JP5454344B2 - CURABLE COMPOSITION, COATING WATERPROOF MATERIAL, AND METHOD FOR PRODUCING THE SAME - Google Patents

Description

  The present invention relates to a curable composition containing an isocyanate group-containing urethane prepolymer excellent in antifoaming properties and rubber elastic properties of a cured product, in particular, tearing performance, a waterproof coating material, and a method for producing the same.

  In applications such as waterproof sealants for building outer walls that have been conventionally formed by ceramic siding, etc., or adhesives for building materials such as resinous sheets such as vinyl chloride sheets, tiles, and wooden boards, etc. The polymer-containing curable composition is easy to work, high adhesion after curing, rubber elasticity properties after curing from low modulus to high modulus (high elongation to low elongation), etc. Widely used for superiority.

  However, when a curable composition containing an isocyanate group-containing urethane prepolymer is reactively cured with moisture such as moisture, the amount of carbon dioxide generated is large when the isocyanate group concentration is high or the curing speed is increased. There is a problem that bubbles are generated inside the cured product due to the generation of carbon dioxide gas or abruptly, resulting in problems such as deterioration of appearance, deterioration of physical properties of rubber such as elongation, and deterioration of adhesiveness. As a means for solving this problem, the present applicant has previously proposed a technique of blending an oxazolidine compound as a latent curing agent with an isocyanate group-containing urethane prepolymer (Patent Documents 1 to 5).

  When a curable composition containing an isocyanate group-containing urethane prepolymer is used for a waterproof coating material, it does not foam when cured with moisture such as moisture. In addition, JIS A6021 (2000) It is necessary to have a performance that can pass the “waterproof coating film”, and in particular, it is strongly required to have excellent tear performance. In this field as well, the present applicant has previously proposed improving the weather resistance by using an oxazolidine compound, but did not consider the tear strength (Patent Document 6).

  In addition, as another technique using an oxazolidine compound, a technique has been proposed in which a hydrocarbon compound or a silyl phosphate ester having a specific pKa value is combined in a combination of an isocyanate group-containing urethane prepolymer and an oxazolidine compound. These are intended to improve the storage stability, and no reference is made to tear strength (Patent Documents 7 and 8). In addition, a technology that combines a urethane compound having a specific oxazolidine group and a terephthalic acid fine particle having a specific particle diameter in an isocyanate group-containing urethane prepolymer has also been proposed, but it has improved anti-foaming properties, heat resistance, and alkali resistance. It is aimed, and tear strength is not mentioned (patent document 9). In addition, a technology has been proposed in which an oxazoly compound is added to an isocyanate group-containing urethane prepolymer to remove a free polyisocyanate compound, and a compound with a specific flash point is blended. Is not mentioned (Patent Document 10).

  From another point of view, there is a technology that uses a polyisocyanate having an allophanate bond for the purpose of imparting performance such as weather resistance to a curable composition such as a paint made of a urethane prepolymer, for example, a specific diisocyanate and a specific one. When the polyisocyanate having a specific allophanate bond obtained by reacting the polyol is reacted with a specific diisocyanate and a hydroxyl group-containing compound, a specific zirconium compound is used as a catalyst, and an allophanate bond-containing polyisocyanate composition The allophanate method used as a specific compound catalyst when the allophanate bond-containing compound is produced by reacting a urethane group-containing compound and an isocyanate group-containing compound is also represented by a specific formula. Allophanate binding It is disclosed that the polyisocyanate having an isocyanate-terminated prepolymer contains an allophanate bond in a polyisocyanate composition containing an isocyanate-terminated prepolymer obtained from a specific diisocyanate monomer and a polymer plasticizer (patents). Literature 11-15). However, these use a large excess of the isocyanate raw material and remove the unreacted isocyanate raw material after the reaction, which has the disadvantage of increasing the production cost.

  In addition, regarding the technique using allophanate bonds, the present applicant has also proposed a technique in which an isocyanate group-containing urethane prepolymer having an allophanate bond in the molecule is combined with a silyl mask body of a low molecular polyol (see FIG. Patent Document 16).

