JP5798870B2 - Sealer - Google Patents

Description

  The present invention relates to a sealer. More specifically, for example, the present invention relates to a sealer that is useful for inorganic building materials such as ceramic building materials and can be suitably used as a sealer for inorganic building materials. The sealer of the present invention can be suitably used, for example, when a sealer film is formed on an inorganic building material in a factory line.

  In recent years, as a sealer excellent in blocking resistance and film-forming property, it contains a resin emulsion containing emulsion particles having a glass transition temperature of 0 to 60 ° C., a pigment and a rheology control agent, and the nonvolatile content of the resin emulsion is 100 mass. A sealer in which the amount of pigment per part is 100 to 400 parts by mass and the amount of the active ingredient of the rheology control agent is 0.1 to 10 parts by mass has been proposed (for example, see Patent Document 1).

  The coating composition for a sealer is excellent in blocking resistance and film-forming property, and further, as properties unique to the sealer, moisture permeability resistance, blocking resistance, color tone retention, substrate adhesion and frost damage resistance The development of a sealer that forms a film with excellent overall properties is awaited.

JP 2010-202854 A

  The present invention has been made in view of the above prior art, and is a sealer that is comprehensively excellent in moisture permeation resistance, blocking resistance, color tone retention, substrate adhesion and frost damage resistance as properties unique to the sealer. Another object of the present invention is to provide an inorganic building material on which a film made of the sealer is formed.

The present invention
(1) A sealer comprising a resin emulsion , wherein emulsion particles are obtained by emulsion polymerization of a monomer component in which the resin emulsion contains an aromatic monomer at a content of 30 to 70% by mass. a resin emulsion containing, further polyfunctional monomer and contains a rheology control agent, the amount is 0.1 to 20 parts by mass der Rukoto active ingredients rheology control agent having a nonvolatile per 100 parts by weight of the resin emulsion Sealer, characterized by
(2) the glass transition temperature of the d Marushon particles is 60 ° C. or more as described in (1) sealer,
(3 ) Furthermore, the film which consists of the sealer as described in said (1) or ( 2 ) containing a photoinitiator, and the sealer as described in any one of ( 4 ) said (1)-( 3 ) is formed. It relates to inorganic building materials.

  According to the present invention, a sealer that is comprehensively excellent in moisture permeation resistance, blocking resistance, color tone retention, substrate adhesion, and frost damage resistance is provided as a property unique to the sealer. The sealer of the present invention is used when a resin emulsion containing emulsion particles obtained by emulsion polymerization of a monomer component containing an aromatic monomer at a content of 30% by mass or more is used. In addition, the effect of further improving the adhesion of the sealer to the base is exhibited. When the glass transition temperature of the emulsion particles is 60 ° C. or higher, an effect that a hard sealer film can be formed is achieved. In addition, when the sealer of the present invention further contains a rheology control agent, the effect of further improving the sealer adhesion to the base, the frost damage resistance and water permeability resistance of the sealer is exhibited. Furthermore, the sealer of the present invention, when it contains a photopolymerization initiator, has an excellent effect that the blocking resistance of the sealer is improved and an inorganic building material on which a sealer film is formed can be efficiently produced. Played.

  Since the inorganic building material of the present invention has a film made of the sealer, it exhibits excellent effects based on the sealer.

  As described above, the sealer of the present invention is a sealer containing a resin emulsion, and further contains a polyfunctional monomer. Since the sealer of the present invention contains a polyfunctional monomer as described above, the sealer of the present invention has an effect of comprehensively excellent in moisture permeability resistance, blocking resistance, color tone retention, substrate adhesion, and frost damage resistance.

  The resin emulsion used for the sealer of the present invention can be prepared by emulsion polymerization of monomer components.

  From the viewpoint of improving the adhesion of the sealer film to the base in all monomer components used as a raw material for the resin emulsion, the content of the aromatic monomer is 30% by mass or more, and the aromatic monomer The content of the monomer other than the monomer is preferably 70% by mass or less, and from the viewpoint of improving the film forming property, the content of the aromatic monomer is 70% by mass or less. The content of monomers other than the system monomers is preferably 30% by mass 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 having 7 to 18 carbon atoms such as benzyl (meth) acrylate, phenylethyl (meth) acrylate, methylbenzyl (meth) acrylate, naphthylmethyl (meth) acrylate and the like. Although (meth) acrylate etc. 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. Of these aromatic monomers, styrene is preferable from the viewpoint of improving the adhesion of the sealer film to the base.

