JP2007303197A - Method of repairing civil engineering construction waterproof structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of repairing a civil engineering construction waterproof structure, which is used for repair of a waterproof structure of a roof, a wall, a floor, a road, etc., and excellent in adhesiveness to an existing coated film, lifting preventive performance, and odor reduction. <P>SOLUTION: The method of repairing the civil engineering construction waterproof structure is used when the civil engineering construction waterproof structure is repaired, and characterized by applying a water-based primer containing: a water-dispersed polyisocyanate composition (A); a resin (B) having an active hydrogen containing group; and water, and then applying a waterproof coating material onto the water-based primer. Alternatively the method is characterized by applying a water-based primer containing the water-dispersed polyisocyanate composition (A), and water, and then applying a waterproof coating material onto the water-based primer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for repairing an existing waterproof structure in the field of civil engineering and architecture. More particularly, the present invention relates to a method for repairing a waterproofing structure for civil engineering buildings, characterized in that an aqueous primer is applied onto an existing waterproof structure and a waterproof coating material is applied thereon.

In general, waterproofing structures for civil engineering buildings that have deteriorated over time so that peeling with the progress of deterioration of the top coat applied to ensure weather resistance and generation of fine cracks called hair cracks from the waterproofing material itself can be seen. It has become.
In renovation of such a waterproof structure, a urethane coating waterproof material is often used (for example, refer to Patent Document 1). At that time, in order to ensure adhesion with a deteriorated waterproof structure, mainly, Solvent based primers have been used.
However, when the solvent-based primer is applied, the coating film deteriorates or the solvent component penetrates into the cracks, so that there is a problem that the existing waterproof structure easily causes a lifting phenomenon.
In addition, since there are concerns about the adverse effects on the work environment and air pollution caused by the volatilizing organic solvent, establishment of a new repair method by reducing the use of organic solvents such as making the primer water-based was expected.
Japanese Patent Laid-Open No. 10-17820

  The object of the present invention is to improve the waterproofing of civil engineering buildings that are excellent in adhesion to existing coatings, anti-lifting and low bromide in the renovation of existing waterproofing structures such as roofs, walls, floors and roads. It is to provide a method for repairing a structure.

  Therefore, as a result of intensive research on the above problems, the present inventors have achieved excellent adhesion to existing civil engineering waterproofing structures, anti-lifting properties and low bromide by using a specific aqueous primer. As a result, the present invention has been completed.

  That is, the present invention applies a water-based primer containing a water-dispersible polyisocyanate composition (A), a resin having an active hydrogen-containing group (B), and water when renovating a civil engineering waterproofing structure. The present invention provides a method for repairing a waterproofing structure for civil engineering buildings, characterized in that a waterproof coating material is applied thereon. Further, the present invention is characterized by applying a water-dispersible polyisocyanate composition (A) and a water-based primer containing water, and coating a waterproofing coating material on the waterproof structure for civil engineering buildings. The construction method of the civil engineering building waterproof structure is provided.

  The renovation method of the present invention uses an aqueous primer containing a specific water-dispersible polyisocyanate composition, a resin, and water, so that it has excellent adhesion to a civil engineering building waterproof structure and good anti-lifting properties. Low bromide is possible.

Hereinafter, the present invention will be described in more detail.
First, the water-dispersible polyisocyanate composition (A) in the present invention contains a polyisocyanate (p).

  As the polyisocyanate (p), various known and usual ones can be used. For example, 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanato) hexanoate, 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4- or 2,4,4- Aliphatic diisocyanates such as trimethylhexamethylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 2-isocyanatoethyl (2,6-diisocyanate) Aliphatic triisocyanates such as hexanoate;

1,3- or 1,4-bis (isocyanatomethylcyclohexane), 1,3- or 1,4-diisocyanatocyclohexane, 3,5,5-trimethyl (3-isocyanatomethyl) cyclohexyl isocyanate, dicyclohexylmethane Alicyclic diisocyanates such as -4,4'-diisocyanate, 2,5- or 2,6-diisocyanatomethylnorbornane; 2,5- or 2,6-diisocyanatomethyl-2-isocyanate propylnorbornane Alicyclic diisocyanates such as m-xylylene diisocyanate, aralkylene diisocyanates such as α, α, α ′, α′-tetramethyl-m-xylylene diisocyanate;

m- or p-phenylene diisocyanate, tolylene-2,4- or 2,6-diisocyanate, diphenylmethane-4,4′-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4′-diisocyanate, 4,4 Aromatic diisocyanates such as' -diisocyanate-3,3'-dimethyldiphenyl, 3-methyl-diphenylmethane-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate; triphenylmethane triisocyanate, tris (isocyanate Aromatic triisocyanates such as natephenyl) thiophosphate;

Diisocyanates or polyisocyanates having a uretdione structure obtained by cyclizing and dimerizing the isocyanate groups of various diisocyanates or triisocyanates as described above; cyclizing and trimerizing the isocyanate groups of various diisocyanates or triisocyanates as described above A polyisocyanate having an isocyanurate structure obtained as described above; a polyisocyanate having a burette structure obtained by reacting various diisocyanates or triisocyanates as described above with water;

A polyisocyanate having an oxadiazine trione structure obtained by reacting various diisocyanates or triisocyanates with carbon dioxide as described above; various diisocyanates or triisocyanates as described above can be converted into polyhydroxy compounds, polycarboxy compounds, and polyamine compounds. Examples thereof include polyisocyanate obtained by reacting with a compound containing active hydrogen. Of these, aliphatic or alicyclic diisocyanates or triisocyanates, aralkylene diisocyanates, or polyisocyanates derived therefrom are particularly preferred.

  The water-dispersible polyisocyanate composition used in the present invention preferably contains a nonionic group in the system.

  By including a nonionic group in the system, the resulting water-dispersible polyisocyanate composition (A) is provided with excellent water dispersibility and is contained in an aqueous dispersion of the composition. Gives water stability.

In order for a nonionic group to be present in the water-dispersible polyisocyanate composition (A), it is preferable to include a vinyl polymer having a nonionic group.
Examples of such vinyl polymers include acrylic polymers, fluoroolefin polymers, vinyl ester polymers, aromatic vinyl polymers, and polyolefin polymers.

  The vinyl polymer containing a nonionic group includes (1) a polymer not containing an isocyanate group as a functional group (hereinafter abbreviated as polymer (q-1)), and (2) an isocyanate group as a functional group. A polymer containing an isocyanate group introduced by copolymerization of a vinyl monomer containing an isocyanate group [hereinafter abbreviated as polymer (q-2)], (3) A polymer containing an isocyanate group as a functional group, which contains an active hydrogen-containing group that reacts with the isocyanate group and a nonionic group (hereinafter abbreviated as polymer (q-3-1)); And a polymer obtained by reaction with polyisocyanate [hereinafter abbreviated as polymer (q-3)].

