JP2012206895A - Polymer cement composition, coating film waterproof material therefrom, and emulsion composition for polymer cement - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer cement composition excellent in the balance of coating aptitude and coating film property.SOLUTION: This composition includes an acrylic resin emulsion which is obtained by emulsion polymerization of an ethylenic unsaturated monomer in the presence of an organic solvent (A) which has no unsaturated group and whose solubility {dissolved quantity to 100 g water} is not higher than 20 g/100 g and water.

Description

  The present invention relates to a polymer cement composition, a waterproof coating material using the same, and an emulsion composition for polymer cement, and more specifically, a rooftop of a building such as a flat roof, a veranda of a building, a wall, a balcony, a bathroom, The present invention relates to a polymer cement composition, a coating film waterproofing material using the polymer cement composition, and an emulsion composition for polymer cement, which are used for waterproof coating technology in the field of civil engineering and construction such as the outer surface of a freezer warehouse.

  Conventionally, as a polymer cement composition for a waterproof coating material, an ethylene-vinyl acetate copolymer (EVA) emulsion obtained by emulsion polymerization using a polyvinyl alcohol resin (PVA resin) as a protective colloid, cement, What used together is used. This polymer cement composition has been used as a waterproof coating material that can be applied by roller coating, but has a problem that the obtained coating film lacks flexibility and weather resistance.

Therefore, in order to improve the coating film properties such as flexibility and weather resistance of the coating film, an acrylic resin that can easily provide a coating film generally exhibiting excellent flexibility and weather resistance instead of EVA emulsion. Polymer cement compositions using emulsions have been proposed.
For example, Patent Document 1 discloses that a hydraulic component containing 10% by mass or more of alumina cement, and a synthetic resin emulsion (acrylic resin) in an amount of 1 to 80 parts by mass in terms of solid content with respect to 100 parts by mass of the hydraulic component. Emulsions) and hydraulic compositions containing 0.1 to 15 parts by weight of shrinkage reducing agents have been proposed.

JP 2006-44958 A

  However, in the composition described in Patent Document 1, when the viscosity of the composition is reduced to such an extent that the composition can be applied with a roller at the time of application, cracking (checking) occurs in the coating film after coating and drying. There was a problem that the waterproof performance would be deteriorated.

  The present invention has been made in view of such circumstances, and is a polymer cement composition excellent in balance between coating suitability and coating film physical properties, a coating film waterproofing material using the same, and an emulsion composition for polymer cement. The purpose is to provide.

  In order to obtain a polymer cement composition having a good balance between coating suitability and coating film properties, the present inventors have focused on organic solvents that have been used as film-forming aids after the completion of emulsion polymerization, and have continued intensive research. It was. As a result, rather than adding an organic solvent afterwards, coexisting during the emulsion polymerization of the acrylic resin emulsion synthesis and selecting an organic solvent that is highly hydrophobic and does not contain an unsaturated group as the organic solvent. Thus, such an acrylic resin emulsion can be obtained satisfactorily, and the polymer cement composition containing such an acrylic resin emulsion has excellent viscosity during coating and elongation when formed into a coating film. The present invention has been completed.

  The reason for this is not clear, but is presumed as follows. That is, when a specific hydrophobic organic solvent conventionally used as a film-forming aid is added after the completion of emulsion polymerization, only the surface of the emulsion particles is softened, but the inside of the particles cannot be softened. In the present invention, an organic solvent (A) having a high hydrophobicity of 20 g / 100 g or less in water and having no unsaturated group is selected, and in the presence of the organic solvent (A), ethylenic is selected. Since the unsaturated monomer is emulsion polymerized, the specific organic solvent (A) can easily penetrate not only into the surface of the emulsion particles but also into the interior during the growth stage of the emulsion particles. It is considered that the elongation of the coating film using this is excellent.

That is, the present invention has an ethylenically unsaturated simple compound in the presence of an organic solvent (A) having a solubility in water [amount dissolved in 100 g of water] of 20 g / 100 g or less and having no unsaturated group, and water. A polymer cement composition containing an acrylic resin emulsion obtained by emulsion polymerization of a monomer is a first gist.
Moreover, this invention makes the 2nd summary the coating-film waterproof material formed by containing a polymer cement composition.
Furthermore, the present invention provides an ethylenically unsaturated simple compound in the presence of an organic solvent (A) having a solubility in water (amount dissolved in 100 g of water) of 20 g / 100 g or less and having no unsaturated group, and water. A third gist is an emulsion composition for polymer cement containing an acrylic resin emulsion obtained by emulsion polymerization of a monomer.

  As described above, the polymer cement composition of the present invention has an organic solvent (A) having a solubility in water [amount dissolved in 100 g of water] of 20 g / 100 g or less and having no unsaturated group, and water. Below, it contains an acrylic resin emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer and a cement component, and has excellent balance between coating suitability and coating film properties.

  Furthermore, the waterproof coating material comprising the polymer cement composition of the present invention has excellent flexibility and weather resistance of the coating film, and also improves the elongation of the coating film. ing.

  Next, embodiments of the present invention will be described in detail. However, the present invention is not limited to this embodiment.

  The polymer cement composition of the present invention includes an acrylic resin emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer in the presence of an organic solvent (A) having no unsaturated group and water, and a cement component It is a composition containing this.

  In the present invention, the organic solvent (A) is allowed to coexist at the time of emulsion polymerization, and the organic solvent (A) has a solubility in water [amount dissolved in 100 g of water] (hereinafter sometimes referred to simply as “solubility”). It is the greatest feature to use those having 20 g / 100 g or less.

Hereinafter, each component will be described.
[Organic solvent having no unsaturated group (A)]
In the present invention, the unsaturated group means a group having a polymerizable double bond such as an ethylenic hydrocarbon group (excluding a cyclic unsaturated hydrocarbon group), and is an organic solvent (A ) Is characterized by not having such an unsaturated group.