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

  Examples of the monomer other than the aromatic monomer include an ethylenically unsaturated monomer. Examples of the ethylenically unsaturated monomer include alkyl (meth) acrylate, hydroxyl group-containing (meth) acrylate, carboxyl group-containing monomer, oxo group-containing monomer, fluorine atom-containing monomer, and nitrogen atom-containing monomer. Examples include monomers and epoxy group-containing monomers, 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 alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and sec-butyl (meth). Acrylate, 2-ethylhexyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, n-lauryl (meth) acrylate, 2- (acetoacetoxy) ethyl (meth) acrylate, etc. The alkyl group having 1 to 18 carbon atoms in the ester group may be an alkyl (meth) acrylate, 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 hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxy Examples include hydroxyl group-containing (meth) acrylates having 1 to 18 carbon atoms in the ester group such as butyl (meth) acrylate, 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 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.

  Examples of the oxo group-containing monomer include (di) ethylene glycol (methoxy) (meta) such as ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and diethylene glycol methoxy (meth) acrylate. ) Acrylate and the like, 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 fluorine atom-containing monomer include fluorine atom-containing alkyl having 2 to 6 carbon atoms in an ester group such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and octafluoropentyl (meth) acrylate. Although (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 acrylamide compounds such as (meth) acrylamide, N, N-dimethylaminopropyl acrylamide and diacetone acrylamide, and nitrogen such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate. Although an atom containing (meth) acrylate compound, N-vinylpyrrolidone, 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 monomer include epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Among the ethylenically unsaturated monomers, from the viewpoint of improving the water resistance of the coating, (meth) acrylic monomers are preferred, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, More preferred are cyclohexyl (meth) acrylate, benzyl (meth) acrylate and glycidyl (meth) acrylate.

  The emulsion particles contained in the resin emulsion may be composed of only one kind of resin prepared by one-stage emulsion polymerization, and a plurality of resin layers prepared by multi-stage emulsion polymerization of the monomer component. You may have.

  When the emulsion particles have a plurality of resin layers, a resin layer obtained by emulsion polymerization of a monomer component containing an aromatic monomer is included in any of the plurality of resin layers. However, it is preferable from the viewpoint of improving the adhesion of the sealer film to the base. This resin layer may be included in any of the plurality of resin layers, but is present in the inner layer of the emulsion particles from the viewpoint of easily forming the coating film of the sealer of the present invention. It is preferable.

  Examples of the method for emulsion polymerization of the monomer component include, for example, an aqueous medium containing a water-soluble organic solvent such as lower alcohol such as methanol and water, an emulsifier dissolved in a medium such as water, and the monomer under stirring. Examples of the method include dropping a component and a polymerization initiator, and a method of dropping a monomer component that has been pre-emulsified with an emulsifier and water into water or an aqueous medium. It is not limited. In addition, what is necessary is just to set the quantity of a medium suitably in consideration of the non volatile matter amount 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 water resistance of the coating, 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 Dai-ichi Kogyo Seiyaku Co., Ltd.], allyloxymethylalkyloxypolyoxyethylene Sulfonate salt [for example, product name: Aqualon KH-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], sulfonate salt of allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene [for example, product name: ADEKA manufactured by ADEKA Corporation Rear soap SE-10 etc.), Ryloxymethylalkoxyethylhydroxypolyoxyethylene 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, Nippon Emulsifier Co., Ltd., trade name: Antox MS-60, etc.), allyloxymethylalkoxyethylhydroxypolyoxyethylene [eg, 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.], allyloxymethylnonylphenoxyethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA Corporation, Product Name: Adekaria Soap E-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, particularly preferably from the viewpoint of improving the polymerization stability per 100 parts by mass of the monomer component. Is 3 parts by mass or more, and 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 further preferably 5 parts by mass or less, from the viewpoint of improving the water permeability of the coating. Particularly preferably, it is 4 parts by mass or less.

  Examples of the polymerization initiator include azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis ( Azo compounds such as 2-diaminopropane) hydrochloride, 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2-methylpropionamidine); persulfates such as potassium persulfate; hydrogen peroxide , Benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, peroxides such as ammonium peroxide, and the like, but the present invention is not limited to such examples. 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 0 from the viewpoint of increasing the polymerization rate and reducing the residual amount of the unreacted monomer component per 100 parts by mass of the monomer component. From the viewpoint of improving the water permeability of the coating, it is preferably 1 part by mass or less, 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 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.

  Moreover, you may add additives, such as chain transfer agents, such as a compound which has thiol groups, such as a tert- dodecyl mercaptan, a pH buffer agent, and a chelating agent, if necessary in the reaction system. 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 monomer component is not particularly limited, but is preferably an inert gas such as nitrogen gas from the viewpoint of increasing the efficiency of the polymerization initiator.