  Examples of the nonionic group include various known and commonly used groups, and among them, a polyoxyalkylene group whose end is blocked with an alkoxy group is preferable.

  Examples of the polyoxyalkylene group include various polyoxyalkylene groups such as a polyoxyethylene group, a polyoxypropylene group, and a polyoxybutylene group; 2 of the above-described oxyalkylene units such as a poly (oxyethylene-oxypropylene) group. A polyoxyalkylene group having a structure in which more than one species are randomly copolymerized; a group in which different polyoxyalkylene groups such as a polyoxyethylene-polyoxypropylene group are bonded in a block form; obtained by ring-opening polymerization of a dioxolane ring And polyoxyalkylene groups that can be used. And as a typical thing of the alkoxy group used for terminal blockage, a methoxy group, an ethoxy group, a butoxy group etc. are mentioned.

  The number average molecular weight of the polyoxyalkylene group is within a range of 130 to 10,000 from the viewpoint of water dispersibility of the polyisocyanate composition and curability of the aqueous primer of the present invention containing the composition, preferably , 150 to 6,000, and most preferably 200 to 2,000.

  The amount of a suitable nonionic group introduced into each of the vinyl polymers (q-1), (q-2) and (q-3-1) allows the polyisocyanate to be easily dispersed in water, and It is the quantity of the range which does not impair the stability of the isocyanate group contained in the dispersion liquid obtained by disperse | distributing a polyisocyanate composition (A) in water. The amount thereof is 10 to 90% by weight of the weight of each of the vinyl polymers (q-1), (q-2) or (q-3-1), more preferably 15 to 70% by weight. The most preferred amount is 20 to 60% by weight.

  As a method for introducing a polyoxyalkylene group into a vinyl polymer (q-1), (q-2) or (q-3-1), 1) a polyoxyalkylene group whose end is blocked with an alkoxy group is used. A method of copolymerizing a vinyl monomer contained therein, 2) a vinyl polymer containing a functional group prepared in advance, and a polyoxy having one end having a functional group that reacts with the functional group blocked with an alkoxy group Examples include a method of reacting an alkylene compound. Among these, the former method 1) is simple and preferable.

  Examples of the monomer used in carrying out the method 1) include, for example, (meth) acrylic acid ester, crotonic acid ester, itaconic acid ester, fumarate having various polyoxyalkylene groups as described above. Examples thereof include unsaturated carboxylic acid esters such as acid esters, and vinyl ethers having the various polyoxyalkylene groups.

  Examples of such unsaturated carboxylic acid esters include monomethoxylated polyethylene glycol, monomethoxylated polypropylene glycol, or monoalkoxylated polyether diol such as a monomethoxylated polyether diol having both oxyethylene units and oxypropylene units. Examples of the compound include esters having a carboxyl group such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, and maleic acid half ester fumaric acid half ester.

  Examples of vinyl ethers include monomethoxylated polyethylene glycol, monomethoxylated polypropylene glycol or vinyl etherified products of monoalkoxy compounds of polyether diol, such as monomethoxylated polyether diol having both oxyethylene units and oxypropylene units. Can be mentioned.

  Also, reactive functional groups such as hydrolyzable silyl groups, blocked active hydrogen-containing groups, and epoxy groups are introduced into the vinyl polymer (q-1), (q-2) or (q-3-1). By doing so, the sclerosis | hardenability of the aqueous primer used by this invention can be improved, and the coating film which has the more superior performance can be obtained.

Among the functional groups described above, the hydrolyzable silyl group is an alkoxy group, a substituted alkoxy group, a phenoxy group, an iminooxy group, an alkenyloxy group, which is a group that is eliminated by hydrolysis and generates a hydroxyl group bonded to a silicon atom. This refers to a silyl group to which a hydrolyzable group such as a halogen atom is bonded. Among such silyl groups, an alkoxysilyl group having an alkoxy group or a substituted alkoxy group bonded as a hydrolyzable group is particularly preferable.
Examples of the alkoxysilyl group include trimethoxysilyl group, triethoxysilyl group, tri-n-propoxysilyl group, tri-n-butoxysilyl group, methyldimethoxysilyl group, ethyldimethoxysilyl group, dimethylmethoxysilyl group, tris (2-methoxy). And ethoxy) silyl group.

Representative examples of the blocked active hydrogen-containing group include a blocked hydroxyl group, a blocked carboxyl group, and a blocked amino group.
Examples of such a blocked hydroxyl group include a hydroxyl group blocked with a triorganosilyl group such as a trimethylsilyl ether group, a triethylsilyl ether group, a dimethylcyclohexylsilyl ether group, or a dimethyl-tert-butylsilyl ether group; And a hydroxyl group blocked as an acetal or ketal obtained by adding an α, β-unsaturated ether compound such as 2-methoxypropene or dihydrofuran.

  Further, the blocked carboxyl group includes a tricarboxysilyl ester group, a triethylsilyl ester group, a dimethylcyclohexylsilyl ester group, a carboxyl group blocked as a triorganosilyl ester such as a dimethyl-tert-butylsilyl ester group; A blocked carboxyl group as a hemiacetal ester or hemiketal ester obtained by adding an α, β-unsaturated ether compound such as ethyl vinyl ether, 2-methoxypropene, dihydrofuran or dihydropyran.

  Examples of the blocked amino group include amino groups blocked as bis (triorganosilyl) amino groups such as bis (trimethylsilyl) amino group, bis (triethylsilyl) amino group, and bis (dimethyl-tert-butylsilyl) amino group; Ketimine obtained by reacting an amino group with a blocked amino group such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and a ketone compound such as acetone, methyl ethyl ketone, methyl isobutyl ketone An amino group blocked as an aldehyde compound or a ketone compound as listed above for use in converting an amino group to an aldimine or ketimine; Blocked amino group, and the like as oxazolidine obtained by response.

  Among the blocked functional groups, a hydroxyl group blocked with a triorganosilyl group is particularly preferable. Since the hydroxyl group blocked with a triorganosilyl group is hydrophobic, by introducing such a group into the vinyl polymer (q), the polyisocyanate composition (A) can be further dispersed in water. In addition, the stability of the isocyanate group contained in the aqueous primer of the present invention can be further enhanced, and a cured coating film having better performance can be obtained.

  Typical examples of the epoxy group include a glycidyl group, a methyl glycidyl group, and an epoxycyclohexyl group.

