JP7419619B2 - Waterproofing material composition, waterproofing method and waterproofing film - Google Patents

Description

The present invention relates to a waterproof material composition, a waterproofing method using the same, and a waterproof coating.

In recent years, from the viewpoint of environmental protection and occupational health, the release of volatile organic compounds (VOC) into the atmosphere from solvent-based paints has become a problem, and a shift to water-based paints is progressing. However, the dry film formation properties of water-based paints mainly depend on the evaporation rate of water, so dry film formation is slower than that of solvent-based paints, and tends to be significantly delayed, especially at low temperatures and high humidity. Therefore, there is a need to improve dry film forming properties.
Conventionally, a waterproofing method is widely known in which a waterproofing film is formed on the surface of an architectural or civil engineering structure made of concrete for the purpose of preventing deterioration of the frame due to water intrusion and water leakage into the interior.
For example, Patent Document 1 describes 55 to 98% by mass of alkyl (meth)acrylate units having an alkyl group having 4 to 10 carbon atoms, 0.1 to 3% by mass of (meth)acrylic acid units, and glycidyl (meth)acrylate units. A vinyl polymer (A) containing 0.1 to 5% by mass as a constituent unit and having a glass transition temperature of -20°C or lower, containing (meth)acrylic acid units as a constituent unit and having a weight average molecular weight of 2000 to 100000. containing a vinyl polymer (B) having an acid value of 50 to 200 mgKOH/g and a glass transition temperature of 0°C or higher, an inorganic hydraulic substance (C), and an aqueous medium; The proportion of the vinyl polymer (B) is 0.3 to 8 parts by mass based on parts by mass, and the proportion of the inorganic hydraulic substance (C) is 10 to 200 parts by mass based on 100 parts by mass of the vinyl polymer (A). An aqueous waterproofing material composition is disclosed.

Japanese Patent Application Publication No. 2009-79184

However, although the waterproof material composition described in Patent Document 1 can form a coating film with excellent tensile strength, its dry film formability sometimes poses a problem. Specifically, if the film is applied in a low temperature and/or high humidity environment, drying film formation will be delayed, so if the film gets wet with night dew or rain during film formation, it will re-emulsify and be washed away, or the film formation time will be significantly reduced. Due to delays, the construction period could be delayed.
The present invention is concerned with the time it takes for a coating before drying to stop re-emulsifying even if it gets wet with water in a low-temperature and/or high-humidity environment (hereinafter referred to as "non-reemulsification time"), and the drying time of the coating. An object of the present invention is to provide a waterproof material composition that can shorten the time required to form a film and form a coating film with excellent tensile strength, a waterproof construction method using the same, and a waterproof film.

The present inventors discovered that the above-mentioned problem was solved by combining a specific anionic vinyl polymer and a specific cationic polymer, and completed the present invention.

The invention is illustrated below.
1. In a waterproof material composition containing (A) an anionic vinyl polymer stabilized by a surfactant, (B) a cationic polymer, and (C) a volatile base,
The above component (B) is selected from allylamine and its salt, N-alkylarylamine and its salt, N,N-dialkylallylamine and its salt, diallylamine and its salt, and N-alkyldiallylamine and its salt or quaternized product. A waterproof material composition comprising a structural unit derived from at least one species.
2. 2. The waterproof material composition according to item 1, wherein the anionic vinyl polymer (A) contains a structural unit derived from an alkyl (meth)acrylate ester and a structural unit derived from an unsaturated acid.
3. The content ratio of the cationic polymer (B) is 0.1 to 10 parts by mass when the content of the anionic vinyl polymer (A) is 100 parts by mass as described in item 1 or 2 above. waterproof material composition.
4. The content ratio of the volatile base (C) is 0.01 to 10 parts by mass when the content of the anionic vinyl polymer (A) is 100 parts by mass. The waterproof material composition according to item 1.
5. The waterproof material composition according to any one of items 1 to 4 above, further comprising (D) another anionic vinyl polymer having a weight average molecular weight of 500 to 100,000 as determined by gel permeation chromatography.
6. 6. The waterproof material composition according to item 5, wherein the anionic vinyl polymer (D) contains a structural unit derived from an alkyl (meth)acrylate ester and a structural unit derived from an unsaturated acid or a salt thereof.
7. The waterproof material composition according to any one of items 1 to 6 above, further comprising (E) a metal crosslinking agent.
8. The waterproof material composition according to any one of items 1 to 7 above, further comprising (F) a filler.
9. A coating step of applying the waterproof material composition according to any one of items 1 to 8 above to an object to be coated, and a film forming step of forming the coating film obtained by the above coating step into a film. A waterproofing method characterized by:
10. 10. The waterproofing method according to item 9, wherein the object to be coated is a structure.
11. 9. A waterproof coating formed by forming a coating film using the waterproof material composition according to any one of items 1 to 8 above.

According to the waterproof material composition of the present invention, even if the coating film before drying gets wet with water, it will re-emulsify, for example, in a low temperature environment of 5° C. or lower and/or a high humidity environment of 80% or higher relative humidity. The time it takes for the coating to dry (non-reemulsification time) and the coating film to dry can be shortened, and the film obtained by drying the coating film (waterproofing film) has excellent tensile strength. Moreover, the above effects can be obtained regardless of the method of manufacturing the composition, for example, even if the composition is obtained by dividing and mixing raw materials or is stored for a long period of time.

FIG. 2 is a schematic cross-sectional view showing a composite with a waterproof film used for evaluation of base crack followability in [Example]. FIG. 2 is a schematic cross-sectional view illustrating base crack followability in [Example]. FIG. 2 is a schematic cross-sectional view illustrating base crack followability in [Example].

The waterproof material composition of the embodiment according to the present invention contains an anionic vinyl polymer (A) stabilized by a surfactant, a cationic polymer (B), and a volatile base (C). , may contain other components (described later) as necessary. Incidentally, this waterproof material composition usually contains a medium such as water or an organic solvent, and a preferable medium is water.

The anionic vinyl polymer (A) is not particularly limited as long as it contains one or more structural units derived from a vinyl monomer having a polymerizable unsaturated bond. Examples of the anionic vinyl polymer (A) include (meth)acrylic polymers and olefin polymers, and among these, (meth)acrylic polymers are preferred.

The above (meth)acrylic polymer is preferably a copolymer (hereinafter referred to as "(meth) ) acrylic polymer (A1). This (meth)acrylic polymer (A1) may further contain structural units derived from other monomers.