  Although the polymerization temperature at the time of carrying out emulsion polymerization of a monomer component does not have limitation, Usually, Preferably it is 50-100 degreeC, More preferably, it is 60-95 degreeC. The polymerization temperature may be constant or may be changed during the polymerization reaction.

  The polymerization time for emulsion polymerization of the 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 emulsion polymerization of the monomer component as described above, a 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 60 ° C. or higher, more preferably 70 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoint of improving blocking resistance. It is. The glass transition temperature of the polymer is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, from the viewpoint of improving the substrate adhesion. The glass transition temperature of the polymer can be easily adjusted by adjusting the composition of the monomer used for the 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 glass used for the monomer component constituting the polymer. Using the transition temperature, the formula:
1 / Tg = Σ (Wm / Tgm) / 100
[Wherein Wm represents the content (% by mass) of the monomer m in the monomer component constituting the polymer, and Tgm represents the glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m. ]
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 methyl methacrylate homopolymer, 100 ° C. for styrene homopolymer, −70 ° C. for 2-ethylhexyl acrylate homopolymer, and − for butyl acrylate homopolymer. 56 ° C., 130 ° C. for methacrylic acid homopolymer, and 95 ° C. for acrylic acid homopolymer.

  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.

  From the viewpoint of improving the storage stability of the emulsion particles, the average particle diameter of the emulsion particles is preferably 30 nm or more, more preferably 50 nm or more, still more preferably 70 nm or more, and particularly preferably 100 nm or more. From the viewpoint of improving the thickness, 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 the nonvolatile content in the resin emulsion is preferably 20% by mass or more from the viewpoint of improving the film forming property, the water permeability of the coating and the frost damage resistance, and preferably 50% from the viewpoint of improving the blocking resistance. It is at most 50% by mass, more preferably at most 50% by mass.

In the present specification, the nonvolatile content in the resin emulsion 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 in resin emulsion (mass%)]
= ([Residue mass] / [resin emulsion 1 g]) × 100
Means the value obtained based on

  The minimum film-forming temperature of the resin emulsion is preferably −10 ° C. or higher, more preferably 5 ° C. or higher, more preferably 20 ° C. or higher, from the viewpoint of increasing the film hardness, and preferably from the viewpoint of improving film formability. It is 90 ° C. or lower, more preferably 75 ° C. or lower, and further preferably 60 ° C. or lower.

  In the present specification, the minimum film-forming temperature is determined by applying a resin emulsion on a glass plate placed on a thermal gradient tester with an applicator so that the thickness is 0.2 mm, and drying the crack. It means the temperature when it occurs.

  The sealer of the present invention has one major feature in that it contains a polyfunctional monomer based on the resin emulsion. Since the sealer of this invention contains a polyfunctional monomer, it is excellent in water 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 mono (meth) acrylates of polyhydric alcohols having 4 to 8 carbon atoms in the alkyl group such as 1,4-butanediol (meth) acrylate and 1,6-hexanediol (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 neopentyl glycol di (meth) Di (meth) acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as acrylates and tripropylene glycol di (meth) acrylates, di (meth) acrylates and propylene oxides of polyethylene glycols having an addition mole number of ethylene oxide of 1 to 50 The number of moles added is 1 Di (meth) acrylate of alkylene oxide having 1 to 50 addition moles of alkylene oxide having 2 to 4 carbon atoms such as di (meth) acrylate of 50 polypropylene glycol and tripropylene glycol di (meth) acrylate; ethoxylation Glycerin tri (meth) acrylate, propylene oxide modified glycerol tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol monohydroxytri (meth) acrylate, trimethylol Tri (meth) acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as propanetriethoxytri (meth) acrylate; pentaerythritol tetra (meth) acrylate And tetra (meth) acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as ditrimethylolpropane tetra (meth) acrylate; pentaerythritol penta (meth) acrylate, dipentaerythritol (monohydroxy) penta (meth) acrylate, etc. A penta (meth) acrylate of a polyhydric alcohol having 1 to 10 carbon atoms; a hexa (meth) acrylate of a polyhydric alcohol having 1 to 10 carbon atoms such as pentaerythritol hexa (meth) acrylate; bisphenol A di (meth) acrylate, Multifunctional (meth) acrylates such as 2- (2′-vinyloxyethoxyethyl) (meth) acrylate and urethane (meth) acrylate epoxy (meth) acrylate are exemplified, but the present invention is limited only to such examples. Something There is no. 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 sealer, an alkyl (meth) acrylate having 2 to 8 alkyl groups having 2 hydroxyl groups and a polyethylene having 1 to 50 moles of ethylene oxide added Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate with 1 to 50 added moles of propylene oxide, tri (meth) acrylate of polyhydric alcohol, tetra (meth) acrylate of polyhydric alcohol, polyhydric alcohol Preferred are penta (meth) acrylate and hexa (meth) acrylate of polyhydric alcohol, 1,4-butanediol (meth) acrylate, polyethylene glycol di (meth) acrylate having 1 to 50 added moles of ethylene oxide, and ditrimethylol. Propanthe La (meth) acrylate and pentaerythritol tri (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 sealer per 100 parts by mass of the nonvolatile content of the resin emulsion, and improves the frost damage resistance. From a viewpoint, Preferably it is 150 mass parts or less, More preferably, it is 120 mass parts or less, More preferably, it is 100 mass parts or less.