  Any functional group of a hydrolyzable silyl group, a blocked active hydrogen-containing group or an epoxy group is introduced into the vinyl polymer (q-1), (q-2) or (q-3-1). In this case, the amount introduced is from the viewpoint of water dispersibility of the polyisocyanate composition (A) and curability of the aqueous primer of the present invention, vinyl polymer (q-1), (q-2) or (q It is the range which is 0.05-2.0 mol per 1000 g of each of 3-1), and the range which is 0.1-1.0 mol is preferable.

  In order to introduce a hydrolyzable silyl group, a blocked active hydrogen-containing group and an epoxy group into the vinyl polymer (q-1), (q-2) or (q-3-1) This method can be applied, but it is easy to introduce it by copolymerizing the vinyl monomer containing the functional group.

  Examples of vinyl monomers having hydrolyzable silyl groups include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltris (2-methoxyethoxy) silane, allyltrimethoxysilane, and 2-trimethoxysilylethyl. Vinyl ether, 3-trimethoxysilylpropyl vinyl ether, 3- (methyldimethoxysilyl) propyl vinyl ether,

3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrin-propoxysilane, Examples include 3- (meth) acryloyloxypropyltriiso-propoxysilane, 3- (meth) acryloyloxypropylmethyldichlorosilane, and the like.

  Examples of vinyl monomers having a hydroxyl group blocked with a triorganosilyl group include 2-trimethylsiloxyethyl (meth) acrylate, 2-trimethylsiloxypropyl (meth) acrylate, 4-trimethylsiloxybutyl (meth) acrylate, 2 -Triethylsiloxyethyl (meth) acrylate, 2-tributylsiloxypropyl (meth) acrylate or 3-triphenylsiloxypropyl (meth) acrylate, 2-trimethylsiloxyethyl vinyl ether, 4-trimethylsiloxybutyl vinyl ether, and the like.

  Examples of vinyl monomers having a silyl ester group include trimethylsilyl (meth) acrylate, dimethyl-tert-butylsilyl (meth) acrylate, dimethylcyclohexyl (meth) acrylate, trimethylsilylcrotonate, and monovinyl-monotrimethylsilyl ester of adipic acid. Can be mentioned.

  Examples of vinyl monomers having a hemiacetal ester group or a hemiketal ester group include 1-methoxyethyl (meth) acrylate, 1-ethoxyethyl (meth) acrylate, 2-methoxy-2- (meth) acryloyloxypropane, Examples include 2- (meth) acryloyloxytetrahydrofuran.

  Examples of the vinyl monomer containing an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, glycidyl vinyl ether, and allyl glycidyl ether.

  In the vinyl polymer (q-2), an isocyanate group is introduced by copolymerization of a vinyl monomer having an isocyanate group, and the amount of the vinyl polymer (q-2) introduced by the resin ( It is preferable that the active hydrogen-containing group in B) or water (B) can be reacted and the stability of the polyisocyanate composition (A) is not impaired. The range is from 0.05 to 2.0 mol, more preferably from 0.1 to 1.5 mol, most preferably 0, per 1000 g of the vinyl polymer (q-2). .2 to 1.0 mol.

  Examples of the vinyl monomer containing an isocyanate group include 2-isocyanatopropene, 2-isocyanate ethyl vinyl ether, 2-isocyanate ethyl methacrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate. .

  An active hydrogen-containing group that reacts with an isocyanate group is introduced into the vinyl polymer (q-3-1). Examples of such active hydrogen-containing groups include known and commonly used groups such as hydroxyl group, carboxyl group, amino group, phosphoric acid group, phosphorous acid group, sulfonic acid group, sulfinic acid group, mercapto group, silanol group, Examples thereof include an active methylene group, a carbamate group, a ureido group, a carboxylic acid amide group, and a sulfonic acid amide group. Among these, preferred are a hydroxyl group, an amino group, a carboxyl group and an active methylene group, and particularly preferred are a hydroxyl group and a carboxyl group. These active hydrogen-containing groups may be introduced alone or two or more of them may be introduced.

  In order to introduce the active hydrogen-containing group into the polymer (q-3-1), various known and conventional methods can be applied as in the case of introducing the nonionic group. A method of copolymerizing a vinyl monomer having an active hydrogen-containing group is simple.

  Among the monomers having an active hydrogen-containing group used when preparing the vinyl polymer (q-3-1), examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methyl (2-hydroxymethyl) acrylate, ethyl (2-hydroxymethyl) acrylate, butyl (2-hydroxymethyl) ) (Meth) acrylic acid esters containing a hydroxyl group such as acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate;

Allyl compounds containing hydroxyl groups such as allyl alcohol and 2-hydroxyethyl allyl ether; Vinyl ether compounds containing hydroxyl groups such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and 6-hydroxyhexyl vinyl ether; N-methylol (meth) Unsaturated carboxylic acid amide compounds having a hydroxyl group such as acrylamide and N-methylolcrotonamide;

Hydroxyl-containing unsaturated fatty acids such as ricinoleic acid; Hydroxyl-containing unsaturated fatty acid esters such as alkyl ricinoleate; Monomers obtained by addition reaction of various hydroxyl-containing monomers as described above with ε-caprolactone adducts Etc. These may be used alone or in combination of two or more.

  Examples of the monomer having a carboxyl group include (meth) acrylic acid, 2-carboxyethyl acrylate, crotonic acid, vinyl acetic acid, monovinyl adipate, monovinyl sebacate, monomethyl itaconate, monomethyl maleate, monomethyl fumarate, and succinate. Acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], hexahydrophthalic acid mono [2- (meth) acryloyloxyethyl], and unsaturated two such as sorbic acid Monocarboxylic acids having a heavy bond; unsaturated dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid.

  Examples of the monomer having an amino group as an active hydrogen-containing group include N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, Nn-butylaminoethyl (meth) acrylate, N-tert. -Secondary amino group-containing vinyl monomers such as -butylaminoethyl (meth) acrylate, N-methylaminoethyl crotonate, N-ethylaminoethyl crotonate, Nn-butylaminoethyl crotonate . These may be used alone or in combination of two or more.

  Examples of monomers having an active methylene group as an active hydrogen-containing group include vinyl acetocetate, 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, and 3-acetoacetoxypropyl (meth) acrylate. , 3-acetoacetoxybutyl (meth) acrylate, 4-acetoacetoxybutyl (meth) acrylate, allyl acetoacetate, 2,3-di (acetoacetoxy) propyl methacrylate, and the like. These may be used alone or in combination of two or more.

  The amount of the active hydrogen-containing group introduced into the polymer (q-3-1) is such that the reaction between the polymer (q-3-1) and the polyisocyanate is easy, and the polymer (q-3-1) The polymer (q-3) obtained by reacting polyisocyanate with polyisocyanate can participate in crosslinking by reacting with the active hydrogen-containing group or water contained in the resin (B) having an active hydrogen-containing group. And a range that does not impair the stability of the polyisocyanate composition (A) is preferable. The amount introduced is from 0.01 to 5.0 mol, preferably from 0.05 to 3.0 mol, most preferably from 0.00 to 0.1 mol per 1,000 g of the polymer (q-3-1). The range is 1 to 2.0 mol.

