JP2007169510A - Adhesive for urethane coating film waterproof material for architecture and air-permeable buffer composite waterproofing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an adhesive for a urethane coating film waterproof material for architecture, which relieves limitation of the Fire Service Law in terms of numerical quantities of product storage and attains formation of non-solvent. <P>SOLUTION: The adhesive for a urethane coating film waterproof material for architecture comprises a urethane prepolymer, an epoxy resin and a hydrolyzable imine compound. The amount of the epoxy resin is 1-100 parts by mass based on 100 parts by mass of the urethane prepolymer. The viscosity of the urethane prepolymer is ≤50 Pa s and that of the epoxy resin is ≤60 Pa s. The amount of the hydrolyzable imine compound is an amount to give an equivalent ratio represented by formula (the number of total groups of isocyanate groups in the urethane prepolymer and epoxy groups in the epoxy resin)/(imino bond in the hydrolyzable imine compound) of 0.7-1.5. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to an adhesive for waterproof urethane film for construction and an air-permeable cushioning waterproof method.

As a method of waterproofing the rooftop of a building, a method in which a waterproof sheet formed in advance at the factory is attached to the base surface using an adhesive (sheet waterproofing method), or a liquid composition is applied to the base surface to be waterproofed. A method of forming a waterproof coating by applying and drying or curing (water-proof coating method) is well known.
In addition, these construction methods are intended to renovate by directly forming a waterproof layer (a waterproof sheet in the waterproof sheet method and a waterproof film in the waterproof film method) on the mortar that is the base of the building rooftop, etc. Further, it is known that water vapor staying in the base is vaporized to cause the waterproof layer to swell and to crack the base.
Therefore, in recent years, in these construction methods, a construction method has been proposed in which a cushioning material (breathable cushioning sheet) having air permeability and cushioning properties is provided between the waterproof layer and the base (see, for example, Patent Document 1). ).

  However, in the construction method described in Patent Document 1 or the like, a urethane or chloroprene adhesive containing a large amount of powder and an organic solvent is added from the viewpoints of adhesiveness (peeling strength) between the base and the ventilation cushion sheet and workability. Therefore, there is a problem that the product storage quantity is greatly restricted under the Fire Service Act and that non-solvent is required from the environmental aspect.

Japanese Patent Laid-Open No. 11-10798

  Therefore, an object of the present invention is to provide an adhesive for waterproofing urethane coating film for construction which can alleviate restrictions on fire fighting law regarding product storage quantity and can also achieve non-solventization.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a composition containing a urethane prepolymer, an epoxy resin, and a hydrolyzable imine compound at a predetermined viscosity and ratio is used for a urethane coating waterproofing material for construction. When used as an adhesive, restrictions on fire storage laws regarding product storage quantities are relaxed, specifically from 1st petroleums and 2nd petroleums to 3rd petroleums and 4th petroleums, The present inventors have found that non-solventization can also be achieved and completed the present invention.

That is, the present invention provides the following (1) to (5).
(1) contains a urethane prepolymer, an epoxy resin and a hydrolyzable imine compound,
Containing 1 to 100 parts by mass of the epoxy resin with respect to 100 parts by mass of the urethane prepolymer;
The urethane prepolymer has a viscosity of 50 Pa · s or less,
The epoxy resin has a viscosity of 60 Pa · s or less,
The equivalent ratio represented by (the total number of isocyanate groups in the urethane prepolymer and epoxy groups in the epoxy resin) / (imino bond in the hydrolyzable imine compound) of the hydrolyzable imine compound is 0. An adhesive for waterproofing urethane film for construction, containing 7 to 1.5.
(2) The adhesive for architectural urethane coating film waterproofing material according to (1), wherein the hydrolyzable imine compound has a viscosity of 30 Pa · s or less.
(3) The hydrolyzable imine compound has an imino (> C = N-) bond derived from a ketone or aldehyde and an amine, and at least one atom of a carbon atom and a nitrogen atom forming the imino bond The adhesive for waterproofing urethane paints for construction according to the above (1) or (2), wherein a branched carbon atom or a ring member carbon atom is bonded to the α-position or β-position.
(4) A ventilation cushioning composite waterproofing method for constructing a urethane coating waterproof material on the surface of a building,
A coating process for applying the waterproofing agent for architectural urethane film waterproofing material according to any one of (1) to (3) above to the surface of a building, and aeration over the adhesive applied by the coating process. A ventilation cushioning composite waterproofing method comprising a sticking step of attaching a cushioning sheet and a construction step of constructing a urethane coating waterproof material on the ventilation cushioning sheet attached by the sticking step in this order.
(5) A structure in which a urethane coating waterproof material is applied to the surface of a building, which is manufactured using the ventilation cushion composite waterproofing method described in (4) above.

  ADVANTAGE OF THE INVENTION According to this invention, the restriction | limiting in the Fire Service Act regarding the product storage quantity can be eased, and the urethane-urethane-coated waterproofing material adhesive for construction which can also achieve non-solvent can be provided. By using an adhesive for waterproofing urethane film, it is possible to provide an air cushioning composite waterproofing method considering the environment.

Hereinafter, the present invention will be described in more detail.
The adhesive for architectural waterproofing membrane for urethane film according to the first aspect of the present invention (hereinafter also simply referred to as “the adhesive of the present invention”) comprises a urethane prepolymer, an epoxy resin and a hydrolyzable imine compound. 1 to 100 parts by mass of the epoxy resin with respect to 100 parts by mass of the urethane prepolymer, the viscosity of the urethane prepolymer is 50 Pa · s or less, and the viscosity of the epoxy resin is 60 Pa · s or less. The equivalent of the hydrolyzable imine compound represented by (total number of isocyanate groups in the urethane prepolymer and epoxy group in the epoxy resin) / (imino bond in the hydrolyzable imine compound) It is a composition contained so that ratio may be set to 0.7-1.5.
Here, in this invention, the viscosity of a urethane prepolymer and an epoxy resin says the value measured under 20 degreeC using the E-type viscosity meter.
Next, each component used for the adhesive of the present invention will be described in detail.