  The sealer of the present invention preferably further contains a rheology control agent. When the sealer of the present invention contains a rheology control agent, excellent effects of improving the adhesion of the sealer to the base, the frost damage resistance and the water permeability of the sealer are exhibited.

  Examples of the rheology control agent include inorganic rheology control agents such as silicates such as water-soluble aluminum silicate, montmorillonite, organic montmorillonite, colloidal alumina; and cellulose derivative rheology control agents such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose. A protein rheology control agent such as casein, sodium caseinate, and ammonium caseinate; an alginate rheology control agent such as sodium alginate; a polyvinyl rheology control agent such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl-benzyl ether copolymer; Sodium acrylate, alkali-soluble poly (meth) acrylic acid- (meth) acrylic Polyacrylic rheology control agents such as acid ester copolymers; polyether rheology control agents such as pluronic polyethers, polyether dialkyl esters, polyether dialkyl ethers, polyether urethane-associated group modified products, and polyether epoxy modified products ; Maleic anhydride copolymer based rheology control agent such as partial ester of vinyl methyl ether-maleic anhydride copolymer, half ester of reaction product of drying oil fatty acid allyl alcohol ester and maleic anhydride; acetylene glycol, xanthan gum, xanthan gum However, the present invention is not limited to such examples. These rheology control agents may be used alone or in combination of two or more.

  Among the rheology control agents, from the viewpoint of imparting thixotropic viscosity to the sealer, polyacrylic acid rheology control agents are preferable, and alkali-soluble rheology control agents are more preferable. 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. These rheology control agents may be used alone or in combination of two or more.

  Of the rheology control agents, polyether rheology control agents are preferred and urethane-associated rheology control agents are more preferred from the viewpoint of imparting Newtonian viscosity to the sealer. Urethane associative rheology control agents can be easily obtained commercially, for example, Adecanol UH-420, Adecanol UH-438, Adecanol UH-450VF [above, trade name, manufactured by ADEKA Corporation] However, the present invention is not limited to such examples. These rheology control agents may be used alone or in combination of two or more.

  In view of the above, the rheology control agent suitable in the present invention includes an alkali-soluble rheology control agent and a urethane-associative rheology control agent, and these may be used alone or in combination of two or more. May be.

  The amount of the active ingredient of the rheology control agent per 100 parts by mass of the nonvolatile content of the resin emulsion is preferably 0.1 parts by mass or more from the viewpoint of improving the adhesion of the sealer to the base, the frost damage resistance and the water permeability of the sealer. More preferably, it is 0.5 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less from the viewpoint of improving the water permeability of the sealer film.

  The sealer of the present invention preferably contains a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator.

  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.

  Among the polymerization initiators, a photopolymerization initiator is preferable. When the sealer of the present invention contains a photopolymerization initiator, the blocking resistance of the sealer is improved and an inorganic building material on which a sealer film is formed can be efficiently produced.

  The amount of the polymerization 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 adhesion of the sealer to the base, the frost damage resistance and the water permeability of the sealer. 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 sealer 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 sealer 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. The pigment may be used as a pigment paste from the viewpoint of improving dispersibility in the aqueous resin composition.

  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, extender pigments are preferable from the viewpoint of economy, and among them, calcium carbonate is more preferable.

  The amount of the pigment per 100 parts by mass of the nonvolatile content of the resin emulsion is preferably 10 parts by mass or more, more preferably 40 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 sealer of the present invention can be easily prepared by mixing a resin emulsion, a polyfunctional monomer, and if necessary, a rheology control agent, a photopolymerization initiator and the like.

  The sealer of the present invention obtained as described above is generally excellent in moisture permeation resistance, blocking resistance, color tone retention, substrate adhesion and frost damage resistance, for example, inorganic materials such as ceramic building materials Useful for building material sealers.

