JP2020076106A - Resin emulsion for ceramic building material - Google Patents

Abstract

To provide a resin composition for a ceramic industry capable of forming a coating film excellent in water proofness, having high elongation strength while being excellent in extensibility, formed on a surface of an outer wall material such as mortar, and excellent in adhesion to a coating film deteriorated by such as an exposure to rainwater, and also to provide a resin emulsion for a ceramic building material favorably usable for the resin composition for a ceramic industry.SOLUTION: A resin emulsion for a ceramic building material includes an emulsion particle having a plurality of resin layers. A monomer component forming an outer layer of the emulsion particle is a monomer component containing an acetoacetoxy group-containing monomer at a content rate of 0.1-10 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition for a sealer for repairing cracks. More specifically, the present invention is suitably used, for example, in repairing a crack or the like caused by aged deterioration in a coating film composed of a top coat, a sealer, etc. formed on the surface of an outer wall of a building or the like. The present invention relates to a crack repair sealer, a crack repair sealer resin composition that can be suitably used for the crack repair sealer, and a method for producing the same.

  Generally, the outer wall of a building is formed of an outer wall material such as mortar, and a base material called a sealer is applied to the surface of the outer wall material. As a resin composition for a sealer excellent in frost damage resistance, water resistance of a coating film and coating film strength, it has a plurality of resin layers obtained by multistage emulsion polymerization of monomer components and has a glass transition temperature of -70 to. A resin composition for a sealer, which contains a resin emulsion containing emulsion particles at 10 ° C. and a pigment, and the amount of the pigment is 185 to 900 parts by weight per 100 parts by weight of the nonvolatile content of the resin emulsion (for example, Patent Document 1). ), A resin emulsion containing emulsion particles having a glass transition temperature of −70 to 10 ° C., a pigment and a rheology control agent are contained, and the amount of the pigment is 185 to 900 parts by weight per 100 parts by weight of the nonvolatile content of the resin emulsion. Parts, and a coating composition for a sealer in which the amount of the active ingredient of the rheology control agent is 0.01 to 5 parts by weight (for example, refer to Patent Document 2). All of the above-mentioned coating compositions for sealers are excellent in frost damage resistance, water permeability of coating films, and coating film strength, and therefore can be suitably used as sealers for outer walls of buildings.

  However, the coating film consisting of a top coat, sealer, etc., formed on the surface of the outer wall of a building is exposed to sunlight for a long period of time and is subject to temperature changes due to day and night temperature change and climate change, and further rainwater. It is deteriorated by the exposure to and becomes a coating film having fine cracks (hair cracks) or cracks on its surface (hereinafter referred to as old coating film).

  Therefore, in recent years, in order to repair cracks and the like that have occurred in old coating films, it is considered to be excellent in water resistance, excellent in extensibility and high in elongation strength, and is considered to be difficult to adhere It is desired to develop a crack repair sealer that forms a coating with excellent adhesion to old coatings such as coatings made of general paints such as paints, acrylic resin-based paints, acrylic silicone resin-based paints, etc. ..

JP, 2011-111488, A JP, 2011-111492, A

  The present invention has been made in view of the above-mentioned prior art, and has excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. An object of the present invention is to provide a crack repair sealer that forms a coating film, and a crack repair sealer resin composition that can be suitably used for the crack repair sealer.

The present invention is
(1) A resin emulsion for ceramic building materials containing emulsion particles having a plurality of resin layers, wherein the monomer component forming the outer layer of the emulsion particles contains 0.1 to 10% by mass of an acetoacetoxy group-containing monomer. A resin emulsion for ceramic building materials, which is a monomer component contained at a content rate of, and (2) an emulsion particle containing the resin emulsion for ceramic building materials and the inorganic filler according to (1) above. The resin composition for ceramic building materials is characterized in that the content of the inorganic filler in the total solid content of the inorganic filler is 80 to 95% by mass.

  According to the present invention, excellent water resistance, high elongation strength as well as excellent elongation, crack repair sealer to form a coating film excellent in adhesion with the old coating film on the surface of the outer wall material such as mortar, And a resin composition for a crack repair sealer which can be suitably used for the crack repair sealer is provided.

  The crack repair sealer resin composition of the present invention is, as described above, a sealer resin composition used for a crack repair sealer for a coating film, containing emulsion particles and an inorganic filler, and emulsion particles and The content of the inorganic filler in the total solid content of the inorganic filler is 80 to 95% by mass, and a monomer component containing an acetoacetoxy group-containing monomer is used as a raw material of the emulsion particles. And The crack repair sealer resin composition of the present invention has the above-mentioned constitutional requirements, and thus has excellent water resistance, high elongation strength as well as excellent extensibility, and an old coating film on the surface of the outer wall material such as mortar. Form a coating film with excellent adhesion.

  The resin composition for a crack repair sealer of the present invention is, for example, emulsion-polymerized with a monomer component containing an acetoacetoxy group-containing monomer, and a resin emulsion containing the obtained emulsion particles and an inorganic filler are mixed. In doing so, the content rate of the inorganic filler in the total solid content of the emulsion particles and the inorganic filler can be adjusted to 80 to 95 mass%.

  The acetoacetoxy group-containing monomer contained in the monomer component, for example, the formula (I):

(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, X ¹ and X ³ are each independently an oxygen atom, a sulfur atom or a group represented by the formula: —N (R ² ) — (R ² is A hydrogen atom or an alkyl group having 1 to 6 carbon atoms), p is 0 or 1, X ² is an alkylene group having 1 to 12 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms, and Y is a substituent. Is a good vinyl group-containing group)
Although the acetoacetoxy group-containing monomer represented by the following is mentioned, the present invention is not limited to such examples.

R ¹ has 1 to 1 carbon atoms from the viewpoint of forming a coating film having excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. It is a C6 alkyl group, Preferably it is a C1-C3 alkyl group.

X ¹ and X ^{3 each} have excellent water resistance, excellent extensibility and high elongation strength, and from the viewpoint of forming a coating film having excellent adhesion to the old coating film on the surface of the outer wall material such as mortar, Independently, it is an oxygen atom, a sulfur atom or a group represented by the formula: —N (R ² ) — (R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and p is 0 or 1. When p is 0, X ² and Y are directly bonded.

X ² has 1 to 1 carbon atoms from the viewpoint of forming a coating film having excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. It is an alkylene group having 12 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms, preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms.

  Y has a substituent from the viewpoint of forming a coating film having excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. It may be a vinyl group-containing group. Examples of the vinyl group-containing group which may have a substituent include, for example, the formula (II):

(In the formula, R ³ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkylthio group having 1 to 6 carbon atoms, R ⁴ is a hydrogen atom or a halogen atom, and q is 0 or 1.)
Examples include groups represented by, but the present invention is not limited to these examples.

R ³ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkylthio group having 1 to 6 carbon atoms. R ⁴ is a hydrogen atom or a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, but the present invention is not limited to these examples. Incidentally, in the formula (II), when q is 0, -C (R ³⁾ group and (X ³⁾ _p - is a group directly bonded.

  Among the acetoacetoxy group-containing monomers represented by the formula (I), it has excellent water resistance, excellent elongation and high elongation strength, and has excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of forming an excellent coating film, the formula (III):

(In the formula, R ⁵ is a hydrogen atom or a methyl group, and r is an integer of 1 to 4.)
The acetoacetoxy group-containing monomer represented by is preferable.

  Specific examples of the acetoacetoxy group-containing monomer include, for example, acetoacetoxymethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (meth) acrylate, allylacetoacetate. , Acetoacetamidoethyl (meth) acrylate, acetoacetic acid vinyl ether, and the like, but the present invention is not limited to these examples. These acetoacetoxy group-containing monomers may be used alone or in combination of two or more.

  Among the acetoacetoxy group-containing monomers, it forms a coating film with excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion with the old coating film on the surface of the outer wall material such as mortar. From the viewpoint, acetoacetoxyethyl (meth) acrylate and allylacetoacetate are preferable, acetoacetoxyethyl methacrylate and allylacetoacetate are more preferable, and from the viewpoint of further improving the elongation property, acetoacetoxyethyl methacrylate is further preferable.

  In addition, in this specification, "(meth) acrylate" means "acrylate" or "methacrylate", "(meth) acryl" means "acryl" or "methacryl", and "(meth) acryloyl" means Means "acryloyl" or "methacryloyl".

  The emulsion particles contained in the resin emulsion may have a single-layer resin layer prepared by one-step emulsion polymerization, or may have a plurality of resin layers prepared by multi-step emulsion polymerization. Good. Among these, the emulsion particles, having a plurality of resin layers, are excellent in water resistance, excellent in extensibility and high in elongation strength, and have good adhesion to the old coating film on the surface of the outer wall material such as mortar. It is preferable from the viewpoint of forming an excellent coating film. When the emulsion particles have a plurality of resin layers, the boundaries between the resin layers do not necessarily need to be clear, and adjacent resin layers may be mixed with each other.