<Urethane prepolymer>
The urethane prepolymer used in the adhesive of the present invention includes a polyol compound and an excess polyisocyanate compound (that is, an excess isocyanate (based on a hydroxyl (OH) group) as in a normal one-pack type polyurethane resin composition. NCO) group) is a reaction product obtained by reacting, and has a viscosity of 50 Pa · s or less.

The polyisocyanate compound for producing such a urethane prepolymer is not particularly limited as long as it is a compound having two or more NCO groups in the molecule. Specific examples thereof include 2,4-tolylene diisocyanate (2,4 -TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI) , 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), and the like; hexamethylene diisocyanate ( HDI), Trimethyl hexamethylene diisocyanate (TMHDI), lysine diisocyanate, aliphatic polyisocyanates such as norbornane diisocyanate methyl (NBDI); trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI) , Cycloaliphatic polyisocyanates such as H ₁₂ MDI (hydrogenated MDI), H ₆ TDI (hydrogenated TDI); polyisocyanate compounds such as polymethylene polyphenylene polyisocyanate; carbodiimide-modified polyisocyanates of these isocyanate compounds; Isocyanurate-modified polyisocyanates of compounds; urethane prepolymers obtained by reacting these isocyanate compounds with polyol compounds described below ; And the like, may be used in combination of two or more even with these alone.
A monoisocyanate compound having only one NCO group in the molecule can also be used by mixing with a diisocyanate compound or the like.

  Further, the polyol compound for producing such a urethane prepolymer is not particularly limited in its molecular weight and skeleton as long as it is a compound having two or more OH groups. Specific examples thereof include low molecular weight polyhydric alcohols. , Polyether polyols, polyester polyols, other polyols, and mixed polyols thereof.

  Specific examples of low molecular weight polyhydric alcohols include ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, (1,3- or 1,4-) butanediol, and pentanediol. , Neopentyl glycol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane (TMP), 1,2,5-hexanetriol, low molecular polyols such as pentaerythritol; saccharides such as sorbitol; etc. Is mentioned.

Next, as the polyether polyol and polyester polyol, those derived from the above low-molecular polyhydric alcohols are usually used. In the present invention, the following aromatic diols, amines and alkanolamines are further used. Those derived from the above can also be suitably used.
Here, specific examples of the aromatic diols include resorcin (m-dihydroxybenzene), xylylene glycol, 1,4-benzenedimethanol, styrene glycol, 4,4′-dihydroxyethylphenol; Bisphenol A structure (4,4'-dihydroxyphenylpropane), bisphenol F structure (4,4'-dihydroxyphenylmethane), brominated bisphenol A structure, hydrogenated bisphenol A structure, bisphenol S structure, bisphenol AF Those having a bisphenol skeleton having a structure;

  Specific examples of amines include ethylenediamine and hexamethylenediamine. Specific examples of alkanolamines include ethanolamine and propanolamine.

As the polyether polyol, for example, at least one selected from the compounds exemplified as the above low molecular polyhydric alcohols, the above aromatic diols, the above amines, and the above alkanolamines, ethylene oxide, propylene oxide, butylene oxide Examples thereof include polyols obtained by adding at least one selected from (tetramethylene oxide), alkylene oxides such as tetrahydrofuran, styrene oxide, and the like.
Specific examples of such polyether polyols include polyethylene glycol, polypropylene glycol (PPG), polypropylene triol, ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), polytetraethylene glycol, sorbitol-based polyol. Etc.
Specific examples of polyether polyols having a bisphenol skeleton include polyether polyols obtained by adding ethylene oxide and / or propylene oxide to bisphenol A (4,4′-dihydroxyphenylpropane).

Similarly, as the polyester polyol, for example, a condensate (condensed polyester polyol) of any one of the low molecular polyhydric alcohols, the aromatic diols, the amines and the alkanolamines with a polybasic carboxylic acid. ); Lactone polyol; polycarbonate polyol; and the like.
Here, as the polybasic carboxylic acid forming the condensed polyester polyol, specifically, for example, glutaric acid, adipic acid, azelaic acid, fumaric acid, maleic acid, pimelic acid, suberic acid, sebacic acid, Hydroxycarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, dimer acid, pyromellitic acid, other low-molecular carboxylic acids, oligomeric acids, castor oil, reaction products of castor oil and ethylene glycol (or propylene glycol), etc. Is mentioned.
Further, as the lactone-based polyol, specifically, for example, a lactone such as ε-caprolactone, α-methyl-ε-caprolactone, ε-methyl-ε-caprolactone was ring-opened and polymerized with an appropriate polymerization initiator. And those having hydroxyl groups at both ends.
Examples of the polyester polyol having a bisphenol skeleton include condensed polyester polyols obtained by using a diol having a bisphenol skeleton instead of the low molecular polyhydric alcohols or together with the low molecular polyhydric alcohols. Specific examples include polyester polyols obtained from bisphenol A and castor oil, polyester polyols obtained from bisphenol A, castor oil, ethylene glycol, and propylene glycol.

  Specific examples of other polyols include acrylic polyols; polybutadiene polyols; polymer polyols having carbon-carbon bonds in the main chain skeleton such as hydrogenated polybutadiene polyols.

  In the present invention, the various polyol compounds exemplified above may be used alone or in combination of two or more.

  As described above, the urethane prepolymer used in the adhesive of the present invention is obtained by reacting a polyol compound with an excess of a polyisocyanate compound. Specific examples thereof include various polyol compounds exemplified above. And combinations of various polyisocyanate compounds.