As the organic solvent (A) having no unsaturated group (hereinafter, sometimes simply referred to as “organic solvent (A)”), an upper limit of solubility is 20 g / 100 g or less, preferably 15 g / 100 g or less, The amount is particularly preferably 10 g / 100 g or less, and most preferably insoluble in water (solubility is 0 g / 100 g). If the organic solvent (A) has a solubility exceeding the upper limit, the polymerization stability is impaired and an acrylic resin emulsion cannot be obtained.
In the present invention, the solubility in water is measured at 23 ° C.

  Moreover, 170-350 degreeC is preferable, as for the boiling point of an organic solvent (A), Most preferably, it is 200-300 degreeC, More preferably, it is 230-280 degreeC. When the boiling point is too low, there is a tendency that the elongation improvement of the coating film is insufficient. When the boiling point is too high, the compatibility with the monomer is lowered and the polymerization stability is lowered.

  As the organic solvent (A), for example, ester solvents, ether solvents, alcohol solvents and the like are used alone or in combination of two or more. Among these, from the viewpoint of polymerization stability and the elongation of the coating film, an ester solvent having 5 to 20 carbon atoms (preferably 6 to 18 carbon atoms), 5 to 20 carbon atoms (preferably 6 to 18 carbon atoms). ) Ether solvents are preferred.

  Examples of the ester solvent include 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (carbon number 12), 2,2,4-trimethyl-1,3-pentanediol diisobutyrate ( Examples thereof include carbon number 16), dibutyl phthalate (carbon number 16), isobutyl adipate, and the like. Of these, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and dibutyl phthalate are preferable, and 2,4 2,4-trimethyl-1,3-pentanediol monoisobutyrate.

  Examples of ether solvents include dipropylene glycol-n-propyl ether, propylene glycol-n-butyl ether, dipropylene glycol-n-butyl ether, tripropylene glycol-n-butyl ether, propylene glycol methyl ether acetate, dipropylene glycol. Methyl ether acetate, propylene glycol diacetate, propylene glycol phenyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono 2-ethyl hexyl ether, diethylene glycol mono 2-ethyl hexyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, ethylene Glycol monoben Ether and the like. Of these, propylene glycol-n-butyl ether is preferable.

  Examples of the alcohol solvent include benzyl alcohol.

[Acrylic resin emulsion]
The acrylic resin emulsion used in the present invention has a solubility in water of 20 g / 100 g or less and an ethylenically unsaturated monomer in the presence of the organic solvent (A) having no unsaturated group and water. It is obtained by emulsion polymerization of a monomer.

The acrylic resin constituting the acrylic resin emulsion is preferably a homopolymer or copolymer of an ethylenically unsaturated monomer, more preferably among ethylenically unsaturated monomers, It is an acrylic copolymer having (meth) acrylic acid alkyl ester as a main component and copolymerized with other ethylenically unsaturated monomers.
In the present invention, the above-mentioned main component of the (meth) acrylic acid alkyl ester means that it contains an amount exceeding 50% by weight of the total ethylenically unsaturated monomer, preferably an ethylenically unsaturated monomer. It means to contain 60% by weight or more of the whole mass.

Hereinafter, the ethylenically unsaturated monomer that is a polymerization component forming the acrylic resin will be described in detail.
Examples of the ethylenically unsaturated monomer include the following (a) to (l). These may be used alone or in combination of two or more.
(A) Alkyl ester of (meth) acrylic acid.
(B) A hydroxyl group-containing ethylenically unsaturated monomer.
(C) A carboxyl group-containing ethylenically unsaturated monomer.
(D) An epoxy group-containing ethylenically unsaturated monomer.
(E) a methylol group-containing ethylenically unsaturated monomer.
(F) Alkoxyalkyl group-containing ethylenically unsaturated monomer.
(G) Cyano group-containing ethylenically unsaturated monomer.
(H) An ethylenically unsaturated monomer having two or more radically polymerizable double bonds.
(I) An ethylenically unsaturated monomer having an amino group.
(J) An ethylenically unsaturated monomer having a sulfonic acid group.
(K) An ethylenically unsaturated monomer having a phosphate group.
(L) Aromatic ethylenically unsaturated monomers.

Among the above (a) to (l), from the viewpoint of the stability of the resulting emulsion particles, the carboxyl group-containing ethylenically unsaturated monomer (c), the ethylenically unsaturated monomer having an amino group (i It is preferable to contain at least one selected from the above as an ethylenically unsaturated monomer component.
The content of the carboxyl group-containing ethylenically unsaturated monomer (c) is preferably from 0.1 to 5% by weight, particularly preferably from 0.3 to 3% by weight, based on the entire ethylenically unsaturated monomer.
Further, the content of the ethylenically unsaturated monomer (i) having an amino group is preferably 0.1 to 5% by weight, particularly preferably 0.3 to 3% by weight, based on the whole ethylenically unsaturated monomer. It is.

  As the acrylic resin used in the present invention, in addition to the above (a) to (l), vinyl propionate, vinyl versatic acid, vinyl pyrrolidone, methyl vinyl ketone, butadiene, ethylene, propylene, vinyl chloride, vinylidene chloride, etc. A monomer can also be used suitably as desired.

Next, the monomers exemplified in the above (a) to (l) will be described in detail.
Examples of the (meth) acrylic acid alkyl ester (a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth). Aliphatic (meth) acrylates such as acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, preferably an alkyl group having 1 to 20 carbon atoms Aliphatic (meth) acrylates, aromatic (meth) acrylates such as benzyl (meth) acrylate, phenyl (meth) acrylate, and the like can be used, and these can be used alone or in combination of two or more. Among these, preferably, an aliphatic (meth) acrylate having 1 to 10 carbon atoms in an alkyl group such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, cyclohexyl (meth) acrylate or the like. It is.

  Examples of the hydroxyl group-containing ethylenically unsaturated monomer (b) include, for example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, and polymers such as polyethylene glycol (meth) acrylate. An alkylene glycol (meth) acrylate etc. are mention | raise | lifted and these are used individually or in combination of 2 or more types. Among them, preferred is a hydroxyalkyl (meth) acrylate having a C2-C4 hydroxyalkyl group or a polyalkylene glycol (meth) acrylate having a C2-C4 alkylene group, and particularly preferred is hydroxyethyl ( (Meth) acrylate.

