JP2017179067A - Resin composition for sealer for crack repair - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealer for crack repair excellent in water resistance and forming a coated film excellent in extensibility and high in elongation strength, formed on a surface of an exterior wall material such as mortar, and excellent in adhesiveness with a coated film deteriorated by exposure to rain water or the like, and a resin composition for the sealer for crack repair capable of being suitably used for the a sealer for crack repair.SOLUTION: There is provided a resin composition for a sealer used for a sealer for repairing cracks of a coated film, containing emulsion particles and an inorganic filler, having percentage content of the inorganic filler in total solid components of the emulsion particles and the inorganic filler of 80 to 95 mass% and using a monomer component containing an acetoacetoxy group-containing monomer as a raw material of the emulsion particles.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition for a sealer for crack repair. More specifically, for example, the present invention is suitably used for repairing cracks or the like caused by aging deterioration in a coating film made of a top coat, a sealer, or the like formed on the surface of an outer wall of a building or the like. The present invention relates to a crack repair sealer that can be used, a resin composition for a crack repair sealer 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 that is excellent in frost damage resistance, water permeability of a coating film and coating film strength, it has a plurality of resin layers formed by multi-stage emulsion polymerization of monomer components, and has a glass transition temperature of −70 to A resin composition for a sealer containing a resin emulsion containing emulsion particles at 10 ° C. and a pigment, and the amount of the pigment per 100 parts by weight of the nonvolatile content of the resin emulsion is 185 to 900 parts by weight (for example, Patent Document 1) See), a resin emulsion containing emulsion particles having a glass transition temperature of −70 to 10 ° C., a pigment and a rheology control agent, and the amount of the pigment per 100 parts by weight of the nonvolatile content of the resin emulsion is 185 to 900 wt. Part of the rheology control agent in an amount of 0.01 to 5 parts by weight of an active ingredient (for example, patent document) 2 reference), and the like have been proposed. The sealer coating composition is excellent in frost damage resistance, water permeability of the coating film and coating film strength, and thus can be suitably used as a sealer for the outer wall of a building.

  However, the topcoat, sealer, and other coatings formed on the outer wall surface of buildings are exposed to sunlight for a long period of time, and are subject to temperature changes due to daytime and nighttime temperature changes and climate change. It becomes a coating film (hereinafter referred to as an old coating film) in which fine cracks (hair cracks) or cracks are generated on the surface.

  Therefore, in recent years, in order to repair cracks and the like occurring in the old paint film, it is excellent in water resistance, extensibility and high elongation strength, and is considered to be difficult to adhere. Development of crack repair sealers that form coatings with excellent adhesion to old coatings such as coatings made of common paints such as paints, acrylic resin paints, and acrylic silicon resin paints is desired. .

JP 2011-111488 A JP 2011-111492 A

  The present invention has been made in view of the prior art, and has excellent water resistance, excellent elongation, high elongation strength, and excellent adhesion to an old coating film on the surface of an outer wall material such as mortar. It is an object of the present invention 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
(1) A resin composition for a sealer used in a sealer for repairing cracks in a coating film, which contains emulsion particles and an inorganic filler, and the content of the inorganic filler in the total solid content of the emulsion particles and the inorganic filler Is a resin composition for a sealer for repairing cracks, wherein a monomer component containing an acetoacetoxy group-containing monomer is used as a raw material for emulsion particles,
(2) A method for producing a resin composition for a sealer used in a sealer for repairing cracks in a coating film, wherein the emulsion is obtained by emulsion polymerization of a monomer component containing an acetoacetoxy group-containing monomer When mixing a resin emulsion containing particles and an inorganic filler, the content of the inorganic filler in the total solid content of the emulsion particles and the inorganic filler is adjusted to 80 to 95% by mass for repairing cracks The manufacturing method of the resin composition for sealers, and (3) It is related with the crack repair sealer characterized by including the resin composition for crack repair sealers as described in said (1).

  According to the present invention, a sealer for repairing a crack that forms a coating film excellent in water resistance, excellent in stretchability and high in tensile strength, and excellent in adhesion to the old coating film on the surface of the outer wall material such as mortar, The present invention also provides a resin composition for a crack repair sealer that can be suitably used for the crack repair sealer.

  As described above, the resin composition for a crack repair sealer according to the present invention is a resin composition for a sealer used for a sealer for repairing a crack in a coating film, and contains emulsion particles and an inorganic filler. 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 for the emulsion particles. And Since the resin composition for a sealer for repairing cracks of the present invention has the above-described constituent requirements, it is excellent in water resistance, excellent in stretchability and high in extension strength, and with an old coating film on the surface of an outer wall material such as mortar. Forms a coating film with excellent adhesion.

  The resin composition for a sealer for repairing cracks according to the present invention is obtained by, for example, subjecting a monomer component containing an acetoacetoxy group-containing monomer to emulsion polymerization and mixing the resulting resin emulsion containing emulsion particles and an inorganic filler. In doing so, the content of the inorganic filler in the total solid content of the emulsion particles and the inorganic filler can be adjusted to 80 to 95% by mass.

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

Wherein 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 has a substituent. A good vinyl group-containing group)
Although the acetoacetoxy group containing monomer represented by these is mentioned, this invention is not limited only to this illustration.

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, R ¹ has 1 to 1 carbon atoms. 6 alkyl group, preferably an alkyl group having 1 to 3 carbon atoms.

X ¹ and X ³ are excellent in water resistance, extensibility and high elongation strength, respectively, 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. 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 is excellent in water resistance, extensibility 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, 12 alkylene group or a C3-C12 cycloalkylene group, Preferably it is a C1-C8 alkylene group, More preferably, it is a C1-C4 alkylene group.

  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, formula (II):

(Wherein R ³ represents 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 represents a hydrogen atom or a halogen atom, and q represents 0 or 1)
Although the group etc. which are represented by these are mentioned, this invention is not limited only to this illustration.

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 only to such illustration. In the formula (II), when q is 0, the —C (R ³ ) group and the (X ³ ) _p — group are directly bonded.

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

(Wherein R ⁵ represents a hydrogen atom or a methyl group, and r represents an integer of 1 to 4)
An acetoacetoxy group-containing monomer represented by

  Specific examples of the acetoacetoxy group-containing monomer include, for example, acetoacetoxymethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (meth) acrylate, allyl acetoacetate , Acetoacetamidoethyl (meth) acrylate, acetoacetate vinyl ether, and the like are mentioned, but the present invention is not limited to such 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, high elongation strength, and excellent adhesion to the old coating film on the surface of outer wall materials such as mortar. From the viewpoint, acetoacetoxyethyl (meth) acrylate and allyl acetoacetate are preferable, acetoacetoxyethyl methacrylate and allyl acetoacetate are more preferable, and acetoacetoxyethyl methacrylate is more preferable from the viewpoint of further improving elongation.