  Among these, a urethane prepolymer obtained by reacting tolylene diisocyanate (TDI) with various polyol compounds (preferably polyethylene glycol, polypropylene glycol, etc.) (hereinafter also referred to as “TDI urethane prepolymer”). However, it is possible to secure a sufficient pot life (about 80 minutes) of the adhesive of the present invention containing the urethane prepolymer, and as a result, before the adhesive itself is cured, a ventilation buffer described later. This is preferable because it easily penetrates into a part of the ventilation layer (nonwoven fabric) of the sheet and the adhesion between the foundation and the ventilation cushioning sheet is further improved.

In the present invention, the viscosity of such a urethane prepolymer is 50 Pa · s or less, preferably 20 to 3 Pa · s, and more preferably 15 to 5 Pa · s. When the viscosity of the urethane prepolymer is within this range, the resulting adhesive of the present invention can be made non-solvent.
Moreover, in this invention, it is preferable that the weight average molecular weights of such a urethane prepolymer are 2000-100000, and it is more preferable that it is 3000-30000. When the weight average molecular weight of the urethane prepolymer is within this range, the workability of the resulting adhesive of the present invention is improved, and it is preferable to achieve non-solventization.

<Epoxy resin>
The epoxy resin used in the adhesive of the present invention is not particularly limited as long as it is a resin composed of a compound having two or more oxirane rings (epoxy groups) in one molecule and has a viscosity of 60 Pa · s or less. Generally, the epoxy equivalent is 90-2000.
As such an epoxy resin, a conventionally known epoxy resin can be used. Specifically, for example, bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, Bifunctional glycidyl such as bisphenol AF type and biphenyl type epoxy compounds having a bisphenyl group, polyalkylene glycol type and alkylene glycol type epoxy compounds, an epoxy compound having a naphthalene ring, and an epoxy compound having a fluorene group Ether type epoxy resin;
Polyfunctional glycidyl ether type epoxy resins such as phenol novolak type, orthocresol novolak type, DPP novolak type, tris-hydroxyphenylmethane type, trifunctional type, tetraphenylolethane type, etc .;
Glycidyl ester type epoxy resin of synthetic fatty acid such as dimer acid;
N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM), tetraglycidyl-m-xylylenediamine, triglycidyl-p-aminophenol, N, N-diglycidyl represented by the following formula (1) An aromatic epoxy resin having a glycidylamino group such as aniline;

Following formula (2) epoxy compound having a tricyclo [5,2,1,0 ^2,6] decane ring represented by, specifically, for example, the cresols or phenols such as dicyclopentadiene and cresol An epoxy compound which can be obtained by a known production method of reacting epichlorohydrin after polymerization;

式中、ｍは、０〜１５の整数を表す。

In formula, m represents the integer of 0-15.

  Cycloaliphatic epoxy resin; epoxy resin represented by Toray Rethiokol's Flep 10 epoxy resin having a sulfur atom in the main chain; urethane modified epoxy resin having urethane bond; polybutadiene, liquid polyacrylonitrile-butadiene rubber or acrylonitrile butadiene rubber Examples thereof include a rubber-modified epoxy resin containing (NBR). These may be used alone or in combination of two or more.

  Among these, a liquid epoxy resin is preferable because the workability of the obtained adhesive of the present invention becomes good and the achievement of non-solvent becomes easier. Specifically, a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are preferable.

  Examples of such epoxy resins include commercially available products such as EP4100 (Asahi Denka Kogyo), Epicoat 828 (Japan Epoxy Resin), Epicoat 806 (Japan Epoxy Resin), Epicoat 154 (Japan Epoxy Resin). Can be used.

In the present invention, the viscosity of such an epoxy resin is 60 Pa · s or less, and preferably 0.01 to 20 Pa · s. When the viscosity of the epoxy resin is within this range, the resulting adhesive of the present invention can be made non-solvent.
Moreover, in this invention, content of such an epoxy resin is 1-100 mass parts with respect to 100 mass parts of said urethane prepolymers, Preferably it is 3-50 mass parts, More preferably, it is 5-5 mass parts. 20 parts by mass. When the content of the epoxy resin is within this range, the resulting adhesive itself of the present invention easily penetrates into a part of the ventilation layer (nonwoven fabric) of the ventilation cushioning sheet described later before curing. Adhesiveness is improved.

<Hydrolyzable imine compound>
The hydrolyzable imine compound used in the adhesive of the present invention is a compound having a carbon-nitrogen double bond group (imine compound) obtained by condensation of a carbonyl compound and an azane or an amine. If it produces | generates, it will not specifically limit.
Such a hydrolyzable imine compound is preferably a compound having an imino (> C═N—) bond derived from a ketone or aldehyde and an amine, and specific examples thereof include a ketone and an amine. Examples include ketimines derived from aldimines derived from aldehydes and amines.

As the ketone or aldehyde used for the synthesis of ketimine or aldimine, widely known ones can be used.
Specifically, for example, methyl isobutyl ketone (MIBK), methyl-t-butyl ketone (MTBK), methyl isopropyl ketone (MIPK), pivalaldehyde (trimethylacetaldehyde), isobutyraldehyde ((( CH ₃ ) ₂ CHCHO), methyl cyclohexanone, ethyl cyclohexanone, methyl cyclohexyl ketone, acetophenone, propiophenone, and the like. These may be used alone or in combination of two or more. Of these, MTBK and MIPK are preferred.

  Other specific examples include diethyl ketone, dipropyl ketone, dibutyl ketone, ethyl propyl ketone, ethyl butyl ketone, butyl propyl ketone, ethyl isopropyl ketone, ethyl amyl ketone, cyclohexanone, and the like. Two or more types may be used in combination. Of these, diethyl ketone, dipropyl ketone, and dibutyl ketone are preferred.

  Furthermore, as other specific examples, ethyl isobutyl ketone represented by the following formula (3), isobutyl propyl ketone represented by the following formula (4), ethyl (2-methylbutyl) represented by the following formula (5) Examples include ketones and diisobutyl ketones represented by the following formula (6). These may be used alone or in combination of two or more. Of these, diisobutyl ketone is preferred.