JP-A-2005-206722 JP 2007-2111040 A JP 2007-284547 A JP 2007-291223 A JP 2009-73882 A JP 2007-289849 A JP-A-11-269244 JP 2002-194048 A Japanese Patent Laying-Open No. 2005-226037 JP 2008-13695 A International Publication WO99 / 52960 International Publication No. WO2002 / 032979 Japanese Patent Laid-Open No. 8-188565 Japanese Patent Laid-Open No. 2001-278943 JP 2002-53634 A Japanese Patent Application No. 2009-169082

  In view of the above-mentioned problems, the present invention has an excellent rubber elastic property, in particular, an excellent cured product, in addition to having excellent antifoaming performance in a curable composition containing an isocyanate group-containing urethane prepolymer. An object of the present invention is to provide a curable composition having a tearing performance (tear strength), a waterproof coating material, and a production method thereof at low cost.

As a result of intensive studies, the present inventors have found that in a system in which an isocyanate group-containing urethane prepolymer is blended with a block amine compound that can be hydrolyzed with water to regenerate active hydrogen, By using an isocyanate group-containing urethane prepolymer having an allophanate bond, the curable composition obtained at low cost has excellent anti-foaming performance and rubber elastic properties, particularly tearing performance. I let you.
That is, the present invention
(1) A curable composition containing an isocyanate group-containing urethane prepolymer (A) obtained by reacting an organic isocyanate compound (a) with a polymer diol (b) and a block amine compound (B). The isocyanate group-containing urethane prepolymer (A) has an allophanate bond in the molecule.
And
(2) The said curable composition has the outstanding characteristic that the tear strength of the hardened | cured material obtained by hardening | curing this with a water | moisture content is 14 N / mm or more.
In the present invention,
(3) After the reaction of the isocyanate group-containing urethane prepolymer (A) having an allophanate bond in the molecule with the organic isocyanate compound (a) and the polymer diol (b), the unreacted organic isocyanate compound (a) It was obtained without any removal operation.
In the present invention,
(4) The organic isocyanate compound (a) is preferably an aromatic diisocyanate,
further,
(5) The aromatic diisocyanate is preferably toluene diisocyanate.
Also,
(6) The polymer diol (b) is preferably a polyoxyalkylene diol having a number average molecular weight of 2,000 or more.
Also,
(7) The block amine compound (B) is preferably an oxazolidine compound.
In the present invention,
(8) Further, one or more selected from the group consisting of a curing accelerating catalyst, a plasticizer, a weathering stabilizer, a filler, a thixotropic agent, an adhesion promoter, a storage stability improver, a colorant and an organic solvent Two or more additives (C) can be blended.
In addition,
(9) The additive (C) is preferably p-toluenesulfonyl isocyanate.
Also,
(10) The additive (C) is preferably a naphthenic solvent.
The second of the present invention is
(11) A waterproofing coating film comprising an isocyanate group-containing urethane prepolymer (A) obtained by reacting an organic isocyanate compound (a) with a polymer diol (b) and a block amine compound (B). And the isocyanate group-containing urethane prepolymer (A) has an allophanate bond in the molecule.
And the third of the present invention is
(12) An isocyanate group-containing urethane prepolymer having an allophanate bond in the molecule by performing the step (Ia) of reacting the organic isocyanate compound (a) with the polymer diol (b) at a temperature of 100 to 180 ° C. A method for producing a curable composition comprising the step (I) of synthesizing A) and the step (III) of mixing the block amine compound (B) with that obtained in the step (I). is there.
In the synthesis step (I),
(13) It is preferable not to carry out the step (Ib) for removing the unreacted organic isocyanate compound (a) after the reaction step (Ia).
and again,
(14) In the reaction step (Ia), the reaction is preferably performed in the presence of a filler.

  By taking the above-described configuration, the curable composition, the waterproof coating material and the method for producing the same of the present invention are excellent in antifoaming performance, excellent in rubber elastic properties, particularly tearing performance, and can be produced at low cost. There is an effect.