  Further, it is preferable to introduce a hydrophobic group having 4 or more total carbon atoms into the vinyl polymer (q-1), (q-2) or (q-3-1). Thereby, while providing the further excellent dispersibility to water to a polyisocyanate composition (A), the stability with respect to the water of the isocyanate group contained in the aqueous primer containing the said composition can be improved further. As a result, the topcoat obtained from the aqueous primer of the present invention has an excellent appearance with less foaming.

  Examples of the hydrophobic group having 4 or more total carbon atoms include n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, and n-octyl group. An alkyl group having 4 or more carbon atoms such as n-dodecyl group, n-octadecyl group, eicosanyl group, docosanyl group; cyclopentyl group, cyclohexyl group, cyclooctyl group, dicyclopentanyl group, bornyl group, isobornyl group A cycloalkyl group having 4 or more carbon atoms, such as

An alkyl group substituted by a cycloalkyl group such as a cyclopentylmethyl group, a cyclohexylmethyl group, a 2-cyclopentylethyl group or a 2-cyclohexylethyl group; a total carbon atom number such as a phenyl group, a 4-methylphenyl group or a 1-naphthyl group; Is an aryl group or substituted aryl group having 6 or more; and further an aralkyl group such as a benzyl group or 2-phenylethyl group.

  Of the hydrophobic groups having 4 or more total carbon atoms, those having 4 to 22 total carbon atoms are preferred from the viewpoint of the stability of the isocyanate group in the aqueous primer used in the present invention to water. Particularly preferred are those having 5 to 18 total carbon atoms. Among these hydrophobic groups, an alkyl group, a cycloalkyl group or an alkyl group substituted with a cycloalkyl group is particularly preferable.

  The introduction amount of the hydrophobic group having 4 or more total carbon atoms is, from the viewpoint of stability of the isocyanate group in the aqueous primer used in the present invention, vinyl copolymers (q-1), (q- It is preferable that the weight ratio of the hydrophobic group contained in each of 2) or (q-3-1) is 1 to 50% by weight, and particularly preferably 5 to 30% by weight.

  Hydrophobic groups having 4 or more total carbon atoms can be obtained by copolymerizing a vinyl monomer having such a group to produce a vinyl polymer (q-1), (q-2) or (q-3- 1). Examples of the monomer having a hydrophobic group having 4 or more total carbon atoms include n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylic acid esters having an alkyl group having 4 to 22 carbon atoms in total, such as (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, docosanyl (meth) acrylate;

Various cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate; cyclopentylmethyl (meth) Cycloalkylalkyl (meth) acrylates such as acrylate, cyclohexylmethyl (meth) acrylate, 2-cyclohexylethyl (meth) acrylate; various aralkyl (meth) acrylates such as benzyl (meth) acrylate or 2-phenylethyl (meth) acrylate ) Acrylates;

Various aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene, vinyltoluene; total carbon atoms such as vinyl pivalate, vinyl versatate or vinyl benzoate 5 or more carboxylic acid vinyl esters; various crotonic acid esters having an alkyl group having 4 to 22 carbon atoms such as crotonic acid-n-butyl and crotonic acid-2-ethylhexyl;

Various unsaturated dibasic acid diesters having at least one alkyl group having 4 to 22 carbon atoms, such as di-n-butyl malate, di-n-butyl fumarate, di-n-butyl itaconate; n -Various alkyl vinyl ethers having an alkyl group having 4 to 22 carbon atoms such as butyl vinyl ether and n-hexyl vinyl ether; various cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether, 4-methylcyclohexyl vinyl ether, etc. Is mentioned.

  In addition to the hydrophobic group having 4 or more total carbon atoms, a known and commonly used monomer copolymerizable with these can be used in combination. Typical examples thereof include (meth) acrylic acid esters having an alkyl group having 3 or less carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth) acrylate; 2 Various ω-alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate or 4-methoxybutyl (meth) acrylate; carboxylic acids having 4 or less total carbon atoms such as vinyl acetate and vinyl propionate A variety of crotonic acid esters having an alkyl group having 3 or less carbon atoms, such as methyl crotonate or ethyl crotonate;

Various unsaturated dibasic acid diesters having an alkyl group having 3 or less carbon atoms such as dimethyl malate, dimethyl fumarate and dimethyl itaconate; containing various cyano groups such as (meth) acrylonitrile and crotononitrile Vinyl monomers; various fluoroolefins such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene;

Various chlorinated olefins such as vinyl chloride or vinylidene chloride; various α-olefins such as ethylene or propylene; various kinds having an alkyl group having 3 or less carbon atoms such as ethyl vinyl ether and n-propyl vinyl ether Alkyl vinyl ethers; tertiary amide group-containing vinyl monomers such as N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine or N-vinylpyrrolidone, etc. Can be mentioned.

  When preparing the above-mentioned vinyl polymer (q-1), (q-2) or (q-3-1), various known and conventional polymerization methods can be applied. Among them, the solution radical polymerization method in an organic solvent is particularly convenient and preferable.

  In applying the solution radical polymerization method, a polymerization initiator can be used. As the polymerization initiator, various known and commonly used compounds can be used. Typical examples include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylbutyronitrile) or 2,2′-azobis (2-methylbutyronitrile). ) Various azo compounds such as tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide Alternatively, various peroxides such as diisopropyl peroxycarbonate can be used.

  As the organic solvent used in the solution radical polymerization method, any compound can be used as long as it is a compound inert to the isocyanate group. For example, aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane and cyclopentane; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; ethyl acetate, Various esters such as n-butyl acetate, n-amyl acetate and ethylene glycol monomethyl ether acetate; various ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone and cyclohexanone;

Polyalkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol dibutyl ether; ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane; N-methylpyrrolidone, dimethylformamide, dimethylacetamide or ethylene carbonate Is mentioned. Such compounds may be used alone or in combination of two or more.

  Since the organic solvent adversely affects the stability and the like of the polyisocyanate composition used in the present invention, it is preferable to use one having as low a water content as possible. In addition, when a material having a relatively high water content is used, the water content can be lowered by performing dehydration by an azeotropic dehydration method or the like in which a part of the solvent is distilled off after completion of the polymerization.

  From the viewpoint of maintaining the dispersibility of the water-dispersible polyisocyanate composition (A) in water and the stability of the isocyanate groups contained in the aqueous primer with respect to water, and obtaining a cured coating film having excellent appearance and performance, The weight average molecular weight of each of the combined (q-1), (q-2), and (q-3-1) is preferably 3,000 to 100,000, and more preferably 5,000 to 40,000. It is preferable.