  On the other hand, as the amine compound used for the synthesis of ketimine or aldimine, widely known compounds can be used, and polyamines having two or more amino groups in the molecule are preferred, and aliphatic polyamines and / or fatty acids are preferred. More preferably, it is a cyclic polyamine. Moreover, it is more preferable that it is a polyamine represented by following formula (7) from a viewpoint that reaction adjustment is easy.

（式中、ｎは、２〜６の整数を表す。）

(In the formula, n represents an integer of 2 to 6.)

  Specific examples of the amine compound include ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,6-hexamethylenediamine, and trimethylhexamethylene. Aliphatic polyamines such as diamine, 1,2-propanediamine, iminobispropylamine, methyliminobispropylamine, 1,5-diamino-2-methylpentane (for example, MPMD manufactured by DuPont Japan); Phenylenediamine, orthophenylenediamine, paraphenylenediamine, m-xylylenediamine (MXDA), diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphe Aromatic polyamines such as rumethane; N-aminoethylpiperazine; monoamines having an ether bond in the main chain such as 3-butoxyisopropylamine; diamines having a polyether skeleton represented by Jeffamine EDR148 manufactured by San Techno Chemical Co .; isophorone Diamine, 1,3-bisaminomethylcyclohexane (for example, 1,3BAC manufactured by Mitsubishi Gas Chemical Co., Inc.), 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine An alicyclic polyamine such as: norbornane diamine (for example, NBDA manufactured by Mitsui Chemicals, Inc.); norbornane skeleton diamine; polyamide amine having an amino group at the molecular end of polyamide; 2,5-dimethyl-2,5 -Hexamethylenediamine, N-cenediamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, Jeffermine D230, Jeffamine D400 manufactured by Sun Techno Chemical Co., which has polypropylene glycol (PPG) as a skeleton, and the like. One species may be used alone, or two or more species may be used in combination.

  Among these, 1,6-hexamethylenediamine, 1,3-bisaminomethylcyclohexane (1,3BAC), norbornanediamine (NBDA), m-xylylenediamine (MXDA), Jeffamine EDR148 (trade name), polyamide An amine is preferred.

Examples of the hydrolyzable imine compound used in the adhesive of the present invention include combinations of various ketones or aldehydes exemplified above and various amines.
Specifically, obtained from MIBK and propylenediamine; obtained from MIPK and / or MTBK and Jeffamine EDR148; obtained from MIPK and / or MTBK and 1,3BAC; MIPK and / or MTBK Obtained from MIPK and / or MTBK and MXDA; obtained from MIPK and / or MTBK and polyamidoamine; obtained from diethyl ketone and MXDA; pivalaldehyde, isobutyl At least one aldehyde selected from the group consisting of an aldehyde and cyclohexanecarboxaldehyde, and at least one selected from the group consisting of NBDA, 1,3BAC, Jeffamine EDR148 and MXDA Those resulting from the combination of the amine; and the like are preferably exemplified.

  Among these, one obtained from MIPK or MTBK and 1,3BAC; one obtained from MIPK or MTBK and NBDA; one obtained from MIPK or MTBK and MXDA is a base using the adhesive of the present invention. Since adhesiveness with a ventilation buffer sheet improves more, it is preferable.

  In the present invention, the viscosity of such a hydrolyzable imine compound is preferably 30 Pa · s or less, and more preferably 0.1 mPa · s to 5 Pa · s. When the viscosity of the hydrolyzable imine compound is within this range, the resulting adhesive of the present invention can be more easily made non-solvent. In addition, the viscosity of a hydrolyzable imine says the value measured under 20 degreeC using the E-type viscosity meter similarly to a urethane prepolymer.

  In the present invention, such a hydrolyzable imine compound is eliminated by heating and refluxing a ketone or an aldehyde and an amine in the absence of a solvent or in the presence of a solvent such as benzene, toluene or xylene. It can be obtained by reacting while removing water azeotropically.

  Furthermore, in the present invention, such a hydrolyzable imine compound is expressed as (total number of isocyanate groups in the urethane prepolymer and epoxy groups in the epoxy resin) / (imino bond in the hydrolyzable imine compound). ) In an equivalent ratio of 0.7 to 1.5, preferably 0.9 to 1.1. If the content of the hydrolyzable imine compound is in this range, the resulting adhesive of the present invention itself can easily penetrate into a part of the ventilation layer (nonwoven fabric) of the ventilation buffer sheet described later before being cured. Adhesiveness with the air cushion sheet is improved.

  The adhesive of the present invention contains 1 to 100 parts by mass of the epoxy resin with respect to 100 parts by mass of the urethane prepolymer, and the hydrolyzable imine compound (isocyanate group and epoxy in the urethane prepolymer). It is contained so that the equivalent ratio represented by the total number of epoxy groups in the resin / (imino bond in the hydrolyzable imine compound) is 0.7 to 1.5.

Moreover, since the adhesive of this invention contains the said urethane prepolymer, the said epoxy resin, and the said hydrolysable imine compound in a predetermined ratio, it can be used without containing an organic solvent. This is because the urethane prepolymer, epoxy resin, and hydrolyzable imine compound used have a relatively low viscosity.
As a result, the adhesive of the present invention can be made non-solvent, the urethane prepolymer corresponds to the 4th petroleum of the Fire Service Act dangerous goods, and the epoxy resin and the hydrolyzable imine compound are the dangerous goods of the same law. Since it falls under Class 3 or Class 4 petroleum, restrictions on fire protection laws will be relaxed with regard to product storage quantities. On the other hand, as described above, the current adhesive for urethane film waterproofing material contains not only powder but also a large amount of organic solvent (for example, toluene, xylene, etc.). It may fall under Class 2 and 2nd Petroleum, and may be subject to restrictions under the Fire Service Law regarding product storage quantity.