  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 inorganic building materials include slate boards, flexible boards, calcium silicate boards, gypsum slag perlite boards, wood chip cement boards, precast concrete boards, ALC boards, gypsum boards, etc., but the present invention is limited only to such illustrations. Is not to be done.

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

  The inorganic building material of the present invention is obtained by applying a sealer to the front and back surfaces of the inorganic building material, and has a coating made of the sealer.

  Examples of the method for applying the sealer to the front and back surfaces of the inorganic building material include an application method using a brush, a bar coater, an applicator, an air spray, an airless spray, a roll coater, a flow coater, etc. It is not limited only to such illustration. The film made of the sealer can be cured by, for example, irradiating with ultraviolet rays, electron beams, or heating.

  As described above, the sealer of the present invention is generally excellent in moisture permeability, blocking resistance, color tone retention, substrate adhesion and frost damage resistance, and is preferably used for, for example, inorganic building materials. 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 mass” unless otherwise specified.

Example 1
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing 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], 850 parts of methyl methacrylate, 50 parts of 2-ethylhexyl acrylate, 80 of butyl acrylate Part, 10 parts of methacrylic acid and 10 parts of acrylic acid were added to prepare a pre-emulsion for dropping.

  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 polymerization.

  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 dropped 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 of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and 1, 1 as a polyfunctional monomer A mixed solution with 500 parts of 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) were added to the flask and left as it was. Maintained for a minute. Thereafter, the content in the flask was filtered through a 300 mesh (JIS mesh, hereinafter the same) wire mesh to obtain a sealer. The glass transition temperature of the emulsion particles contained in the obtained sealer was 70 ° C., and the nonvolatile content of the sealer was 40% by mass.

Example 2
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing 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], 850 parts of methyl methacrylate, 50 parts of 2-ethylhexyl acrylate, 80 of butyl acrylate Part, 10 parts of methacrylic acid and 10 parts of acrylic acid were added to prepare a pre-emulsion for dropping.

  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 polymerization.

  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 dropped 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, 15 parts of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and 1, 1 as a polyfunctional monomer A mixed solution of 150 parts of 4-butanediol diacrylate and 150 parts of polyethylene glycol diacrylate (addition mole number of ethylene oxide: 9), 2,2,4-trimethyl-1,3-pentanediol mono as a film forming aid 200 parts of isobutyrate [manufactured by Chisso Corporation, product number: CS-12], 700 parts of deionized water and 5 parts of defoaming agent [manufactured by San Nopco, trade name: SN deformer 777] were added to the flask. And maintained for 120 minutes. Then, the sealer was obtained by filtering the contents in a flask with a 300 mesh metal-mesh. The glass transition temperature of the emulsion particles contained in the obtained sealer was 70 ° C., and the nonvolatile content of the sealer was 40% by mass.

Example 3
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing 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], 850 parts of methyl methacrylate, 50 parts of 2-ethylhexyl acrylate, 80 of butyl acrylate Part, 10 parts of methacrylic acid and 10 parts of acrylic acid were added to prepare a pre-emulsion for dropping.

  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 polymerization.

  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 dropped 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 of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and 1, 1 as a polyfunctional monomer A mixed solution of 500 parts of 4-butanediol diacrylate and 500 parts of ditrimethylolpropane tetraacrylate, 2165 parts of deionized water, and 5 parts of a defoaming agent (manufactured by San Nopco, trade name: SN deformer 777) are placed in the flask. Added and maintained for 120 minutes. Then, the sealer was obtained by filtering the contents in a flask with a 300 mesh metal-mesh. The glass transition temperature of the emulsion particles contained in the obtained sealer was 70 ° C., and the nonvolatile content of the sealer was 40% by mass.

Example 4
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing 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], 850 parts of methyl methacrylate, 50 parts of 2-ethylhexyl acrylate, 80 of butyl acrylate Part, 10 parts of methacrylic acid and 10 parts of acrylic acid were added to prepare a pre-emulsion for dropping.

  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 polymerization.

  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 dropped 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-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and 1, 1 as a polyfunctional monomer A mixed solution with 500 parts of 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) were added to the flask and left as it was. For 25 minutes, and further 25 parts of a rheology control agent [manufactured by Nippon Shokubai Co., Ltd., trade name: Acreset WR-507, active ingredient content: 30%] was added to the flask, and the state was maintained for 30 minutes. . Then, the sealer was obtained by filtering the contents in a flask with a 300 mesh metal-mesh. The glass transition temperature of the emulsion particles contained in the obtained sealer was 70 ° C., and the nonvolatile content of the sealer was 40% by mass.