The (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, Isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate Examples include n-octyl acid, nonyl (meth)acrylate, decyl (meth)acrylate, and dodecyl (meth)acrylate. The number of structural units derived from these compounds contained in the (meth)acrylic polymer (A1) can be one or more. The main compound forming this (meth)acrylic polymer (A1) is preferably a (meth)acrylic acid alkyl ester in which the alkyl group in the ester moiety has 4 or more carbon atoms. Particularly preferred compounds are n-butyl acrylate and 2-ethylhexyl acrylate. In addition, in a preferred embodiment of the above (meth)acrylic acid alkyl ester, the compound whose alkyl group in the ester moiety has 4 or more carbon atoms is preferably 20% by mass based on the entire (meth)acrylic acid alkyl ester. More preferably, it is used in an amount of 30% by mass or more.

The content ratio of the structural units derived from the (meth)acrylic acid alkyl ester constituting the above (meth)acrylic polymer (A1) is preferably 10% when the total of all structural units is 100% by mass. ~99.9% by weight, more preferably 30~99.5% by weight, even more preferably 50~98% by weight.

Examples of the unsaturated acids include carboxylic acid monomers, sulfonic acid monomers, phosphonic acid monomers, phosphoric acid monomers, and the like.
Examples of the carboxylic acid monomer include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
Examples of the sulfonic acid monomer include vinyl sulfonic acid, halogenated vinyl sulfonic acid, styrene sulfonic acid, acrylamide methylpropanesulfonic acid, and the like.
Examples of the phosphonic acid monomer include vinyl phosphoric acid.
As the unsaturated acid, a carboxylic acid monomer is preferable.
Further, examples of the salts of the unsaturated acids include sodium salts, potassium salts, ammonium salts, and the like.

The number of structural units derived from unsaturated acids or salts thereof contained in the (meth)acrylic polymer (A1) may be one or two or more.
The (meth)acrylic polymer (A1) may contain both a structural unit derived from an unsaturated acid and a structural unit derived from a salt of an unsaturated acid.

Content ratio of structural units derived from unsaturated acids or salts thereof (structural units derived from unsaturated acids and structures derived from salts of unsaturated acids) constituting the above (meth)acrylic polymer (A1) When both units are included, the ratio of the total amount thereof is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, when the total of all structural units is 100% by mass. , more preferably 0.5 to 5% by mass.

When the (meth)acrylic polymer (A1) further contains other structural units derived from other monomers, the other structural units include (meth)acrylic acid alkoxyalkyl ester, aromatic vinyl compound , a structural unit derived from a vinyl cyanide compound, an unsaturated compound containing a hydroxyl group, an unsaturated compound containing an amino group, an unsaturated compound containing an amide group, a polyfunctional compound having two or more polymerizable unsaturated bonds, etc. I can do it.

The above-mentioned (meth)acrylic acid alkoxyalkyl esters include methoxymethyl (meth)acrylate, ethoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and (meth)acrylate. ) 2-propoxyethyl acrylate, 2-butoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, and the like.
Examples of the aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, p-ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, and vinylnaphthalene. etc.
Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, α-ethyl acrylonitrile, α-isopropylacrylonitrile, and the like.

The hydroxy group-containing unsaturated compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene , o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, 2-hydroxymethyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4- Hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinylnaphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7 -Hydroxymethyl-1-isopropenylnaphthalene, 8-hydroxymethyl-1-isopropenylnaphthalene, p-vinylbenzyl alcohol, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2 -butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, and the like.

The above amino group-containing unsaturated compounds include aminoethyl (meth)acrylate, propylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, diethylaminomethyl (meth)acrylate, and phenyl (meth)acrylate. Examples include aminoethyl, p-aminostyrene, N-vinyldiethylamine, N-acetylvinylamine, (meth)acrylamine, and N-methylacrylamine.
Examples of the amide group-containing unsaturated compound include acrylamide, N-methylacrylamide, methacrylamide, N-methylmethacrylamide, N-methylolacrylamide, diacetone acrylamide, and the like.

The above polyfunctional compounds include divinylbenzene, divinyltoluene, allyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Examples include diallyl phthalate, diallyl maleate, diallyl fumarate, triallyl cyanurate, triallyl isocyanurate, and the like.

The other structural units are preferably structural units derived from aromatic vinyl compounds and structural units derived from vinyl cyanide compounds.

When the above (meth)acrylic polymer (A1) further contains other structural units derived from other monomers, the upper limit of the content ratio is based on the total of all structural units as 100% by mass. In this case, the amount is preferably 60% by weight, more preferably 50% by weight, and even more preferably 30% by weight.

In the present invention, the (meth)acrylic polymer (A1) is preferably the main component of the anionic vinyl polymer (A), and the content ratio of the anionic vinyl polymer (A) to the whole is preferably is 40% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more.
Moreover, the number of anionic vinyl polymers (A) contained in the waterproof material composition of the embodiment according to the present invention may be one type or two or more types. That is, the anionic vinyl polymer (A) may be composed of one or more types of (meth)acrylic polymer (A1), or may be composed of (meth)acrylic polymer (A1) and It may also consist of another anionic vinyl polymer (hereinafter referred to as "other polymer (A2)"). Other polymers (A2) include ethylene/vinyl acetate copolymers and the like.

The weight average molecular weight in terms of polystyrene (hereinafter referred to as "weight average molecular weight") determined by gel permeation chromatography of the anionic vinyl polymer (A) is preferably over 100,000. In this point, it differs from other anionic vinyl polymers (D) that can be contained in the composition and will be described later.
Further, the glass transition temperature of the anionic vinyl polymer (A) is usually 20°C or lower, preferably 0°C or lower, more preferably -10°C or lower, still more preferably -20°C or lower, particularly preferably - The temperature is below 30°C. This glass transition temperature can be calculated from the so-called Fox equation depending on the type of monomer forming the structural unit constituting the polymer.
The waterproof material composition of the embodiment according to the present invention may contain a plurality of anionic vinyl polymers (A) having different weight average molecular weights and/or glass transition temperatures.

The anionic vinyl polymer (A) preferably has a specific shape, more preferably particulate, still more preferably in an emulsion state in an aqueous medium, and even more preferably in an emulsion state in an aqueous medium. It is particularly preferable that there be.

In the waterproof material composition of the embodiment of the present invention, the anionic vinyl polymer (A) is stabilized in dispersion in a medium by a surfactant.
The surfactant is not particularly limited, and can be at least one selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Among these, nonionic surfactants are preferred, and a combination of nonionic surfactants and anionic surfactants is also a preferred embodiment.
In the waterproof material composition of the embodiment according to the present invention, at least a part of the nonionic surfactant which is a preferred surfactant is mainly coated with the granular anionic vinyl polymer (A) which is a preferred embodiment. The anionic vinyl polymer (A) is dispersed and stabilized in the medium.