  A water-dispersible polyisocyanate composition (A) can be prepared by mixing the polymer (q-1) or (q-2) prepared as described above with a polyisocyanate (p). The mixing ratio of the polymer (q-1) or (q-2) and the polyisocyanate (p) is expressed by weight ratio from the viewpoint of the appearance and coating performance of the cured coating film obtained from the aqueous primer of the present invention ( p) / [(q-1) or (q-2)] = 30/70 to 85/15, preferably (p) / [(q-1) or (q-2)] = 50 / It is especially preferable that it is 50-80 / 20.

  When the polyisocyanate composition (A) is prepared by mixing the polyisocyanate (p) and the vinyl polymer (q-1) or (q-2), the temperature is generally 20 to 150 ° C., preferably 20 to 100. It is preferable to mix at a temperature in the range of ° C.

  The vinyl polymer (q-3-1) and the polyisocyanate (r) are mixed with the polyisocyanate (r) with respect to the equivalent number of active hydrogen-containing groups contained in the vinyl polymer (q-3-1). The vinyl polymer (q-3) containing an isocyanate group, which is one of the vinyl polymers (q), is prepared by reacting so that the equivalent number of isocyanate groups contained in is excessive. be able to. By reacting the polymer (q-3-1) and the polyisocyanate (r) at a ratio such that the equivalent ratio of the isocyanate group to the active hydrogen-containing group is greater than 1, the polyisocyanate (r) and the vinyl polymer A water-dispersible polyisocyanate composition (A) that is a mixture with (q-3) can be obtained. In this case, a polyisocyanate composition (A) having a higher polyisocyanate content can be obtained by adding polyisocyanate (r) as necessary.

  As the polyisocyanate (r) used in preparing the water-dispersible polyisocyanate composition (A), the above-mentioned polyisocyanate (p) can be used.

  The vinyl polymer (q-3-1) and the polyisocyanate (r) are the equivalent number of isocyanate groups contained in the polyisocyanate (r) / vinyl polymer from the viewpoint of the appearance and performance of the cured coating film. The equivalent number of active hydrogen-containing groups contained in (q-3-1) is in the range of 2 to 300, preferably 5 to 250, more preferably 10 to 100.

  Moreover, in the polyisocyanate composition (A) prepared from the polymer (q-3-1) and the polyisocyanate (r), a suitable ratio of the polyisocyanate (r) and the polymer (q-3) From the viewpoint of coating film appearance and coating film performance, the weight ratio is (r) / (q-3) = 30/70 to 85/15, preferably (r) / (q-3) = 50 / 50-80 / 20.

  To react the polyisocyanate (r) with the polymer (q-3-1), 1) a method in which both components are charged together and reacted, and 2) the polyisocyanate (r) is polymerized (q-3- The method of reacting while adding the solution of 1), the method of reacting while adding the polyisocyanate (r) to the solution of the polymer (q-3-1), etc. can be applied.

Of these, the method 1) or 2) is preferred from the viewpoint of suppressing the formation of gel.
In reacting both these components, the mixture of both components may be left for a long time in an inert gas atmosphere at a relatively low temperature of about 10 ° C. to less than 50 ° C. or stirred for a long time. It is preferable to heat and stir at a temperature of about ~ 130 ° C for about 0.5 to 20 hours. In carrying out such a reaction, a known and commonly used catalyst that accelerates the reaction between the isocyanate group and the active hydrogen-containing group may be added.

  In preparing the polymer (q-3-1), the polyisocyanate (r) is used in place of a part of the solvent or the total amount of the solvent to prepare the polymer (q-3-1). One of the polyisocyanate compositions (A) used in the present invention can also be prepared by allowing the polymer (q-3-1) and the polysocyanate (r) to proceed in parallel. .

The aqueous primer of the present invention comprises the water-dispersible polyisocyanate composition (A), a resin (B) having an active hydrogen-containing group, and water.
Such a resin (B) is not limited as long as it has an active hydrogen-containing group capable of reacting with an isocyanate group. Such active hydrogen-containing groups include hydroxyl groups, carboxyl groups, sulfonic acid groups, sulfinic acid groups, phosphoric acid groups, phosphorous acid groups, amino groups, carboxylic acid amide groups, sulfonic acid amide groups, carbamate groups, ureido groups, and acetoacetyl groups. And a group containing an active methylene group such as Of these, preferred are a hydroxyl group, a carboxyl group, and an active methylene group, and particularly preferred are a hydroxyl group and a carboxyl group.
Further, the resin (B) is mixed with water to form a water-soluble type, a water-dispersible type such as a colloidal dispersion or an emulsion.

  Such resins (B) include vinyl acetate resins, styrene-butadiene resins, styrene-acrylonitrile resins, acrylic resins, fluoroolefin resins, silicon-modified vinyl polymers, vinyl heavy resins such as polyvinyl alcohol. Synthetic resins other than vinyl polymers such as polyester resins, polyurethane resins, phenol resins, melamine resins, epoxy resins, alkyd resins, polyamide resins, polyether resins, silicon resins; animals And natural polymers such as protein, starch, cellulose derivatives, dextrin and gum arabic. Of these, preferred are vinyl polymers and various synthetic resins other than vinyl polymers.

  The amount of the active hydrogen-containing group contained in the resin (B) is 0.1 to 6 moles per 1000 g of the solid content of the resin, preferably from the viewpoint of the curability of the aqueous primer of the present invention and the performance of the cured coating film. 0.2-4 mol, most preferably 0.4-3 mol. Moreover, these resin may be used individually and may use 2 or more types together.

  When preparing an aqueous primer from the polyisocyanate composition (A) and the resin (B) having an active hydrogen-containing group, a suitable mixing ratio of the two depends on the curability of the aqueous primer and the performance of the resulting cured coating film. In view of the above, (1) the equivalent number of isocyanate groups in the polyisocyanate composition, (2) the active hydrogen-containing groups contained in the resin (B) and the blocked activities contained in the vinyl polymer (q). The ratio (1) / (2) to the total number of equivalents of hydrogen-containing groups is 0.1 to 5, preferably 0.3 to 3, and most preferably 0.5 to 2.

  The aqueous primer used in the present invention can also be prepared by mixing the water-dispersible polyisocyanate composition (A) and water. In this case, in order to obtain such an aqueous primer, 10 to 1,000 parts by weight with respect to 100 parts by weight of the polyisocyanate composition (A) from the viewpoint of appearance and performance of a cured coating film obtained from the paint. And preferably 50 to 500 parts by weight of water are added to mix them.

