was filtered through a 300-mesh wire mesh to obtain an aqueous resin composition for paint. The glass transition temperature of the emulsion particles contained in the obtained aqueous resin composition for coatings was 70 ° C., and the nonvolatile content of the aqueous resin composition for coatings was 40% by mass.

Experimental example [Preparation of test plate 1]
Dispersant [Kao Co., Ltd., trade name: Demol EP] 60 parts, Dispersant [Daiichi Kogyo Seiyaku Co., Ltd., trade name: DISCOAT N-14] 50 parts, Wetting agent [Kao Co., Ltd. , Trade name: Emulgen LS-106] 10 parts, propylene glycol 60 parts, deionized water 210 parts, titanium oxide [manufactured by Ishihara Sangyo Co., Ltd., product number: CR-95] 1000 parts, foam suppressor [San Nopco Co., Ltd.] Manufactured, trade name: Nopco 8034L] and 500 parts of glass beads (diameter: 1 mm) were dispersed with a homodisper at a rotational speed of 3000 min ^{-1 for} 60 minutes to prepare a white paste.

  300 parts of an acrylic resin emulsion [made by Nippon Shokubai Co., Ltd., trade name: Acryset EX-41], 135 parts of the white paste obtained above, film forming aid (15 parts of butyl cellosolve, 2,2,4-trimethyl- 15 parts of 1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number: CS-12], 10 parts of black paste [manufactured by Yokohama Kasei Co., Ltd., trade name: Unirant 88] and foam suppressor [ A base coat paint was prepared by mixing 1.5 parts of San Nopco Co., Ltd., trade name: Nopco 8034L].

Next, the base coat paint obtained above was applied to an uneven base material (trade name: UB board light, product number: SS3 × 10T12-00, small scotta tone) manufactured by Ube Board Co., Ltd., and an airless spray [Anest Iwata Corporation ) Made] at a coating amount of 100 g / m ² to obtain a coated plate.

Each of the aqueous resin compositions for paints obtained in Examples 1 to 7 and Examples 9 to 10 was separately applied on the base coat film of the paint plate obtained above, and the surface temperature of the paint plate was 60 ° C. Each test was performed by applying airless spray (manufactured by Anest Iwata Co., Ltd.) at an application amount of 100 g / m ² at a temperature of ± 5 ° C., leaving it at room temperature for 5 minutes, and then irradiating with ultraviolet rays (500 mJ). Two plates were obtained.

[Preparation of test plate 2]
The aqueous resin compositions for paints obtained in Example 8 and Comparative Example 1 were separately applied in the same manner as in Example 1 and the surface temperature of the paint plate was 60 ° C. ± 5 ° C. After applying at an application amount of 100 g / m ² using an airless spray [manufactured by Anest Iwata Co., Ltd., product number: EX-700], it is dried for 10 minutes with a hot air dryer at 100 ° C., so that two test plates each. Got.

<Blocking resistance>
Immediately after producing the two test plates obtained above, they were put in a hot air dryer at 50 ° C., and the coated surfaces of the two test plates were overlapped, and 500 g / cm ² (about 490 kPa) was applied to the surface of the obtained laminate. ) Was applied and left for 6 hours. Next, while keeping the contact surface of the test plate from moving, the laminate is placed in an 80 ° C. hot air dryer as it is, and a load of 500 g / cm ² (about 490 kPa) is applied to the surface of the laminate. Left for hours. Thereafter, while keeping the contact surface of the test plate from moving, the laminate was placed in a 5 ° C. incubator for 2 hours and then left in a 25 ° C. incubator for 6 hours.

The above series of operations is defined as one cycle, and after 10 cycles (160 hours in total), the two test plates constituting the laminate are slowly peeled off to visually check the state of the coating film. Observed and evaluated based on the following evaluation criteria.
(Evaluation criteria)
25: No abnormality is observed.
20: Although there is peeling resistance, no abnormality is observed in the coating film.
15: There is peeling resistance, and a mark is observed in a part of the coating film.
10: There is peeling resistance, and peeling is recognized in a part of the coating film.
0: The test plates cannot be separated from each other.

<Color tone retention>
The appearance of the test plate was visually observed, and the color tone retention was evaluated based on the following evaluation criteria.
(Evaluation criteria)
25: The color of the background is not changed and the color tone is maintained.
20: The color of the base is partially changed, but the color tone of the substrate is maintained.
15: The color of the base is partially changed, and the color tone of the base material is slightly changed.
10: The color of the base is changed to spots or the color tone of the substrate is clearly changed.
0: The color of the base is changed as a whole, and the color tone of the base material is clearly changed.