The present invention will be described in detail below.
The curable composition of the present invention is characterized in that the isocyanate group-containing urethane prepolymer (A) used as a curing component has an allophanate bond in the molecule. By blending the block amine compound (B) with this curing component, the resulting curable composition is prevented from foaming due to the generation of carbon dioxide gas when cured with moisture such as moisture (moisture in the atmosphere). In addition, the resulting cured product exhibits the effect of excellent rubber elastic properties such as tensile strength, elongation, and tear strength, particularly tear performance (tear strength). In addition, the hardened | cured material by the water | moisture content of the curable composition of this invention is based on the prescription | regulation that tear performance is 14 N / mm or more in the test of below-mentioned JIS A6021 (2000) "waterproofing film for construction". It has a suitable performance. First, an isocyanate group-containing urethane prepolymer (A) having an allophanate bond in the molecule used in the present invention (hereinafter abbreviated as urethane prepolymer (A)) will be described. The urethane prepolymer (A) is a reaction of the organic isocyanate compound (a) and the polymer diol (b) with an isocyanate group excess with respect to the alcoholic hydroxyl group of the raw material, that is, the reaction of the number of moles of isocyanate groups with respect to the moles of hydroxyl groups. The molar ratio (= isocyanate group mole number / hydroxyl mole number) is 1.3 to 3.0, more preferably 1.5 to 2.5, particularly preferably 1.8 to 2.2, and the reaction temperature is 100. It is obtained by reacting at a relatively high temperature of ˜180 ° C., preferably 100 to 150 ° C., and is characterized by having an isocyanate group in the molecule and an allophanate bond. When the reaction molar ratio is less than 1.3, the viscosity of the urethane prepolymer (A) to be obtained is increased and workability is lowered, and when it exceeds 3.0, the unreacted organic isocyanate compound (a) is preferably increased. Absent. If the reaction temperature is less than 100 ° C., the content of allophanate bonds in the molecule is lowered and the rubber elastic properties are lowered, and if it exceeds 180 ° C., the viscosity is increased and workability is lowered, which is not preferable.

  0.1-10 mass% is preferable and, as for content of the isocyanate group of a urethane prepolymer (A), 0.5-5 mass% is more preferable. When the isocyanate group content is less than 0.1% by mass, the urethane prepolymer (A) increases in viscosity. When the isocyanate group content exceeds 10% by mass, carbon dioxide gas is generated when cured with moisture. This is not preferable because the amount increases and foaming occurs in the cured product.

  In the urethane prepolymer (A), branching due to allophanate bonds in the molecule is formed, so that the average functionality (number of functional groups) of the isocyanate groups of the urethane prepolymer (A) is Although the organic isocyanate compound (a) and the polymer diol (b) are both bifunctional, the number exceeds 2. As a result, when the urethane prepolymer (A) is cured with moisture such as moisture, it is sufficiently reticulated, and the resulting cured product has extremely excellent rubber elastic properties, particularly tear strength. The average functionality of the isocyanate group of the urethane prepolymer (A) is 2.1 or more, more preferably 2.1 to 4.0, even more preferably 2.1 to 3.0, and particularly preferably 2.1 to 2.5. . If it is less than 2.1, it is not preferable because the rubber elastic property after curing is lowered.

  In the reaction, first, a urethane bond is formed by a urethanization reaction to produce a urethane intermediate resin having an isocyanate group and a urethane bond. At this stage, the functionality of the isocyanate group of the urethane intermediate resin is theoretically as low as 2 and the molecular form is close to a linear shape. Therefore, when curing with moisture such as moisture, reticulation does not progress, and the rubber elasticity after curing Physical properties remain bad. Thereafter, the reaction proceeds further, and the active hydrogen of this urethane bond reacts with the isocyanate group of another urethane intermediate resin molecule to form an allophanate bond, resulting in branching, whereby the functionality of the isocyanate group exceeds 2. Since the polyfunctional urethane prepolymer (A) is produced, the cured product due to moisture is sufficiently reticulated, and the rubber elastic properties are excellent. In this reaction, the urethanization and allophanatization reactions may be simultaneously performed at a high temperature of 100 to 180 ° C. from the beginning, or after only the urethanization reaction is initially performed at an intermediate temperature of 50 to 90 ° C. The allophanatization reaction may be performed at a high temperature of 180 ° C.