Examples of the nonionic surfactants include polyoxyalkylene alkyl ether, which is an alkylene oxide adduct to an aliphatic alcohol; polyoxyalkylene phenyl ether or polyoxyalkylene alkylphenyl ether, which is an alkylene oxide adduct to an aromatic alcohol. (Polyoxyalkylene aryl ether); Glycerin fatty acid ester; Polyoxyalkylene glycerin fatty acid ester, which is an alkylene oxide adduct to glycerin fatty acid ester; Polyoxyalkylene pentaerythritol fatty acid ester, which is an alkylene oxide adduct to pentaerythritol fatty acid ester; Fatty acid polyoxyalkylene fatty acid ester which is an alkylene oxide adduct to sorbitan fatty acid ester; sorbitan fatty acid ester; polyoxyalkylene sorbitan fatty acid ester which is an alkylene oxide adduct to sorbitan fatty acid ester; sorbitan fatty acid ester; sucrose fatty acid ester; pentaerythritol fatty acid ester; Polyoxyalkylene alkylamines, which are alkylene oxide adducts to aliphatic amines; polyoxyalkylene fatty acid amides, which are alkylene oxide adducts to fatty acid amides; polyoxyalkylene (hardened) castor oil; polyoxyalkylene-modified diorganopolysiloxanes ; polyglyceryl-modified silicone; glyceryl-modified silicone; sugar-modified silicone; perfluoropolyether surfactant; polyoxyethylene/polyoxypropylene block copolymer; alkylpolyoxyethylene/polyoxypropylene block copolymer ether. Among these, polyoxyalkylene alkyl ether and polyoxyalkylene alkylphenyl ether are preferred. In addition, the number of nonionic surfactants contained in the above-mentioned surfactant may be one type or two or more types.

Examples of the anionic surfactants include sulfonic acid-based anionic surfactants, carboxylic acid-based anionic surfactants, sulfuric acid-based anionic surfactants, phosphate-based anionic surfactants, and the like. Among these, sulfonic acid-based anionic surfactants are preferred. In addition, the anionic surfactant contained in the above-mentioned surfactant may be one type or two or more types.

The content ratio of the surfactant is preferably 0.1 to 10 parts by mass when the content of the anionic vinyl polymer (A) is 100 parts by mass in order to sufficiently obtain the effects of the present invention. , more preferably 0.2 to 5 parts by mass.
When a nonionic surfactant and an anionic surfactant are used together as a surfactant to stabilize the dispersion of the anionic vinyl polymer (A) in a medium, the content ratio of these is not limited, but both When the total of be.

The content ratio of the anionic vinyl polymer (A) contained in the waterproof material composition of the embodiment according to the present invention is determined from the above components (A) to (C) so that the effects of the present invention can be sufficiently obtained. When the total amount is 100% by mass, it is preferably 20 to 99% by mass, more preferably 40 to 99% by mass, and still more preferably 60 to 95% by mass.

The above-mentioned cationic polymer (B) is preferably a polymer that is dissolved in the waterproof material composition and imparts toughness and the like to the film obtained by coating and drying.

The above cationic polymer (B) includes allylamine and salts thereof, N-alkylarylamine and salts thereof, N,N-dialkylallylamine and salts thereof, diallylamine and salts thereof, N-alkyldiallylamine and salts thereof, or quaternary It is a polymer containing a structural unit derived from at least one kind selected from compounds, and this polymer may be either a homopolymer or a copolymer. Examples of the salts of the above polymers include neutralized products with inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, acetic acid, propionic acid, butyric acid, citric acid, lactic acid, and malic acid. Further, examples of quaternized products include quaternized products using alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide, and benzyl chloride.
From the viewpoint of ensuring film-forming properties, the lower limit of the total amount of structural units derived from the above compound contained in the cationic polymer (B) is preferably 20 It is % by mass, more preferably 50% by mass, even more preferably 70% by mass.

（式中、Ｒ^１は、水素原子又はアルキル基である。） The structural unit derived from diallylamine is exemplified by the following general formula (1).

(In the formula, R ¹ is a hydrogen atom or an alkyl group.)

Examples of the N-alkylarylamine include N-methylallylamine, N-ethylallylamine, and the like, and examples of the N,N-dialkylallylamine include N,N-dimethylallylamine, N,N-diethylallylamine, and the like.
Examples of the N-alkyl diallylamine include N-methyl diallylamine, N-ethyl diallylamine, N-propyl diallylamine, and the like. In addition, examples of the quaternized products include diallyldimethylammonium chloride, diallyldiethylammonium chloride, diallymethylethylammonium chloride, diallyldipropylammonium chloride, and the like.

It is particularly preferable that the cationic polymer (B) contains a structural unit derived from at least one selected from allylamine and its salts, and diallylamine and its salts.

The cationic polymer (B) may contain other structural units, such as sulfur dioxide; N,N-dialkylaminoalkyl (meth)acrylate and its salt or quaternized product; N,N-dialkylaminoalkyl (Meth)acrylamide and its salts or quaternized products; Vinylimidazole and its salts or quaternized products; vinylpyridine and its salts or quaternized products; Unsaturated compounds having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate ; (Meth)acrylic acid alkyl esters such as methyl (meth)acrylate and ethyl (meth)acrylate; Vinyl carboxylates such as vinyl acetate and vinyl propionate; Structural units derived from unsaturated acids, (meth)acrylamide, etc. It can be done.

It is particularly preferable that the cationic polymer (B) contains a structural unit derived from at least one selected from allylamine and its salts, and diallylamine and its salts. The latter structural unit derived from diallylamine is preferably a structural unit in the above general formula (1) in which R ¹ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.

The weight average molecular weight of the cationic polymer (B) is preferably 500 to 200,000, more preferably 1,000 to 50,000, since the effects of the present invention can be sufficiently obtained.

The number of cationic polymers (B) contained in the waterproof material composition of the embodiment according to the present invention may be one type, or two or more types.
The cationic polymer (B) is preferably a polymer that dissolves in water, which is a preferred medium in the present invention.

The content ratio of the cationic polymer (B) contained in the waterproof material composition of the embodiment according to the present invention is determined by the content ratio of the anionic vinyl polymer (A), since the effects of the present invention can be sufficiently obtained. is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight.

The volatile base (C) is a component that stabilizes the dispersion of the cationic polymer (B) in the medium in the waterproof material composition. When this waterproof material composition is applied, this volatile base (C) volatilizes from the coating film, promoting gelation (coagulation hardening) between the anionic vinyl polymer (A) and the cationic polymer (B). do.
Examples of the volatile base (C) include ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine, tributylamine, and other alkyl amines. , alkanolamines such as diethanolamine, diisopropanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, alkylene polyamines such as ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, ethyleneimine, pyrrolidine, piperidine, piperazine, morpholine etc. Among these, ammonia is preferred from the viewpoint of quick drying of the coating film.