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

  The emulsion particles contained in the resin emulsion may have a single-layer resin layer prepared by one-stage emulsion polymerization or a plurality of resin layers prepared by multi-stage emulsion polymerization. Also good. Among these, the emulsion particles having a plurality of resin layers are excellent in water resistance, extensibility and high elongation strength, and have good adhesion to the old coating film on the surface of the outer wall material such as mortar. This is preferable from the viewpoint of forming an excellent coating film. When the emulsion particles have a plurality of resin layers, the boundary between the resin layers is not necessarily 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, extensibility 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 the viewpoint, it is preferably 1 to 5 layers, more preferably 1 to 3 layers, still more preferably 2 or 3 layers, and still more preferably 3 layers.

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

  When the emulsion particles have a single resin layer, the content of the acetoacetoxy group-containing monomer in the monomer component X is excellent in water resistance, extensibility, high elongation strength, and outer wall materials such as mortar From the viewpoint of forming a coating film excellent in adhesion to the old coating film on the surface of the film, 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 Hereinafter, it is 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 other monomers include nitrogen atom-containing monomers, alkyl (meth) acrylates, carboxyl group-containing monomers, aromatic monomers, hydroxyl group-containing (meth) acrylates, and silane group-containing monomers. , Oxo group-containing monomers, fluorine atom-containing monomers, epoxy group-containing monomers, UV-absorbing monomers, UV-stable monomers, etc., but the present invention is limited to such examples only. Is not to be done. These monomers may be used alone or in combination of two or more. Among these other monomers, it forms a coating film that has excellent water resistance, extensibility, high elongation strength, and excellent adhesion to the old coating film on the surface of outer wall materials such as mortar. From the viewpoint, nitrogen atom-containing monomers, alkyl (meth) acrylates, carboxyl group-containing monomers and aromatic monomers are preferred. These monomers may be used alone or in combination of two or more.

  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, N -N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, methylenebis (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, (meth) acrylamide compounds such as diacetone (meth) acrylamide, nitrogen such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Child-containing (meth) acrylate compounds, N- vinylpyrrolidone, but like (meth) acrylonitrile, the present invention is not limited only to those exemplified. These nitrogen atom-containing monomers may be used alone or in combination of two or more. Among these nitrogen atom-containing monomers, it has excellent water resistance, excellent elongation and high elongation strength, and forms a coating with excellent adhesion to the old coating on the surface of outer wall materials such as mortar. (Meth) acrylamide compounds and (meth) acrylonitrile are preferable, (meth) acrylamide and acrylonitrile are more preferable, and acrylamide and acrylonitrile are more preferable.

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

  In the present invention, 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, an acetoacetoxy group It is preferable to use the containing monomer and the nitrogen atom-containing monomer in combination. As described above, 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 of them leads to excellent elongation and high elongation strength. A coating film excellent in adhesiveness with the old coating film on the surface can be formed.

  Mass ratio of acetoacetoxy group-containing monomer and nitrogen atom-containing monomer (acetoacetoxy group-containing monomer / nitrogen atom-containing monomer) is excellent in water resistance, extensibility and high elongation strength 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 10/90 or more, more preferably 15/85 or more, and further preferably 20/80 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 95/5 Hereinafter, it is more preferably 90/10 or less, and still more preferably 85/15 or less.

  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, extensibility and high elongation strength, and the surface of the outer wall material such as mortar. From the viewpoint of forming a coating film excellent in adhesion with the above old coating film, it is preferably 0.2% by mass or more, more preferably 0.6% by mass or more, and further preferably 1% by mass or more. From the viewpoint of forming a coating film excellent in adhesion, 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% by mass or less, more preferably Is 16% by mass or less, more preferably 10% by mass or less.

  Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and sec-butyl (meth). Alkyl having 1 to 18 carbon atoms in an ester group such as acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, tridecyl (meth) acrylate, n-lauryl (meth) acrylate Although (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These alkyl (meth) acrylates may be used alone or in combination of two or more. Among these alkyl (meth) acrylates, it forms excellent coatings with excellent water resistance, excellent stretchability, high elongation strength, and excellent adhesion to old coatings on the surface of outer wall materials such as mortar. From the viewpoint, an alkyl (meth) acrylate having 4 to 8 carbon atoms in the alkyl group is preferable, an alkyl (meth) acrylate having 6 to 8 carbon atoms is more preferable, and 2-ethylhexyl (meth) acrylate is more preferable. 2-ethylhexyl acrylate is even more preferred.

  The content of the alkyl (meth) acrylate in the monomer component X is excellent in water resistance, 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 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more, excellent in water resistance, extensibility and high elongation strength, mortar, etc. From the viewpoint of forming a coating film excellent in adhesion with the old coating film on the surface of the outer wall material, it 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 such examples. These carboxyl group-containing monomers may be used alone or in combination of two or more. Among these carboxyl group-containing monomers, excellent water resistance, extensibility and high elongation strength, forming a coating film with excellent adhesion to the old coating film on the surface of outer wall materials such as mortar (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, extensibility and high elongation strength, and excellent adhesion to the old paint film on the surface of the outer wall material such as mortar. From the viewpoint of forming a coated film, it is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more, excellent in water resistance, extensibility and high elongation strength. 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, 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 monomers such as styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, and vinyltoluene, and aralkyl (meth) acrylate. However, the present invention is not limited to such examples. Examples of the aralkyl (meth) acrylate include aralkyl having 7 to 18 carbon atoms such as benzyl (meth) acrylate, phenylethyl (meth) acrylate, methylbenzyl (meth) acrylate, naphthylmethyl (meth) acrylate and the like. Although (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These aromatic monomers may be used alone or in combination of two or more. Among these aromatic monomers, it has excellent water resistance, excellent elongation, high elongation strength, and excellent adhesion to the old coating on the surface of outer wall materials such as mortar. In view of the above, a styrene monomer is preferable, and styrene is more preferable.

  The content of the aromatic monomer in the monomer component X is excellent in water resistance, extensibility and high elongation strength, and excellent adhesion to the old paint film on the surface of the outer wall material such as mortar. From the viewpoint of forming a coated film, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, excellent in water resistance, extensibility and high elongation strength. 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, 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 include hydroxyl group-containing (meth) acrylates having 1 to 18 carbon atoms in the ester group such as butyl (meth) acrylate, but the present invention is not limited to such examples. These 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, vinyltri Examples include chlorosilane, γ- (meth) acryloyloxypropylhydroxysilane, and γ- (meth) acryloyloxypropylmethylhydroxysilane, but the present invention is not limited to such 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) (meta) such as ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and diethylene glycol methoxy (meth) acrylate. ) Acrylate and the like, but the present invention is not limited to such examples. These oxo group-containing monomers may be used alone or in combination of two or more.