  As said carboxyl group-containing ethylenically unsaturated monomer (c), (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid etc. can be used, for example, These are independent or 2 types. These are used together. Among these, (meth) acrylic acid and itaconic acid are more preferable. In the case of dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, these monoesters and monoamides may be used.

  Examples of the epoxy group-containing ethylenically unsaturated monomer (d) include glycidyl (meth) acrylate, allyl glycidyl ether, methyl glycidyl (meth) acrylate, and the like. These may be used alone or in combination of two or more. Used. Of these, glycidyl (meth) acrylate is preferred.

  Examples of the methylol group-containing ethylenically unsaturated monomer (e) include N-methylol (meth) acrylamide, dimethylol (meth) acrylamide and the like, and these may be used alone or in combination of two or more.

  Examples of the alkoxyalkyl group-containing ethylenically unsaturated monomer (f) include N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, methoxyethyl (meth) acrylate, and methoxypropyl (meth). Examples include acrylates, alkoxyalkyl (meth) acrylates such as ethoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate, and polyalkylene glycol monoalkoxy (meth) acrylates such as polyethylene glycol monomethoxy (meth) acrylate. It is used alone or in combination of two or more.

  Examples of the cyano group-containing ethylenically unsaturated monomer (g) include (meth) acrylonitrile.

  Examples of the ethylenically unsaturated monomer (h) having two or more radical polymerizable double bonds include divinylbenzene, polyoxyethylene di (meth) acrylate, and polyoxypropylene di (meth). Di (meth) acrylates such as acrylate, neopentyl glycol di (meth) acrylate, butanediol di (meth) acrylate, tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. These are used alone or in combination of two or more.

  Examples of the ethylenically unsaturated monomer (i) having an amino group include N such as (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, and N, N-diethylaminoethyl (meth) acrylate. , N-dialkylaminoalkyl (meth) acrylate and the like, and these may be used alone or in combination of two or more. Of these, (meth) acrylamide is preferred.

  Examples of the ethylenically unsaturated monomer (j) having a sulfonic acid group include vinyl sulfonic acid and vinyl styrene sulfonic acid (salt). These may be used alone or in combination of two or more.

  Examples of the ethylenically unsaturated monomer (k) having a phosphoric acid group include vinylphosphonic acid, vinyl phosphate, acid phosphoxyethyl (meth) acrylate, acid phosphoxypropyl (meth) acrylate, and bis [(meta ) Acryloyloxyethyl] phosphate, diphenyl-2- (meth) acryloyloxyethyl phosphate, dibutyl-2- (meth) acryloyloxyethyl phosphate, dioctyl-2 (meth) acryloyloxyethyl phosphate, etc. These may be used alone or in combination of two or more.

  Examples of the aromatic ethylenically unsaturated monomer (l) include styrene, vinyltoluene, α-methylstyrene, and the like. These may be used alone or in combination of two or more. Of these, styrene is preferable.

  In the present invention, (meth) acryloyloxy means acryloyloxy or methacryloyloxy, (meth) acrylic acid means acrylic acid or methacrylic acid, and (meth) acrylic means acrylic or methacrylic. As used herein, (meth) acrylate means acrylate or methacrylate.

  The acrylic resin emulsion used in the present invention is a homopolymer or copolymer of the monomer. During the polymerization, in addition to the monomer, a protective colloid agent (dispersion) Stabilizers), polymerization initiators, polymerization regulators, and surfactants can be used as appropriate. Furthermore, as a post-addition, other components such as a plasticizer and a film-forming aid can be used as appropriate.

Examples of the protective colloid agent (dispersion stabilizer) include polyvinyl alcohol resin (PVA resin).
As such a PVA-based resin, a conventionally known PVA-based resin used for emulsion polymerization in the synthesis of an acrylic resin emulsion may be used.

  In this invention, it is preferable that the usage-amount of PVA-type resin is 0.01-20 weight part with respect to 100 weight part of the whole ethylenically unsaturated monomer, More preferably, 0.1-10 weight part Particularly preferred is 0.5 to 5 parts by weight. If the amount of PVA resin used is too small, the amount of protective colloid at the time of emulsion polymerization will be insufficient and the polymerization stability will tend to be poor. If the amount used is too large, the viscosity of the acrylic resin emulsion will be low. There is a tendency to increase and decrease stability.

  Further, as the polymerization initiator, either water-soluble or oil-soluble can be used. For example, alkyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, t-butyl cumi Ruperoxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 3, 3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, di-isobutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butylperoxyisobutyrate, etc. Organic peroxides, 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2 ' -Azobis (2-methylbutyronitrile), potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, ammonium (amine) salt of 4,4'-azobis-4-cyanovaleric acid, 2,2 ' -Azobis (2-methylamidooxime) dihydrochloride, 2,2'-azobis (2-methylbutanamidoxime) dihydrochloride tetrahydrate, 2,2'-azobis {2-methyl-N- [1,1- Bis (hydroxymethyl) -2-hydroxyethyl] -propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) ) -Propionamide], various redox catalysts (in this case, as an oxidizing agent, ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, p-methane hydroperoxide and the like, and sodium sulfite, acidic sodium sulfite, Rongalite, ascorbic acid and the like are used as the reducing agent.

  These polymerization initiators may be used alone or in combination of two or more. Among these, potassium persulfate, sodium persulfate, redox catalyst (oxidizer: potassium persulfate, sodium persulfate, reducing agent: sodium sulfite, acidic sodium sulfite, Rongalite, ascorbic acid) are superior in polymerization stability. Etc. are suitable.

  The amount of the polymerization initiator used is preferably in the range of 0.01 to 5 parts by weight, more preferably 0.03 to 3 parts by weight, based on 100 parts by weight of the whole ethylenically unsaturated monomer. It is more preferable. When the amount of the polymerization initiator used is too small, the polymerization rate tends to be slow, and when it is too large, the molecular weight of the resulting copolymer is lowered, which tends to be undesirable in terms of water resistance.