  Furthermore, as described above, the adhesive of the present invention easily penetrates into a part of a ventilation layer (nonwoven fabric) of a ventilation cushioning sheet, which will be described later, before curing, so that the adhesion between the base and the ventilation cushioning sheet is improved. Play. In addition, since this evaluation of adhesiveness is basically evaluated by the peel strength when the ventilation layer of the ventilation cushioning sheet is destroyed (material destruction), as shown in the examples described later, the adhesion of the present invention is also evaluated. The adhesive and the current adhesive for waterproofing urethane film have the same evaluation. However, the adhesive of the present invention is excellent in adhesion between a polyvinyl chloride (PVC) sheet generally used as a waterproof sheet and a concrete or urethane coating waterproof material. For example, when repairing a PVC sheet In addition, it is possible to apply the air cushioning composite waterproofing method as it is without removing the PVC sheet, and it is also possible to directly apply the urethane film waterproofing agent on the PVC sheet, and to the part where the air cushioning sheet is not attached. Has an advantage that a PVC sheet can be attached.

In one preferred embodiment, the adhesive of the present invention contains a hydrolysis catalyst for the hydrolyzable imine compound.
The hydrolysis catalyst is not particularly limited, and specific examples thereof include carboxylic acids such as 2-ethylhexanoic acid and oleic acid; phosphoric acids such as polyphosphoric acid, ethyl acid phosphate and butyl acid phosphate; dibutyltin dilaurate, dioctyltin dilaurate Organometallics such as; and the like.
When such a hydrolysis catalyst is contained, hydrolysis of the hydrolyzable imine compound by moisture (water) is promoted, and the resulting adhesive of the present invention has good curability at low temperatures, This is preferable because the adhesion to the ventilation cushioning sheet is improved.

  In this invention, it is preferable that it is 0.01-30 mass parts with respect to 100 mass parts of said hydrolysable imine compounds, and, as for content of a hydrolysis catalyst, it is more preferable that it is 0.1-20 mass parts. .

In one preferred embodiment, the adhesive of the present invention contains a silane coupling agent.
The silane coupling agent is not particularly limited, and specific examples thereof include aminosilane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, ketimine silane, a mixture or a reaction product thereof, or a reaction thereof with polyisocyanate. And the like.

  The aminosilane is not particularly limited as long as it is a compound having an amino group or imino group and a hydrolyzable silicon-containing group. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl Methyldimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2- (aminoethyl) -3 -Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl)- 3-A Roh propyl ethyl diethoxy silane, and the like.

Examples of vinyl silane include vinyl trimethoxy silane, vinyl triethoxy silane, and tris- (2-methoxy ethoxy) vinyl silane.
Examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethylmethyl. Examples include dimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
Examples of methacrylic silane include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.
Examples of the isocyanate silane include isocyanate propyl triethoxy silane and isocyanate propyl trimethoxy silane.
Examples of ketimine silanes include ketiminated propyltrimethoxysilane and ketiminated propyltriethoxysilane.

It is preferable that content of a silane coupling agent is 0.1-10 mass parts with respect to 100 weight part of said urethane prepolymers.
It is preferable for the content of the silane coupling agent to be in this range because the adhesion between the substrate and the ventilation cushioning sheet is improved.

  The adhesive of the present invention can contain various additives as required in addition to the above-mentioned various components within a range not impairing the object of the present invention. Examples of the additive include a filler, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, an adhesiveness imparting agent, and a dispersing agent.

Fillers include calcium carbonate, carbon black, silica (white carbon), clay talc, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, quicklime, carbonates (for example, magnesium carbonate, zinc carbonate, Pepper), alumina hydrate (eg, hydrous aluminum hydroxide), diatomaceous earth, barium sulfate (eg, precipitated barium sulfate), mica, alumina sulfate, lithopone, asbestos, graphite, molybdenum disulfide, pumice powder, glass powder , Silica sand, zeolite; surface treated products of these fatty acids, resin acids, fatty acid esters, higher alcohol-added isocyanate compounds, etc .; glass balloons; resin balloons;
In the present invention, not only granular materials but also fibrous materials can be used as the filler, and specific examples thereof include glass fibers and carbon fibers.

Here, examples of calcium carbonate include heavy calcium carbonate and precipitated calcium carbonate (light calcium carbonate, colloidal calcium carbonate). Moreover, the surface treatment calcium carbonate which surface-treated these with a fatty acid, resin acid, fatty acid ester, a higher alcohol addition isocyanate compound, etc. can also be used.
Specifically, examples of the heavy calcium carbonate that has not been surface-treated include Whiten SSB Red (manufactured by Shiroishi Kogyo Co., Ltd.), Super S (manufactured by Maruo Calcium Co., Ltd.), and the like. Ryton A-4 (manufactured by Bihoku Powder Chemical Co., Ltd.), Snow Light (manufactured by Maruo Calcium Co., Ltd.) and the like. Examples of precipitated calcium carbonate that has not been surface-treated include Shiraka Hana A and Brilliant-1500 (both manufactured by Shiroishi Kogyo Co., Ltd.), and examples of surface-treated precipitated calcium carbonate include Viscolite MBP (manufactured by Shiroishi Kogyo Co., Ltd.). And Calfine 200 (manufactured by Maruo Calcium Co., Ltd.).

Moreover, as carbon black, for example, SAF (Super Abrasion Furnace), ISAF (Intermediate Super Abrasion Furnace), HAF (High Abrasion FurFurce), FEF (Fast Extruding FurP). Furnace), FT (Fine Thermal), MT (Medium Thermal) and the like.
Specifically, as the SAF, Seast 9 (manufactured by Tokai Carbon Co., Ltd.), ISAF as Show Black N220 (manufactured by Showa Cabot Corporation), HAF as Seast 3 (manufactured by Tokai Carbon Co., Ltd.), and FEF as HTC # 100 ( Chubu Carbon Co., Ltd.). As GPF, Asahi # 55 (Asahi Carbon Co., Ltd.), Seest 5 (Tokai Carbon Co., Ltd.), SRF Asahi # 50 (Asahi Carbon Co., Ltd.), Mitsubishi # 5 (Mitsubishi Chemical Co., Ltd.), FT Asahi Thermal (manufactured by Asahi Carbon Co., Ltd.), HTC # 20 (manufactured by Chubu Carbon Co., Ltd.), Asahi # 15 (manufactured by Asahi Carbon Co., Ltd.) and the like are exemplified.