Example 5
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing 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], 490 parts of methyl methacrylate, 450 parts of styrene, 40 parts of butyl acrylate, methacryl 10 parts of acid and 10 parts of acrylic acid were added to prepare a pre-emulsion for dropping.

  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 polymerization.

  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 dropped 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 of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and 1, 1 as a polyfunctional monomer A mixed solution of 500 parts of 4-butanediol diacrylate and 500 parts of polyethylene glycol diacrylate (addition moles of ethylene oxide: 9), 2165 parts of deionized water and a defoaming agent [trade name: SN Nopco Co., Ltd. Deformer 777] 5 parts was added into the flask and maintained for 120 minutes. Then, the sealer was obtained by filtering the contents in a flask with a 300 mesh metal-mesh. The glass transition temperature of the emulsion particles contained in the obtained sealer was 92 ° C., and the nonvolatile content of the sealer was 40% by mass.

Example 6
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing 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], 680 parts of methyl methacrylate, 200 parts of 2-ethylhexyl acrylate, 100 of butyl acrylate Part, 10 parts of methacrylic acid and 10 parts of acrylic acid were added to prepare a pre-emulsion for dropping.

  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 polymerization.

  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 dropped 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-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and 1, 1 as a polyfunctional monomer A mixed solution of 250 parts of 4-butanediol diacrylate and 250 parts of ditrimethylolpropane tetraacrylate, 1260 parts of deionized water, and 5 parts of a defoaming agent (manufactured by San Nopco, trade name: SN deformer 777) are placed in the flask. Added and maintained for 120 minutes. Then, the sealer was obtained by filtering the contents in a flask with a 300 mesh metal-mesh. The glass transition temperature of the emulsion particles contained in the obtained sealer was 30 ° C., and the nonvolatile content of the sealer was 40% by mass.

Example 7
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing 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], 420 parts of methyl methacrylate, 450 parts of styrene, 110 parts of 2-ethylhexyl acrylate Then, 10 parts of methacrylic acid and 10 parts of acrylic acid were added to prepare a pre-emulsion for dropping.

  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 polymerization.

  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 dropped 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-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and 1, 1 as a polyfunctional monomer A mixed solution with 500 parts of 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) were added to the flask and left as it was. For 25 minutes, and further 25 parts of a rheology control agent [manufactured by Nippon Shokubai Co., Ltd., trade name: Acreset WR-507, active ingredient content: 30%] was added to the flask, and the state was maintained for 30 minutes. . Then, the sealer was obtained by filtering the contents in a flask with a 300 mesh metal-mesh. The glass transition temperature of the emulsion particles contained in the obtained sealer was 70 ° C., and the nonvolatile content of the sealer was 40% by mass.

Example 8
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing 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], 850 parts of methyl methacrylate, 50 parts of 2-ethylhexyl acrylate, 80 of butyl acrylate Part, 10 parts of methacrylic acid and 10 parts of acrylic acid were added to prepare a pre-emulsion for dropping.

  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 polymerization.

  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 dropped 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, a mixed solution of 25 parts of 2,2′-azobis (2-methylbutyronitrile) and 500 parts of 1,4-butanediol diacrylate as a polyfunctional monomer, deionized 1260 parts of 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. Then, the sealer was obtained by filtering the contents in a flask with a 300 mesh metal-mesh. The glass transition temperature of the emulsion particles contained in the obtained sealer was 70 ° C., and the nonvolatile content of the sealer was 40% by mass.

Example 9
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing 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, 640 parts of isobornyl acrylate, butyl acrylate 40 Part, 10 parts of methacrylic acid and 10 parts of acrylic acid were added to prepare a pre-emulsion for dropping.

  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 polymerization.

  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 dropped 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 of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and 1, 1 as a polyfunctional monomer A mixed solution of 500 parts of 4-butanediol diacrylate and 500 parts of polyethylene glycol diacrylate (addition moles of ethylene oxide: 9), 2165 parts of deionized water and a defoaming agent [trade name: SN Nopco Co., Ltd. Deformer 777] 5 parts was added into the flask and maintained for 120 minutes. Then, the sealer was obtained by filtering the contents in a flask with a 300 mesh metal-mesh. The glass transition temperature of the emulsion particles contained in the obtained sealer was 136 ° C., and the nonvolatile content of the sealer was 40% by mass.

Example 10
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing 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], 850 parts of methyl methacrylate, 50 parts of 2-ethylhexyl acrylate, 80 of butyl acrylate Part, 10 parts of methacrylic acid and 10 parts of acrylic acid were added to prepare a pre-emulsion for dropping.

  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 polymerization.