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

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

  Examples of the benzotriazole-based UV-absorbing monomer include 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -2H-benzotriazole, 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) acryloyloxyhex Ruphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 ′ -Tert-butyl-5 '-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-tert-butyl-3'-(meth) acryloyloxyethyl Phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meta ) Acrylyloxyethylphenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydride Xyl-5 ′-(meth) acryloyloxyethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(β- (meth) acryloyloxyethoxy) -3′- tert-butylphenyl] -4-tert-butyl-2H-benzotriazole and the like, 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.

  Examples of the benzophenone-based UV-absorbing monomer include 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone, 2- 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 such examples. These benzophenone-based ultraviolet absorbing monomers may be used alone or in combination of two or more.

  Examples of UV-stable monomers include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine. 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) 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-sia -4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano- Examples include 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like. However, the present invention is not limited to such examples. These ultraviolet stable monomers may be used alone or in combination of two or more.

  The content of other monomers in the monomer component X is excellent in water resistance, extensibility and high elongation strength, and excellent adhesion to the old paint film on the surface of the outer wall material such as mortar. From the viewpoint of forming a coating film, it is preferably 90% by mass or more, more preferably 92% by mass or more, and still more preferably 95% by mass or more, excellent in water resistance, extensibility, high elongation strength, mortar, etc. From the viewpoint of forming a coating film excellent in adhesion with 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%. It is below mass%.

  When the emulsion particles have a plurality of resin layers, the outermost layer of the emulsion particles has excellent water resistance, extensibility and high elongation strength, and 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, it is preferably formed of a polymer obtained by emulsion polymerization of a monomer component. In this case, layers other than the outermost layer, for example, when the emulsion particles are formed of two resin layers, the inner layer, and when the emulsion particles are formed of three resin layers, the intermediate layer and the inner layer are The same kind of monomer as that used for the monomer component can be used. Emulsion particles having a plurality of resin layers can be prepared, for example, by subjecting the monomer component to multistage emulsion polymerization under the same polymerization method and polymerization conditions as in the case of emulsion polymerization of the monomer component.

  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 obtained by emulsion polymerization of monomer components forming the inner layer, and the outer layer in the presence of the obtained emulsion particles. The monomer component to be formed can be prepared by emulsion polymerization. In this case, the monomer component forming the inner layer is excellent in water resistance, excellent in elongation and high in tensile strength, and has excellent adhesion to the old coating on the surface of the outer wall material such as mortar. From the viewpoint of formation, it is preferably composed of an aromatic monomer, and preferably composed of styrene. In addition, the monomer component that forms the outer layer has excellent water resistance, extensibility and high elongation strength, and forms a coating film with excellent adhesion to the old coating film on the surface of outer wall materials such as mortar. From this point of view, the monomer component X is preferable.

  When the emulsion particles have two resin layers, the mass ratio between the resin layer constituting the inner layer and the resin layer constituting the outer layer (resin constituting the inner layer / resin constituting 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, more preferably 15/85 or more, and from the viewpoint of improving the film forming property and adhesion, preferably 30/70 or less, more preferably 25/75 or less, and further preferably Is 20/80 or less.

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

  When the emulsion particles have three resin layers, they form a coating film with excellent water resistance, excellent elongation, high elongation strength, and excellent adhesion to the old coating film on the surface of outer wall materials such as mortar. The content of the resin layer constituting the inner layer (first layer) is 10 to 30% by mass, and the resin constituting the intermediate layer (second layer) between the inner layer and the outer layer It is preferable that the content rate of a layer is 30-50 mass%, and the content rate of the resin layer which comprises the outer layer (3rd layer) is 30-50 mass%.

  Emulsion particles can be prepared by emulsion polymerization of monomer components. As a method for emulsion polymerization of the monomer component, for example, an aqueous medium containing a water-soluble organic solvent such as methanol and a lower alcohol, and water, an emulsifier is dissolved in a medium such as water, and a single amount is obtained 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. It is not limited. In addition, what is necessary is just to set the quantity of a medium suitably in consideration of the non volatile matter amount contained in the resin emulsion obtained.

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

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

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

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

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

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

  Reactive emulsifiers are excellent in water resistance, extensibility and high elongation strength, and form a coating with excellent adhesion to the old coating on the surface of outer wall materials such as mortar, as well as a crack repair sealer. From the viewpoint of increasing the content of the inorganic filler in the resin composition for use, a non-nonylphenyl emulsifier is preferable from the viewpoint of environmental protection.

  Examples of the reactive emulsifier include propenyl-alkylsulfosuccinic acid ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, polyoxyethylene alkylpropenyl phenyl ether ammonium sulfate [for example, trade name: manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Aqualon HS-10, Aqualon BC-10, etc.], sulfonate salts of allyloxymethylalkyloxypolyoxyethylene (for example, Dairon Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.), allyloxymethylnonylphenoxy Sulphonate salt of ethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA, trade name: Adekaria soap SE-10, etc.], allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate salt [for example, (strain Made by ADEKA, trade names: Adekari Soap SR-10, SR-30, etc.], bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salt [for example, manufactured by Nippon Emulsifier Co., Ltd., trade name: Antox MS- 60, etc.], allyloxymethylalkoxyethylhydroxypolyoxyethylene [for example, manufactured by ADEKA, trade name: Adekaria soap ER-20, etc.], polyoxyethylene alkylpropenyl phenyl ether [for example, Daiichi Kogyo Seiyaku Co., Ltd. Product name: Aqualon RN-20, etc.], allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene [for example, product made by ADEKA, product name: Adecalia Soap NE-10, etc.] The invention is limited to only such examples No. 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, and further preferably 3 parts by mass or more from the viewpoint of improving the polymerization stability. 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 mortar, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, more preferably 5 parts by mass or less.

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

  The amount of the polymerization initiator 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 that is 0.03 parts by mass or more, excellent in water resistance, excellent in stretchability and high in extension strength, and excellent in adhesion with the old coating film on the surface of the outer wall material such as mortar. Preferably it is 1 mass part or less, More preferably, it is 0.5 mass part or less.

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

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

  In addition, in the reaction system, for example, an appropriate amount of additives such as a chain transfer agent such as a compound having a thiol group such as tert-dodecyl mercaptan, a pH buffering agent, a chelating agent, and a film forming aid may be appropriately added to the flask. May be added. Since the amount of the additive varies depending on the type, it cannot be determined unconditionally, but is usually preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts per 100 parts by mass of the monomer component. Part by mass.

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

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

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

  Emulsion particles are obtained by emulsion polymerization of the monomer component 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, extensibility and high elongation strength, 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 it is 100,000 or more, More preferably, it is 300,000 or more, More preferably, it is 550,000 or more, Most preferably, it is 600,000 or more. The upper limit of the weight average molecular weight of the polymer is not particularly limited because it is difficult to measure the weight average molecular weight when it has a cross-linked structure, but when it does not have a cross-linked structure, the film-forming property is improved. From the viewpoint, it is preferably 5 million or less.

  In addition, in this specification, the weight average molecular weight of a polymer uses gel permeation chromatography [manufactured by Tosoh Corporation, product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel GMHXL-L in series. ] Is used to mean the weight average molecular weight (in terms of polystyrene) measured.