The content ratio of the volatile base (C) contained in the waterproof material composition of the embodiment according to the present invention is such that the content of the anionic vinyl polymer (A) is determined so that the effects of the present invention can be sufficiently obtained. In the case of 100 parts by mass, the amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.

The waterproof material composition of the embodiment according to the present invention may contain other polymers, additives, etc. depending on the purpose, use, etc.
The other polymer is preferably an anionic vinyl polymer having a weight average molecular weight of 500 to 100,000 as determined by gel permeation chromatography (hereinafter referred to as "anionic vinyl polymer (D)"). This anionic vinyl polymer (D) may be either a homopolymer or a copolymer as long as it contains a structural unit derived from a vinyl monomer having a polymerizable unsaturated bond. Further, the weight average molecular weight is preferably 1,000 to 100,000, more preferably 3,000 to 60,000, since the effects of the present invention are further improved.

Examples of the anionic vinyl polymer (D) include (meth)acrylic polymers and olefin polymers, and among these, (meth)acrylic polymers are preferred.

The above (meth)acrylic polymer is preferably a copolymer (hereinafter referred to as "(meth) ) acrylic polymer (D1). This (meth)acrylic polymer (D1) may further contain structural units derived from other monomers. These structural units can be made from the various monomers listed above, which are used to form the structural units constituting the anionic vinyl polymer (A).

The number of structural units derived from the (meth)acrylic acid alkyl ester contained in the (meth)acrylic polymer (D1) may be one or more.

The content ratio of the structural units derived from the (meth)acrylic acid alkyl ester constituting the above (meth)acrylic polymer (D1) is preferably 10% when the total of all structural units is 100% by mass. ~95% by weight, more preferably 20~95% by weight, even more preferably 40~90% by weight.

The number of structural units derived from unsaturated acids or salts thereof contained in the (meth)acrylic polymer (D1) may be one or two or more.
The (meth)acrylic polymer (D1) may contain both a structural unit derived from an unsaturated acid and a structural unit derived from a salt of an unsaturated acid; , potassium salt, ammonium salt, etc.).

Content ratio of structural units derived from unsaturated acids or salts thereof (structural units derived from unsaturated acids and structures derived from salts of unsaturated acids) constituting the above (meth)acrylic polymer (D1) When both units are included, the ratio of the total amount thereof is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, when the total of all structural units is 100% by mass. Contains a certain amount or more of a structural unit derived from an unsaturated acid or a salt thereof, and by converting this into a salt, it gives the anionic vinyl polymer (D) the property of dissolving in water or becoming an emulsified state and dispersing it. can do.

When the (meth)acrylic polymer (D1) further contains other structural units derived from other monomers, the other structural units are CH ₂ =C(R)-CO-O-X (In the formula, R is a hydrogen atom or a methyl group, and X is a polyalkyl (meth)acrylate group) Macromonomer containing a terminal (meth)acryloyl group, (meth)acrylic acid alkoxyalkyl ester, aromatic Structural units derived from vinyl compounds, vinyl cyanide compounds, unsaturated compounds containing hydroxy groups, unsaturated compounds containing amino groups, unsaturated compounds containing amide groups, polyfunctional compounds having two or more polymerizable unsaturated bonds, etc. can do.

The other structural unit is preferably a structural unit derived from a terminal (meth)acryloyl group-containing macromonomer, particularly preferably a structure derived from a terminal (meth)acryloyl group-containing macromonomer having a weight average molecular weight of 100,000 or less. It is a unit.

When the above (meth)acrylic polymer (D1) further contains other structural units derived from other monomers, the upper limit of the content ratio is based on the total of all structural units as 100% by mass. In this case, the amount is preferably 60% by weight, more preferably 50% by weight, and even more preferably 30% by weight.

The anionic vinyl polymer (D) contained in the waterproof material composition of the embodiment of the present invention may be one type or two or more types as long as it has the above properties. That is, the anionic vinyl polymer (D) may be composed of one or more types of (meth)acrylic polymer (D1), or may be composed of (meth)acrylic polymer (D1) and It may also consist of another anionic vinyl polymer (hereinafter referred to as "other polymer (D2)"). Other polymers (D2) include ethylene/vinyl acetate copolymers and the like.

In the present invention, the (meth)acrylic polymer (D1) is preferably the main component of the anionic vinyl polymer (D), and the content ratio of the anionic vinyl polymer (D) to the whole is preferably is 50% by mass or more, more preferably 60% by mass or more.

The content ratio of the anionic vinyl polymer (D) contained in the waterproof material composition of the embodiment according to the present invention is determined based on the content ratio of the anionic vinyl polymer (A), since the effects of the present invention can be obtained more fully. When the content is 100 parts by mass, it is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass.
In the waterproof material composition of the embodiment according to the present invention, the anionic vinyl polymer (A) is dispersed and stabilized in the medium by a surfactant, and when this anionic vinyl polymer (D) is included. After the composition is applied, the volatile base contained in the composition evaporates, and gelation is promoted by the formation of a polyion complex with the cationic polymer (B), so that the effects of the present invention are more fully exerted. This is considered to be what can be obtained. In particular, when the surfactant that contributes to dispersion stabilization of the anionic vinyl polymer (A) is mainly a nonionic surfactant, even if the charge is neutralized by the cationic polymer (B), it will not aggregate. It is presumed that the problem of difficulty in hardening is eliminated by the presence of the anionic vinyl polymer (D), and cohesive hardening is promoted.

Suitable additives for the waterproof material composition of the embodiment of the present invention include a metal crosslinking agent (hereinafter referred to as "metal crosslinking agent (E)") and a filler (hereinafter referred to as "filler (F)"). , thickeners, pigment dispersants, leveling agents, antifoaming agents, colored pigments, cement, crosslinking agents, plasticizers, antibacterial agents, preservatives, fungicides, algaecides, film-forming aids, antifreeze agents, It can contain substances commonly used in paints, waterproofing materials, etc., such as solvents, ultraviolet absorbers, and antioxidants.

The metal crosslinking agent (E) is an anionic vinyl polymer (A) (if it contains an anionic vinyl polymer (D) when the coating film is formed into a film, an anionic vinyl polymer (A) and It is a component that crosslinks the anionic vinyl polymer (D), and preferably ions such as calcium, aluminum, magnesium, zinc, barium, strontium, titanium, zirconium, tin, manganese, and salts (inorganic salts, organic acid salts, etc.), oxides, hydroxides, or complexes. Specific examples include aluminum sulfate, aluminum acetate, zinc acetate, zinc oxide, zinc acetylacetone, zinc ammonium complex, calcium acetate, calcium hydroxide, calcium acetylacetone, etc. Particularly preferred metal crosslinking agents (E) include hydroxide Calcium.