The water-based primer used in the present invention can be used as a clear paint containing no pigment, and can also be used as a colored paint by blending various known organic or inorganic pigments.
In addition, the water-based primer includes additives suitable for various applications, for example, a filler, a leveling agent, a thickener, an antifoaming agent, an organic solvent, an ultraviolet absorber, an antioxidant, or a pigment dispersion. Various known and commonly used additives such as an agent can be blended and used.

  Examples of pigments include organic pigments such as carbon black, phthalocyanine blue, phthalocyanine green, and quinacridone red; extender pigments such as titanium oxide, iron oxide, titanium yellow, and copper chrome black; and aluminum flakes. And inorganic flake pigments such as pearl mica.

  When preparing the colored paint, the total amount of the solid content of the polyisocyanate composition (A) and the solid content of the resin (B) or 100 parts by weight of the solid content of the polyisocyanate composition (A) What is necessary is just to mix | blend a pigment in the ratio that a pigment will be 0.1-300 weight part with respect to 100 weight part, Preferably, it will be 0.2-200 weight part.

Moreover, as said ultraviolet absorber, well-known and usual various compounds, such as a benzotriazole type compound, an oxalic acid anilide type | system | group, and a hydroxybenzophenone series, can be mentioned.
As the antioxidant, known and commonly used compounds such as hindered amine compounds, hindered phenol compounds, and phosphorus compounds can be used. The addition amount of the antioxidant is 100 parts by weight of the solid content of the polyisocyanate composition (A) or the total amount of the solid content of the polyisocyanate composition (A) and the resin (B). What is necessary is just to mix | blend a pigment in the ratio which will be 0.2-10 weight part with respect to 100 weight part, and preferably 0.5-5 weight part for an ultraviolet absorber and / or antioxidant.

  In the present invention, a waterproof primer is applied to a civil engineering building waterproof structure to be repaired after the aqueous primer thus obtained is applied. The existing civil engineering waterproofing structure is composed of at least two layers including a base and a waterproof material layer provided thereon. After the water-based primer is coated on the existing waterproof material layer to form a primer layer, a waterproof coating material is further applied to form a waterproofing structure for civil engineering buildings that is excellent in anti-lifting and low bromide properties. Obtainable.

  Concrete uses of waterproofing structures for civil engineering buildings obtained in this way include buildings such as walls, roofs, verandas, balconies, eaves, rooftops, floors, bathrooms, kitchens, building parking lots, and underground buildings. Structures of objects; civil structures such as roads, subways, underground shopping streets, common grooves, viaducts, girder roads, etc.

  Examples of the base of the civil engineering waterproof structure include various known and commonly used inorganic base materials, hardened bodies manufactured from calcium compounds, woods, and various metal plates such as iron and aluminum. Examples of inorganic substrates include hardened bodies manufactured from calcium compounds such as calcium silicate, calcium aluminate, calcium sulfate, and calcium oxide; ceramics obtained by sintering metal oxides such as alumina, silica, and zirconia; Tiles obtained by sintering viscous minerals; various glasses. And as a hardened body manufactured from a calcium compound, hardened | cured material of cement composition like concrete and mortar, slate, lightweight cellular concrete (ALC) hardened body, dolomite plaster hardened body, gypsum plaster hardened body, calcium silicate board, etc. Is mentioned.

  Examples of coating waterproofing materials include asphalt waterproofing materials; various synthetic polymer roofing waterproofing materials such as vulcanized rubber sheet, non-vulcanized butyl rubber roofing, vinyl chloride resin roofing, rubberized asphalt sheet; urethane coating Examples of the waterproof membrane include various waterproof membranes such as a waterproof membrane, a chloroprene-based waterproof membrane, and an acrylic waterproof membrane.

When applying the waterproof coating material, a reinforcing cloth or the like can be used for the purpose of reinforcing the waterproof coating layer obtained by coating.
As the reinforcing fabric, various known and commonly used ones are used. For example, various organic fibers such as glass fiber, amide fiber, aramid fiber, vinylon fiber, polyester fiber or phenol fiber; carbon fiber, metal fiber, ceramic Examples include various inorganic fibers such as fibers. These may be used alone or in combination. Examples of the fiber form include plain weave, satin weave, non-woven fabric, and mat shape.

  In addition, a liquid primer can be used on the surface of the substrate between the substrate and the existing waterproof material layer for the purpose of bringing the waterproof material layer and the substrate into close contact with each other. Various known and commonly used primers are used, but typical ones are a one-part moisture-curing urethane primer, two-part bisphenol A type epoxy / polyamine-based primer, unsaturated polyester-based primer, vinyl. Examples include ester-based primers, acrylic primers, and rubber-based primers.

  Further, a ventilation cushioning sheet can be provided between the base and the existing waterproofing material layer for the purpose of improving the followability and preventing the occurrence of blisters when a crack occurs in the base. Various known and commonly used aeration buffer sheets are used. Asphalt sheets such as polymer-modified asphalt sheets; ethylene propylene rubber sheets, chlorosulfonated polyethylene sheets, vinyl chloride resin sheets, chlorinated polyethylene sheets And rubber sheets such as butyl rubber sheet; synthetic resin foam sheets; synthetic nonwoven sheets and the like.

  The civil engineering building waterproof structure refurbishment method of the present invention is a method in which a water-based primer is coated on the above existing waterproofing material layer to be repaired, and then dried to form a primer layer. It is something to apply. In this case, a top coat can be further applied and cured as required.

  Next, the present invention will be described in detail with reference examples, examples and comparative examples, but the present invention is not limited thereto. All parts and% in the text are based on weight unless otherwise specified.

  First, the water-dispersible polyisocyanate composition will be described with reference to examples and comparative examples. First, polyisocyanates used in the examples and comparative examples will be described.

Polyisocyanate (p-1)
Hexamethylene diisocyanate (hereinafter abbreviated as HDI) -based isocyanurate type polyisocyanate "Bernock DN-980S" [Dai Nippon Ink Chemical Co., Ltd. isocyanate group content (hereinafter abbreviated as NCO group content) 21% by weight, non-volatile content 100%]

Polyisocyanate (p-2)
Solvent removed from “Bernock DN-950” (Dainippon Ink & Chemicals, Inc., ethyl acetate solution), an adduct type polyisocyanate of HDI and triol. NCO group content 17% by weight, non-volatile content 100%.