  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 dropped 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, 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 the polymerization initiator and 500 parts of 1,4-butanediol diacrylate as a polyfunctional monomer, 1260 parts of deionized water and a defoaming agent (trade name: SN deformer 777 manufactured by San Nopco) 5 A portion was added to the flask and maintained for 120 minutes. Thereafter, the content in the flask was filtered through a 300 mesh (JIS mesh, hereinafter the same) wire mesh to obtain a sealer. The glass transition temperature of the emulsion particles contained in the obtained sealer was 70 ° C., and the nonvolatile content of the sealer was 40% by mass.

Separately from the sealer, 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.), a wetting agent [Kao Co., Ltd., trade name: Emulgen LS-106] 10 parts, deionized water 210 parts, titanium oxide [Ishihara Sangyo Co., Ltd., product number: CR-97] 200 parts, calcium carbonate [Takehara Chemical Industry ( Co., Ltd., light calcium carbonate] 600 parts, talc [manufactured by Nippon Talc Co., Ltd., product number: MICROACE S-3] 200 parts, antifoaming agent [manufactured by San Nopco Co., Ltd., trade name: Nopco 8034L] and glass After mixing 200 parts of beads (diameter: 1 mm) under stirring with a disper, the mixture is aged by stirring for 60 minutes at a rotational speed of 3000 min ⁻¹ , filtered through a 100 mesh wire net, and the non-volatile content is 75% by mass. White To obtain a pigment paste. The non-volatile content in the pigment paste was determined by the same method as the non-volatile content in the resin emulsion.

Next, while stirring 125 parts of the sealer obtained above with a homodisper at a rotational speed of 1500 min ^−1, 47 parts of the pigment paste obtained above was added to the sealer to obtain a mixture. Thereafter, a cellulose derivative thickener [Daicel Chemical Industries, Ltd.] so that the viscosity is 65 ± 1 KU when measured at 25 ° C. using a Craves unit viscometer [manufactured by Brookfield, product number: KU-1]. Manufactured, product number: SP600, active ingredient content: 3%] is added to the mixture obtained above, and subsequently stirred with a homodisper at a rotational speed of 1500 mim ^-1 for 30 minutes to obtain a pigment-containing sealer. It was. In order to stabilize the sealer, it was left to stand at room temperature for 1 day before use.

Example 11
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing 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], 850 parts of methyl methacrylate, 50 parts of 2-ethylhexyl acrylate, 80 of butyl acrylate Part, 10 parts of methacrylic acid and 10 parts of acrylic acid were added to prepare a pre-emulsion for dropping.

  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 polymerization.

  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 dropped 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 the polymerization initiator and 500 parts of 1,4-butanediol diacrylate as a polyfunctional monomer, 1260 parts of deionized water and a defoaming agent (trade name: SN deformer 777 manufactured by San Nopco) 5 Part of the flask was added to the flask and maintained as it was for 120 minutes. Further, a rheology control agent [manufactured by Nippon Shokubai Co., Ltd., trade name: Acryset WR-507, active ingredient content: 30%] Was added to the inside and maintained as it was for 30 minutes. Then, the sealer was obtained by filtering the contents in a flask with a 300 mesh metal-mesh. The glass transition temperature of the emulsion particles contained in the obtained sealer was 70 ° C., and the nonvolatile content of the sealer was 40% by mass.

Next, while stirring 125 parts of the sealer obtained above with a homodisper at a rotational speed of 1500 min ^−1, 47 parts of the pigment paste prepared in the same manner as in Example 10 was added to the sealer to obtain a mixture. Obtained. Thereafter, a cellulose derivative thickener [Daicel Chemical Industries, Ltd.] so that the viscosity is 65 ± 1 KU when measured at 25 ° C. using a Craves unit viscometer [manufactured by Brookfield, product number: KU-1]. Manufactured, product number: SP600, active ingredient content: 3%] is added to the mixture obtained above, and subsequently stirred with a homodisper at a rotational speed of 1500 mim ^-1 for 30 minutes to obtain a pigment-containing sealer. It was. In order to stabilize the sealer, it was left to stand at room temperature for 1 day before use.

Comparative Example 1
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing 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], 850 parts of methyl methacrylate, 50 parts of 2-ethylhexyl acrylate, 80 of butyl acrylate Part, 10 parts of methacrylic acid and 10 parts of acrylic acid were added to prepare a pre-emulsion for dropping.

  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 polymerization.

  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 dropped 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, 500 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number: CS-12] as a film forming aid. And 5 parts of defoaming agents (manufactured by San Nopco Co., Ltd., trade name: SN deformer 777) were added to the flask and maintained as it was for 120 minutes. Then, the sealer was obtained by filtering the contents in a flask with a 300 mesh metal-mesh. The glass transition temperature of the emulsion particles contained in the obtained sealer was 70 ° C., and the nonvolatile content of the sealer was 40% by mass.