When the waterproofing material composition of the embodiment according to the present invention contains a metal crosslinking agent (E), the content ratio is determined based on anionic vinyl When the content of the aggregate (A) is 100 parts by mass, it is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass.

The filler (F) may be either a solid body or a hollow body, or a combination thereof. Examples of solid bodies include fillers (inorganic fillers) made of inorganic materials such as silica sand, calcium carbonate, barium sulfate, silicon oxide, titanium oxide, talc, mica, kaolin, clay, ferrite, gypsum, and diatomaceous earth. In addition, the hollow bodies include inorganic hollow bodies such as shirasu balloons, perlite, glass (silica) balloons, fly ash balloons, alumina balloons, zirconia balloons, and carbon balloons, as well as phenol balloons, epoxy balloons, urea balloons, saran balloons, Examples include organic hollow bodies such as polystyrene balloons, polymethacrylate balloons, polyvinyl alcohol balloons, and styrene/acrylic balloons.
Among these, inorganic fillers are preferable as the filler (F) because they can improve the tensile strength of the coating film.

The shape of the filler (F) is not particularly limited, and may be spherical, flat, linear, amorphous, etc., and the shape may be either uniform or non-uniform.

When the waterproof material composition of the embodiment according to the present invention contains the filler (F), the content ratio is determined by the anionic vinyl polymer because the film obtained by drying the coating film has excellent tensile strength. When the content of (A) is 100 parts by weight, it is preferably 0.1 to 1000 parts by weight, more preferably 0.5 to 500 parts by weight, and still more preferably 1 to 300 parts by weight.

Thickeners include organic substances such as carboxymethyl cellulose, methyl cellulose, hydroxy cellulose, sodium polyacrylate, polyethylene oxide, alginic acid, natural polysaccharides and their derivatives, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl ether maleic acid, bentonite, and silica fume. , aerosil, sepiolite, attapulgite, and other inorganic fibers. These thickeners may be used alone or in combination of two or more.
Examples of the pigment dispersant include higher fatty acid salts, polycarboxylic acids, polyvinyl alcohol, methylcellulose, ethylcellulose, carboxymethylcellulose, polyethylene glycol, and the like. These thickeners may be used alone or in combination of two or more.
Examples of antifoaming agents include antifoaming agents such as silicone compounds, fats and oils, fatty acids, fatty acid esters, and phosphoric acid esters, and partially modified versions thereof. These thickeners may be used alone or in combination of two or more.
As the colored pigment, either an organic pigment or an inorganic pigment may be used. Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacudrine pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments. Examples include polycyclic pigments such as dye lakes, nitro pigments, nitroso pigments, aniline black, fluorescent pigments, etc. In addition, examples of inorganic pigments include titanium oxide, carbon black, red iron, cadmium red, molybdenum orange, yellow iron oxide, yellow lead, titanium yellow, chrome green, chromium oxide, cobalt blue, manganese violet, and the like. These pigments may be used alone or in combination of two or more.
Examples of the cement include ordinary Portland cement, early strength Portland cement, fly ash cement, blast furnace cement, colloid cement, and alumina cement.

The method for manufacturing the waterproof material composition of the embodiment of the present invention is not particularly limited, and may be a method of mixing the raw materials made of the above components all at once or mixing them in portions. Further, the obtained composition may be stored as necessary. When storing the composition, it is preferably stored at 0°C to 40°C under sealed conditions.

The waterproof material composition according to the embodiment of the present invention may be in the form of one material containing all the components, or may be in the form of two or more materials, such as separating the cationic polymer (B) or the filler (F). It is also possible to have a form consisting of the following, and mix all of them together at the time of use. The solid content in the waterproof material composition is preferably 30 to 85%, particularly preferably 40 to 80%.

The viscosity of the waterproof material composition of the embodiment of the present invention is appropriately selected depending on the properties of the object to be coated, etc., but it is preferably 100° C. when measured with a B-type viscometer at a temperature of 25° C. and a rotation speed of 12 rpm. ~100,000 mPa·s, more preferably 1,000 – 100,000 mPa·s.

By using the waterproof material composition of the embodiment of the present invention, the time required for the coating film to stop re-emulsifying even if it gets wet with water (non-re-emulsification time) and the coating film before drying after being applied to the object to be coated can be The time it takes to dry and form a film can be shortened.
For example, a waterproofing material composition is applied to a flat object under conditions of an air temperature of 5° C. and a relative humidity of 80% at a coating amount of 2 kg/m ² (dry thickness of about 1000 μm), When measuring the non-reemulsification time and film formation time, the non-reemulsification time is preferably within 8 hours, more preferably within 5 hours, and the film formation time is preferably within 20 hours, more preferably within 16 hours. I can do it.

In addition, the film (waterproof film) obtained using the waterproof material composition of the embodiment of the present invention has excellent tensile strength, and a method according to JIS A6021 is performed using a film sample with a thickness of 1000 μm. The tensile strength measured by the method can be preferably 1.3 N/mm ² or more.

A waterproofing method according to an embodiment of the present invention includes a coating step of applying the waterproof material composition to the surface of an object to be coated, and a film forming step of forming the obtained coating film into a film.
The paint applied to the surface of the object to be coated may be only the above-mentioned waterproofing material composition, or the above-mentioned waterproofing material composition, as well as a base conditioning material, an undercoat material (primer), an intermediate coating material, and a top coating material. At least one of the known coating compositions used may be combined.
Furthermore, after applying the waterproof material composition of the present invention, it is also possible to apply mortar or concrete, or to lay molded products such as sheets and panels.

The above-mentioned objects to be coated include, for example, cement concrete, asphalt concrete, fiber-reinforced concrete, lightweight aerated concrete (ALC), flexible boards cast on site or molded in factories, plastics (including FRP), heat insulating materials, and wood. Examples include all materials used in the fields of architecture and civil engineering, such as materials, metals, and glass. In addition, the above-mentioned materials with finishes such as finishing paints, single-layer elastic coatings, micro-elastic coatings, spray tiles, elastic tiles, lysine, stucco, plaster, surface covering materials, tiling, etc., and water-repellent coatings are also available. The above-mentioned materials coated with a waterproof material, as well as the materials coated with a waterproof material such as asphalt waterproofing, sheet waterproofing, and paint film waterproofing, can also be used as coated objects (these are collectively referred to as "coated objects M"). Furthermore, the object to be coated may also be a material whose surface is coated with a paint such as acrylic resin, acrylic urethane resin, acrylic silicone resin, fluororesin, or inorganic paint.
Preferred objects to be coated include the roof of a building, the floor of a rooftop, the floor or wall of an open hallway, the floor or wall of a balcony, an exterior wall, an exterior basement wall, an interior wall of a water tank, steel and concrete bridges, and piers. , civil engineering structures such as piers, embankments, tunnel inner walls, water tanks, water tanks, dams, steel towers, and road surfaces.