  The number of resin layers constituting the emulsion particles is excellent in water resistance, excellent in extensibility and high in elongation strength, and forms a coating film excellent in adhesion with the old coating film on the surface of the outer wall material such as mortar. From the viewpoint, it is preferably 1 to 5 layers, more preferably 1 to 3 layers, further preferably 2 or 3 layers, and still more preferably 3 layers.

  When the emulsion particles have a single-layer resin layer, the emulsion particles composed of the single-layer resin layer can be prepared by using the monomer component X and emulsion-polymerizing the monomer component X.

  When the emulsion particles have a single-layer resin layer, the content of the acetoacetoxy group-containing monomer in the monomer component X has excellent water resistance, excellent extensibility and high elongation strength, and is an outer wall material such as mortar. From the viewpoint of forming a coating film having excellent adhesion to the old coating film on the surface of, the content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more. From the viewpoint of forming a coating film having excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar, preferably 10% by mass. The amount is below, more preferably 8% by mass or less, and further preferably 5% by mass or less.

  As the monomer component X, a monomer other than the acetoacetoxy group-containing monomer (hereinafter, simply referred to as “other monomer”) can be used.

  Examples of the other monomer include a nitrogen atom-containing monomer, an alkyl (meth) acrylate, a carboxyl group-containing monomer, an aromatic monomer, a hydroxyl group-containing (meth) acrylate, and a silane group-containing monomer. Examples include oxo group-containing monomers, fluorine atom-containing monomers, epoxy group-containing monomers, ultraviolet absorbing monomers, and ultraviolet stable monomers, but the present invention is limited to such examples. It is not something that will be done. These monomers may be used alone or in combination of two or more kinds. Among these other monomers, it forms a coating film having excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion with the old coating film on the surface of the outer wall material such as mortar. From the viewpoint, a nitrogen atom-containing monomer, an alkyl (meth) acrylate, a carboxyl group-containing monomer and an aromatic monomer are preferable. These monomers may be used alone or in combination of two or more kinds.

  Examples of the nitrogen atom-containing monomer include (meth) acrylamide, diacetone (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N. -N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, methylenebis (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, N, (Meth) acrylamide compounds such as N-dimethylaminopropyl (meth) acrylamide and diacetone (meth) acrylamide, nitrogen atom-containing (meth) acrylate compounds such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, N- Examples thereof include vinylpyrrolidone and (meth) acrylonitrile, but the present invention is not limited to these examples. These nitrogen atom-containing monomers may be used alone or in combination of two or more. Among these nitrogen atom-containing monomers, it forms a coating film with excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion to the old coating film on the surface of outer wall materials such as mortar. From this viewpoint, (meth) acrylamide compounds and (meth) acrylonitrile are preferable, (meth) acrylamide and acrylonitrile are more preferable, and acrylamide and acrylonitrile are further preferable.

  The content of the nitrogen atom-containing monomer in the monomer component X is excellent in water resistance, excellent in extensibility and high in elongation strength, and excellent in adhesion to the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of forming a coating film, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, which is excellent in water resistance and elongation. From the viewpoint of forming a coating film having high elongation strength and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar, preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably It is 5 mass% or less.

  In the present invention, excellent acetoacetoxy group from the viewpoint of forming a coating film having excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. It is preferable to use the containing monomer and the nitrogen atom-containing monomer in combination. In this way, when the acetoacetoxy group-containing monomer and the nitrogen atom-containing monomer are used in combination, the synergistic effect of the combined use of both is more excellent in extensibility and high in elongation strength, and is excellent for the outer wall material such as mortar. A coating film having excellent adhesion to the old coating film on the surface can be formed.

  The mass ratio of the acetoacetoxy group-containing monomer and the nitrogen atom-containing monomer (acetoacetoxy group-containing monomer / nitrogen atom-containing monomer) is excellent in water resistance, excellent in extensibility and high in elongation strength. , 10 or more, more preferably 15/85 or more, still more preferably 20/80 or more, from the viewpoint of forming a coating film having excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of forming a coating film having excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar, it is preferably 95/5. Or less, more preferably 90/10 or less, still more preferably 85/15 or less.

  In addition, the total content of the acetoacetoxy group-containing monomer and the nitrogen atom-containing monomer in the monomer component X is excellent in water resistance, excellent in extensibility and high in elongation strength, and the surface of the outer wall material such as mortar. From the viewpoint of forming a coating film having excellent adhesion to the old coating film, the content is preferably 0.2% by mass or more, more preferably 0.6% by mass or more, still more preferably 1% by mass or more, and water resistant. From the viewpoint of forming a coating film having excellent properties, high elongation strength and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar, preferably 20% by mass or less, more preferably Is 16% by mass or less, more preferably 10% by mass or less.

  Examples of alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth). Alkyl having 1 to 18 carbon atoms in the ester group such as acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, tridecyl (meth) acrylate, and n-lauryl (meth) acrylate. Examples thereof include (meth) acrylate, but the present invention is not limited to such examples. These alkyl (meth) acrylates may be used alone or in combination of two or more. Among these alkyl (meth) acrylates, a coating film having excellent water resistance, excellent extensibility and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar is formed. From the viewpoint, an alkyl (meth) acrylate in which the alkyl group has 4 to 8 carbon atoms is preferable, an alkyl (meth) acrylate in which the carbon number is 6 to 8 is more preferable, and 2-ethylhexyl (meth) acrylate is further preferable. 2-Ethylhexyl acrylate is even more preferred.

  The content of the alkyl (meth) acrylate in the monomer component X was excellent in water resistance, excellent in extensibility and high in elongation strength, and excellent in adhesion to the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of forming a coating film, it is preferably 30% by mass or more, more preferably 35% by mass or more, further preferably 40% by mass or more, and it has excellent water resistance, excellent extensibility and high elongation strength, and mortar, etc. From the viewpoint of forming a coating film having excellent adhesion to the old coating film on the surface of the outer wall material, the content is preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less.

  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 only these examples. These carboxyl group-containing monomers may be used alone or in combination of two or more kinds. Among these carboxyl group-containing monomers, it forms a coating film with excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion with the old coating film on the surface of outer wall materials such as mortar. From this viewpoint, (meth) acrylic acid is preferable, and acrylic acid is more preferable.

  The content of the carboxyl group-containing monomer in the monomer component X is excellent in water resistance, excellent in extensibility and high in elongation strength, and excellent in adhesion to the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of forming a coating film, it is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and it has excellent water resistance, excellent extensibility and high elongation strength, and mortar. From the viewpoint of forming a coating film having excellent adhesion to the old coating film on the surface of the outer wall material such as, it is preferably 8% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. ..

  Examples of the aromatic monomer include styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, styrene monomers such as vinyltoluene, aralkyl (meth) acrylate, and the like. However, the present invention is not limited to such examples. Examples of the aralkyl (meth) acrylate include aralkyl having an aralkyl group having 7 to 18 carbon atoms such as benzyl (meth) acrylate, phenylethyl (meth) acrylate, methylbenzyl (meth) acrylate, and naphthylmethyl (meth) acrylate. Examples thereof include (meth) acrylate, but the present invention is not limited to such examples. These aromatic monomers may be used alone or in combination of two or more. Among these aromatic monomers, it forms a coating film with excellent water resistance, excellent extensibility and high elongation strength, and excellent adhesion to the old coating film on the surface of outer wall materials such as mortar. From this viewpoint, styrene-based monomers are preferable, and styrene is more preferable.

  The content of the aromatic monomer in the monomer component X has excellent water resistance, excellent extensibility and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of forming a coating film, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, which is excellent in water resistance, excellent in extensibility and high in elongation strength, and mortar. From the viewpoint of forming a coating film having excellent adhesion to the old coating film on the surface of the outer wall material, the content is preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 50% by mass or less. ..

  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 thereof include hydroxyl group-containing (meth) acrylates having an ester group having 1 to 18 carbon atoms such as butyl (meth) acrylate, but the present invention is not limited to these examples. These hydroxyl group-containing (meth) acrylates may be used alone or in combination of two or more.

  Examples of the silane group-containing monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, vinyltrimethoxysilane. Examples thereof include chlorosilane, γ- (meth) acryloyloxypropylhydroxysilane, and γ- (meth) acryloyloxypropylmethylhydroxysilane, but the present invention is not limited to these examples. These silane group-containing monomers may be used alone or in combination of two or more.

  Examples of the oxo group-containing monomer include (di) ethylene glycol (methoxy) (meth), such as ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and diethylene glycol methoxy (meth) acrylate. ) Acrylate, etc., but the present invention is not limited to such examples. These oxo group-containing monomers may be used alone or in combination of two or more kinds.

  Examples of the fluorine atom-containing monomer include fluorine atom-containing alkyl having an ester group of 2 to 6 carbon atoms such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate and octafluoropentyl (meth) acrylate. Examples thereof include (meth) acrylate, but the present invention is not limited to such examples. These fluorine atom-containing 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 these examples. These epoxy group-containing monomers may be used alone or in combination of two or more kinds.

  Examples of the UV absorbing monomer include benzotriazole-based UV absorbing monomer and benzophenone-based UV absorbing monomer, but the present invention is not limited to these examples. These ultraviolet absorbing monomers may be used alone or in combination of two or more kinds.