Experimental example [Preparation of test plate 1]
Each of the sealers obtained in Examples 1 to 7 and Examples 9 to 11 was aired on a ceramic base material in which a concavo-convex shape was formed on the surface with the surface temperature of the base material being 60 ° C. ± 5 ° C. A test plate was obtained by applying at a coating amount of 100 g / m ² using a spray [manufactured by Anest Iwata Co., Ltd.], leaving it to stand at room temperature for 5 minutes, and then irradiating with ultraviolet rays (500 mJ).

[Preparation of test plate 2]
Each sealer obtained in Example 8 and Comparative Example 1 was sprayed on a ceramic base material having an uneven surface formed on the surface with the surface temperature of the base material being 60 ° C. ± 5 ° C. [Anest Iwata Co., Ltd.] was applied at a coating amount of 100 g / m ^{2 and} dried with a hot air dryer at 100 ° C. for 10 minutes to obtain a test plate.

<Water resistance>
A funnel (diameter: 10 cm) is placed on the coating formed on the test plate, and the contact portion of both is sealed with a silicone-based bath bond (manufactured by Konishi Co., Ltd.) and conforms to the “funnel method” defined in JIS K5400. Then, the amount of water reduction after 24 hours was measured, and the water permeation resistance was evaluated based on the following evaluation criteria.
(Evaluation criteria)
20: 0.03mL / cm ² less than 15: 0.03mL / cm ² or more, 0.05 mL / cm ² less than 10: 0.05mL / cm ² or more, 0.08 mL / cm ² less than 5: 0.08 mL / cm ² or more, less than 0.1 mL / cm ² 0: 0.1 mL / cm ² or more

<Blocking resistance>
After preparing the test plate, it was immediately put in a 60 ° C. hot air dryer, the coated surfaces were overlapped, a load of 500 g / cm ² (about 490 kPa) was applied to the surface of the obtained laminate, and the test plate was left for 48 hours.

Next, after the test plates were cooled to room temperature, the test plates were slowly peeled off, the state of the coating was visually observed, and evaluated based on the following evaluation criteria.
(Evaluation criteria)
20: No abnormality is observed.
15: Although there is peeling resistance, no abnormality is observed in the film.
10: There is peeling resistance, and a mark remains on a part of the film.
5: There exists peeling resistance and peeling is recognized by a part of 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)
20: The color of the background is not changed and the color tone is maintained.
15: The color of the base is partially changed, but the color tone of the substrate is maintained.
10: The base color is partially changed, and the color tone of the base material is slightly changed.
5: The color of the ground has changed to spots, or the color tone of the substrate has clearly changed.
0: The color of the base is changed as a whole, and the color tone of the base material is clearly changed.

<Base material adhesion>
The coating on the test plate is cut with a cutter knife so that a 2-mm square grid is formed in 100 squares. A peel test was conducted in accordance with JIS K5400, the remaining grids were counted, and evaluated based on the following evaluation criteria.
(Evaluation criteria)
20: All remaining 15: 98 to 99 cells remaining 10: 90 to 97 cells remaining 5: 80 to 89 cells remaining 0: 79 cells remaining

<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 water at 20 ° C. 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 20: 300 cycle 15: No problem at 200 cycle, but crack occurred at 300 cycle No problem at 10: 150 cycle, but crack at 200 cycle 5: No problem at 100 cycle, 150 Cracks occur in cycle 0: Cracks occur in 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, each of the sealers obtained in each example has a film that is comprehensively excellent in moisture permeation resistance, blocking resistance, color tone retention, substrate adhesion, and frost damage resistance. It can be seen that it forms.

The sealer of the present invention is expected to be used as an aqueous one-part sealer, for example, on the front or back surface of ceramic building materials.

Claims (4)

A sealer containing a resin emulsion , wherein the resin emulsion contains emulsion particles obtained by emulsion polymerization of a monomer component containing an aromatic monomer at a content of 30 to 70% by mass. an emulsion, further contains a polyfunctional monomer and rheology control agents, and wherein the amount from 0.1 to 20 parts by mass der Rukoto active ingredients rheology control agent having a nonvolatile per 100 parts by weight of the resin emulsion Sealer to do. The sealer according to claim 1 , wherein the emulsion particles have a glass transition temperature of 60 ° C. or higher. Furthermore, the sealer of Claim 1 or 2 containing a photoinitiator. The inorganic building material in which the film which consists of the sealer in any one of Claims 1-3 is formed.