Specific examples of waterproofing methods include primers to ensure the adhesion of the coating film of waterproofing material compositions to the coated object, waterproofing material compositions, and protection to protect the coating film from ultraviolet rays and give it design properties. Examples include a construction method in which finishing materials are laminated in order. If necessary, reinforcing the paint film by adding a reinforcing fabric such as woven or non-woven fabric made of polyester fiber or glass fiber, or attaching a non-woven fabric with a ventilation layer to a moisture-rich base. Alternatively, it is also possible to cover the base with a sheet that forms an insulating or ventilation layer to prevent the paint film from swelling due to the influence of moisture on the base.

In the above coating step, means using a brush, roller brush, rake, trowel, spray, etc. can be applied. The number of times of coating on the object to be coated is not particularly limited, and may be one time (single layer coating) or two or more times (multilayer coating). Furthermore, the thickness of the coating film to be formed is not particularly limited, and can be appropriately set depending on the application.

In the above-mentioned film forming step, by leaving the coating film formed on the surface of the object to be coated (curing), the film can be formed in a short time and a waterproof film can be formed. The coating conditions are not particularly limited, but a waterproof coating can be formed, for example, at a low temperature of 5° C. or lower and/or in a high humidity environment of 80% or higher relative humidity. In film formation, the volatile base (C) is evaporated from the formed coating film, and the anionic functional groups of the anionic vinyl polymer (A) and/or the anionic vinyl polymer (D) contained in the coating film are removed. This is achieved by promoting gelation (coagulation hardening) with the cationic polymer (B) which has become a cationic state.
By gelling the paint film before it dries, the paint components will not be re-emulsified even if it gets wet with water, and the non-re-emulsification time can be shortened. Furthermore, the formation of a film in a water-containing state becomes faster, and the film formation time can be shortened.

The waterproof film according to the embodiment of the present invention has particularly excellent ability to follow base cracks, preferably when the thickness is at least 500 μm. For example, if cracks occur in the base of a concrete structure coated with a waterproofing material composition due to hardening and shrinkage of the concrete, the film will flexibly follow the elongation of the waterproofing film caused by this without breaking. performance is demonstrated. Therefore, by forming a waterproof film on the roof, outer wall, etc. of a concrete structure, it is possible to suppress deterioration of the structure itself and prevent rainwater from leaking into the interior.

EXAMPLES Hereinafter, embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, in the following, "parts" and "%" are based on mass unless otherwise specified.

1. Raw materials for manufacturing waterproof material compositions Raw materials for manufacturing waterproof material compositions include emulsions containing anionic vinyl polymers dispersed and stabilized in a medium with surfactants, aqueous solutions of cationic polymers, and other anionic vinyl polymers. a dispersion of a coalesce, an aqueous solution of a volatile base, a metal crosslinker and a filler.

1-1. Emulsion The following (AX-1) to (AX-4) were used as emulsions containing anionic vinyl polymers whose dispersion was stabilized in a medium by a surfactant.

1-1-1. Emulsion (AX-1)
68 parts of ion-exchanged water was placed in a flask, and the internal temperature was set at 80°C. Then, while flowing nitrogen gas into the flask, 77 parts of 2-ethylhexyl acrylate, 12 parts of methyl methacrylate, 10 parts of acrylonitrile, 1 part of methacrylic acid, 2 parts of polyoxyethylene alkenyl ammonium sulfate (anionic surfactant), and alkyldiphenyl ether were added. A mixed solution consisting of 0.5 part of sodium disulfonate (anionic surfactant) was continuously added dropwise while stirring. On the other hand, 0.6 part of ammonium persulfate was continuously added dropwise. A polymerization reaction was carried out for 5 hours to obtain an emulsion (AX-1) with a solid content concentration of 60% containing an anionic vinyl polymer (A-1) whose dispersion was stabilized by these anionic surfactants. When the total solid content in this emulsion (AX-1) is 100%, the anionic vinyl polymer (A-1) consisting of 2-ethylhexyl acrylate units, methyl methacrylate units, acrylonitrile units, and methacrylic acid units. The concentration is 97.6% and the total concentration of anionic surfactants is 2.4%. Further, the calculated Tg of the anionic vinyl polymer (A-1) is -73°C.

1-1-2. Emulsion (AX-2)
68 parts of ion-exchanged water was placed in a flask, and the internal temperature was set at 80°C. Then, while flowing nitrogen gas into the flask, a mixture of 77 parts of 2-ethylhexyl acrylate, 12 parts of styrene, 10 parts of acrylonitrile, 1 part of methacrylic acid, and 2 parts of polyoxyethylene higher alcohol ether (nonionic surfactant) was added. was added dropwise continuously under stirring. On the other hand, 0.2 part of ammonium persulfate was continuously added dropwise. A polymerization reaction was carried out for 5 hours to obtain an emulsion (AX-2) with a solid content concentration of 60% containing an anionic vinyl polymer (A-2) whose dispersion was stabilized by a nonionic surfactant. When the total solid content in this emulsion (AX-2) is 100%, the concentration of the anionic vinyl polymer (A-2) consisting of 2-ethylhexyl acrylate units, styrene units, acrylonitrile units, and methacrylic acid units is 98.0%, and the concentration of nonionic surfactant is 2.0%. Further, the calculated Tg of the anionic vinyl polymer (A-2) is -73°C.

1-1-3. Emulsion (AX-3)
68 parts of ion-exchanged water was placed in a flask, and the internal temperature was set at 80°C. Then, while flowing nitrogen gas into the flask, 77 parts of 2-ethylhexyl acrylate, 12 parts of styrene, 10 parts of acrylonitrile, 1 part of methacrylic acid, 2 parts of polyoxyethylene styrenated phenyl ether (nonionic surfactant), and alkyldiphenyl ether were added. A mixed solution consisting of 0.5 part of sodium disulfonate (anionic surfactant) was continuously added dropwise while stirring. On the other hand, 0.2 part of ammonium persulfate was continuously added dropwise. A polymerization reaction was carried out for 5 hours to obtain an emulsion (AX-3) with a solid content concentration of 60% containing an anionic vinyl polymer (A-3) whose dispersion was stabilized by these surfactants. When the total solid content in this emulsion (AX-3) is 100%, the concentration of the anionic vinyl polymer (A-3) consisting of 2-ethylhexyl acrylate units, styrene units, acrylonitrile units, and methacrylic acid units is 97.6%, and the concentrations of nonionic surfactant and anionic surfactant are 1.95% and 0.49%, respectively. Further, the calculated Tg of the anionic vinyl polymer (A-3) is -73°C.