Specific examples of silica include fumed silica, calcined silica, precipitated silica, hydrophobic silica, ground silica, fused silica, silicone fine powder, anhydrous fine powder silicic acid, hydrous fine powder silicic acid, hydrous aluminum silicate, Hydrous calcium silicate etc. are mentioned.
Specific examples of the clay include wax stone clay, kaolin clay (kaolinite, halloysite), pyrophyllite clay, sericite clay, and calcined clay.

Examples of the antiaging agent include hindered phenol compounds and hindered amine compounds.
Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.
Examples of the adhesion imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and epoxy resins.
The above additives can be used in combination as appropriate.

  The method for producing the adhesive of the present invention is not particularly limited. For example, the urethane prepolymer, the epoxy resin, the hydrolyzable imine compound, and various additives (hydrolysis catalyst, silane coupling agent) that are optionally added. The same applies hereinafter) using a roll, a kneader, an extruder, a universal agitator, etc .; the epoxy resin and the hydrolyzable imine compound, and various additives added as desired, such as a kneader, a planetary mixer, etc. And a method of mixing the adhesion-imparting agent component prepared by mixing with a urethane prepolymer on-site at the time of use.

The ventilation cushioning composite waterproofing method according to the second aspect of the present invention (hereinafter also simply referred to as “the construction method of the present invention”) is a ventilation cushioning composite waterproofing method in which a urethane coating waterproofing material is constructed on the surface of a building. In addition, the above-described adhesive for urethane film waterproofing material for building according to the first aspect of the present invention is applied to the surface of the building, and the air cushion is applied to the adhesive applied by the application step. It is a construction method comprising a sticking step of sticking a sheet and a construction step of applying a urethane coating film waterproof material to the ventilation cushion sheet attached by the sticking step in this order.
Next, each process in the construction method of the present invention will be described in detail.

<Application process>
The coating process in the construction method of the present invention is a process of coating the adhesive of the present invention on the surface of a building (the ground surface that requires waterproofing).
Various methods can be used as a method of applying the adhesive of the present invention in the application step, and examples thereof include roller coating and spray coating.
Moreover, it is preferable that the application quantity of the adhesive agent apply | coated by the said application | coating process is 100-400 g / m < ² > from a viewpoint of the adhesive improvement of a foundation | substrate and a ventilation buffer sheet.

<Paste process>
The sticking step in the method of the present invention is a step of sticking a ventilation cushioning sheet on the adhesive applied by the coating step.
Below, it demonstrates using sectional drawing (FIG. 1) which shows an example of the suitable embodiment of the ventilation | gas_flowing cushioning sheet used by this invention.
As shown in FIG. 1, the ventilation buffer sheet 1 is comprised by the ventilation layer (nonwoven fabric) 2 and the water shielding layer (special film layer) 3 laminated | stacked on it.
In the present invention, a waterproofing agent holding layer (not shown) laminated on the water shielding layer 3 may be configured.

In the present invention, the non-woven fabric 2 is not particularly limited, and various non-woven fabrics that have been used as an underlay cushioning material can be used. Specific examples thereof include polypropylene fiber, polyethylene fiber, polyester fiber, and polyamide. Nonwoven fabrics composed of fibers, acrylic fibers, vinylon fibers, blended fibers of these, and the like can be mentioned. Among these, a nonwoven fabric made of polyester fibers (polyester nonwoven fabric) is preferable because of its excellent cost, strength and durability of the breathable cushion sheet.
Moreover, in this invention, it is preferable that the thickness of the said nonwoven fabric 2 is 1.0-3.0 mm from viewpoints, such as ventilation | gas_flowing performance and the buffer performance with respect to a foundation | substrate.

In the present invention, the water shielding layer 3 is not limited as long as it is a layer made of a material having water shielding properties.
Moreover, in this invention, it is preferable that the thickness of the said water shielding layer 3 is 0.02-3.0 mm from viewpoints, such as a softness | flexibility and durability.

  The ventilation cushion sheet used in the construction method of the present invention is the HVS sheet used in the Urban Roof HVS method proposed by the applicant, the Urban roof sheet used in the Urban Roof UVS method, and the CV- used in the Urban Roof CV-FC method. An F sheet or the like is preferably used.

<Construction process>
The construction process in the construction method of the present invention is a process of constructing a urethane coating film waterproof material on the ventilation cushioning sheet pasted by the pasting process.
The urethane coating film waterproofing material is not particularly limited, and those conventionally used as a one-component moisture-curable polyurethane composition or a two-component moisture-curable polyurethane composition can be used. Pole, U-8000, U-8000HC, Urban roof T, Urban roof EU-ONE, etc. are preferably used.

This will be described with reference to a schematic view (FIG. 2) for explaining an example of the air-permeable cushioning waterproofing method of the present invention comprising these steps.
As shown in FIG. 2, the air-permeable cushioning waterproofing method first applies an adhesive to the surface of the base 4 to provide an adhesive layer 5, and then a nonwoven fabric and a water shielding layer on the adhesive layer 5. A waterproof cushioning film 6 made of is attached, and then a urethane coating waterproof material is provided on the ventilation cushioning sheet 6 to provide a waterproof coating 7, and then a top coat 8 is applied and cured as necessary. Is done.
Further, the water staying in the base 4 is released into the atmosphere as water vapor through the ventilation buffer sheet 6. From the viewpoint of promoting this release, a decylinder as shown in FIG. 3 is provided. Is preferred. FIG. 3 is a schematic cross-sectional view for explaining an example around the de-cylinder.
As shown in FIG. 3, the cylinder removal 9 is fixed on the ventilation cushioning sheet 6 using screws 10, and the waterproof coating 7 is provided on the ventilation cushioning sheet 6 and the cylinder removal 9.