  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 the film forming property. From the viewpoint of forming a coating film excellent in water resistance, excellent in stretchability and high in tensile strength, and excellent in adhesion with the old coating film on the surface of the outer wall material such as mortar, preferably -20. C. or lower, more preferably −25 ° C. or lower, and further preferably −30 ° C. or lower.

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

  In emulsion particles having three resin layers of inner layer, intermediate layer and outermost layer, the glass transition temperature of the inner resin layer is excellent in water resistance, extensibility and high elongation strength, and outer wall materials such as mortar From the viewpoint of forming a coating film excellent in adhesiveness with the old coating film on the surface of the film, it is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, and further preferably 90 ° C. or higher to improve the film forming property. From the viewpoint, it 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, extensibility 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 the viewpoint, it is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, and still more preferably 90 ° C. or higher. It is 110 degrees C or less. In addition, the glass transition temperature of the outer resin layer is preferably −70 ° C. or higher, more preferably −65 ° C. or higher, and further preferably −60 ° C. or higher from the viewpoint of improving the film forming property, and has excellent 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, it is preferably -20 ° C or lower, more preferably -25. ° C or lower, more preferably -30 ° C or lower.

  In addition, the glass transition temperature of the emulsion particles as a whole is excellent in water resistance, extensibility 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 the viewpoint, it is preferably −70 ° C. or higher, more preferably −60 ° C. or higher, and further preferably −50 ° C. or higher. Excellent water resistance, excellent extensibility and high elongation strength, and surface of outer wall material such as mortar From the viewpoint of forming a coating film excellent in adhesion with the above old coating film, it is preferably 10 ° C. or less, more preferably 5 ° C. or less, and further preferably 0 ° C. or less.

  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 for the monomer component.

In the present specification, the glass transition temperature of the resin layer constituting the emulsion particles is determined by using the glass transition temperature of the monomer homopolymer used in the monomer component constituting the polymer, formula:
1 / Tg = Σ (Wm / Tgm) / 100
[Wherein Wm represents the content (% by mass) of the monomer m in the monomer component constituting the polymer, and Tgm represents the glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m. ]
The temperature calculated | required based on the Formula of Fox (Fox) represented by these.

  In this specification, unless otherwise indicated, the glass transition temperature of the resin layer which comprises emulsion particles means the glass transition temperature calculated | required based on the said Fox (Fox). For example, the glass transition temperature of the entire resin layer constituting the emulsion particles having a plurality of resin layers corresponds to the mass fraction of each monomer in all monomer components used in the multistage emulsion polymerization. It means the glass transition temperature determined from the glass transition temperature of the homopolymer of the monomer. For monomers with unknown glass transition temperature, such as special monomers and polyfunctional monomers, the total amount of monomers with unknown glass transition temperature in the monomer component is the mass fraction. If 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 with unknown glass transition temperature in the monomer component exceeds 10% by mass, the glass transition temperature of the polymer is determined by differential scanning calorimetry (DSC) or differential calorimetry. (DTA), thermomechanical analysis (TMA), etc.

  The glass transition temperature of the resin layer can be easily adjusted by adjusting the composition of the monomer component. In consideration of the glass transition temperature of the resin layer constituting the emulsion particles, the composition of the monomer component used as a raw material for the resin layer constituting the emulsion particles can be determined.

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

  In addition, when the emulsion particles are composed of a plurality of resin layers, the solubility parameter (hereinafter also referred to as SP value) of the resin layer constituting the outer layer is larger than the SP value of the resin layer constituting the inner layer. High is preferable from the viewpoint of improving the flexibility and film-forming property of the coating film. Also, the difference (absolute value) between the SP value of the resin layer constituting the inner layer and the resin layer constituting the outer layer is 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 the binary solution. In general, substances having similar SP values tend to be mixed with each other. Therefore, the SP value is also a measure for judging the ease of mixing of 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, and further preferably 200 nm or more from the viewpoint of improving the mechanical stability of the emulsion particles themselves, and has excellent water resistance and extensibility. In addition, from the viewpoint of forming a coating film having high elongation strength and excellent adhesion with 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, and further preferably 300 nm or less. is there.

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

  The 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. 60% by mass or less.

The amount of non-volatile content in the resin emulsion was determined by weighing 1 g of the resin emulsion and drying it with a hot air dryer at a temperature of 110 ° C. for 1 hour.
[Non-volatile content in resin emulsion (mass%)]
= ([Residue mass] / [resin emulsion 1 g]) × 100
Means the value obtained based on

  Moreover, 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 this specification, the minimum film-forming temperature of the resin emulsion is such that the resin emulsion is applied on a glass plate placed on a thermal gradient tester with an applicator so that the thickness is 0.2 mm, and cracks are not generated. It means the temperature when it occurs.

  The resin composition for a sealer for crack repair 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 for the emulsion particles There is one major feature in that is used.

  The resin composition for a sealer for repairing cracks according to the present invention uses a monomer component containing an acetoacetoxy group-containing monomer as a raw material for emulsion particles, so that the total solid content of emulsion particles and inorganic fillers is used. Despite the inorganic filler content of 80 to 95% by mass, it has excellent water resistance, extensibility and high elongation strength, and adheres to the old paint film on the surface of the outer wall material such as mortar. A coating film excellent in 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 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, but and carbon black, the present invention is not limited only to those exemplified. These may be used alone or in combination of two or more. Among these inorganic fillers, from the viewpoint of forming 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 the outer wall material such as mortar. Carbonates are preferred, alkali metal carbonates and alkaline earth metal carbonates are more preferred, sodium carbonate, sodium bicarbonate and calcium carbonate are more preferred, and calcium carbonate is even more preferred.

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

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

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

  In addition, the average particle diameter of an inorganic filler means the volume average particle diameter measured using the laser diffraction scattering method particle size distribution measuring apparatus [Beckman Coulter company make, 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 still more preferably 600 from the viewpoint of improving the coating film strength and improving the economic efficiency. More than mass parts, more preferably 700 parts by mass or more, excellent water resistance, excellent elongation, 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 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, extensibility and high elongation strength, and adhesion to the old paint film on the surface of the outer wall material such as mortar. From the viewpoint of forming an excellent coating film, it is 80% by mass or more, excellent in water resistance, extensibility and high elongation strength, and adherence 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, it is 95% by mass or less, preferably 94% by mass or less, more preferably 93% by 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 expressed by the formula:
[Content of inorganic filler (% by mass) in the total solid content of emulsion particles and inorganic filler]
= [(Inorganic filler) / (Solid content of resin emulsion + Inorganic filler)] × 100
Means the value obtained based on

  In addition, the content of the emulsion particles in the total solid content of the emulsion particles and the inorganic filler is excellent in water resistance, extensibility and high elongation strength, and adheres to the old paint 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, excellent in water resistance, extensibility and high elongation strength. From the viewpoint of forming a coating film excellent in adhesion to the old coating film on the surface of the outer wall material such as, the content is 20% by mass or less.