1-1-4. Emulsion (AX-4)
68 parts of ion-exchanged water was placed in a flask, and the internal temperature was set at 80°C. Then, while flowing nitrogen gas into the flask, a mixture of 45 parts of 2-ethylhexyl acrylate, 44 parts of styrene, 10 parts of acrylonitrile, 1 part of methacrylic acid, and 2 parts of polyoxyethylene higher alcohol ether (nonionic surfactant) was added. was added dropwise continuously under stirring. On the other hand, 0.2 part of ammonium persulfate was continuously added dropwise. A polymerization reaction was carried out for 5 hours to obtain an emulsion (AX-4) with a solid content concentration of 60% containing an anionic vinyl polymer (A-4) whose dispersion was stabilized by a nonionic surfactant. When the total solid content in this emulsion (AX-4) is 100%, the concentration of the anionic vinyl polymer (A-4) consisting of 2-ethylhexyl acrylate units, styrene units, acrylonitrile units, and methacrylic acid units is 98.0%, and the concentration of nonionic surfactant is 2.0%. Further, the calculated Tg of the anionic vinyl polymer (A-4) is -14°C.

1-2. Cationic Polymer Commercially available products consisting of aqueous solutions of cationic polymers having a solid content concentration of 20% were used.
1-2-1. Aqueous solution of polyallylamine “PAA-03” (trade name) manufactured by Nitto Bo Medical Co., Ltd., which is an aqueous solution with a solid content concentration of 20%, was used. The weight average molecular weight of this polymer is 3,000.
1-2-2. Aqueous solution of diallylamine hydrochloride/sulfur dioxide copolymer “PAS-92” (trade name) manufactured by Nitto Bo Medical Co., Ltd., which is an aqueous solution with a solid content concentration of 20%, was used. The weight average molecular weight of this polymer is 5,000.
1-2-3. Aqueous solution of dimethylaminoethyl methacrylate sulfate polymer “Unisense KPV100LU” (trade name) manufactured by Senka, which is an aqueous solution with a solid content concentration of 27%, was used. The weight average molecular weight of this polymer is 20,000 to 100,000.

1-3. Aqueous solution of volatile base 25% aqueous ammonia was used.

1-4. Dispersions containing other anionic vinyl polymers The following (DX-1) and (DX-2) were used.

1-4-1. Dispersion liquid (DX-1)
118 parts of methyl ethyl ketone was placed in a flask, and the internal temperature was adjusted to 80°C. Thereafter, while flowing nitrogen gas into the flask, a mixed solution of 50 parts of methyl methacrylate, 32 parts of ethyl acrylate, 18 parts of methacrylic acid, and 1.3 parts of mercaptoethanol was continuously added dropwise with stirring. On the other hand, 5.7 parts of 2,2'-azobis(2-methylbutyronitrile) was continuously added dropwise with stirring. The polymerization reaction was carried out for 5 hours. After that, the solid polymer is removed, 235 parts of water, and 15 parts of 25% ammonia water are mixed, and an anionic vinyl having methyl methacrylate units, ethyl acrylate units, and ammonium methacrylate units is produced. A dispersion (DX-1) containing the polymer (D-1) was obtained. The concentration of the anionic vinyl polymer (D-1) is 30%. Further, the weight average molecular weight of the anionic vinyl polymer (D-1) determined by GPC (polystyrene equivalent) is 8,700, and the calculated Tg is 56°C.

1-4-2. Dispersion liquid (DX-2)
118 parts of methyl ethyl ketone was placed in a flask, and the internal temperature was adjusted to 80°C. Thereafter, while flowing nitrogen gas into the flask, 32 parts of methyl methacrylate, 21 parts of ethyl acrylate, 18 parts of methacrylic acid, and 29 parts of polybutyl acrylate having a weight average molecular weight of 5,500 having a methacryloyl group at one end, and A mixed solution consisting of 1.3 parts of mercaptoethanol was continuously added dropwise while stirring. On the other hand, 5.7 parts of 2,2'-azobis(2-methylbutyronitrile) was continuously added dropwise with stirring. The polymerization reaction was carried out for 5 hours. Thereafter, desolvation is performed, and the solid polymer, 235 parts of water, and 15 parts of 25% ammonia water are mixed, and methyl methacrylate units, ethyl acrylate units, ammonium methacrylate units, and the above polybutyl acrylate are mixed. A dispersion (DX-2) containing an anionic vinyl polymer (D-2) having a structural unit derived from was obtained. The concentration of the anionic vinyl polymer (D-2) is 30%. Further, the weight average molecular weight of the anionic vinyl polymer (D-2) is 8,800, and the calculated Tg is 16°C.

1-5. Metal crosslinking agent Calcium hydroxide powder was used.
1-6. Filler A mixed powder (hereinafter referred to as "inorganic powder") consisting of 58% calcium carbonate, 25% clay, and 17% silica sand was used.

2. Production and evaluation of waterproof material composition Example 1
A waterproofing material composition having the composition shown in Table 1 by mixing emulsion (AX-1), polyallylamine aqueous solution, 25% ammonia water, calcium hydroxide powder, and inorganic powder at once. I got it. The numbers listed in Table 1 refer to active ingredients for component (C) and water, and mean solid content for components other than component (C) and water.

Next, the waterproof material composition immediately after preparation was applied to the surface of a polyvinyl chloride board so that the film thickness after drying was 1000 μm as shown in Table 1. Then, the coating film was measured for non-reemulsification time and film formation time under conditions of a temperature of 5°C and a relative humidity of 80% using the following method to evaluate film formation properties (see Table 1). . Note that the specific gravity of the dry membrane is 1.4 (the same applies to other Examples and Comparative Examples).
(1) Non-reemulsification time One drop of water was placed on the surface of the coating film using a dropper, a pencil was placed vertically on top of the drop, and the pencil was pressed continuously 10 times with a load of 20 gf. Thereafter, the pencil was removed and the water was visually observed for cloudiness. The time from immediately after the 10th press until the water stopped becoming cloudy was measured.
(2) Film Formation Time A pencil was placed vertically on the surface of the coating film, and a load of 1 kg was applied to the pencil for 10 seconds. Thereafter, the pencil was removed, and the time until no pencil marks remained on the surface of the coating film was measured.