In the reaction, the urethane prepolymer (A) is highly functionalized by reacting the isocyanate group of another urethane intermediate resin molecule with the active hydrogen of the urea bond generated by a small amount of water to form a biuret bond, or Although the isocyanate groups of the urethane intermediate resin may be highly functionalized by forming isocyanurate bonds, their content is small, and the functionalization of the isocyanate groups of this urethane prepolymer (A) is mainly allophanate. This is due to the bond. The generation of the allophanate bonds, infrared spectroscopy urethane prepolymer (A) in an infrared absorption spectrum measured by (IR), be confirmed by observed pair of absorption at 1720 cm ^-1 and 1690 cm ^-1 it can. Moreover, it can also confirm with the signal by the allophanate coupling | bonding of 8.5 ppm vicinity by analysis of a NMR spectrum.

  As a method for producing the urethane prepolymer (A), an organic isocyanate compound (a) and a polymer diol (b) are charged in a reaction vessel such as glass or stainless steel in the aforementioned reaction molar ratio, and a reaction catalyst. And in the presence or absence of a reaction solvent, the step (Ia) of reacting at 100 to 180 ° C., preferably 100 to 150 ° C. is performed, and after the reaction, unreacted organic isocyanate is obtained by distillation or extraction. A method for producing the urethane prepolymer (A) without carrying out the step (Ib) for removing the compound (a) can be mentioned. This production method does not require the step (Ib) of removing the unreacted organic isocyanate compound (a) after the usual reaction when synthesizing the urethane prepolymer (A) having an allophanate bond. It has a great advantage that it can be manufactured at a low cost. In addition, if there is a margin in terms of cost, it is possible to perform an operation for removing the unreacted organic isocyanate compound (a). In this synthesis reaction, when the isocyanate group reacts with moisture, the resulting urethane prepolymer (A) thickens. Therefore, it is preferable to carry out the reaction in a state where moisture is blocked, such as nitrogen gas replacement and nitrogen gas flow. . In addition, this synthesis reaction can also be performed in the presence of a filler such as heavy calcium carbonate, which will be described later, and this production method provides a curable composition simultaneously with the synthesis of the urethane prepolymer (A). This is preferable in that the process can be shortened.

Examples of the reaction catalyst include compounds similar to those mentioned as the metal-based catalyst among the curing acceleration catalysts described later, and can be used alone or in combination. However, zirconium and fatty acids are easy to promote the allophanatization reaction. The salt of is preferred, and zirconium octylate is more preferred. Moreover, as the reaction solvent, the same compounds as those mentioned as the organic solvent described later can be used.
The urethane prepolymer (A) can be used as a one-component moisture-curable curing component that reacts and cures at room temperature when the isocyanate contained in the molecule comes into contact with moisture.

  Examples of the organic isocyanate compound (a) in the present invention include a bifunctional organic diisocyanate (a ′), a monofunctional organic monoisocyanate, and an organic polyisocyanate having more than two functions. As the organic diisocyanate (a ′), Specific examples include an aromatic diisocyanate in which an isocyanate group is bonded to an aromatic carbon, and an aliphatic diisocyanate in which an isocyanate group is bonded to an aliphatic carbon. The aliphatic diisocyanate further includes an aromatic ring. An alicyclic diisocyanate having an isocyanate group bonded to an aliphatic carbon, an alicyclic diisocyanate having an alicyclic ring, and an aliphatic diisocyanate composed only of an aliphatic carbon.

  The molecular weight of the organic isocyanate compound (a) is preferably a low molecular weight organic diisocyanate monomer (monomer) of less than 1,000 and further 500 or less in that the viscosity of the resulting urethane prepolymer (A) can be lowered. In the present invention, the high molecular weight means that the number average molecular weight is 1,000 or more, and the low molecular weight means that the number average molecular weight is less than 1,000.

  Examples of aromatic diisocyanate monomers include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, or mixtures thereof, such as diphenylmethane diisocyanates (MDIs); 2,4-toluene diisocyanate, 2,6- Toluene diisocyanates (TDIs) such as toluene diisocyanate or a mixture thereof; other examples include phenylene diisocyanate, diphenyl diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate and the like.