  The polymerization initiator may be added in advance to the polymerization can, may be added immediately before the start of polymerization, or may be added in the middle of polymerization as necessary. Alternatively, it may be added in advance to the monomer mixture, or may be added to an emulsion comprising the monomer mixture. In addition, when adding the polymerization initiator, the polymerization initiator may be separately dissolved in a solvent or the above monomer and added, or the dissolved polymerization initiator may be further added in an emulsified form.

Examples of the polymerization regulator include chain transfer agents and pH buffering agents.
Examples of the chain transfer agent include alcohols such as methanol, ethanol, propanol and butanol; aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, furfural and benzaldehyde; n-dodecyl mercaptan, thioglycolic acid and thioglycolic acid And mercaptans such as octyl and thioglycerol. These may be used alone or in combination of two or more.

  The use of this chain transfer agent is effective in terms of carrying out the polymerization stably, but may reduce the degree of polymerization of the acrylic resin and lower the elastic modulus of the resulting coating film. Therefore, specifically, the amount of the chain transfer agent used is preferably 0.01 to 1 part by weight, more preferably 0.01 to 0. 0 parts by weight based on 100 parts by weight of the whole ethylenically unsaturated monomer. It is preferably 5 parts by weight. When the amount of the chain transfer agent used is too small, the effect as a chain transfer agent tends to be insufficient. When the amount of use is too large, the elastic modulus of the coating film tends to decrease.

  Examples of the pH buffering agent include soda ash (sodium carbonate), sodium bicarbonate, potassium bicarbonate, monosodium phosphate, monopotassium phosphate, disodium phosphate, trisodium phosphate, sodium acetate, acetic acid. Examples include ammonium, sodium formate, and ammonium formate. These may be used alone or in combination of two or more.

  The amount of the pH buffer used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the whole ethylenically unsaturated monomer. When the amount of the pH buffer used is too small, the effect as a polymerization regulator tends to be insufficient, and when the amount used is too large, the reaction tends to be inhibited.

Examples of the surfactant include alkyl or alkyl allyl sulfate, alkyl or alkyl allyl sulfonate, dialkyl sulfosuccinate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium alkyl sulfonate, and the like. Anionic surfactants of: cationic surfactants such as alkyltrimethylammonium chloride and alkylbenzylammonium chloride; polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene carboxylic acid ester, polyoxyethylene glycol type, Nonionic surfactants such as polyoxyethylene propylene glycol type; and ammonium = α-sulfonato-ω-1- (allyloxymethyl) ) Alkyloxypolyoxyethylene, α-sulfo-ω- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy-poly (oxy-1,2-ethanediyl) ammonium salt, polyoxyethylene alkylpropenyl Examples thereof include phenyl ether, and these may be used alone or in combination of two or more.
A reactive surfactant having a double bond in the molecule may be used.

  The amount of the surfactant used is usually preferably 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, particularly 100 parts by weight of the whole ethylenically unsaturated monomer. The range is preferably 0.5 to 5 parts by weight. If the amount of the surfactant used is too small, there is a tendency to become unstable in terms of polymerization stability, and if it is too large, the average particle diameter of the resulting copolymer tends to be too small, and the result There is a tendency that the viscosity of the emulsion composition becomes too high to cause problems such as deterioration in workability.

  Examples of the plasticizer include an adipate plasticizer, a phthalic acid plasticizer, and a phosphoric acid plasticizer.

  The film-forming auxiliary agent is not particularly limited and may be appropriately selected from known ones. Examples thereof include hydrocarbon solvents, alcohol solvents, ether alcohols and ether solvents, esters and ether esters. System solvents and the like.

Specifically, the hydrocarbon solvent includes, for example, mineral spirits, petroleum mixed solvents, and the like, and the alcohol solvent includes, for example, benzyl alcohol, and the ether alcohol and ether solvents. For example, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (cellosolve solvent), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), dipropylene glycol monomethyl ether (DPM), propylene Glycol n-butyl ether (PnB), dipropylene glycol n-butyl ether (DPnB), ethylene glycol mono-2-ethylhexyl ether (E G), and the like. Furthermore, examples of the ester and ether ester solvents include diethylene glycol monobutyl ether acetate (BCA), 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (texanol), and the like.
These may be used individually by 1 type and may use 2 or more types together.

  The amount of the plasticizer and film-forming aid used can be appropriately selected as long as the object of the present invention is not impaired. For example, the plasticizer is based on 100 parts by weight of the whole ethylenically unsaturated monomer Usually 0.1 to 50 parts by weight, and the film-forming aid is usually 0.1 to 50 parts by weight with respect to 100 parts by weight of the whole ethylenically unsaturated monomer.

Next, the production of the acrylic resin emulsion used in the present invention will be described.
The acrylic resin emulsion used in the present invention has, for example, a solubility in water of 20 g / 100 g or less, and in the presence of an organic solvent (A) having no unsaturated group and water, the above (a) to (a) to It can be produced by emulsion polymerization of an ethylenically unsaturated monomer such as (l).
In this polymerization process, an acrylic resin emulsion having an acrylic resin as a dispersoid is produced.

  In the acrylic resin emulsion, the dispersoid is the above acrylic resin, and as the dispersion medium, a dispersion medium in which the acrylic resin containing the organic solvent (A) is a dispersoid is used. Water is mainly used.

As a polymerization method of the acrylic resin emulsion used in the present invention,
[1] A method in which the whole amount of the organic solvent (A), water, ethylenically unsaturated monomer, surfactant and the like is charged and polymerized by heating.
[2] Water, surfactant, ethylenically unsaturated monomer and part of organic solvent (A) are charged into a reaction can, polymerized by heating, and then remaining ethylenically unsaturated monomer and organic solvent A method in which (A) is added dropwise or dividedly and polymerization is continued;
[3] A method in which water, a surfactant and the like are charged and the temperature is raised, and then the whole amount of the organic solvent (A) is dropped or dividedly added to the ethylenically unsaturated monomer and the reaction can for polymerization.
Of these, the methods [2] and [3] are preferred in that the polymerization temperature can be easily controlled.