  Examples of the benzotriazole-based ultraviolet absorbing monomer include 2- [2'-hydroxy-5 '-(meth) acryloyloxymethylphenyl] -2H-benzotriazole and 2- [2'-hydroxy-5'-. (Meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxymethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2' -Hydroxy-5 '-(meth) acryloylaminomethyl-5'-tert-octylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyloxypropylphenyl] -2H-benzo Triazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyhexylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'-(meth) acryloyloxy Ethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'. -Hydroxy-5'-tert-butyl-3 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyloxyethylphenyl] -5-chloro -2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyl Oxyethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(β- (meth) acryloyloxyethoxy) -3'-tert-butylphenyl] -4-tert -Butyl-2H-benzotriazole and the like can be mentioned, but the present invention is not limited to such examples. These benzotriazole-based UV absorbing monomers may be used alone or in combination of two or more kinds.

  Examples of the benzophenone-based UV absorbing monomer include 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone, and 2-hydroxy-4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone. Hydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone, 2-hydroxy-3-tert-butyl-4- Examples include [2- (meth) acryloyloxy] butoxybenzophenone, but the present invention is not limited to these examples. These benzophenone-based UV absorbing monomers may be used alone or in combination of two or more kinds.

  Examples of the UV stable monomer include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine and 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine. , 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano- 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-croto Noylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2 , 2,6,6-Tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2, 2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like can be mentioned, but the present invention is not limited to these examples. Absent. These UV stable monomers may be used alone or in combination of two or more kinds.

  The content of the other monomer in the monomer component X was excellent in water resistance, excellent in extensibility and high in elongation strength, and excellent in adhesion to the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of forming a coating film, preferably 90% by mass or more, more preferably 92% by mass or more, further preferably 95% by mass or more, excellent in water resistance, excellent in extensibility and high in elongation strength, mortar, etc. From the viewpoint of forming a coating film having excellent adhesion to the old coating film on the surface of the outer wall material, it is preferably 99.9% by mass or less, more preferably 99.7% by mass or less, and further preferably 99.5% by mass or less. It is not more than mass%.

  When the emulsion particles have a plurality of resin layers, the outermost layer of the emulsion particles is excellent in water resistance, excellent in elongation and high elongation strength, adhesion with the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of forming an excellent coating film, it is preferably formed of a polymer obtained by emulsion-polymerizing a monomer component. In this case, layers other than the outermost layer, for example, the inner layer when the emulsion particles are formed of two resin layers, the intermediate layer and the inner layer when the emulsion particles are formed of three resin layers A monomer of the same type as the monomer used for the monomer component can be used. Emulsion particles having a plurality of resin layers can be prepared, for example, by multistage emulsion polymerization of the monomer components under the same polymerization method and polymerization conditions as those used for emulsion polymerization of the monomer components.

  When the emulsion particles have two resin layers, an inner layer and an outer layer, the emulsion particles having the inner layer and the outer layer are emulsion-polymerized with the monomer components forming the inner layer, and the outer layer is formed in the presence of the obtained emulsion particles. It can be prepared by emulsion polymerization of the monomer component to be formed. In this case, the monomer component forming the inner layer has excellent water resistance, high elongation strength as well as excellent elongation, and a coating film excellent in adhesion with the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of formation, the aromatic monomer is preferable, and styrene is preferable. Further, the monomer component forming the outer layer has excellent water resistance, excellent elongation and high elongation strength, and forms a coating film with excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. From this viewpoint, the monomer component X is preferable.

  When the emulsion particles have two resin layers, the mass ratio of the resin layer forming the inner layer and the resin layer forming the outer layer (the resin layer forming the inner layer / the resin forming the outer layer) The layer) is preferably 5 / from the viewpoint of forming a coating film having excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. 95 or more, more preferably 10/90 or more, further preferably 15/85 or more, and from the viewpoint of improving the film-forming property and the adhesiveness, preferably 30/70 or less, more preferably 25/75 or less, further preferably Is 20/80 or less.

  When the emulsion particles have three resin layers of the inner layer, the intermediate layer and the outer layer, the emulsion particles having the three resin layers of the inner layer, the intermediate layer and the outer layer are obtained by emulsion polymerization of the monomer components forming the inner layer. Prepared by emulsion-polymerizing the monomer component forming the intermediate layer in the presence of the obtained emulsion particles, and emulsion-polymerizing the monomer component forming the outer layer in the presence of the obtained emulsion particles. be able to. In this case, the monomer component forming the inner layer has excellent water resistance, high elongation strength as well as excellent elongation, and a coating film excellent in adhesion with the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of formation, the aromatic monomer is preferable, and styrene is preferable. The monomer component forming the intermediate layer has excellent water resistance, excellent extensibility and high elongation strength, and forms a coating film having excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. From the viewpoint, 0 to 10 mass% of acetoacetoxy group-containing monomer, 60 to 90 mass% of alkyl (meth) acrylate, 1 to 25 mass% of aromatic monomer, and 0 to 5 mass% of carboxyl group-containing monomer. And preferably containing 1 to 15 mass% of the nitrogen atom-containing monomer. Further, the monomer component forming the outer layer has excellent water resistance, excellent elongation and high elongation strength, and forms a coating film with excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. From this viewpoint, the monomer component X is preferable.

  When the emulsion particles have three resin layers, it forms a coating film that has excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. From the viewpoint, the content of the resin layer forming the inner layer (first layer) is 10 to 30% by mass, and the resin forming the intermediate layer (second layer) between the inner layer and the outer layer. The content of the layer is preferably 30 to 50% by mass, and the content of the resin layer constituting the outer layer (third layer) is preferably 30 to 50% by mass.

  Emulsion particles can be prepared by emulsion-polymerizing a monomer component. As a method of emulsion-polymerizing a monomer component, for example, an aqueous medium containing a water-soluble organic solvent such as a lower alcohol such as methanol and water, an emulsifier is dissolved in a medium such as water, a single amount under heating and stirring. A method of dropping a body component and a polymerization initiator, a method of dropping a monomer component previously emulsified with an emulsifier and water into water or an aqueous medium, and the like, the present invention is only such a method. It is not limited. In addition, the amount of the medium may be appropriately set in consideration of the amount of nonvolatile components contained in the obtained resin emulsion.

  Examples of emulsifiers include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, and polymeric emulsifiers. These emulsifiers may be used alone or in combination of two or more kinds.

  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; The polyoxyethylene alkyl sulfate salt; the polyoxyethylene alkyl aryl sulfate salt; the dialkyl sulfosuccinate salt; the aryl sulfonic acid-formalin condensate; the fatty acid salts such as ammonium laurate and sodium stearate, and the like are included in the present invention. It is not limited to the examples.

  Examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, condensates of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, ethylene oxide and aliphatic compounds. Examples thereof include condensation products with amines, but the present invention is not limited to these examples.

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

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

  Examples of the polymeric emulsifier include poly (meth) acrylic acid salts such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl (meth) acrylates such as polyhydroxyethyl acrylate; Examples thereof include polymers having one or more types of monomers as copolymerization components, but the present invention is not limited to these examples.

  Reactive emulsifiers have excellent water resistance, excellent extensibility and high elongation strength, and form a coating film with excellent adhesion to the old coating film on the surface of outer wall materials such as mortar, as well as a sealer for crack repair. It can be preferably used from the viewpoint of increasing the content of the inorganic filler in the resin composition for use, and among them, the 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, polyoxyethylene alkylpropenyl phenyl ether ammonium sulfate [eg, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10, Aqualon BC-10, etc.], sulfonate salt of allyloxymethylalkyloxypolyoxyethylene [eg, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10], allyloxymethylnonylphenoxy Sulfonate salt of ethylhydroxypolyoxyethylene [eg, manufactured by ADEKA, trade name: ADEKA REASOAP SE-10, etc.], allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [eg, manufactured by ADEKA, Trade name: ADEKA rear soap SR-10, SR-30, etc.], bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salt (for example, Nippon Emulsifier Co., Ltd., trade name: Antox MS-60 etc.) , Allyloxymethylalkoxyethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA, trade name: Adecariasoap ER-20, etc.], polyoxyethylene alkylpropenyl phenyl ether [for example, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Trade name: Aqualon RN-20, etc.], allyloxymethylnonylphenoxyethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA, trade name: Adecaria Soap NE-10 etc.] and the like, but the present invention is It is not limited to such an example. Any of these reactive emulsifiers may be used alone or in combination of two or more.

  The amount of the emulsifier per 100 parts by mass of the monomer component is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, from the viewpoint of improving the polymerization stability, and the water resistance. From the viewpoint of forming a coating film having excellent adhesion, high elongation strength and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar, preferably 10 parts by mass or less, more preferably It is 8 parts by mass or less, more preferably 5 parts by mass or less.

  When polymerizing the monomer components, a polymerization initiator can be used. 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) and 2,2-azobis (2-methylpropionamidine); persulfates such as potassium persulfate and ammonium persulfate; Examples thereof include hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and peroxides such as ammonium peroxide, but the present invention is not limited to these examples. These polymerization initiators may be used alone or in combination of two or more kinds.