  Examples of the araliphatic diisocyanate monomer include xylylene diisocyanate, and examples of the aliphatic diisocyanate monomer include hexamethylene diisocyanate, pentamethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, and the like. Includes cyclohexane diisocyanate, methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, and the like. In addition, dimers of these diisocyanates such as carbodiimide-modified diisocyanate and uretdione-modified diisocyanate are also included.

  Examples of the organic monoisocyanate include butyl monoisocyanate, hexyl monoisocyanate, and phenyl monoisocyanate. Examples of the organic polyisocyanate include biuretized trimer, isosinurated trimer, and polymethylene of the organic diisocyanate (a ′). Polyphenyl polyisocyanate (also referred to as crude MDI or polymeric MDI) and the like can be used, and these can be used alone or in combination of two or more. Among them, the urethane prepolymer (A) obtained has a low viscosity and depends on moisture. In view of good rubber elastic properties of the cured product, organic diisocyanate (a ′), aromatic diisocyanate, and particularly toluene diisocyanate are preferred.

  The polymer diol (b) in the present invention has a polystyrene-reduced number average molecular weight by gel permeation chromatography of 1,000 or more, further 2,000 or more, more preferably 2,000 to 30,000, especially 2,000 to 2,000. Those of 20,000 are preferred. When the number average molecular weight is less than 1,000, the rubber elastic properties and adhesiveness of the cured product due to moisture of the urethane prepolymer (A) to be obtained are not preferable.

  Specific examples of the polymer diol (b) include polyester diols, polycarbonate diols, polyoxyalkylene diols, copolymerized diols thereof, and the like. Examples of polyester diols include succinic acid, adipic acid, sebacic acid, Dicarboxylic acids such as azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, alkyl esters such as methyl ester and ethyl ester of these dicarboxylic acids, Or one or more of these acid anhydrides of dicarboxylic acid and the like, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4- Butanegio 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, Examples include polyester diols obtained by a dehydration condensation reaction with one or more low molecular diols such as 1,4-cyclohexanedimethanol and ethylene oxide or propylene oxide adduct of bisphenol A. Further, lactone polyester diols obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone using the low-molecular diols as initiators may also be mentioned.

  As the polycarbonate diol, dehydrochlorination reaction of low molecular diols and phosgene used for the synthesis of the polyester diol described above, or transesterification reaction of low molecular diols with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, etc. What is obtained is mentioned.

  As the polyoxyalkylene-based diol, one or more cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran are used as initiators with the same low molecular diols as those used in the synthesis of the polyester diol. Ring-opening addition polymerization or copolymerization, polyoxyethylene diol, polyoxypropylene diol, polyoxybutylene diol, polyoxytetramethylene diol, poly- (oxyethylene)-(oxypropylene) -random or block Examples thereof include copolymer diols, and polyester ether diols and polycarbonate ether diols using the above polyester diols and polycarbonate diols as initiators. Moreover, the diol which made the molecular terminal the hydroxyl group by making these polyoxyalkylene type diols and the above-mentioned organic diisocyanate (a) react with an isocyanate group by hydroxyl group excess is also mentioned.

  Furthermore, the polyoxyalkylene-based diol has a molecular weight distribution [ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (GPC) = Mw / Mn] of 1.6 or less. Particularly, a narrow one of 1.0 to 1.3 is preferable in that the viscosity of the resulting urethane prepolymer (A) can be reduced, and the rubber elastic properties after curing with moisture are good.

  Further, in the present invention, the cyclic ether compound such as propylene oxide is subjected to ring-opening addition polymerization using a low molecular monoalcohol such as methyl alcohol, ethyl alcohol, propyl alcohol or the like as an initiator without departing from the object of the present invention. Polyoxyalkylene monools such as polyoxypropylene monools, or polyoxypropylene triols obtained by ring-opening addition polymerization of cyclic ether compounds such as propylene oxide using glycerol or trimethylolpropane as an initiator. A small amount of tri- or higher functional polyoxyalkylene polyol can also be used.