  The resin composition for a sealer for repairing cracks according to the present invention can be easily prepared by, for example, mixing a resin emulsion containing the emulsion particles, the inorganic filler, and a crosslinking agent if necessary. The order of mixing these components is arbitrary, and for example, these components may be mixed together.

  Examples of the crosslinking agent include melamine crosslinking agent, oxazoline crosslinking agent, acrylamide crosslinking agent, polyamide crosslinking agent, epoxy crosslinking agent, isocyanate crosslinking agent, aziridine crosslinking agent, titanate crosslinking agent, urea crosslinking. Agents, alkyl alcoholated urea-based crosslinking agents, hydrazine compounds, carbodiimide compounds, zirconium compounds, zinc compounds, titanium compounds, aluminum compounds, and the like, but the present invention is limited to such examples only. It is not a thing. These crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent is preferably set as appropriate according to the type of the crosslinking agent.

  Among these cross-linking agents, from the viewpoint of forming a coating film excellent in water resistance, excellent in stretchability and high in extension strength, and excellent in adhesion with the old coating film on the surface of the outer wall material such as mortar, Oxazoline-based 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. It is not limited only to hunt illustration. These oxazoline-based crosslinking agents may be used alone or in combination of two or more. The oxazoline-based crosslinking agent can be easily obtained commercially, for example, manufactured by Nippon Shokubai Co., Ltd., trade names: Epocross WS-500, Epocross WS-700, Epocross K-2010, Epocross K- 2020, Epochros K-2030, and the like, but the present invention is not limited to such 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.

  In addition, the content of the non-volatile content in the resin composition for a crack repair sealer of the present invention is excellent in water resistance, extensibility and high elongation strength, and with the old coating film on the surface of the outer wall material such as mortar. From the viewpoint of forming a coating film excellent in 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, may contain only the resin composition for a crack repair sealer, and further contains an additive. Also good.

  Examples of additives include colorants such as pigments, leveling agents, UV absorbers, UV stabilizers, antioxidants, polymerization inhibitors, fillers, coupling agents, rust inhibitors, antibacterial agents, and metal deactivators. Agent, wetting agent, antifoaming agent, surfactant, reinforcing agent, plasticizer, lubricant, anti-fogging agent, anticorrosive agent, pigment dispersant, flow control agent, peroxide decomposing agent, mold decoloring agent, fluorescent enhancement White agent, organic flame retardant, inorganic flame retardant, anti-dripping agent, melt flow modifier, antistatic agent, anti-algae agent, anti-mold agent, flame retardant, slip agent, metal chelating agent, anti-blocking agent, Examples include heat stabilizers, processing stabilizers, dispersants, thickeners, rheology control agents, foaming agents, anti-aging agents, preservatives, antistatic agents, silane coupling agents, antioxidants, and film forming aids. 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 generally determined, it is preferable to appropriately determine the amount depending on the type of the additive.

  In addition, the non-volatile content in the sealer of the present invention is excellent in water resistance, excellent in stretchability and high in extension strength, and excellent in adhesion to the old paint 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 from the viewpoint of improving handleability, it is preferably 80% by mass or less, more preferably 70% by mass or less.

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

  Examples of the exterior building material include a metal substrate, a resin substrate, and an inorganic substrate. Examples of the metal substrate include an aluminum plate, an iron plate, an aluminum galvanized steel plate, a stainless steel plate, and a tin plate. Examples of the resin substrate 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 and JIS A5430. Examples of ceramic building materials include tiles and outer wall materials. Ceramic building materials are obtained by adding inorganic fillers, fibrous materials, etc. to hydraulic glue, which is a raw material for inorganic cured bodies, molding the resulting mixture, curing the resulting molded body, and curing it. It is done. Examples of the inorganic base material constituting the exterior of the building include mortar board, flexible board, calcium silicate board, gypsum slag perlite board, wood chip cement board, precast concrete board, ALC board, gypsum board, etc. The invention is not limited to such examples.

  Examples of the paint used as a raw material for the old coating film formed on the surface of the outer layer base material include common solvent-based resin paints such as fluororesin paints, acrylic resin paints, and acrylic silicon resin paints. In addition, water-based resin paints and the like can be mentioned, but the present invention is not limited to such examples.

  Among old paint films, old paint films made of fluororesin-based paints have a small surface polarity and are inferior in wettability and interaction with organic compounds, so a new paint film is generally formed on the old paint film. It is thought that it is difficult to make it adhere. From this, the fact that the newly formed coating film on the old coating film is excellent in adhesion to the old coating film made of a fluororesin paint means that the newly formed coating film is only a fluororesin paint. In addition, it is considered that the adhesiveness to an old coating film formed from a general paint such as an acrylic resin paint or an acrylic silicon resin paint is excellent.

  On the other hand, the crack repair sealer of the present invention is excellent in adhesion with 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 water resistance. It is formed from not only fluororesin paints but also general paints such as acrylic resin paints and acrylic silicon resin paints other than fluororesin paints. It can be suitably used when repairing cracks and the like of an old coating film.

  The crack repair sealer of the present invention may be applied by only one layer, or may be applied by recoating so that two or more layers of the coating film are formed. When overcoating so that two or more layers are formed, only a part of the coating may be formed by the crack repair sealer of the present invention, and all the coatings may be repaired by the crack of the present invention. It may be formed 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, static coating, and the like. 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, for example, 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 generated in the old coating film.

  In addition, the thickness of the coating film formed using the crack repair sealer of the present invention is excellent in water resistance, extensibility and high elongation strength, 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 coating amount of the base coating for repair depends on the type of the base material and cannot be determined unconditionally, but it has excellent water resistance, extensibility, high elongation strength, and external walls such as mortar. From the viewpoint of forming a coating film excellent in adhesion with the old coating film on the surface of the material, it is usually preferable that the nonvolatile content is about ²⁰ to 1000 g / m ² .

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

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

Production Example 367.9 parts of deionized water, 12.5 parts of a dispersant [manufactured by San Nopco Co., Ltd., trade name: Nop Cosperth 44C], calcium carbonate [heavy calcium carbonate, manufactured by Nitto Flour Industry Co., Ltd., product number: NS # 100] 500 parts, calcium carbonate [heavy calcium carbonate, manufactured by Nitto Flour Chemical Co., Ltd., product number: SS # 80] 500 parts, antifoaming agent [manufactured by San Nopco, trade name: Nopco 8034L] Thickening was performed by stirring 60.0 parts of a thickener diluted to 0 part and 3% [manufactured by Daicel Chemical Industries, Ltd., product number: SP-850] at 3000 min ^{-1 for} 30 minutes, 100 mesh (JIS The mixture was filtered through a mesh (mesh, the same applies hereinafter) wire mesh 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
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser, 43.0 parts of deionized water was charged.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier 72.0 parts of 2-ethylhexyl acrylate, 1.0 part of acetoacetoxyethyl methacrylate, 20.0 parts of styrene, 3.0 parts of acrylic acid and 4.0 parts of acrylonitrile were prepared to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dripping, 1% by mass of the total amount of the monomer components was added to the flask, 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 into the flask to initiate emulsion polymerization.