  The amount of the polymerization initiator per 100 parts by mass of the monomer component is preferably 0.01 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. From the viewpoint of forming a coating film having an amount of 0.03 parts by mass or more, excellent water resistance, excellent elongation properties and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar, It is preferably 1 part by mass or less, more preferably 0.5 part by mass or less.

  The method of adding the polymerization initiator is not particularly limited. Examples of the addition method include batch charging, divided charging, and continuous dropping. From the viewpoint of accelerating the end time of the polymerization reaction, a part of the polymerization initiator may be added to the flask before or after the addition of the monomer component into the reaction system.

  In order to accelerate the decomposition of the polymerization initiator, for example, a reducing agent such as sodium hydrogen sulfite, a decomposition agent for the polymerization initiator such as a transition metal salt such as ferrous sulfate is added to the reaction system in an appropriate amount. Good.

  In addition, in the reaction system, if necessary, for example, a chain transfer agent such as a compound having a thiol group such as tert-dodecyl mercaptan, a pH buffer, a chelating agent, an additive such as a film formation auxiliary is added in an appropriate amount in the flask. May be added in. The amount of the additive cannot be unconditionally determined because it varies depending on its type, but is usually 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass per 100 parts by mass of the monomer component. It is a mass part.

  The atmosphere for emulsion-polymerizing the monomer component is not particularly limited, but an inert gas such as nitrogen gas is preferable from the viewpoint of increasing the efficiency of the polymerization initiator.

  The polymerization temperature when emulsion-polymerizing the 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-polymerizing the monomer component is not particularly limited and may be appropriately set depending on the progress of the polymerization reaction, but is usually about 2 to 9 hours.

  Emulsion particles are obtained by emulsion-polymerizing the monomer components as described above.

  The polymer constituting the emulsion particles may have a crosslinked structure. The weight average molecular weight of the polymer is excellent in water resistance, high elongation strength as well as excellent elongation, from the viewpoint of forming a coating film excellent in adhesion with the old coating film on the surface of the outer wall material such as mortar, It is preferably 100,000 or more, more preferably 300,000 or more, further preferably 550,000 or more, and particularly preferably 600,000 or more. The upper limit of the weight average molecular weight of the polymer is not particularly limited, if it has a crosslinked structure, it is difficult to measure the weight average molecular weight, but if it does not have a crosslinked structure, it improves the film-forming property. From the viewpoint, it is preferably 5 million or less.

  In the present specification, the weight average molecular weight of the polymer is gel permeation chromatography [manufactured by Tosoh Corp., product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel GMHXL-L in series. ] It means the weight average molecular weight (polystyrene conversion) measured using.

  In the emulsion particles having a single resin layer, the glass transition temperature of the resin layer is preferably −70 ° C. or higher, more preferably −65 ° C. or higher, and further preferably −60 ° C., from the viewpoint of improving film forming properties. From the viewpoint of forming a coating film having excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar, it is preferably -20. C. or lower, more preferably -25.degree. C. or lower, still more preferably -30.degree. C. or lower.

  In an emulsion particle having two resin layers of an inner layer and an outer layer, the glass transition temperature of the resin layer of the inner layer is excellent in water resistance, excellent in extensibility and high in elongation strength, and on the surface of the outer wall material such as mortar. From the viewpoint of forming a coating film having excellent adhesion to the old coating film, it is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, even more preferably 90 ° C. or higher, and preferably from the viewpoint of improving film forming properties. Is 120 ° C. or lower, more preferably 115 ° C. or lower, still more preferably 110 ° C. or lower. Further, the glass transition temperature of the resin layer of the outer layer is preferably −70 ° C. or higher, more preferably −65 ° C. or higher, further preferably −60 ° C. or higher, from the viewpoint of improving film forming properties, and is excellent in water resistance. From the viewpoint of forming a coating film having excellent elongation and high elongation strength and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar, preferably -20 ° C or less, more preferably -25 ° C. C. or lower, more preferably -30.degree. C. or lower.

  In an emulsion particle having three resin layers of an inner layer, an intermediate layer and an outermost layer, a glass transition temperature of the resin layer of the inner layer is excellent in water resistance, excellent in extensibility and high in elongation strength, and an outer wall material such as mortar. From the viewpoint of forming a coating film having excellent adhesiveness with the old coating film on the surface of, the temperature is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, and further preferably 90 ° C. or higher, which improves the film-forming property. From the viewpoint, the temperature is preferably 120 ° C. or lower, more preferably 115 ° C. or lower, and further preferably 110 ° C. or lower. The glass transition temperature of the resin layer of the intermediate layer is excellent in water resistance, excellent in extensibility and high in elongation strength, and forms a film excellent in adhesion to the old film on the surface of the outer wall material such as mortar. From the viewpoint, it is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, further preferably 90 ° C. or higher, and from the viewpoint of improving the film-forming property, preferably 120 ° C. or lower, more preferably 115 ° C. or lower, further preferably It is 110 ° C or lower. Further, the glass transition temperature of the resin layer of the outer layer is preferably −70 ° C. or higher, more preferably −65 ° C. or higher, further preferably −60 ° C. or higher, from the viewpoint of improving film forming properties, and is excellent in water resistance. From the viewpoint of forming a coating film having excellent elongation and high elongation strength and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar, preferably -20 ° C or less, more preferably -25 ° C. C. or lower, more preferably -30.degree. C. or lower.

  Further, the glass transition temperature of the emulsion particles as a whole is excellent in water resistance, excellent in extensibility and high in elongation strength, and forms a coating film excellent in adhesion with the old coating film on the surface of the outer wall material such as mortar. From the viewpoint, it is preferably −70 ° C. or higher, more preferably −60 ° C. or higher, still more preferably −50 ° C. or higher, and has excellent water resistance, excellent elongation and high elongation strength, and the surface of outer wall material such as mortar From the viewpoint of forming a coating film having excellent adhesion to the old coating film, the temperature is preferably 10 ° C or lower, more preferably 5 ° C or lower, and further preferably 0 ° C or lower.

  The glass transition temperature of the emulsion particles of the resin layer constituting the emulsion particles can be easily adjusted by adjusting the type and amount of the monomer used as the monomer component.

Incidentally, in the present specification, the glass transition temperature of the resin layer constituting the emulsion particles, using the glass transition temperature of the homopolymer of the monomer used in the monomer component constituting the polymer, formula:
1 / Tg = Σ (Wm / Tgm) / 100
[In the formula, Wm represents the content rate (% 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. ]
It means the temperature determined based on the Fox equation.

  In the present specification, the glass transition temperature of the resin layer constituting the emulsion particles means the glass transition temperature obtained based on the Fox, unless otherwise specified. For example, the glass transition temperature of the entire resin layer constituting the emulsion particles having a plurality of resin layers, the mass fraction of each monomer in all the monomer components used in the multi-stage emulsion polymerization and the corresponding Means the glass transition temperature obtained from the glass transition temperature of the homopolymer of the monomer. Incidentally, for monomers whose glass transition temperature is unknown, such as special monomers and polyfunctional monomers, the total amount of monomers whose glass transition temperature is unknown in the monomer component is the mass fraction. When it is 10% by mass or less, the glass transition temperature can be determined using only the monomer whose glass transition temperature is known. When the total amount of monomers whose glass transition temperature in the monomer component is unknown exceeds 10% by mass in terms of mass fraction, the glass transition temperature of the polymer is measured by differential scanning calorimetry (DSC), differential calorimetric analysis. (DTA), thermomechanical analysis (TMA), etc.

  The glass transition temperature of the resin layer can be easily adjusted by adjusting the composition of the monomer components. The composition of the monomer component used as the raw material of the resin layer forming the emulsion particles can be determined in consideration of the glass transition temperature of the resin layer forming the emulsion particles.

  The glass transition temperature of the polymer is, for example, −70 ° C. for a homopolymer of 2-ethylhexyl acrylate, 18 ° C. for a homopolymer of acetoacetoxyethyl methacrylate, 28.3 ° C. for a homopolymer of allyl acetoacetate, and styrene of styrene. 100 ° C. for homopolymer, 95 ° C. for homopolymer of acrylic acid, 96 ° C. for homopolymer of acrylonitrile, 165 ° C. for homopolymer of acrylamide, −56 ° C. for n-butyl acrylate homopolymer, n -Butylmethacrylate homopolymer is 20 ° C, methylmethacrylate homopolymer is 105 ° C, and γ-methacryloyloxypropyltrimethoxysilane homopolymer is 70 ° C.

  When the emulsion particles are composed of a plurality of resin layers, the solubility parameter of the resin layer forming the outer layer (hereinafter, also referred to as SP value) is higher than the SP value of the resin layer forming the inner layer. A high value is preferable from the viewpoint of improving the flexibility and film-forming property of the coating film. Further, the difference (absolute value) between the SP value of the resin layer forming the inner layer and the SP value of the resin layer forming the outer layer may be large from the viewpoint of forming a layer separation structure in the emulsion particles. preferable.

  The SP value is a value defined by the regular solution theory introduced by Hildebrand and is also a measure of the solubility of a binary solution. Generally, substances having similar SP values tend to be easily mixed with each other. Therefore, the SP value is also a standard for determining the ease of mixing the solute and the solvent.