As a polymerization condition in the polymerization method shown in the above [1] to [3], for example, a temperature range of about 40 to 100 ° C. is usually suitable as a polymerization condition in the polymerization method of the above [1]. The reaction may be performed for about 1 to 8 hours later.
The polymerization conditions in the above polymerization method [2] include polymerization of 1 to 50% by weight of the ethylenically unsaturated monomer usually at 40 to 90 ° C. for 0.1 to 4 hours, and then the remaining ethylenically unsaturated monomer. For example, the saturated monomer may be dropped or dividedly added over about 1 to 7 hours, and then aged for about 1 to 3 hours at the above temperature.
And as polymerization conditions in the polymerization method of the above [3], water is charged into a polymerization can, the temperature is raised to 40 to 90 ° C., and the monomer mixture is dropped or added in portions over about 2 to 7 hours. And aging at the above temperature for about 1 to 3 hours.

  Stirring of the above-mentioned emulsion during emulsification can be performed using a stirring device in which the components are mixed and equipped with stirring blades such as homodispers and paddle blades. There is no problem as long as the temperature during emulsification is such that the mixture does not react during emulsification.

  The amount of the organic solvent (A) used is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 8 parts by weight, more preferably 1 to 1 part by weight based on 100 parts by weight of the ethylenically unsaturated monomer. 5 parts by weight. If the amount of the organic solvent (A) used is too small, a tendency to improve the elongation of the coating film tends to be insufficient. If the amount used is too large, the polymerization stability tends to decrease.

In the polymerization of the acrylic resin emulsion, the organic solvent (A) and other organic solvent (B) may be used in an amount of 0.5 parts by weight or less.
Examples of other organic solvents include alcohols such as methanol, ethanol, propanol, and butanol that have the chain transfer effect.

  In addition, the acrylic resin emulsion used in the present invention is appropriately added with additives such as organic pigments, inorganic pigments, water-soluble additives, pH adjusters, preservatives, antifoaming agents, and antioxidants as necessary. It can be blended.

  The average particle diameter of the acrylic resin in the acrylic resin emulsion is preferably in the range of 50 to 700 nm, particularly 100 to 500 nm, and more preferably 150 to 350 nm. If the particle size is too small, the viscosity of the emulsion becomes too high and the dispersibility of the emulsion tends to decrease when admixed with cement. If the particle size is too large, a dense coating film can be obtained when forming the coating film. Is difficult, and there is a tendency that it is not preferable in terms of strength. The measurement of the average particle diameter is based on the light scattering method.

  The average particle diameter of the acrylic resin can be set within a predetermined range by appropriately adjusting the prescription used at the time of polymerization, for example, by adjusting the stirring speed at the time of polymerization, etc. Can be set to

  The glass transition temperature (Tg) of the acrylic resin is in the range of 0 to −70 ° C., more preferably −10 to −60 ° C., particularly −20 to −40, in view of improving the low-temperature elongation of the coating film. It is preferable that it is ° C. If the glass transition temperature is too high, the film-forming temperature of the coating film will be too high, especially when it is difficult to obtain sufficient strength during on-site construction in winter, and if it is too low, it will tend to cause tackiness of the coating film. Is seen.

The glass transition temperature (Tg) of the acrylic resin used was a value calculated by the Fox equation shown in the following equation (1).
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ +... + W _n / Tg _n (1)
In the above formula (1), W _n from W ₁ represents the weight fraction of each monomer using, Tg _n from Tg ₁ is the glass transition temperature (unit of a homopolymer of each monomer Indicates an absolute temperature “K”). The absolute temperature is calculated as absolute temperature “K” = Celsius temperature “° C.” + 273.15.

The acrylic resin emulsion has a solid content concentration (nonvolatile content concentration) of preferably 45% by weight or more, particularly 45 to 70% by weight, and more preferably 50 to 60% by weight. From the viewpoint of sex.
In addition, solid content concentration in this invention means solid content concentration after drying at 105 degreeC for 1 hour.

  The viscosity of the acrylic resin emulsion is preferably 10 to 50000 mPa · s, particularly 10 to 10000 mPa · s, more preferably 10 to 5000 mPa · s in terms of handling.

The acrylic resin emulsion used in the present invention may contain additives such as fats and oils.
Examples of the fat include soybean oil, Amany oil, castor oil, corn oil, cottonseed oil, olive oil, palm oil, rapeseed oil, safflower oil, sesame oil and the like. These may be used alone or in combination of two or more. Of these, the use of soybean oil, olive oil, sesame oil, and especially soybean oil is effective for imparting waterproofness without impeding the improvement of checking.

  The amount of the fat is preferably 1 to 50 parts by weight, particularly 2 to 40 parts by weight, more preferably 5 to 20 parts by weight, with respect to 100 parts by weight of the acrylic resin in the acrylic resin emulsion. The amount of 6 to 10 parts by weight is particularly desirable for imparting waterproofness.

  The mixing method of the acrylic resin emulsion and additives such as fats and oils is, for example, a method in which after the polymerization of the acrylic resin emulsion is completed, the additive is added afterwards and charged into the polymerization can with stirring. Can be given.

In the polymer cement composition of the present invention, a polyoxyalkylene compound can be used together with the acrylic resin emulsion from the viewpoint of improving the coatability.
Specific examples of the polyoxyalkylene compound include polyalkylene glycol and monoetherified products, monoether monoesterified products, dietherified products, monoesterified products, and diesterified products of polyalkylene glycol.
The polyalkylene glycol is obtained by polymerization or copolymerization of alkylene oxides such as ethylene oxide (EO) and propylene oxide (PO). From the viewpoint of handling properties, it is preferable that the amount of hydrophilic EO is larger than that of hydrophobic PO.