Reference Example 1 [Preparation of Polyisocyanate Composition (A)]
After charging 429 parts of diethylene glycol diethyl ether (hereinafter abbreviated as EDE) into a four-necked flask equipped with a stirrer, thermometer, cooling pipe, and nitrogen introduction pipe, the temperature was raised to 110 ° C. under a nitrogen stream, Methoxypolyethyleneglycol methacrylate having a number average molecular weight of 400 oxyethylene groups (hereinafter abbreviated as MPEGMA) 400 parts, cyclohexyl methacrylate (hereinafter abbreviated as CHMA) 200 parts, methyl methacrylate (hereinafter abbreviated as MMA) A mixed solution consisting of 400 parts, 45 parts of t-butylperoxy-2-ethylhexanoate (hereinafter abbreviated as TBPEH) and 5 parts of t-butylperoxybenzoate was added dropwise over 5 hours. After the dropping, the mixture was reacted at 110 ° C. for 9 hours to obtain an acrylic polymer solution having a nonvolatile content of 70% and a weight average molecular weight of 18,000. Hereinafter, this is abbreviated as an acrylic polymer (q-1).

  Next, 200 parts of polyisocyanate (p-1) and 100 parts of vinyl polymer (q-1) were charged into a reactor similar to that used for the preparation of the acrylic polymer and heated to 50 ° C. under a nitrogen stream. After raising the temperature, the mixture was stirred and mixed at the same temperature for 1 hour to obtain a water-dispersible polyisocyanate composition having a non-volatile content of 90% and an NCO group content of 14.0% by weight. Hereinafter, this is abbreviated as a polyisocyanate composition (A-1).

Reference Example 2 [Preparation of Polyisocyanate Composition (A)]
In place of 400 parts of MPEGMA, 200 parts of CHMA and 400 parts of MMA, as a vinyl monomer, 500 parts of MPEGMA, 50 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), 150 parts of CHMA, MMA Polymerization was carried out in the same manner as in Reference Example 1 except that 300 parts were used to obtain an acrylic polymer solution having a nonvolatile content of 70% and a weight average molecular weight of 17,000. Hereinafter, this is abbreviated as a vinyl polymer (q-2).

  Next, 200 parts of polyisocyanate (p-1) and 100 parts of vinyl polymer (q-2) were charged into a reactor similar to that used for the preparation of the acrylic polymer and heated to 90 ° C under a nitrogen stream. After raising the temperature, the reaction was conducted with stirring at the same temperature for 6 hours to obtain a water-dispersible polyisocyanate composition having a nonvolatile content of 90% and an NCO group content of 13.0% by weight. Hereinafter, this is abbreviated as a polyisocyanate composition (A-2).

Reference Example 3 [Preparation of Polyisocyanate Composition (A)]
In a reactor similar to that used for preparing the acrylic polymer of Reference Example 1, 200 parts of polyisocyanate (p-2) and 100 parts of vinyl polymer (q-2) were charged, and 90 ° C. under a nitrogen stream. Then, the reaction was conducted with stirring at the same temperature for 6 hours to obtain a water-dispersible polyisocyanate composition having a nonvolatile content of 90% and an NCO group content of 13.0% by weight. Hereinafter, this is abbreviated as a polyisocyanate composition (A-3).

Reference Example 4 [Preparation of polyisocyanate composition (A)]
In a reactor similar to Reference Example 1, 34 parts of EDE, 36 parts of methoxypolyethylene glycol having a number average molecular weight of 560, and 100 parts of polyisocyanate (p-1) were charged, and the temperature was raised to 90 ° C. over 30 minutes. The reaction was carried out at 90 ° C. for 6 hours to obtain a polyisocyanate modified with methoxypolyethylene glycol having a nonvolatile content of 80% and an NCO group content of 11.0% by weight. Hereinafter, this is abbreviated as a polyisocyanate composition (A-4).

Reference Example 5 [Preparation of Resin (B)]
5 parts “Hytenol N-08” (anionic emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), “Emulgen 931” (nonionic emulsifier manufactured by Kao Corp.) 5 parts in the same reactor as in Reference Example 1 After adding 270 parts of deionized water and heating to 80 ° C. under a nitrogen stream, an aqueous solution having 0.8 part of ammonium persulfate dissolved in 16 parts of deionized water is added. Further, a mixed solution consisting of 80 parts of n-butyl acrylate (hereinafter abbreviated as BA), 99 parts of MMA, 4 parts of acrylic acid and 17 parts of HEMA was added dropwise over 3 hours. After dropping, the mixture was reacted for 2 hours, then cooled to 25 ° C., neutralized with 1.5 parts of 28% aqueous ammonia, mixed with 500 parts of water and 30 parts of EDE, and had a nonvolatile content of 20% and a solid content hydroxyl value. A hydroxyl group-containing acrylic resin emulsion of 35 mg KOH / g was obtained. Hereinafter, this resin is abbreviated as an aqueous resin (B-1).

Reference Example 6 [Preparation of Resin (B)]
Polymerization was carried out in the same manner as in Reference Example 10, except that 100 parts of BA, 96 parts of MMA and 4 parts of acrylic acid were used instead of 80 parts of BA, 99 parts of MMA, 4 parts of acrylic acid and 17 parts of HEMA. Thus, an acrylic resin emulsion having a nonvolatile content of 40% was obtained. Hereinafter, this is abbreviated as an aqueous resin (B-2).

Reference Example 7 [Preparation of Topcoat T-1]
ACRIDIC 48-261 (Dainippon Ink & Chemicals, Inc., acrylic resin solution, non-volatile content 60%, hydroxyl value 36 mg KOH / mg) 100 parts, Taipei CR-93 (Ishihara Sangyo Co., Ltd., titanium oxide) 41 Part and 17.7 parts of butyl acetate were kneaded with three rolls to obtain a white paint base. The top coating agent T-1 was obtained by adding 151.6 parts of this white paint base and 21.6 parts of Bernock DN-950.

Preparation of a substrate (BA-1) provided with a waterproof material layer On a flexible plate, 0.2 kg of PRIADEC T-44 (a moisture curable urethane primer manufactured by Dainippon Ink & Chemicals, Inc.) as a primer with a brush. After coating at a coating amount of / m ² , the primer layer was molded by curing for 1 day in an atmosphere of a temperature of 20 ° C. and a humidity of 60% RH. Next, on the primer layer, the main agent and curing agent of Dick Urethane N [Dai Nippon Ink Chemical Co., Ltd., two-component urethane resin for waterproofing material] has a weight ratio of main agent / curing agent of 1/2. After being applied so as to be an application amount of 2.0 kg / m ² using a gold iron, the mixture thus formulated (hereinafter abbreviated as WP-1) was heated at a temperature of 20 ° C. and a humidity of 60% RH. Cured for 1 day under atmosphere. Further, after applying the top coat T-1 at a coating amount of 0.3 kg / m ² , it was cured for 1 day in an atmosphere of a temperature of 20 ° C. and a humidity of 60% RH, and exposed for 5000 hours with a sunshine weatherometer, and polyurethane A base (BA-1) provided with a water-based waterproofing material layer was obtained.