<Weather resistance>
The side surface and back surface of the test body are sealed with aluminum tape, and the color difference (L ₀ , a ₀ , b ₀ ) of the coating surface of the test plate on which the aqueous resin composition for paint is applied is measured by a color difference meter [Nippon Denshoku Manufactured by Kogyo Co., Ltd., trade name: spectroscopic color difference meter SE-2000], and further subjected to a 1000-hour weather resistance test under the following weather resistance test conditions.

[Test conditions for weather resistance test]
-Weather resistance tester: Metal weather [Daipura Wintes Co., Ltd., product number: KU-R]
・ Irradiation: UV irradiation for 4 hours in an atmosphere with a temperature of 65 ° C. and a relative humidity of 50% (irradiation intensity: 80 mW / cm ² )
・ Wetting: Irradiation with ultraviolet rays for 4 hours in an atmosphere with a temperature of 35 ° C. and a relative humidity of 98% (irradiation intensity: 80 mW / cm ² )
・ Water shower: 30 seconds each before and after wetting

After the end of the weather resistance test, the color difference (L ₁ , a ₁ , b ₁ ) of the coating film surface of the test plate is measured with the color difference meter, and the change value (ΔE) of the E value is expressed by
ΔE = [(L ₁ −L ₀ ) ₂ + (a ₁ −a ₀ ) ₂ + (b ₁ −b ₀ ) ₂ ] _1/2
And evaluated based on the following evaluation criteria.
(Evaluation criteria)
25: ΔE is less than 2.0 20: ΔE is 2.0 or more and less than 4.05 15: ΔE is 4.0 or more and less than 6.0 10: ΔE is 6.0 or more and less than 8.0 0: ΔE Is 8.0 or more

<Frost resistance>
After sealing the side surface of the test plate with a silicone bath bond (manufactured by Konishi Co., Ltd.), it was frozen for 2 hours by cooling to −20 ° C. in the atmosphere using a freeze-thaw tester, and then 2 hours in 20 ° C. water. The operation for immersion was set to 1 cycle, and the operation was performed for 300 cycles while observing the occurrence of cracks on the coating surface using a magnifying glass having a magnification of 30 times every 100 cycles, and evaluated based on the following evaluation criteria.
(Evaluation criteria)
No problem at 25: 300 cycles No problem at 20: 200 cycles, but cracks occurred at 300 cycles No problems at 10: 100 cycles, but cracks occurred at 200 cycles 0: Cracks occurred at 100 cycles

<Comprehensive evaluation>
Total evaluation (full score: 100 points) was performed by summing up the scores of each evaluation.

  From the results shown in Table 1, all of the aqueous resin compositions for paints obtained in each example have blocking resistance, color tone retention, weather resistance, and frost damage resistance as compared with Comparative Example 1. It turns out that the coating film which was excellent comprehensively is formed.

  Therefore, the aqueous resin composition for paints obtained in each example can be suitably used for paints for inorganic building materials, and for example, suitably used for coating the outer walls of buildings including inorganic building materials. You can see that you can.

Claims (5)

A water-based resin composition used for coatings, comprising a hydrophobic resin emulsion, a polyfunctional monomer and a rheology control agent, wherein the hydrophobic resin emulsion contains 50% by mass or more of a hydrophobic monomer. A hydrophobic resin emulsion obtained by emulsion polymerization of a functional monomer component, wherein the hydrophobic monomer is alkyl (meth) acrylate, fluorine atom-containing alkyl (meth) acrylate, epoxy group-containing (meth) acrylate and aromatic A hydrophobic monomer selected from a series monomer, the polyfunctional monomer is a polyfunctional monomer containing 1,4-butanediol di (meth) acrylate, and the rheology control agent is (meth) acrylic acid alkyl ester and (meth) alkali-consisting of polymers obtained by polymerizing a monomer component containing acrylic acid It paints aqueous resin composition, which is a type rheology control agent.   The aqueous resin composition for paints according to claim 1, wherein the glass transition temperature of the emulsion particles of the hydrophobic resin emulsion is 60 ° C or higher.   Furthermore, the aqueous resin composition for coating materials of Claim 1 or 2 containing a photoinitiator.   The coating material for inorganic building materials containing the aqueous resin composition for coating materials in any one of Claims 1-3.   The inorganic building material in which the coating film which consists of the aqueous resin composition for coating materials in any one of Claims 1-3 is formed.