  The average particle diameter of the emulsion particles is preferably 100 nm or more, more preferably 150 nm or more, further preferably 200 nm or more, from the viewpoint of improving the mechanical stability of the emulsion particles themselves, and is excellent in water resistance and extensibility. From the viewpoint of forming a coating film having high elongation strength and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar, preferably 400 nm or less, more preferably 350 nm or less, further preferably 300 nm or less. is there.

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

  The nonvolatile content in the resin emulsion is preferably 30% by mass or more, more preferably 40% by mass or more from the viewpoint of improving productivity, and preferably 70% by mass or less, more preferably from the viewpoint of improving handleability. It is 60 mass% or less.

The nonvolatile content in the resin emulsion was calculated 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, and the resulting residue was used as the nonvolatile content.
[Nonvolatile content in resin emulsion (% by mass)]
= ([Mass of residue] ÷ [resin emulsion 1 g]) x 100
Means the value obtained based on.

  The minimum film forming temperature of the resin emulsion is preferably −20 to 50 ° C. from the viewpoint of improving the film forming property. The minimum film forming temperature of the resin emulsion can be adjusted, for example, by adjusting the glass transition temperature of the entire emulsion particles or the glass transition temperature of the outermost resin layer.

  In addition, in the present specification, the minimum film-forming temperature of the resin emulsion is determined by applying the resin emulsion onto a glass plate placed on a thermal gradient tester with an applicator so that the thickness becomes 0.2 mm, and cracks are generated. It means the temperature at which it occurs.

  The resin composition for a crack repair sealer of the present invention contains an inorganic filler. In the present invention, the content of the inorganic filler in the total solid content of the emulsion particles and the inorganic filler is 80 to 95% by mass, and a monomer component containing an acetoacetoxy group-containing monomer as a raw material of the emulsion particles. Has one major feature.

  The crack repair sealer resin composition of the present invention, since the monomer component containing the acetoacetoxy group-containing monomer is used as a raw material of the emulsion particles, the total solid content of the emulsion particles and the inorganic filler. Despite having an inorganic filler content of 80 to 95% by mass, it has excellent water resistance, excellent extensibility and high elongation strength, and adheres well to the old coating film on the surface of the outer wall material such as mortar. A coating film having excellent properties can be formed.

  Examples of the inorganic filler include alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate; alkaline earth metal carbonates such as magnesium carbonate, calcium carbonate and barium carbonate; ammonium carbonate and hydrogen carbonate. Carbonates such as ammonium carbonate salts such as ammonium, zinc oxide particles, aluminum oxide particles, magnesium oxide particles, beryllium oxide particles, calcium oxide particles, zirconium oxide particles, alumina particles, titanium dioxide particles, silica particles, magnesium hydroxide particles, Aluminum hydroxide particles, calcium silicate particles, aluminum silicate particles, silicon carbide particles, silicon nitride particles, boron nitride particles, calcium sulfate particles, barium sulfate particles, magnesium carbonate particles, glass particles, kaolin, talc, mica powder, metal particles, Although carbon black and the like can be mentioned, the present invention is not limited to such examples. These may be used alone or in combination of two or more. Among these inorganic fillers, from the viewpoint of forming a coating film having excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion with the old coating film on the surface of the outer wall material such as mortar. , Carbonates are preferred, alkali metal carbonates and alkaline earth metal carbonates are more preferred, sodium carbonate, sodium hydrogen carbonate and calcium carbonate are even more preferred, and calcium carbonate is even more preferred.

  The carbonate content in the inorganic filler forms a coating film that has excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. From the viewpoint, it is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and the upper limit value is 100% by mass.

  Examples of the shape of the inorganic filler include a spherical shape, a fibrous shape, a scaly shape, a conical shape, a crushed shape, a flat shape, and an irregular shape, but the present invention is not limited to such examples.

  The average particle size of the inorganic filler is excellent in water resistance, has excellent elongation and high elongation strength, and from the viewpoint of forming a coating film excellent in adhesion with the old coating film on the surface of the outer wall material such as mortar. , Preferably 0.3 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, which is excellent in water resistance, excellent in extensibility and high in elongation strength, and is an old coating on the surface of outer wall material such as mortar. From the viewpoint of forming a coating film having excellent adhesion to the film, the thickness is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 50 μm or less.

  The average particle diameter of the inorganic filler means the volume average particle diameter measured using a laser diffraction / scattering particle size distribution analyzer [Beckman Coulter, Inc., product number: LS13320].

  The amount of the inorganic filler per 100 parts by mass of the nonvolatile content of the resin emulsion is preferably 400 parts by mass or more, more preferably 500 parts by mass or more, and further preferably 600, from the viewpoint of improving coating film strength and economic efficiency. A coating amount of not less than 100 parts by mass, more preferably not less than 700 parts by mass, which is excellent in water resistance, excellent in extensibility and high in elongation strength, and excellent in adhesion to the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of forming a film, it is preferably 1900 parts by mass or less.

  The content of the inorganic filler in the total solid content of the emulsion particles and the inorganic filler is excellent in water resistance, excellent in extensibility and high in elongation strength, and adheres to the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of forming an excellent coating film, the content is 80% by mass or more, the water resistance is excellent, the extensibility is excellent and the elongation strength is high, and the adhesion with the old coating film on the surface of the outer wall material such as mortar is excellent. From the viewpoint of forming an excellent coating film, it is 95 mass% or less, preferably 94 mass% or less, more preferably 93 mass% or less.

In the present specification, the content of the inorganic filler in the total solid content of the emulsion particles and the inorganic filler is represented by the formula:
[Content (mass%) of inorganic filler in total solid content of emulsion particles and inorganic filler]
= [(Inorganic filler) / (solid content of resin emulsion + inorganic filler)] x 100
Means the value obtained based on.

  Further, the content of the emulsion particles in the total solid content of the emulsion particles and the inorganic filler is excellent in water resistance, has excellent elongation and high elongation strength, and adheres to the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of forming a coating film having excellent properties, it is 5% by mass or more, preferably 6% by mass or more, more preferably 7% by mass or more, and has excellent water resistance, excellent extensibility and high elongation strength, and mortar. From the viewpoint of forming a coating film having excellent adhesion with the old coating film on the surface of the outer wall material such as 20% by mass or less.

  The resin composition for a crack repair sealer of the present invention can be easily prepared, for example, by mixing the resin emulsion containing the emulsion particles, the inorganic filler, and optionally a crosslinking agent. The order of mixing these components is arbitrary, and, for example, these components may be mixed together.

  As the crosslinking agent, for example, melamine-based crosslinking agent, oxazoline-based crosslinking agent, acrylamide-based crosslinking agent, polyamide-based crosslinking agent, epoxy-based crosslinking agent, isocyanate-based crosslinking agent, aziridine-based crosslinking agent, titanate-based crosslinking agent, urea-based crosslinking agent Agents, alkyl alcohol urea cross-linking agents, hydrazine compounds, carbodiimide compounds, zirconium compounds, zinc compounds, titanium compounds, polyvalent metal compounds such as aluminum compounds, and the like, the present invention is limited only to such examples Not a thing. These crosslinking agents may be used alone or in combination of two or more kinds. The amount of the cross-linking agent is preferably set appropriately according to the type of the cross-linking agent and the like.

  Among these cross-linking agents, excellent water resistance, high elongation strength with excellent extensibility, from the viewpoint of forming a coating film excellent in adhesion with the old coating film on the surface of the outer wall material such as mortar, Oxazoline crosslinking agents and hydrazine compounds are preferred.

  Examples of the oxazoline-based crosslinking agent include 2,2′-bis (2-oxazoline), 1,2-bis (2-oxazolin-2-yl) ethane, and 1,4-bis (2-oxazolin-2-yl). ) Butane, 1,8-bis (2-oxazolin-2-yl) butane, 1,4-bis (2-oxazolin-2-yl) cyclohexane, 1,2-bis (2-oxazolin-2-yl) benzene , 1,3-bis (2-oxazolin-2-yl) benzene, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2 -Isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like can be mentioned, but the present invention is limited only to such examples. Not a thing. These oxazoline-based crosslinking agents may be used alone or in combination of two or more kinds. The oxazoline-based cross-linking agent can be easily obtained commercially, and for example, manufactured by Nippon Shokubai Co., Ltd., trade names: Epocros WS-500, Epocros WS-700, Epocros K-2010, Epocros K-. 2020, Epocros K-2030 and the like, but the present invention is not limited to these examples.

  Examples of the hydrazine compound include adipic acid dihydrazide and a polymer having a dihydrazide group, but the present invention is not limited to such examples. These compounds may be used alone or in combination of two or more kinds.

  Incidentally, the content of nonvolatile components in the resin composition for crack repair sealer of the present invention is excellent in water resistance, high elongation strength as well as excellent in extensibility, with the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of forming a coating film having excellent adhesion, it is preferably 40% by mass or more, more preferably 50% by mass or more, and from the viewpoint of improving handleability, preferably 80% by mass or less, more preferably 70% by mass. % Or less.