Preparation of a substrate (BA-2) provided with a waterproof material layer On a flexible plate, Boncoat 2310 (a vinyl acetate resin emulsion manufactured by Dainippon Ink & Chemicals, Inc.) as a primer was diluted twice with water, The primer layer was applied with a roll brush at a coating amount of 0.2 kg / m ² and dried for 6 hours in an atmosphere of a temperature of 20 ° C. and a humidity of 60% RH to form a primer layer. Next, on the primer layer, Boncoat 3660H [Acrylic-styrene resin emulsion manufactured by Dainippon Ink & Chemicals, Inc.] 117 parts, sodium tripolyphosphate 1.5 g, demole EP 1.5 parts, ethylene glycol 3 parts, 1.5 parts of SN deformer 154 (San Nopco Co., Ltd. defoaming agent), 1.5 parts of Neugen EA-120 (Daiichi Kogyo Seiyaku Co., Ltd. wetting agent), Cell Top HP-103 (Kohjin Co., Ltd. fluidity regulator) 1.5 parts, NS-200 (Nitto Powder Co., Ltd. calcium carbonate) 72 parts, SS-30 (Nitto Powder Co., Ltd. product) 64 parts of calcium carbonate, 6 parts of cold water # 70 (filler made by Nitto Flourishing Co., Ltd.), 2 parts of Taipei R-550 (titanium oxide made by Ishihara Sangyo Co., Ltd.), Himetrozu 90SH-15000 ( Shin-Etsu Chemical ( ), A waterproofing material (hereinafter abbreviated as WP-2) obtained by dispersing 0.3 part of a thickener) and 1 part of 28% aqueous ammonia with a disper, using a gold iron, 2.0 kg / M ² , and dried for 10 days in an atmosphere of temperature 20 ° C. and humidity 60% RH, and further exposed for 5000 hours with a sunshine weatherometer, at least an acrylic rubber waterproofing material layer A substrate (BA-2) provided with

Example 1
10 parts of polyisocyanate composition (A-1) and 50 parts of aqueous resin (B-1) were mixed to prepare an interlayer primer (V-1).

Immediately after preparing the interlayer primer (V-1) thus obtained, a roller brush was used on the waterproof material layer of the base (BA-1) provided with the waterproof material layer prepared in advance as follows. The coating was applied so that the coating amount was 0.2 kg / m ² . Next, after drying for 6 hours in an atmosphere of a temperature of 20 ° C. and a humidity of 60% RH, Dick Urethane N was applied at 2 kg / m ² and cured for 10 days. The obtained cured coating film was evaluated for adhesive strength, lifting (swelling) of the waterproofing material of the substrate, odor during primer application, and water resistance. The evaluation results are shown in Table 1.

Examples 2-7
The polyisocyanate compositions (A-1) to (A-4), the aqueous resins (B-1) to (B-2) and water were mixed in the ratios described in Table 1, and the interlayer primer (V-2 ) To (V-7) were prepared. Subsequently, it replaced with the interlayer primer (V-1), and except having used each interlayer primer immediately after preparation, it applied and cured like Example 1 and obtained the cured coating film. The cured coating film thus obtained was evaluated for adhesive strength, lifting (swelling) of the waterproofing material, odor during primer application, and water resistance. The evaluation results are shown in Table 1.

Comparative Example 1
Coating and curing were performed in the same manner as in Example 1 except that Priadec T-44 was used as an interlayer primer to obtain a cured coating film. The cured coating film thus obtained was evaluated for adhesive strength, lifting (swelling) of the waterproofing material, odor during primer application, and water resistance. The evaluation results are shown in Table 1.

Comparative Example 2
Coating and curing were carried out in the same manner as in Example 4 except that Priadec T-44 was used as an interlayer primer to obtain a cured coating film. The cured coating film thus obtained was evaluated for adhesive strength, lifting (swelling) of the waterproofing material, odor during primer application, and water resistance. The evaluation results are shown in Table 1.

Comparative Example 3
This paint immediately after preparation is used by replacing the interlayer primer for comparison prepared by mixing 10 parts of the polyisocyanate composition (p-1) and 30 parts of the aqueous resin (B-2) with the interlayer primer (V-1). Except for the above, coating and drying were performed in the same manner as in Example 1 to obtain a cured coating film. The cured coating film thus obtained was evaluated for coating film appearance and water resistance. The evaluation results are shown in Table 1.

Comparative Example 4
A cured coating film was obtained by applying and drying in the same manner as in Example 1 except that the interlayer primer was not applied. The cured coating film thus obtained was evaluated for coating film appearance and water resistance. The evaluation results are shown in Table 1.

<< Footnotes in Table 1 >>
Each numerical value indicating the use ratio of the raw materials is assumed to be in parts by weight.

"Adhesive strength":
A cured coating film dried at a temperature of 20 ° C. and a humidity of 60% RH for 10 days was cut into a 1-inch width using a cutter knife, peeled at 90 ° C., and the adhesive strength was evaluated based on the resistance.

“Odor”:
The odor during the interlayer primer coating work was evaluated by a sensory test. The level at which no odor was given was indicated by ◎, the level at which it slightly smells was indicated by ○, and the level at which a clear odor was generated was indicated by ×.

"Lifting":
Between the time when the interlayer primer was applied and when the waterproof material was applied, the case where the substrate surface showed an abnormality such as undulation was marked with ×, and the case where no change was observed was marked with ◎.

"water resistant":
After being immersed in deionized water heated to 50 ° C. for 24 hours and then dried for 2 days at a temperature of 20 ° C. and a humidity of 60% RH, a 1-inch wide cut was made using a cutter knife, and 90 ° Peeling peeling was performed, and water resistance was evaluated based on the peeling resistance.

Retention rate [%] = (peeling resistance after water resistance test / adhesion strength) × 100

Claims (4)

When rehabilitating a civil engineering waterproofing structure, a water-dispersible polyisocyanate composition (A), a resin (B) having an active hydrogen-containing group, and an aqueous primer containing water are applied, and a waterproof coating material is applied thereon. A construction method for waterproofing civil engineering buildings, characterized by applying a coating. A civil engineering building characterized by applying a water-based primer containing a water-dispersible polyisocyanate composition (A) and water, and applying a waterproof coating material on the water-resistant polyisocyanate composition (A) when renovating the civil engineering waterproofing structure. Repair method for waterproof structure. The method for repairing a waterproofing structure for civil engineering buildings according to claim 1 or 2, wherein the water-dispersible polyisocyanate composition (A) is a water-dispersible polyisocyanate composition having a nonionic group in the system. The repair method of the civil engineering waterproofing structure according to claim 3, wherein the water-dispersible polyisocyanate composition having a nonionic group contains a vinyl polymer having a nonionic group.