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

  Thereafter, 25% aqueous ammonia was added, pH [measured at 23 ° C. using Horiba, Ltd., product number: F-23, the same applies hereinafter] was adjusted 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 mesh to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the whole emulsion particle 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 with a homodisper at 1000 min ⁻¹ , 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 used 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 80% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickening agent (manufactured by Daicel Chemical Industries, Ltd.) diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.] part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

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

  Of the obtained pre-emulsion for dripping, 1% by mass of the total amount of the monomer components was added to the flask, 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 into the flask to initiate emulsion polymerization.

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

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

  The glass transition temperature of the whole emulsion particle 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 with a homodisper at 1000 min ⁻¹ , 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 used 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 80% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickener [manufactured by Daicel Chemical Industries, Ltd.] diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM viscometer (manufactured by Tokyo Keiki Co., Ltd.) part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

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

  Of the obtained pre-emulsion for dripping, 1% by mass of the total amount of the monomer components was added to the flask, 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 into the flask to initiate emulsion polymerization.

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

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

  The glass transition temperature of the whole emulsion particle 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 with a homodisper at 1000 min ⁻¹ , 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 used 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 80% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickening agent (manufactured by Daicel Chemical Industries, Ltd.) diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.] part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier , 57.0 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 prepared to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dripping, 1% by mass of the total amount of the monomer components was added to the flask, 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 into the flask to initiate emulsion polymerization.

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

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

  The glass transition temperature of the whole emulsion particle 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 with a homodisper at 1000 min ⁻¹ , 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 used 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 80% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickening agent (manufactured by Daicel Chemical Industries, Ltd.) diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.] part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier , 57.0 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 prepared to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dripping, 1% by mass of the total amount of the monomer components was added to the flask, 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 into the flask to initiate emulsion polymerization.

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

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

  The glass transition temperature of the whole emulsion particle 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 with a homodisper at 1000 min ⁻¹ , 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 used 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 80% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickener [manufactured by Daicel Chemical Industries, Ltd.] diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM viscometer (manufactured by Tokyo Keiki Co., Ltd.) part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier , 68.0 parts of 2-ethylhexyl acrylate, 5.0 parts of acetoacetoxyethyl methacrylate, 20.0 parts of styrene, 3.0 parts of acrylic acid and 4.0 parts of acrylamide were prepared to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dripping, 1% by mass of the total amount of the monomer components was added to the flask, 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 into the flask to initiate emulsion polymerization.

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

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

  The glass transition temperature of the whole emulsion particle 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 with a homodisper at 1000 min ⁻¹ , 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 used 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 80% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickener [manufactured by Daicel Chemical Industries, Ltd.] diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM viscometer (manufactured by Tokyo Keiki Co., Ltd.) part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier , 60.0 parts of 2-ethylhexyl acrylate, 1.0 part of acetoacetoxyethyl methacrylate, 36.0 parts of styrene and 3.0 parts of acrylic acid were prepared to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dripping, 1% by mass of the total amount of the monomer components was added to the flask, 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 into the flask to initiate emulsion polymerization.

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

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

  The glass transition temperature of the whole emulsion particle 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 with a homodisper at 1000 min ⁻¹ , 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 used 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 80% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickener [manufactured by Daicel Chemical Industries, Ltd.] diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM viscometer (manufactured by Tokyo Keiki Co., Ltd.) part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier 60.0 parts of 2-ethylhexyl acrylate, 1.0 part of allyl acetoacetate, 32.0 parts of styrene, 3.0 parts of acrylic acid and 4.0 parts of acrylonitrile were prepared to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dripping, 1% by mass of the total amount of the monomer components was added to the flask, 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 into the flask to initiate emulsion polymerization.

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

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

  The glass transition temperature of the whole emulsion particle 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 with a homodisper at 1000 min ⁻¹ , 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 used 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 80% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickener [manufactured by Daicel Chemical Industries, Ltd.] diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM viscometer (manufactured by Tokyo Keiki Co., Ltd.) part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  6.9 parts of deionized water in a dropping funnel, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka 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 dripping, 1% by mass of the total amount of the monomer components was added to the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 4 parts were added into the flask to initiate the polymerization.

  Next, the remainder 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 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 allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier, Second stage pre-emulsion comprising 70.0 parts 2-ethylhexyl acrylate, 1.0 part acetoacetoxyethyl methacrylate, 2.0 parts styrene, 3.0 parts acrylic acid and 4.0 parts acrylonitrile, 3.5% excess 2.9 parts of an aqueous ammonium sulfate solution and 2.0 parts of a 2.5% aqueous sodium hydrogen sulfite solution were dropped into the flask over 90 minutes. After completion of the dropping, 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 mesh to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the whole emulsion particle contained in the resin emulsion obtained above was −38.4 ° C. The average particle diameter of the emulsion particles was 250 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above with a homodisper at 1000 min ⁻¹ , 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 used 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 90% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , BM type viscometer [Tokyo Keiki Co., Ltd.] in thickener viscosity at 25 ° C. in the rotation speed 30min ^-1 was diluted to 3% a 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  6.9 parts of deionized water in a dropping funnel, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka 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 dripping, 1% by mass of the total amount of the monomer components was added to the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 4 parts were added into the flask to initiate the polymerization.

  Next, the remainder 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 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 allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier, 2nd stage pre-emulsion consisting of 66.0 parts 2-ethylhexyl acrylate, 5.0 parts acetoacetoxyethyl methacrylate, 2.0 parts styrene, 3.0 parts acrylic acid and 4.0 parts acrylonitrile, 3.5% excess 2.9 parts of an aqueous ammonium sulfate solution and 2.0 parts of a 2.5% aqueous sodium hydrogen sulfite solution were dropped into the flask over 90 minutes. After completion of the dropping, 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 mesh to obtain a resin emulsion having a nonvolatile content of 50% by mass.

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

Next, while dispersing 100 parts of the resin emulsion obtained above with a homodisper at 1000 min ⁻¹ , 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 used 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 90% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickening agent (manufactured by Daicel Chemical Industries, Ltd.) diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.] part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  6.9 parts of deionized water in a dropping funnel, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka 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 dripping, 1% by mass of the total amount of the monomer components was added to the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 4 parts were added into the flask to initiate the polymerization.

  Next, the remainder 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 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 allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier, 2nd stage pre-emulsion consisting of 60.0 parts 2-ethylhexyl acrylate, 1.0 part acetoacetoxyethyl methacrylate, 12.0 parts styrene, 3.0 parts acrylic acid and 4.0 parts acrylonitrile, 3.5% excess 2.9 parts of an aqueous ammonium sulfate solution and 2.0 parts of a 2.5% aqueous sodium hydrogen sulfite solution were dropped into the flask over 90 minutes. After completion of the dropping, 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 mesh to obtain a resin emulsion having a nonvolatile content of 50% by mass.