  The sealer of the present invention contains the resin composition for a crack repair sealer, and may contain only the resin composition for a crack repair sealer, and further contains an additive. Good.

  Examples of the additives include coloring agents such as pigments, leveling agents, ultraviolet absorbers, ultraviolet stabilizers, antioxidants, polymerization inhibitors, fillers, coupling agents, rust preventives, antibacterial agents, metal deactivating agents. Agents, wetting agents, defoaming agents, surfactants, reinforcing agents, plasticizers, lubricants, antifogging agents, anticorrosion agents, pigment dispersants, flow control agents, peroxide decomposing agents, template decolorizing agents, fluorescent enhancing agents. Whitening agent, organic flameproofing agent, inorganic flameproofing agent, anti-dripping agent, melt flow modifier, antistatic agent, antialgal agent, antifungal agent, flame retardant, slip agent, metal chelating agent, antiblocking agent, Heat resistance stabilizer, processing stabilizer, dispersant, thickener, rheology control agent, foaming agent, anti-aging agent, antiseptic agent, antistatic agent, silane coupling agent, antioxidant, film forming aid, etc. However, the present invention is not limited to such examples. These additives may be used alone or in combination of two or more.

  Since the amount of the additive varies depending on the type of the additive and cannot be determined unconditionally, it is preferable to appropriately determine the amount of the additive according to the type of the additive.

  The content of non-volatile components in the sealer of the present invention is excellent in water resistance, excellent in extensibility and high in elongation strength, and a coating film excellent in adhesion with the old coating film on the surface of the outer wall material such as mortar. Is preferably 40% by mass or more, more preferably 50% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, from the viewpoint of improving handleability.

  The crack repair sealer of the present invention obtained as described above has excellent water resistance, excellent elongation and high elongation strength, and excellent adhesion to the old coating film on the surface of the outer wall material such as mortar. Since the coating film is formed, it can be suitably used, for example, when repairing exterior building materials that form the outer wall of a building.

  Examples of the building material for the exterior include metal base materials, resin base materials, and inorganic base materials. Examples of the metal base material include an aluminum plate, an iron plate, an aluminum zinc plated steel plate, a stainless steel plate, and a tin plate. Examples of the resin base material include an acrylic resin plate, a vinyl chloride resin plate, a polycarbonate plate, an ABS resin plate, a polyester plate, a polyethylene plate, and a polypropylene plate. Examples of the inorganic base material include ceramic building materials and glass base materials described in JIS A5422, JIS A5430 and the like. Examples of ceramic building materials include roof tiles and outer wall materials. Ceramic building materials are obtained by adding an inorganic filler, a fibrous material, etc. to a hydraulic glue that is a raw material for an inorganic cured product, molding the resulting mixture, curing the resulting molded product, and curing it. Be done. Examples of the inorganic base material that constitutes the exterior of the building include mortar boards, flexible boards, calcium silicate boards, gypsum slag perlite boards, wood chip cement boards, precast concrete boards, ALC boards, and gypsum boards. The invention is not limited to only these examples.

  As the paint used as a raw material for the old coating film formed on the surface of the outer layer base material, for example, a general solvent-based resin paint such as a fluororesin-based paint, an acrylic resin-based paint, or an acrylic silicon resin-based paint. However, the present invention is not limited to such examples.

  Among the old paint films, the old paint film made of fluororesin paint has a small surface polarity and is inferior in wettability and interaction with organic compounds, so a new paint film is generally formed on the old paint film. It is believed that it is difficult to make them adhere to each other. From this, the fact that the newly formed coating film on the old coating film has excellent adhesion to the old coating film made of the fluororesin coating material means that the newly formed coating film is only the fluororesin coating material. In addition, it is considered that the adhesiveness to the old coating film formed from a general coating material such as acrylic resin coating material or acrylic silicone resin coating material is excellent.

  On the other hand, the crack repair sealer of the present invention is excellent in adhesion to an old coating film made of a paint such as a fluororesin-based paint which is considered to be difficult to adhere, and further has a water resistance. It is made of not only fluororesin-based paint but also general paints such as acrylic resin-based paint and acrylic silicone resin-based paint other than fluororesin-based paint because it has excellent elongation and high elongation strength. It can be suitably used when repairing cracks and the like in the old coating film.

  The crack repair sealer of the present invention may be applied by only one layer, or may be applied by overcoating so as to form a coating film of two or more layers. When multiple coatings are formed so that a coating film of two or more layers is formed, only a part of the coating film may be formed by the crack repair sealer of the present invention, and all coating films are crack repaired of the present invention. You may form with a sealer.

  Examples of the method for forming a coating film using the crack repair sealer of the present invention include dip coating, brush coating, roll brush coating, spray coating, roll coating, spin coating, dip coating, bar coating, flow coating, and static coating. Examples of the coating method include electrocoating, die coating, and trowel coating, but the present invention is not limited to such examples.

  The coating film formed using the crack repair sealer of the present invention may be dried at room temperature, or may be dried by heating. Since the crack repair sealer of the present invention can be dried at room temperature, it is possible to improve workability in the field of repairing cracks and the like formed in the old coating film.

  Further, the thickness of the coating film formed by using the crack repair sealer of the present invention has excellent water resistance, high elongation strength as well as excellent extensibility, and the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of forming a coating film having excellent adhesion, it is usually preferably about 10 to 1000 μm.

The amount of the base coating for repair applied to the base material cannot be determined unconditionally because it varies depending on the type of the base material, etc., but it has excellent water resistance, excellent extensibility, and high elongation strength. From the viewpoint of forming a coating film having excellent adhesion to the old coating film on the surface of the material, it is generally preferable that the nonvolatile content is about ²⁰ to 1000 g / m ² .

  As described above, the old coating film on the surface of the outer wall material such as mortar can be repaired.

  Next, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the following examples, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

Production example Deionized water 367.9 parts, dispersant [San Nopco Ltd., trade name: Nopcos Perth 44C] 12.5 parts, calcium carbonate [heavy calcium carbonate, Nitto Koka Kogyo Co., Ltd., product number: NS # 100] 500 parts, calcium carbonate [heavy calcium carbonate, manufactured by Nitto Koka Kogyo KK, product number: SS # 80] 500 parts, antifoaming agent [manufactured by San Nopco KK, trade name: Nopco 8034L] 5. Aging was performed by stirring 6 parts of 0 parts and a thickening agent (manufactured by Daicel Chemical Industries, Ltd., product number: SP-850) diluted to 3% at 3000 min ^{-1 for} 30 minutes to obtain 100 mesh (JIS. The mixture was filtered through a metal mesh (mesh, the same below) to obtain a calcium carbonate paste having a nonvolatile content of 70% by mass. The nonvolatile content in the calcium carbonate paste was determined by the same method as the nonvolatile content in the resin emulsion.