Examples of the monoetherified product include polyoxyethylene monooleyl ether, polyoxyethylene monocetyl ether, polyoxyethylene monostearyl ether, polyoxyethylene monolauryl ether, polyoxyethylene monododecyl ether, polyoxyethylene monononylphenol ether, Examples include polyoxyethylene monooctyl phenyl ether.
Examples of the monoether monoester product include methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, propoxypolyethylene glycol (meth) acrylate, and the like.
Examples of the diether compound include polyoxyethylene dioleyl ether, polyoxyethylene dicetyl ether, polyoxyethylene distearyl ether, polyoxyethylene dilauryl ether, polyoxyethylene didodecyl ether, polyoxyethylene dinonyl phenol ether, Examples thereof include oxyethylene dioctyl phenyl ether.

Examples of monoester products include polyoxyethylene mono (meth) acrylate, polyoxyethylene monooleate, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monobovine fatty acid ester, polygluterin monostearate. Examples include rates.
Examples of the diesterified product include polyoxyethylene di (meth) acrylate, polyoxyethylene dioleate, polyoxyethylene dilaurate, polyoxyethylene distearate, polyoxyethylene dibovine fatty acid ester, polyglycerin distearate and the like. Illustrated.

  The weight average molecular weight of the polyoxyalkylene compound is preferably 1000 or more, particularly preferably 1500 to 10,000, and further preferably 2000 to 5000, from the viewpoint of suppressing cracking of the coating film. If the weight average molecular weight of the polyoxyalkylene compound is too low, the effect of suppressing cracking tends to be low, and if it is too high, the viscosity tends to be high and the leveling property tends to decrease.

  In the present invention, the weight average molecular weight means a weight average molecular weight in terms of standard polystyrene molecular weight.

  The content of the polyoxyalkylene compound is preferably 0.5 to 15 parts by weight, particularly preferably 1 to 12 parts by weight, and still more preferably 1.5 to 100 parts by weight of the solid content of the acrylic resin emulsion. -10 parts by weight. If the content of the polyoxyalkylene compound is too small, coating film cracking (checking) after coating and drying cannot be sufficiently suppressed, and the waterproof performance tends to be inferior. There is a tendency for the strength of the film to decrease.

  Thus, in the present invention, an emulsion composition for polymer cement containing the acrylic resin emulsion obtained above is obtained.

Furthermore, in this invention, a polymer cement composition is obtained by mixing the said acrylic resin emulsion and cement.
[cement]
Examples of cement components include ordinary Portland cement, alumina cement, early strength Portland cement, ultra-high strength Portland cement, medium heat Portland cement, low heat Portland cement, sulfate resistant Portland cement, blast furnace cement, fly ash cement, silica cement, etc. Among them, Portland cement is preferable from the viewpoint of workability.

  The blending amount of the cement is preferably 3 to 500 parts by weight, more preferably 30 to 350 parts by weight with respect to 100 parts by weight of the solid content of the acrylic resin emulsion.

  Thus, an acrylic resin emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer in the presence of the organic solvent (A) and water, and a composition containing a cement component are obtained. As a result, the polymer cement composition of the present invention is obtained.

  The blending method of the acrylic resin emulsion and cement is not particularly limited. For example, in the production process of [I] acrylic resin emulsion, during the late ripening at the time of polymerization of the ethylenically unsaturated monomer Method of blending cement, [II] Method of blending cement into acrylic resin emulsion after completion of polymerization of ethylenically unsaturated monomer, and [III] Polymerization of ethylenically unsaturated monomer into cement Examples include a method of blending the acrylic resin emulsion after completion.

  The polymer cement composition can be used as mortar or concrete by further blending water, sand or gravel. In the present invention, these are also included in the category of cement components.

  The amount of water to be used as mortar or concrete is preferably 50% by weight or less, more preferably 30% by weight or less, based on the solid content of the polymer cement composition.

  In addition, the amount of sand and gravel when used as mortar or concrete is preferably 30 to 300% by weight, more preferably 50 to 150% by weight, based on the solid content of the polymer cement composition. Is preferred.

  The polymer cement composition of the present invention includes a cement water reducing agent or fluidizing agent (for example, lignin-based, naphthalene-based, melamine-based, carboxylic acid-based, etc.), shrinkage reducing agent (for example, glycol) Ethers, polyethers, etc.), cold-resistant agents (eg, calcium chloride), waterproofing agents (eg, stearic acid), rust inhibitors (eg, phosphates), viscosity modifiers (eg, methylcellulose, hydroxy) Ethyl cellulose, polyvinyl alcohol, etc.), dispersants (eg, polycarboxylic acids, inorganic phosphorus, etc.), antifoaming agents (eg, silicon, mineral oils, etc.), preservatives, reinforcing agents (eg, steel fibers, glass fibers) , Synthetic fibers, carbon fibers, etc.) may be used alone or in combination of two or more.

  In addition to the above components, various aggregates such as pozzolanic materials such as calcium carbonate, kaolin, clay, diatomaceous earth, silica fume, fly ash, blast furnace slag, and natural and artificial lightweight aggregates may be blended.

  The polymer cement composition preferably has a viscosity of 5000 mPa · s or less, particularly preferably 50 to 4500 mPa · s, more preferably 100, as measured with a B-type viscometer at 23 ° C. and a rotation speed of 10 rpm. ˜4000 mPa · s. When the viscosity is too low, the inorganic powder tends to settle and the uniformity of the coating film tends to be impaired. When the viscosity is too high, the workability during coating tends to be reduced.

  In addition, when using a polymer cement composition as a mortar, as in general mortar, an essential component and an optional component are added, and after adding an appropriate amount of water, a kneader or the like is used. It can be prepared by kneading.

  The polymer cement composition of the present invention has an ethylenicity in the presence of an organic solvent (A) that has a solubility in water (dissolution amount in 100 g of water) of 20 g / 100 g or less and that has no unsaturated group, and water. It contains an acrylic resin emulsion obtained by emulsion polymerization of an unsaturated monomer and a cement component, and has excellent flexibility and weather resistance of the coating film, and excellent elongation of the coating film. Therefore, it is useful to use it as a coating film waterproofing agent.

  The waterproof coating material using the polymer cement composition of the present invention can be obtained, for example, by applying the polymer cement composition with a roller, a plastering brush or a trowel, or spraying with a spray.