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

Next, while dispersing 100 parts of the resin emulsion obtained above with a homodisper at 1000 min ⁻¹ , 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 used 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 90% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickening agent (manufactured by Daicel Chemical Industries, Ltd.) diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.] part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  6.9 parts of deionized water in a dropping funnel, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier And 15.0 parts of styrene was prepared, and the pre-emulsion for dripping was prepared.

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

  Next, the remainder 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 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 allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier, A second pre-emulsion comprising 65.0 parts 2-ethylhexyl acrylate, 1.0 part acetoacetoxyethyl methacrylate, 12.0 parts styrene, 3.0 parts acrylic acid, 2.0 parts acrylonitrile and 2.0 parts acrylamide. Then, 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 completion of the dropping, 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 mesh to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the whole emulsion particle contained in the resin emulsion obtained above was −31.6 ° C. The average particle diameter of the emulsion particles was 250 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above with a homodisper at 1000 min ⁻¹ , 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 used so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and calcium carbonate paste contained in the resin emulsion obtained above was 92% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickening agent (manufactured by Daicel Chemical Industries, Ltd.) diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.] part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  6.9 parts of deionized water in a dropping funnel, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka 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 dripping, 1% by mass of the total amount of the monomer components was added to the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and a 3.5% ammonium persulfate aqueous solution 1 4 parts were added into the flask to initiate the polymerization.

  Next, the remainder 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 completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 15.0 parts of deionized water, 6.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier, A second pre-emulsion comprising 26.0 parts 2-ethylhexyl acrylate, 11.5 parts styrene, 0.5 part acrylic acid and 2.0 parts acrylonitrile, 2.9 parts 3.5% aqueous ammonium persulfate and 2. 2.0 parts of 5% aqueous sodium hydrogen sulfite solution was dropped into the flask over 90 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Next, 15.0 parts of deionized water, 6.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier 3 stage pre-emulsion consisting of 26.0 parts 2-ethylhexyl acrylate, 1.0 part acetoacetoxyethyl methacrylate, 8.5 parts styrene, 2.5 parts acrylic acid and 2.0 parts acrylonitrile, 3.5% 2.9 parts of an aqueous ammonium persulfate solution and 2.0 parts of a 2.5% aqueous sodium hydrogen sulfite solution were added dropwise into the flask over 90 minutes. After completion of the dropping, 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 mesh to obtain a resin emulsion having a nonvolatile content of 50% by mass.

  The glass transition temperature of the whole emulsion particle contained in the resin emulsion obtained above was −13.8 ° C. The average particle diameter of the emulsion particles was 250 nm.

Next, while dispersing 100 parts of the resin emulsion obtained above with a homodisper at 1000 min ⁻¹ , 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 used so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and calcium carbonate paste contained in the resin emulsion obtained above was 92% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickener [manufactured by Daicel Chemical Industries, Ltd.] diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM viscometer (manufactured by Tokyo Keiki Co., Ltd.) part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier , 68.0 parts of 2-ethylhexyl acrylate, 27.0 parts of styrene, 3.0 parts of acrylic acid and 2.0 parts of acrylonitrile were prepared to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dripping, 1% by mass of the total amount of the monomer components was added to the flask, 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 into the flask to initiate emulsion polymerization.

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

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

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

Next, while dispersing 100 parts of the resin emulsion obtained above with a homodisper at 1000 min ⁻¹ , 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 used 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 80% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , BM type viscometer [Tokyo Keiki Co., Ltd.] in thickener viscosity at 25 ° C. in the rotation speed 30min ^-1 was diluted to 3% a 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier , 68.0 parts of 2-ethylhexyl acrylate, 29.0 parts of styrene and 3.0 parts of acrylic acid were prepared to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dripping, 1% by mass of the total amount of the monomer components was added to the flask, 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 into the flask to initiate emulsion polymerization.

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

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

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

Next, while dispersing 100 parts of the resin emulsion obtained above with a homodisper at 1000 min ⁻¹ , 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 used 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 80% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickener [manufactured by Daicel Chemical Industries, Ltd.] diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM viscometer (manufactured by Tokyo Keiki Co., Ltd.) part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier , 68.0 parts of 2-ethylhexyl acrylate, 29.0 parts of styrene and 3.0 parts of acrylic acid were prepared to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dripping, 1% by mass of the total amount of the monomer components was added to the flask, 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 into the flask to initiate emulsion polymerization.

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

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

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

Next, while dispersing 100 parts of the resin emulsion obtained above with a homodisper at 1000 min ⁻¹ , 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 used 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 an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickening agent (manufactured by Daicel Chemical Industries, Ltd.) diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM type viscometer [manufactured by Tokyo Keiki Co., Ltd.] part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier , 68.0 parts of 2-ethylhexyl acrylate, 29.0 parts of styrene and 3.0 parts of acrylic acid were prepared to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dripping, 1% by mass of the total amount of the monomer components was added to the flask, 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 into the flask to initiate emulsion polymerization.

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

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

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

Next, while dispersing 100 parts of the resin emulsion obtained above with a homodisper at 1000 min ⁻¹ , 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-based antifoaming agent (manufactured by San Nopco Co., Ltd., trade name: SN deformer 777) so that the nonvolatile content is 45% by mass, BM is added to the mixture obtained above. Thickener diluted to 3% with a type viscometer [manufactured by Tokyo Keiki Co., Ltd.] at a rotational speed of 30 min ⁻¹ at 25 ° C. to 15000 mPa · s [manufactured by Daicel Chemical Industries, Ltd., product number: SP-850] was added, and the mixture was stirred at a rotational speed of 1000 min ^-1 for 15 minutes to obtain a resin composition for a crack repair sealer.

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

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier , 68.0 parts of 2-ethylhexyl acrylate, 29.0 parts of styrene and 3.0 parts of acrylic acid were prepared to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dripping, 1% by mass of the total amount of the monomer components was added to the flask, 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 into the flask to initiate emulsion polymerization.

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

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

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

Next, while dispersing 100 parts of the resin emulsion obtained above with a homodisper at 1000 min ⁻¹ , 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 used so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and calcium carbonate paste contained in the resin emulsion obtained above is 70% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickener [manufactured by Daicel Chemical Industries, Ltd.] diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM viscometer (manufactured by Tokyo Keiki Co., Ltd.) part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

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

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier , 68.0 parts of 2-ethylhexyl acrylate, 29.0 parts of styrene and 3.0 parts of acrylic acid were prepared to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dripping, 1% by mass of the total amount of the monomer components was added to the flask, 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 into the flask to initiate emulsion polymerization.