Example 1
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 2-ethylhexyl acrylate 72.0 parts, acetoacetoxyethyl methacrylate 1.0 part, styrene 20.0 parts, acrylic acid 3.0 parts and acrylonitrile 4.0 parts were charged to prepare a dropping pre-emulsion.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 Then, 4 parts was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% ammonium persulfate aqueous solution and 6.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Then, 25% ammonia water was added, pH [measured by Horiba, Ltd., product number: F-23, measured at 23 ° C., and so on] was adjusted to 9.0 to terminate the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was -40.8 ° C. The average particle size of the emulsion particles was 220 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the production example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 80% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Example 2
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 2-ethylhexyl acrylate 60.0 parts, acetoacetoxyethyl methacrylate 1.0 part, styrene 32.0 parts, acrylic acid 3.0 parts and acrylonitrile 4.0 parts were prepared to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 Then, 4 parts was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% ammonium persulfate aqueous solution and 6.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Then, 25% ammonia water was added to adjust the pH to 9.0 and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of all the emulsion particles contained in the resin emulsion obtained above was −25.3 ° C. The average particle size of the emulsion particles was 220 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the production example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 80% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Example 3
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 2-ethylhexyl acrylate 46.0 parts, acetoacetoxyethyl methacrylate 1.0 part, styrene 46.0 parts, acrylic acid 3.0 parts and acrylonitrile 4.0 parts were prepared to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 Then, 4 parts was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% ammonium persulfate aqueous solution and 6.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Then, 25% ammonia water was added to adjust the pH to 9.0 and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was -4.4 ° C. The average particle size of the emulsion particles was 220 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the production example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 80% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Example 4
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: Adecaria Soap SR-10] as an emulsifier. , 5 parts of 2-ethylhexyl acrylate, 5.0 parts of acetoacetoxyethyl methacrylate, 31.0 parts of styrene, 3.0 parts of acrylic acid and 4.0 parts of acrylonitrile were charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 Then, 4 parts was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% ammonium persulfate aqueous solution and 6.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Then, 25% ammonia water was added to adjust the pH to 9.0 and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was −23.1 ° C. The average particle size of the emulsion particles was 220 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the production example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 80% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Example 5
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 5 parts of 2-ethylhexyl acrylate, 5.0 parts of acetoacetoxyethyl methacrylate, 34.0 parts of styrene, 3.0 parts of acrylic acid and 1.0 part of acrylonitrile were charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 Then, 4 parts was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% ammonium persulfate aqueous solution and 6.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Then, 25% ammonia water was added to adjust the pH to 9.0 and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was −23.0 ° C. The average particle size of the emulsion particles was 220 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the production example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 80% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Example 6
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 2-ethylhexyl acrylate 68.0 parts, acetoacetoxyethyl methacrylate 5.0 parts, styrene 20.0 parts, acrylic acid 3.0 parts and acrylamide 4.0 parts were charged to prepare a dropping pre-emulsion.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 Then, 4 parts was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% ammonium persulfate aqueous solution and 6.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Then, 25% ammonia water was added to adjust the pH to 9.0 and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was −36.6 ° C. The average particle size of the emulsion particles was 220 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the production example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 80% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Example 7
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 2-ethylhexyl acrylate 60.0 parts, acetoacetoxyethyl methacrylate 1.0 parts, styrene 36.0 parts and acrylic acid 3.0 parts were charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 Then, 4 parts was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% ammonium persulfate aqueous solution and 6.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Then, 25% ammonia water was added to adjust the pH to 9.0 and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of all the emulsion particles contained in the resin emulsion obtained above was −25.3 ° C. The average particle size of the emulsion particles was 220 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the production example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 80% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Example 8
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 2-ethylhexyl acrylate 60.0 parts, allyl acetoacetate 1.0 part, styrene 32.0 parts, acrylic acid 3.0 parts and acrylonitrile 4.0 parts were charged to prepare a dropping pre-emulsion.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 Then, 4 parts was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% ammonium persulfate aqueous solution and 6.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Then, 25% ammonia water was added to adjust the pH to 9.0 and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of all the emulsion particles contained in the resin emulsion obtained above was −25.3 ° C. The average particle size of the emulsion particles was 220 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the production example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 80% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Example 9
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  6.9 parts of deionized water in a dropping funnel, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester [manufactured by ADEKA, trade name: Adecaria Soap SR-10] as an emulsifier. Then, 20.0 parts of styrene was charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 4 parts was added to the flask to initiate the polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 30.1 parts of deionized water, 12.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier, A second pre-emulsion consisting of 70.0 parts of 2-ethylhexyl acrylate, 1.0 part of acetoacetoxyethyl methacrylate, 2.0 parts of styrene, 3.0 parts of acrylic acid and 4.0 parts of acrylonitrile, 3.5% excess. 2.9 parts of an ammonium sulfate aqueous solution and 2.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 90 minutes. After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was -38.4 ° C. The average particle size of the emulsion particles was 250 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the Production Example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 90% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Example 10
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  6.9 parts of deionized water in a dropping funnel, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester [manufactured by ADEKA, trade name: Adecaria Soap SR-10] as an emulsifier. Then, 20.0 parts of styrene was charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 4 parts was added to the flask to initiate the polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 30.1 parts of deionized water, 12.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier, A second stage pre-emulsion consisting of 66.0 parts of 2-ethylhexyl acrylate, 5.0 parts of acetoacetoxyethyl methacrylate, 2.0 parts of styrene, 3.0 parts of acrylic acid and 4.0 parts of acrylonitrile, 3.5% excess. 2.9 parts of an ammonium sulfate aqueous solution and 2.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 90 minutes. After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was −35.1 ° C. The average particle size of the emulsion particles was 250 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the Production Example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 90% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Example 11
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  6.9 parts of deionized water in a dropping funnel, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester [manufactured by ADEKA, trade name: Adecaria Soap SR-10] as an emulsifier. Then, 20.0 parts of styrene was charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 4 parts was added to the flask to initiate the polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 30.1 parts of deionized water, 12.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier, A second stage pre-emulsion consisting of 60.0 parts of 2-ethylhexyl acrylate, 1.0 part of acetoacetoxyethyl methacrylate, 12.0 parts of styrene, 3.0 parts of acrylic acid and 4.0 parts of acrylonitrile, 3.5% excess. 2.9 parts of an ammonium sulfate aqueous solution and 2.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 90 minutes. After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of all the emulsion particles contained in the resin emulsion obtained above was −25.3 ° C. The average particle size of the emulsion particles was 250 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the Production Example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 90% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Example 12
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  6.9 parts of deionized water in a dropping funnel, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester [manufactured by ADEKA, trade name: Adecaria Soap SR-10] as an emulsifier. And 15.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 4 parts was added to the flask to initiate the polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 30.1 parts of deionized water, 12.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier, A second stage pre-emulsion consisting of 65.0 parts of 2-ethylhexyl acrylate, 1.0 part of acetoacetoxyethyl methacrylate, 12.0 parts of styrene, 3.0 parts of acrylic acid, 2.0 parts of acrylonitrile and 2.0 parts of acrylamide. , 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was -31.6 ° C. The average particle size of the emulsion particles was 250 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the Production Example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 92% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of a silicone antifoaming agent (manufactured by San Nopco Ltd., trade name: SN deformer 777) so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickener diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Example 13
39.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  6.9 parts of deionized water in a dropping funnel, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester [manufactured by ADEKA, trade name: Adecaria Soap SR-10] as an emulsifier. Then, 20.0 parts of styrene was charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 4 parts was added to the flask to initiate the polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Then, 15.0 parts of deionized water, 6.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASORP SR-10] as an emulsifier, A second stage pre-emulsion consisting of 26.0 parts of 2-ethylhexyl acrylate, 11.5 parts of styrene, 0.5 part of acrylic acid and 2.0 parts of acrylonitrile, 2.9 parts of a 3.5% ammonium persulfate aqueous solution and 2. 2.0 parts of 5% aqueous sodium hydrogen sulfite solution was added dropwise into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Next, 15.0 parts of deionized water and 6.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 2 ethylhexyl acrylate 26.0 parts, acetoacetoxyethyl methacrylate 1.0 part, styrene 8.5 parts, acrylic acid 2.5 parts and acrylonitrile 2.0 parts, 3rd stage pre-emulsion, 3.5% 2.9 parts of ammonium persulfate aqueous solution and 2.0 parts of 2.5% sodium bisulfite aqueous solution were dropped into the flask over 90 minutes. After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was -13.8 ° C. The average particle size of the emulsion particles was 250 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the production example is adjusted so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above is 92% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Comparative Example 1
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 2-ethylhexyl acrylate 68.0 parts, styrene 27.0 parts, acrylic acid 3.0 parts and acrylonitrile 2.0 parts were charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 Then, 4 parts was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% ammonium persulfate aqueous solution and 6.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Then, 25% ammonia water was added to adjust the pH to 9.0 and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was −35.4 ° C. The average particle size of the emulsion particles was 250 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the production example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 80% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Comparative example 2
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 2-ethylhexyl acrylate 68.0 parts, styrene 29.0 parts and acrylic acid 3.0 parts were charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 Then, 4 parts was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% ammonium persulfate aqueous solution and 6.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Then, 25% ammonia water was added to adjust the pH to 9.0 and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was −35.4 ° C. The average particle size of the emulsion particles was 250 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the production example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 80% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Comparative Example 3
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 2-ethylhexyl acrylate 68.0 parts, styrene 29.0 parts and acrylic acid 3.0 parts were charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 Then, 4 parts was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% ammonium persulfate aqueous solution and 6.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Then, 25% ammonia water was added to adjust the pH to 9.0 and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was −35.4 ° C. The average particle size of the emulsion particles was 250 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the production example is adjusted so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above is 50% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Comparative Example 4
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 2-ethylhexyl acrylate 68.0 parts, styrene 29.0 parts and acrylic acid 3.0 parts were charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 Then, 4 parts was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% ammonium persulfate aqueous solution and 6.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Then, 25% ammonia water was added to adjust the pH to 9.0 and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was −35.4 ° C. The average particle size of the emulsion particles was 250 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

After adding an appropriate amount of dilution water and an appropriate amount of a silicone antifoaming agent (manufactured by San Nopco Ltd., trade name: SN deformer 777) to the mixture obtained above so that the nonvolatile content becomes 45% by mass, BM -Type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at a rotation speed of 30 min ^-1 at a viscosity of 15000 mPa · s at a viscosity of 15,000 mPa · s thickening agent [manufactured by Daicel Chemical Industries, Ltd., product number: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Comparative Example 5
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 2-ethylhexyl acrylate 68.0 parts, styrene 29.0 parts and acrylic acid 3.0 parts were charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 Then, 4 parts was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% ammonium persulfate aqueous solution and 6.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Then, 25% ammonia water was added to adjust the pH to 9.0 and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was −35.4 ° C. The average particle size of the emulsion particles was 250 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the production example was adjusted so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 70% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Comparative Example 6
43.0 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 2-ethylhexyl acrylate 68.0 parts, styrene 29.0 parts and acrylic acid 3.0 parts were charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1% by mass of the total amount of the monomer components was added to the flask and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 Then, 4 parts was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% ammonium persulfate aqueous solution and 6.0 parts of a 2.5% sodium hydrogen sulfite aqueous solution were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Then, 25% ammonia water was added to adjust the pH to 9.0 and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was −35.4 ° C. The average particle size of the emulsion particles was 250 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above at 1000 min ⁻¹ with a homodisper, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [JNC ( Co., Ltd., product number: CS-12] was added to the resin emulsion so that the film-forming temperature was 0 ° C. to obtain a mixture.