  In addition, although the thickness of the said coating-film waterproofing material changes with enforcement places etc., it is 0.3-5 mm normally, Preferably it is 0.5-3 mm, Most preferably, it is 0.7-2 mm.

  Examples of the object on which the waterproof coating material is formed include, for example, a rooftop of a building made of mortar, concrete, iron plate, asphalt, a sloped roof, an outer wall, a fence, a veranda, a roof balcony, an external corridor, a staircase, a building Underground refills, underground joints, underground pits, miscellaneous drainage tanks, indoor or underground water tanks such as fireproof water tanks, waterproof parts around sash frames, water storage tanks, and the like.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the following examples and the like, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

First, prior to the examples and comparative examples, the acrylic resin emulsions shown below were prepared.
<Preparation of acrylic resin emulsion 1>
1. In a container, 28 parts of water, 1.3 parts of surfactant (trade name “Adekaria soap SR-10” manufactured by ADEKA), (product name “Adekaria soap ER-30” manufactured by ADEKA) 5 parts, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (made by EASTMAN, trade name “Texanol”, solubility: insoluble, boiling point: 253 ° C.) 3.6 as organic solvent (A) Parts, butyl acrylate 66.9 parts, methyl methacrylate 31.6 parts, acrylic acid 0.5 parts, methacrylamide 1 part, and monomer emulsified mixture (ethylenically unsaturated monomer 100.0 parts) Was prepared.
Next, in a stainless steel reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen introduction tube and a dropping funnel, 31 parts of water (product name “ADEKA rear soap ER-30” manufactured by ADEKA) was added. Three parts were weighed and kept at 80 ° C.
Subsequently, 10% of the monomer emulsion mixture prepared above was added to the stainless steel reaction vessel, and 1.7 parts of 10% sodium persulfate (polymerization initiator) was added to the reaction vessel. The reaction was allowed for 30 minutes. Thereafter, the remaining monomer emulsified mixture and 4.6 parts of 10% sodium persulfate were dropped into a glass reaction vessel over 4 hours, and polymerization was carried out at 80 ° C.
After completion of the dropwise addition, ripening was performed at 80 ° C. for 60 minutes, and 0.5 part of 10% aqueous solution of t-butyl hydroperoxide and 0.6 part of 10% aqueous solution of acidic sodium sulfite were added to perform additional polymerization for 1 hour. The reaction was completed to obtain an acrylic resin emulsion 1 having a solid content of 58% (average particle size: 300 nm).
In addition, the glass transition temperature (Tg) of acrylic resin was -20 degreeC.

<Preparation of acrylic resin emulsion 2>
Instead of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (trade name “Texanol”) as the organic solvent (A), 2,2,4-trimethyl-1,3-pentanediol dino Acrylic resin emulsion in the same manner as the acrylic resin emulsion 1 except that isobutyrate (trade name “CS-16”, manufactured by Chisso Corporation, solubility: 0.00015 g / 100 g, boiling point: 280 ° C.) was used. 2 (solid content: 52.3%) was obtained (average particle size: 300 nm). In addition, the glass transition temperature (Tg) of acrylic resin was -20 degreeC.

<Preparation of acrylic resin emulsion 3>
Instead of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (trade name “Texanol”) as the organic solvent (A), propylene glycol-n-butyl ether (trade name, manufactured by Dow Chemical Co., Ltd.) An acrylic resin emulsion 3 (solid content: 52.3%) was obtained in the same manner as the acrylic resin emulsion 1 except that “Dawanol PnB”, solubility: 6 g / 100 g, boiling point: 170 ° C. was used. (Average particle diameter: 300 nm). In addition, the glass transition temperature (Tg) of acrylic resin was -20 degreeC.

<Preparation of acrylic resin emulsion 4>
Instead of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (trade name “Texanol”) as the organic solvent (A), dibutyl phthalate (trade name “DBP” manufactured by Sankyo Chemical Co., Ltd.) Acrylic resin emulsion 4 (solid content: 52.3%) was obtained in the same manner as the acrylic resin emulsion 1 except that the solubility was 0.0013 g / 100 g and the boiling point was 340 ° C. Diameter: 300 nm). In addition, the glass transition temperature (Tg) of acrylic resin was -20 degreeC.

<Preparation of acrylic resin emulsion 5 (for comparative example)>
At the time of emulsion polymerization of the ethylenically unsaturated monomer, the same amount of the acrylic resin emulsion 1 is added without adding the organic solvent (A) [2,2,4-trimethyl-1,3-pentanediol monoisobutyrate]. An acrylic resin emulsion 5 was obtained in the same manner as in the preparation of the acrylic resin emulsion 1 except that the amount to be added later was added.
That is, in a container, 28 parts of water, 1.3 parts of a surfactant (trade name “Adeka Soap SR-10” manufactured by ADEKA), (product name “Adeka Soap ER-30” manufactured by ADEKA) 1.5 parts, 66.9 parts of butyl acrylate, 31.6 parts of methyl methacrylate, 0.5 part of acrylic acid, and 1 part of methacrylamide were weighed and mixed with a monomer emulsion (ethylenically unsaturated monomer 100. 0 parts) was prepared.
Next, in a stainless steel reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen introduction tube and a dropping funnel, 31 parts of water (product name “ADEKA rear soap ER-30” manufactured by ADEKA) was added. Three parts were weighed and kept at 80 ° C.
Subsequently, 10% of the previously prepared monomer emulsion mixture was added to the stainless steel reaction vessel, and then 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (manufactured by EASTMAN). (Trade name "Texanol") 3.6 parts, 1.7 parts of 10% sodium persulfate (polymerization initiator) was added to the reaction vessel and allowed to react for 30 minutes. Thereafter, the remaining monomer emulsified mixture and 4.6 parts of 10% sodium persulfate were dropped into a glass reaction vessel over 4 hours, and polymerization was carried out at 80 ° C.
After completion of the dropwise addition, ripening was performed at 80 ° C. for 60 minutes, and 0.5 part of 10% aqueous solution of t-butyl hydroperoxide and 0.6 part of 10% aqueous solution of acidic sodium sulfite were added to perform additional polymerization for 1 hour. The reaction was completed to obtain an acrylic resin emulsion 5 having a solid content of 58% (average particle size: 300 nm). In addition, the glass transition temperature (Tg) of acrylic resin was -20 degreeC.