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

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

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

Next, while dispersing 100 parts of the resin emulsion obtained above with a homodisper at 1000 min ⁻¹ , 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 used so that the solid content of the calcium carbonate paste in the total solid content of the emulsion particles and calcium carbonate paste contained in the resin emulsion obtained above is 98% by mass. After adding an appropriate amount of diluting water and an appropriate amount of a silicone-based antifoaming agent (trade name: SN deformer 777 manufactured by San Nopco Co., Ltd.) so that the nonvolatile content is 60% by mass. , A thickener [manufactured by Daicel Chemical Industries, Ltd.] diluted to 3% so that the viscosity at 25 ° C. at a rotation speed of 30 min ⁻¹ is 15000 mPa · s with a BM viscometer (manufactured by Tokyo Keiki Co., Ltd.) part: SP-850] was added, by stirring for 15 minutes at a rotation speed of 1000min ^-1, cracking repair sealer resin composition It was.

Experimental Example As physical properties of the resin composition for a crack repair sealer obtained in each example or each comparative example, water resistance, stretchability, 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 crack repair sealer 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 The test plate was obtained by drying for 14 days in an atmosphere at 23 ° C. and a relative humidity of 50%. A funnel (diameter: 10 cm) is placed on the coating film formed on the obtained test plate, and the contact portion of both is sealed with a silicone bath bond (manufactured by Konishi Co., Ltd.). The amount of water reduction after 24 hours was measured according to the “Method”, and 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 point: 1 0.0 mL / cm ² or more (failed)

[Elongation and elongation strength]
Spread a release paper on a metal plate, and apply the resin composition for a crack repair sealer obtained in each Example or each Comparative Example so that the thickness after drying is 0.5 mm. After drying 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 release coating paper is turned upside down The test piece was obtained by allowing it to stand for another 7 days and drying.

  Next, this test piece was punched into dumbbell-shaped No. 2 as defined in 4.1 of JIS K6251 and the release paper was removed to obtain a test piece. Attach the obtained test piece so that the distance between chucks of the tensile tester is 60 mm, and apply a tensile load until the test piece breaks at a pulling speed of 200 mm / min. The elongation of the test piece at break And the maximum tensile load was calculated | required and the extensibility and elongation strength were evaluated based on the following evaluation criteria.

(1) Evaluation criteria for elongation: 50 points: elongation is 50% or more 30 points: elongation is 30% or more and less than 50% 10 points: elongation is 10% or more and less than 30% 0 point: elongation is 10 <% (Failed)

(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 inlet tube, a thermometer, and a reflux condenser. In a dropping funnel, 417 parts of deionized water, 60 parts of a 25% aqueous solution of emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10], emulsifier [trade name: ADEKA rear soap, manufactured by ADEKA Corporation] SR-10] 60 parts, 270 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate, 100 parts of n-butyl methacrylate, 500 parts of methyl methacrylate, 10 parts of hydroxyethyl methacrylate, 10 parts of γ-methacryloyloxypropyltrimethoxysilane and A pre-emulsion for dripping consisting of 10 parts of acrylic acid was prepared. Among them, 77 parts corresponding to 5% of the total amount of all monomer components were added to the flask, and the temperature was raised to 70 ° C. while gently blowing nitrogen gas. Polymerization was started by adding 10 parts of an aqueous ammonium persulfate solution. Thereafter, the remainder of the dropping pre-emulsion, 30 parts of 5% aqueous ammonium persulfate solution and 20 parts of 5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the contents of the flask were maintained at 70 ° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh metal-mesh. The non-volatile content 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 a dispersant (trade name: Demol EP, manufactured by Kao Corporation), a 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 rotational speed of 3000 min ^{−1 for} 60 minutes.

Next, 5 parts of butyl cellosolve and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by JNC Corporation, product number: CS as a film forming aid to 100 parts of the resin emulsion obtained above. -12] 5 parts were added, and further 21.5 parts of water and 0.5 parts of 25% aqueous ammonia were added. After stirring for 30 minutes with a homodisper at a rotational speed of 1500 min ^-1, the white color obtained above 30 parts of paste and 0.5 part of an antifoaming agent (manufactured by San Nopco Co., Ltd., trade name: Nopco 8034L) were added, and at 25 ° C. using a Craves unit viscometer [manufactured by Brookfield, product number: KU-1] By adding a thickener [manufactured by Nippon Shokubai Co., Ltd., trade name: Acryset WR-503A] so that the viscosity when measured was 61 KU, stirring was performed for 30 minutes in this state. The use paint was prepared.

(3) Preparation of test piece for evaluation Next, the coating film of the base material coated with the fluororesin-based coating was deteriorated by exposing it to the outdoors, and the coating film with cracks on the surface of the coating film was replaced with the old coating film. The resin composition for a crack repair sealer 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. And dried for 2 days in an atmosphere having a relative humidity of 50%, and the evaluation paint obtained above was further applied so that the thickness after drying was 100 g / m ^2. Was dried by standing in an atmosphere of 23 ° C. and 50% relative humidity for 2 days to obtain a test piece for evaluation.

(4) Cross cut test After cutting 25 squares (vertical: 5 squares, horizontal: 5 squares) into a 2 mm square grid pattern with a sharp blade on the coating film of the evaluation test piece obtained above, In accordance with JIS Z1522, the cellophane pressure-sensitive adhesive tape having a width of 25 mm was rubbed with a finger so that the cellophane pressure-sensitive 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. Of the produced 25 squares, the number of peeled squares was counted, and the adhesion was evaluated based on the following evaluation criteria.

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

〔Comprehensive evaluation〕
A total evaluation (maximum of 200 points) was performed by summing up the evaluation scores for each test item. In addition, the resin composition for the crack repair sealer which has one evaluation of 0 points | pieces in physical property evaluation fails.

  From the results shown in Table 1, the resin compositions for the crack repair sealer obtained in each example are all excellent in water resistance, extensibility, high elongation strength, and difficult to adhere. It turns out that the coating film excellent in adhesiveness with the old coating film which consists of a fluororesin type coating material considered to be exists is formed.

Claims (3)

  A resin composition for a sealer used in a sealer for repairing cracks in a coating film, which contains emulsion particles and an inorganic filler, and the content of the inorganic filler in the total solid content of the emulsion particles and the inorganic filler is 80 to A resin composition for a crack repairing sealer, which is 95% by mass and uses a monomer component containing an acetoacetoxy group-containing monomer as a raw material for emulsion particles.   A method for producing a resin composition for a sealer used for a sealer for repairing cracks in a coating film, comprising emulsion particles obtained by emulsion polymerization of a monomer component containing an acetoacetoxy group-containing monomer. A resin for a sealer for repairing cracks, wherein the content of the inorganic filler in the total solid content of the emulsion particles and the inorganic filler is adjusted to 80 to 95% by mass when the resin emulsion and the inorganic filler to be mixed are mixed A method for producing the composition.   A crack repair sealer comprising the resin composition for a crack repair sealer according to claim 1.