The calcium carbonate paste obtained in the Production Example was prepared so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and the calcium carbonate paste contained in the resin emulsion obtained above was 98% by mass. After adding to the mixture obtained in step 1, and further adding an appropriate amount of dilution water and an appropriate amount of silicone antifoaming agent [San Nopco Ltd., trade name: SN deformer 777] so that the nonvolatile content becomes 60% by mass. , A BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.], a thickening agent diluted by 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ becomes 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., No .: SP-850] was added, and the mixture was stirred at a rotation speed of 1000 min ⁻¹ for 15 minutes to obtain a resin composition for a sealer for crack repair.

Experimental Example As the physical properties of the resin composition for a sealer for repairing cracks obtained in each Example or each Comparative Example, water resistance, elongation, elongation strength and adhesion were examined based on the following methods. The results are shown in Table 1.

〔water resistant〕
The resin composition for a sealer for crack repair obtained in each Example or each Comparative Example was applied to a flexible board (manufactured by Nippon Test Panel Co., Ltd.) so that the thickness after drying was 0.5 mm, and the temperature was A test plate was obtained by drying by allowing to stand for 14 days in an atmosphere having a relative humidity of 50% at 23 ° C. A funnel (diameter: 10 cm) was placed on the coating film formed on the obtained test plate, and the contact portion between the two was sealed with a silicone-based bath bond (manufactured by Konishi Co., Ltd.). The amount of water reduction after 24 hours was measured according to the "Method", and the water resistance was evaluated based on the following evaluation criteria.

(Evaluation criteria)
50 points: less than 0.3 mL / cm ² 30 points: 0.3 mL / cm ² or more, less than 0.5 mL / cm ² 10 points: 0.5 mL / cm ² or more, less than 1.0 mL / cm ² 0 points: 1 0.0mL / cm ² or more (failed)

[Elongation and elongation strength]
A release paper is laid on a metal plate, and the crack-repair sealer resin composition obtained in each Example or each Comparative Example is applied on the release paper so that the thickness after drying becomes 0.5 mm. After releasing by standing for 7 days in an atmosphere having a temperature of 23 ° C. and a relative humidity of 50%, the formed coating film is peeled off, and the peeled coating film is turned upside down to release paper. The sample was dried by allowing it to stand for another 7 days to obtain a test piece.

  Next, this test piece was punched out into a dumbbell-shaped No. 2 shape specified in 4.1 of JIS K6251 and the release paper was removed to obtain a test piece. The obtained test piece was attached so that the chuck-to-chuck distance of the tensile tester was 60 mm, and a tensile load was applied at a tensile speed of 200 mm / min until the test piece broke, and the elongation rate of the test piece at rupture Then, the maximum tensile load was obtained, and the extensibility and the elongation strength were evaluated based on the following evaluation criteria.

(1) Evaluation criteria for elongation 50 points: elongation rate is 50% or more 30 points: elongation rate is 30% or more, less than 50% 10 points: elongation rate is 10% or more, less than 30% 0 point: elongation rate is 10 Less than% (fail)

(2) elongation strength criteria 50 points: maximum tensile load 2.0 N / mm ² or more 30 points: maximum tensile load 1.5 N / mm ² or more, 2.0 N / mm ² less than 10 points: Maximum tensile load There 1.0 N / mm ² or more, 1.5 N / mm ² less than 0 point: maximum tensile load is less than 1.0 N / mm ² (failed)

[Adhesion]
A cross-cut test was conducted in accordance with JIS K5600-5-6.
(1) Preparation of Resin Emulsion 796 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introducing tube, a thermometer and a reflux cooling tube. In a dropping funnel, 417 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10], an emulsifier [made by ADEKA Co., Ltd., trade name: ADEKA REASOAP SR-10] 60 parts, 2-ethylhexyl acrylate 270 parts, n-butyl acrylate 100 parts, n-butyl methacrylate 100 parts, methyl methacrylate 500 parts, hydroxyethyl methacrylate 10 parts, γ-methacryloyloxypropyltrimethoxysilane 10 parts and A dropping pre-emulsion consisting of 10 parts of acrylic acid was prepared, and 77 parts, which was 5% of the total amount of all the monomer components, was added to the flask, and the temperature was raised to 70 ° C. while slowly blowing nitrogen gas. % Aqueous solution of ammonium persulfate was added to initiate polymerization. Then, the rest of the dropping pre-emulsion, 30 parts of a 5% ammonium persulfate aqueous solution and 20 parts of a 5% sodium bisulfite aqueous solution were uniformly added dropwise into the flask over 240 minutes.

  After the dropping was completed, the content in the flask was maintained at 70 ° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. The obtained reaction solution was cooled to room temperature and then filtered through a 300-mesh wire net to prepare a resin emulsion. The content of nonvolatile components in this resin emulsion was 43%, and the glass transition temperature of the resin constituting the emulsion particles contained in the resin emulsion was 9 ° C.

(2) Preparation of coating material for evaluation 210 parts of deionized water, 60 parts of dispersant [manufactured by Kao Corporation, trade name: DEMOL EP], dispersant [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: DISCOAT N] -14] 50 parts, wetting agent [manufactured by Kao Corporation, trade name: Emulgen LS-106] 10 parts, propylene glycol 60 parts, titanium oxide [manufactured by Ishihara Sangyo Co., Ltd., product number: CR-95] 1000 parts and A white paste was prepared by dispersing 200 parts of glass beads (diameter: 1 mm) with a homodisper at a rotation speed of 3000 min ^{−1 for} 60 minutes.

Next, 100 parts of the resin emulsion obtained above was added with 5 parts of butyl cellosolve as a film forming aid and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by JNC Corporation, product number: CS -12] 5 parts were added, 21.5 parts of water and 0.5 part of 25% ammonia water were further added, and the mixture was stirred for 30 minutes with a homodisper at a rotation speed of 1500 min ^-1 , and then the white color obtained above was obtained. 30 parts of the paste and 0.5 parts of an antifoaming agent (manufactured by San Nopco Ltd., trade name: Nopco 8034L) were added, and the mixture was added at 25 ° C. using a Krebs unit viscometer [manufactured by Brookfield, product number: KU-1]. A thickening agent [manufactured by Nippon Shokubai Co., Ltd., trade name: Acreset WR-503A] was added so that the viscosity when measured was 61 KU, and the coating material for evaluation was prepared by stirring for 30 minutes in that state. did.

(3) Preparation of test piece for evaluation Next, the coating film of the base material coated with the fluororesin-based coating was exposed to the outdoors to deteriorate, and the coating film in which cracks were generated on the surface of the coating film was the old coating film. The resin composition for a sealer for crack repair obtained in each Example or each Comparative Example was applied on the coating film so that the thickness after drying was 500 g / m ^2, and the temperature was 23 ° C. After drying by allowing to stand for 2 days in an atmosphere with relative humidity of 50%, the coating composition for evaluation obtained above is further applied so that the thickness after drying is 100 g / m ^2, and the temperature is Was allowed to stand for 2 days in an atmosphere having a relative humidity of 23 ° C. and a relative humidity of 50% to obtain a test piece for evaluation.

(4) Cross-cutting test After making a 25-cut (vertical: 5 squares, horizontal: 5 squares) cut in a 2 mm square grid pattern with a sharp blade in the coating film of the evaluation test piece obtained above, According to JIS Z1522, a cellophane adhesive tape having a width of 25 mm was rubbed with a finger so that the cellophane adhesive tape was closely adhered in a grid pattern, allowed to stand in the atmosphere at 25 ° C. for 5 minutes, and then peeled off. The number of peeled squares was counted from the 25 squares prepared, and the adhesion was evaluated based on the following evaluation criteria.

(Evaluation criteria)
50 points: The number of peeled grids is 0 40 points: The number of peeled grids is 1 to 4 30 points: The number of peeled grids is 5 to 9 20: The number of peeled grids is 10 to 19 0 points: 20 or more peeled cells (failed)

〔Comprehensive evaluation〕
A total evaluation (maximum of 200 points) was performed by summing the evaluation scores in each test item. A resin composition for a sealer for repairing cracks, which has even one 0-point evaluation in the physical property evaluation, fails.

  From the results shown in Table 1, all of the resin compositions for crack repair sealers obtained in each Example have excellent water resistance, excellent elongation and high elongation strength, and thus it is difficult to adhere them. It can be seen that a coating film excellent in adhesion with the old coating film made of a fluororesin-based coating, which is considered to be present, is formed.

Claims (2)

  A resin emulsion for ceramic building materials containing emulsion particles having a plurality of resin layers, wherein the monomer component forming the outer layer of the emulsion particles contains an acetoacetoxy group-containing monomer in an amount of 0.1 to 10% by mass. A resin emulsion for ceramic building materials, which is a monomer component contained in 1.   The ceramics building material resin emulsion according to claim 1 and an inorganic filler are contained, and the content of the inorganic filler in the total solid content of the emulsion particles and the inorganic filler is 80 to 95% by mass. Resin composition for building materials.