<Preparation of acrylic resin emulsion (impossible polymerization)>
Instead of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (trade name “Texanol”) as the organic solvent (A), propylene glycol methyl ether (manufactured by Dow Chemical Company, trade name “Dawanol”) Except for using “PM”, solubility: ∞, boiling point: 120 ° C.), the polymerization did not proceed and the acrylic resin emulsion could not be obtained in the same manner as the preparation of the acrylic resin emulsion 1 described above. .

  Further, instead of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (trade name “Texanol”) as the organic solvent (A), dipropylene glycol dimethyl ether (trade name, manufactured by Dow Chemical Co., Ltd.) Polymerization does not proceed and an acrylic resin emulsion is obtained when the same procedure as in the preparation of the acrylic resin emulsion 1 is used except that “Dawanol DMH”, solubility: 53 g / 100 g, boiling point: 175 ° C.) is used. I could not.

[Example 1]
The acrylic resin emulsion 1 obtained above is cooled to room temperature (25 ° C.), and 2.2 parts of a 10% caustic soda aqueous solution as a neutralizing agent is added to 100 parts of the solid content of the acrylic resin emulsion 1. After the addition, 6 parts (3 parts in terms of solid content) of a 50% aqueous solution of a polyoxyalkylene compound [manufactured by NOF Corporation, Dodox DSP E-20 (Mw = 2000)] is added and diluted with water. After preparing an emulsion composition having a solid content (nonvolatile content) of 55% and a pH of 7 to 10, 135 parts of Portland cement was added and stirred at 1000 rpm for 1 minute using a disper to obtain a polymer cement composition.

"viscosity"
The viscosity of the polymer cement composition was measured at 23 ° C. and a rotation speed of 10 rpm using a BH viscometer (manufactured by Tokyo Keiki Co., Ltd.).
The viscosity is preferably 5000 mPa · s or less.

《Coating strength, coating elongation》
The polymer cement composition was poured into a mold having a width of 25 cm, a depth of 25 cm, and a thickness of 2 mm, and cured at a temperature of 20 ° C. ± 2 ° C. and a humidity of 65% ± 10%. A 7 day old paint film was punched into the shape of No. 2 dumbbell. Using a tensile tester, a dumbbell was sandwiched between the chucks at a distance of 60 mm, a tensile test was performed at a speed of 200 mm / min, and the film strength and film elongation were calculated from the maximum tensile load and the distance between the marked lines at break.
The calculation method is based on the following equations (1) and (2).
TB = PB / A (1)
TB: Coating film strength (N / mm ² )
PB: Maximum tensile load (N)
A: Cross-sectional area (mm ² )
E = [(L-20) / 20] × 100 (2)
E: Film elongation (%)
L: Distance between marked lines at break Note that the coating film strength is preferably 0.7 N / mm ² or more, and the coating film elongation is preferably 200% or more.

[Examples 2 to 4, Comparative Example 1]
A polymer cement composition was prepared according to Example 1 except that the type of acrylic resin emulsion was changed to that shown in Table 1 below.
And each characteristic was evaluated like Example 1 using each polymer cement composition. The results are also shown in Table 1 below.

  From the results of Table 1 above, the Examples show acrylic resin emulsions 1 to 4 obtained by emulsion polymerization of ethylenically unsaturated monomers in the presence of a specific water-soluble organic solvent (A). Therefore, it was excellent in a good balance between coating suitability and coating film properties.

  On the other hand, in Comparative Example 1, the organic solvent (A) was added to the acrylic resin emulsion obtained by emulsion polymerization of the ethylenically unsaturated monomer without the organic solvent (A). Therefore, the film elongation was inferior.

  The polymer cement composition of the present invention is useful in the field of civil engineering / architecture, and in particular, as a coating film waterproofing material composition, a roof of a building, a sloped roof, a veranda, a roof balcony, an outer wall, a fence, an external corridor, a staircase , Indoor or underground water tanks such as underground backfill parts of buildings, underground joints, underground pits and miscellaneous drainage tanks, fireproof water tanks, waterproofing parts around sash frames, water tanks for water supply, floors and peripheral walls of subways, etc. It is very useful to use in

Claims (9)

  An ethylenically unsaturated monomer is emulsion-polymerized in the presence of water and an organic solvent (A) having a solubility in water (dissolution amount in 100 g of water) of 20 g / 100 g or less and having no unsaturated group. A polymer cement composition comprising an acrylic resin emulsion obtained in the above manner.   The polymer cement composition according to claim 1, wherein the boiling point of the organic solvent (A) is 170 to 350 ° C.   3. The polymer cement composition according to claim 1, wherein the organic solvent (A) is an ester solvent having 5 to 20 carbon atoms or an ether solvent having 5 to 20 carbon atoms.   3. The polymer cement composition according to claim 1, wherein the organic solvent (A) is 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.   The amount of the organic solvent (A) used is 0.1 to 10 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer, according to any one of claims 1 to 4. Polymer cement composition.   The polymer cement composition according to any one of claims 1 to 5, wherein the ethylenically unsaturated monomer contains at least a carboxyl group-containing ethylenically unsaturated monomer.   The polymer cement composition according to any one of claims 1 to 6, wherein the ethylenically unsaturated monomer contains at least an amino group-containing ethylenically unsaturated monomer.   A waterproofing coating film comprising the polymer cement composition according to any one of claims 1 to 7.   An ethylenically unsaturated monomer is emulsion-polymerized in the presence of water and an organic solvent (A) having a solubility in water (dissolution amount in 100 g of water) of 20 g / 100 g or less and having no unsaturated group. An emulsion composition for polymer cements, comprising an acrylic resin emulsion obtained in the above manner.