Furthermore, in order to confirm the physical properties of the film formed by the waterproof material composition, the following evaluations were performed.
(3) Tensile strength and elongation at break The waterproof material composition was applied to the surface of a polyvinyl chloride board (300 mm x 300 mm x 5 mm) so that the film thickness after drying would be 1000 μm as shown in Table 1. It was applied to. After curing in accordance with JIS A6021 "Waterproof materials for architectural coatings" to obtain a waterproof film, a tensile test was conducted (see Table 1).
(4) Substrate crack followability On the surface of the slate board 10 (150 mm x 75 mm x 5 mm, with a V cut (groove 12) on the back side in the longitudinal center to make it easier to split) shown in Figure 1. "Aron water-based primer" manufactured by Toagosei Co., Ltd. was applied at 0.1 kg/m ² and allowed to cure for 24 hours at a temperature of 23° C. and a humidity of 50% to form a primer layer. Thereafter, a waterproof material composition is applied to the surface of this primer layer so that the film thickness after drying becomes 1000 μm, and is cured for 7 days at a temperature of 23° C. and a humidity of 50% to form a waterproof film 20. Obtained 100 bodies.
Next, in order not to damage the waterproof coating 20, the slate plate 10 constituting the composite 100 was divided in half along the groove 12 to obtain a composite evaluation sample 102 with a waterproof coating shown in FIG. . This composite evaluation sample 102 with a waterproof film has a structure in which slate plates with a waterproof film (10X, 10Y) divided into two parts each having a size of 75 mm x 75 mm are connected by a waterproof film.
Thereafter, as shown in Figures 3(A) and (B), the slate board was pulled in the longitudinal direction at a speed of 5 mm/min at a temperature of 23°C and a humidity of 50%, and pinned to the waterproof coating. The tensile width (substrate crack following width) at the time when defects such as holes and breaks occurred was measured (see Table 1). In Table 1, when the base crack follow-up width is 5 mm or more, it is written as "○", when it is 3 mm or more and less than 5 mm, it is written as "Δ", and when it is less than 3 mm, it is written as "x".

Examples 2 to 11
Emulsion (AX-2), (AX-3) or (AX-4), polyallylamine aqueous solution or diallylamine hydrochloride/sulfur dioxide copolymer aqueous solution, 25% ammonia water, dispersion (DX-1) or (DX-2), calcium hydroxide powder, and inorganic powder were mixed together to obtain a waterproof material composition having the structure shown in Table 1.
Thereafter, evaluation was performed in the same manner as in Example 1, and the results are also listed in Table 1.

Comparative examples 1 and 2
Emulsion (AX-2) or (AX-3), diethylaminoethyl methacrylate sulfate polymer aqueous solution, 25% ammonia water, dispersion (DX-2), and inorganic powder are mixed together. A waterproof material composition having the structure shown in Table 1 was obtained.
Thereafter, evaluation was performed in the same manner as in Example 1, and the results are also listed in Table 1.

The following is clear from Table 1.
Comparative Examples 1 and 2 are examples in which a diethylaminoethyl methacrylate sulfate polymer, which is not included in the present invention, is used as the cationic polymer, and the non-reemulsification time and film formation time are long, and the film has sufficient tensile strength. It wasn't. On the other hand, Examples 1 to 11 are examples of waterproof material compositions of the present invention, in which the non-reemulsification time is shortened to 8 hours or less, the film formation time is shortened to 18 hours or less, and twice that of Comparative Examples 1 and 2. It can be seen that the above tensile strength was obtained.

Examples 12 and 13
The composition of Example 11 was prepared by a different manufacturing method and evaluated in the same manner as in Example 1, and the results are also listed in Table 2.
For example, the waterproof material composition of Example 12 was prepared by mixing predetermined amounts of emulsion (AX-3), 25% ammonia water, dispersion (DX-2), calcium hydroxide powder, and water. Afterwards, the mixture was stored at 40° C. under sealed conditions. After 180 days had passed, a predetermined amount of polyallylamine aqueous solution and inorganic powder were added to this mixture and mixed to obtain a waterproof material composition.

Example 14
The composition of Example 11 was stored under sealed conditions at 40° C. for 180 days, and then evaluated in the same manner as in Example 1, and the results are also listed in Table 2.

The following is clear from Table 2.
In Examples 12 to 14, as in Examples 1 to 11, the non-reemulsification time was shortened to within 8 hours, the film formation time was shortened to within 18 hours, and the tensile strength was more than twice that of Comparative Examples 1 and 2. was gotten. From the above, it can be seen that even if the raw materials are mixed and left for a long period of time, the film forming properties and film physical properties do not change.

The waterproofing material composition of the present invention has a short non-reemulsification time under low temperature and high humidity conditions, so even under such conditions, there is a concern that the coating film will get wet with night dew or rain and reemulsify. There is no need to avoid this, and the film formation time is short, so the next process can be carried out as scheduled and without delaying the construction period. In addition, it can be applied to all materials used in the construction and civil engineering field such as concrete, mortar, slate, metal, glass, and resin, as well as to the base coated with various coating materials and waterproofing materials. It is possible to form a waterproof film that has excellent properties and can follow cracks in the base.

10: Slate plate 10X, 10Y: Divided slate plate 12: Groove 20: Waterproof coating 100: Composite with waterproof coating 102: Composite with waterproof coating evaluation sample

Claims (9)

(A) an anionic vinyl polymer stabilized by a surfactant, (B) a cationic polymer, (C) a volatile base , and (D) a weight average molecular weight of 500 to 500 by gel permeation chromatography. 100,000 and another anionic vinyl polymer ,
The component (B) is selected from allylamine and its salt, N-alkylarylamine and its salt, N,N-dialkylallylamine and its salt, diallylamine and its salt, and N-alkyldiallylamine and its salt or quaternized product. Component (D) is a polymer containing a structural unit derived from at least one type of (meth)acrylic acid alkyl ester, and a structural unit derived from an unsaturated acid or a salt thereof. A waterproof material composition characterized by being a polymer containing . The waterproof material composition according to claim 1, wherein the anionic vinyl polymer (A) contains a structural unit derived from an alkyl (meth)acrylate ester and a structural unit derived from an unsaturated acid. The content ratio of the cationic polymer (B) is 0.1 to 10 parts by mass when the content of the anionic vinyl polymer (A) is 100 parts by mass, according to claim 1 or 2. waterproof material composition. Any one of claims 1 to 3, wherein the content ratio of the volatile base (C) is 0.01 to 10 parts by mass when the content of the anionic vinyl polymer (A) is 100 parts by mass. The waterproof material composition according to item 1. The waterproof material composition according to any one of claims 1 to 4 , further comprising (E) a metal crosslinking agent. The waterproof material composition according to any one of claims 1 to 5 , further comprising (F) a filler. The method comprises a coating step of applying the waterproof material composition according to any one of claims 1 to 6 to an object to be coated, and a film forming step of forming a coating film obtained by the coating step into a film. A waterproofing method characterized by: The waterproofing method according to claim 7 , wherein the object to be coated is a structure. A waterproof coating formed by forming a coating film using the waterproof material composition according to any one of claims 1 to 6 .

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