The structure which concerns on the 3rd aspect of this invention is manufactured using the ventilation buffer composite waterproofing method which concerns on the 2nd aspect of this invention mentioned above, The urethane coating-film waterproofing material was constructed on the surface of the building It is a structure.
The construction method of the present invention is used for the surface of a building (underlying surface that requires waterproofing), and by using the construction method of the present invention, a structure in which a urethane coating waterproof material is applied to the surface of the building is manufactured. The
Specific examples of such a structure include a structure in which a urethane coating waterproof material is applied to a rooftop of a building, a veranda of a house, a fence, or the like. Of these, on the rooftops of buildings and verandas of houses, there are many embodiments in which structures are manufactured using the method of the present invention at the site. The aspect installed after manufacturing may be sufficient.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

<TDI urethane prepolymer (urethane prepolymer 1)>
As TDI urethane prepolymer (urethane prepolymer 1), polyoxypropylene triol having a number average molecular weight of 4000 (Excenol 4030, manufactured by Asahi Glass Co., Ltd.) and polyoxypropylene diol having a number average molecular weight of 2000 (Exenol 2020, manufactured by Asahi Glass Co., Ltd.) Tolylene diisocyanate (mixing ratio of 2,4- and 2,6-tolylene diisocyanate is 80/20, manufactured by Mitsui Takeda Chemical Co., Cosmonate T-80), in the presence of tin catalyst, in a nitrogen stream, A urethane prepolymer (NCO%: 2.9%) synthesized by reacting at 80 ° C. for 24 hours was used.
The urethane prepolymer 1 had a viscosity of 8 Pa · s when measured at 20 ° C. using an E-type viscometer.

<HDI urethane prepolymer (urethane prepolymer 2)>
As an HDI prepolymer (urethane prepolymer 2), polyoxypropylene triol having a number average molecular weight of 4000 (Excenol 4030, manufactured by Asahi Glass Co., Ltd.) and polyoxypropylene diol having a number average molecular weight of 2000 (Exenol 2020, manufactured by Asahi Glass Co., Ltd.) A urethane prepolymer (NCO%: 2.4%) synthesized by mixing and reacting at 80 ° C. for 18 hours in a nitrogen stream in the presence of a tin catalyst was used.
The viscosity of the urethane prepolymer 2 was 10 Pa · s when measured at 20 ° C. using an E-type viscometer.

<XDI prepolymer (urethane prepolymer 3)>
As an XDI prepolymer (urethane prepolymer 3), a polyoxypropylene triol having a number average molecular weight of 4000 (Exenol 4030, manufactured by Asahi Glass Co., Ltd.) and a polyoxypropylene diol having a number average molecular weight of 2000 (Exenol 2020, manufactured by Asahi Glass Co., Ltd.) A urethane prepolymer (NCO%: 4.2%) synthesized by mixing and reacting at 80 ° C. for 18 hours in a nitrogen stream in the presence of a tin catalyst was used.
The viscosity of the urethane prepolymer 3 was 11 Pa · s when measured at 20 ° C. using an E-type viscometer.

<MDI prepolymer (urethane prepolymer 4)>
As an MDI prepolymer (urethane prepolymer 4), polyoxypropylene triol having a number average molecular weight of 4000 (Exenol 4030, manufactured by Asahi Glass Co., Ltd.) and polyoxypropylene diol having a number average molecular weight of 2000 (Exenol 2020, manufactured by Asahi Glass Co., Ltd.) A urethane prepolymer (NCO%: 3.1%) synthesized by mixing and reacting at 80 ° C. for 8 hours in a nitrogen stream in the presence of a tin catalyst was used.
The viscosity of the urethane prepolymer 4 was 15 Pa · s when measured at 20 ° C. using an E-type viscometer.

<IPDI prepolymer (urethane prepolymer 5)>
As an IPDI prepolymer (urethane prepolymer 5), polyoxypropylene triol having a number average molecular weight of 4000 (Exenol 4030, manufactured by Asahi Glass Co., Ltd.) and polyoxypropylene diol having a number average molecular weight of 2000 (Exenol 2020, manufactured by Asahi Glass Co., Ltd.) A urethane prepolymer (NCO%: 3.3%) synthesized by mixing and reacting at 80 ° C. for 18 hours in a nitrogen stream in the presence of a tin catalyst was used.
The viscosity of the urethane prepolymer 5 was 12 Pa · s when measured at 20 ° C. using an E-type viscometer.

<TMXDI urethane prepolymer (urethane prepolymer 6)>
As TMXDI-based urethane prepolymer (urethane prepolymer 6), polycarbonate diol (Braxel CD220, manufactured by Daicel Chemical Industries, Ltd., weight average molecular weight 2000) is mixed with TMXDI (manufactured by Nippon Cytec Industries, Inc.), and in the presence of a tin catalyst, A urethane prepolymer (NCO%: 2.6%) synthesized by reacting at 80 ° C. for 8 hours in a nitrogen stream was used.
The viscosity of the urethane prepolymer 6 was 16 Pa · s when measured at 20 ° C. using an E-type viscometer.

<Epoxy resin 1>
As epoxy resin 1, bisphenol A type (EP4100, Asahi Denka Kogyo) was used.
The viscosity of the epoxy resin 1 was 12 Pa · s when measured at 20 ° C. using an E-type viscometer.

<Hydrolyzable imine compound (ketimine 1)>
As ketimine 1, 100 g of norbornanediamine (NBDA, Mitsui Toatsu Chemical Co., Ltd.) and 200 g of methyl isopropyl ketone (MIPK) are placed in a flask together with 200 g of toluene, and reacted for 20 hours while removing generated water by azeotropic distillation. The compound represented by the structural formula shown below was used.
The viscosity of ketimine 1 was 0.03 Pa · s as measured at 20 ° C. using an E-type viscometer.

<Hydrolyzable imine compound (Aldimine 1)>
As aldimine 1, a compound represented by the following structural formula synthesized by reacting 1 mol of hexamethylenediamine and 2 mol of 2-methylpentanal for 20 hours while removing generated water by azeotropy was used. .
The viscosity of aldimine 1 was 1 Pa · s when measured at 20 ° C. using an E-type viscometer.

<Various additives>
(1) Carbon fiber: VGCF (manufactured by Showa Denko)
(2) Surface treated calcium carbonate: Calfine 200 (manufactured by Maruo Calcium)
(3) Heavy calcium carbonate: Snowlight S (manufactured by Maruo Calcium)
(4) Hydrophobic silica: Aerosil RY-200 (Nippon Aerosil Co., Ltd.)
(5) Silicone fine powder: KMP-701 (manufactured by Shin-Etsu Silicone)

(Examples 1-15, Comparative Examples 1-6)
Each component mentioned above was mix | blended by the component ratio (mass part) shown in the following Table 1, and the adhesive agent for urethane-coated waterproofing | waterproof materials for construction was prepared. In addition, about the compounding quantity of ketimine 1 or aldimine 1, in the following Table 1, it puts in parenthesis in the lower column of a mass part (the total number of the epoxy groups of the isocyanate group in a urethane prepolymer, and the epoxy resin in an epoxy resin). The equivalent ratio represented by / (imino bond in ketimine 1 or aldimine 1) is also described.
Further, the blending was performed by mixing an adhesion-imparting agent master batch prepared by previously mixing components other than the urethane prepolymer with a kneader and the urethane prepolymer immediately before application to the mortar.
Further, in Comparative Examples 5 and 6, a one-component urethane adhesive and a one-component chloroprene adhesive corresponding to the first petroleum were used as the adhesives for the waterproof urethane film waterproofing material for current construction, respectively. .
The obtained adhesive was applied on a mortar (size: 7 cm × 7 cm × 1 cm) so that the coating amount was 300 g / m ² , and after 20 minutes, a ventilation cushioning sheet (trade name: Urban Roof HVS sheet, manufactured by Yokohama Rubber Co., Ltd.) ) Was attached to the structure sample.
For the obtained structural sample, the peel strength between the mortar and the ventilation buffer sheet (mortar / sheet peel strength) was measured by the following method as an evaluation of adhesion.

<Mortar / sheet peel strength>
The peel strength was determined by peeling the adhesion surface (180 degree peel) by pulling the mortar and the air cushioning sheet in the direction of 180 ° C. at a pulling speed of 50 mm / min according to JIS A1439-1997. The tensile strength (kgf / 25 mm) at the time of peeling was measured. The results are shown in Table 1 below. In addition, a measurement is performed about the initial state (after 20 degreeC x 7 days curing) of each obtained structure sample, and after hot water resistant aging (after 20 degreeC x 7 days curing + 50 degreeC warm water x 7 days immersion) It was. In each of Examples 1 to 15 and Comparative Examples 5 and 6, the peel strength when the ventilation layer of the ventilation cushioning sheet was destroyed (material destruction) was measured.

  From the results shown in Table 1, the adhesives obtained in Examples 1 to 15 containing an epoxy resin and a hydrolyzable imine compound at a predetermined ratio with respect to the urethane prepolymer were obtained in Comparative Examples 1 to 4. The mortar / sheet peel strength was found to be superior to that of the conventional adhesive, and the mortar / sheet equal to or higher than the adhesives of the current products of Comparative Examples 5 and 6 without using a solvent. It was found to have peel strength.

FIG. 1 is a cross-sectional view showing an example of a preferred embodiment of a ventilation cushioning sheet used in the present invention. FIG. 2 is a schematic view for explaining an example of the ventilation cushioning composite waterproofing method of the present invention. FIG. 3 is a schematic cross-sectional view for explaining an example around the decylinder.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Ventilation buffer sheet 2 Nonwoven fabric 3 Water shielding layer 4 Base 5 Adhesive layer 6 Ventilation cushion sheet 7 Waterproof coating 8 Top coat 9 Cylinder 10 Screw

Claims (5)

Containing urethane prepolymer, epoxy resin and hydrolyzable imine compound,
The epoxy resin is contained in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the urethane prepolymer,
The urethane prepolymer has a viscosity of 50 Pa · s or less,
The epoxy resin has a viscosity of 60 Pa · s or less,
The equivalent ratio represented by (the total number of isocyanate groups in the urethane prepolymer and epoxy groups in the epoxy resin) / (imino bond in the hydrolyzable imine compound) of the hydrolyzable imine compound is 0. An adhesive for waterproofing urethane film for construction, containing 7 to 1.5.   The adhesive for waterproofing urethane paints for construction according to claim 1, wherein the hydrolyzable imine compound has a viscosity of 30 Pa · s or less.   The hydrolyzable imine compound has an imino (> C═N—) bond derived from a ketone or an aldehyde and an amine, and the α-position of at least one of a carbon atom and a nitrogen atom forming the imino bond Alternatively, the adhesive for waterproofing urethane paints for construction according to claim 1 or 2, wherein the adhesive has a structure in which a branched carbon atom or a ring member carbon atom is bonded to the β-position. It is a ventilation cushioning composite waterproofing method that constructs urethane film waterproofing material on the surface of the building,
An application step of applying the waterproofing agent for architectural urethane film waterproofing material according to any one of claims 1 to 3 to a surface of a building, and a ventilation cushioning sheet on the adhesive applied by the application step A ventilation cushioning composite waterproofing method comprising a pasting step for pasting and a construction step for constructing a urethane coating waterproof material on the breathable cushioning sheet pasted by the pasting step in this order.   A structure in which a urethane coating waterproof material is applied to the surface of a building, which is manufactured using the ventilation buffer composite waterproof method according to claim 4.

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