  The “system” such as the polyoxyalkylene-based diol refers to 50% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more of the portion excluding the hydroxyl group in 1 mol of the molecule. If it is constituted, it means that the remaining part may be modified with ester, urethane, polycarbonate, polyamide, poly (meth) acrylate, polyolefin, etc., but 95% by mass or more of the molecule excluding hydroxyl group. Most preferably, it is composed of polyoxyalkylene. In the present invention, (meth) acrylate means acrylate or methacrylate.

  The compounds listed as the polymer diol (b) can be used singly or in combination of two or more. Among these, the rubber elastic properties and adhesion of the cured product due to moisture of the urethane prepolymer (A) to be obtained. From the viewpoint of good properties, a polymer, preferably a polyoxyalkylene-based diol having a number average molecular weight of 2,000 or more is preferable, and further a polymer, a polyoxypropylene-based diol having a number average molecular weight of 2,000 or more is preferable. preferable.

  Next, the block amine compound (B) in this invention is demonstrated. The blocked amine compound (B) is a compound obtained by dehydrating an active hydrogen bonded to a nitrogen atom of a compound having a primary and / or secondary amino group with a compound having a carbonyl group such as a ketone or an aldehyde, thereby blocking the compound. The curable composition obtained by blending this with the urethane prepolymer (A) does not react while being sealed and stored in a container, but it is opened and applied to the construction object and moisture. When contacted with moisture, the block amine compound (B) is hydrolyzed to regenerate the active hydrogen bonded to the nitrogen atom, and the regenerated active hydrogen reacts with the isocyanate group of the urethane prepolymer (A) to cause crosslinking / Since it cures, it functions as a so-called latent curing agent.

This is because when the curable composition is cured in contact with moisture, the isocyanate group in the urethane prepolymer (A) reacts with the moisture and cures while generating carbon dioxide gas before the block amine compound (B). Hydrolyzes with water, regenerates active hydrogens of primary and / or secondary amino groups, and the rate at which these active hydrogens from amino groups react with isocyanate groups Since it is faster than the rate of reaction with the group, it does not generate carbon dioxide, but forms a urea bond and cures. Therefore, the resulting cured product is not foamed by carbon dioxide.
The amount of the block amine compound (B) used is such that the amount of active hydrogen bonded to the nitrogen atom that is hydrolyzed and regenerated by the amine compound (B) is 0.1 per mole of the isocyanate group of the urethane prepolymer (A). It is preferable to use it so that it may become 1-2 mol, and also 0.3-1.1 mol.

  Specific examples of the block amine compound (B) include a ketimine compound, an aldimine compound, an oxazolidine compound, or any mixture thereof, which is a compound having a primary and / or secondary amino group, and a ketimine compound. Is a dehydration reaction between a compound having a primary amino group and a ketone, an aldimine compound is a dehydration reaction between a compound having a primary amino group and an aldehyde, and the oxazolidine compound is a first such as monoethanolamine or diethanolamine. It can be obtained by a dehydration reaction between an amino alcohol having a secondary amino group or a secondary amino group and an aldehyde.

  Examples of the compound having a primary and / or secondary amino group include polyamines, polyaminosilanes, amino alcohols and the like, and these can be used alone or in admixture of two or more. Examples of the polyamine include ethylenediamine, phenylenediamine, diethylenetriamine, triethylenetetraamine, methylaminopropylamine, 3,3′-diaminodipropylamine, and the like. Examples of the polyaminosilane include N-6-aminoethyl-γ-aminopropyltrimethoxysilane, N-6-aminoethyl-γ-aminopropylmethyldimethoxysilane, and the like. Examples of amino alcohols include monoethanolamine and diethanolamine.

  Examples of the ketones include methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 4-methyl-2-pentanone, 2-heptanone, 4-heptanone, diisopropyl ketone, diisobutyl ketone, and the like. Aliphatic ketones; aromatic ketones such as propiophenone and benzophenone; cyclic ketones such as cyclopentanone, cyclohexanone and methylcyclohexanone; β-dicarbonyl compounds such as ethyl acetoacetate, or any mixture thereof. Can be mentioned.

  Examples of the aldehydes include propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-pentylaldehyde, 2-methylbutyraldehyde, n-hexylaldehyde, 2-methylpentanal, n-heptylaldehyde, n-octylaldehyde, and benzaldehyde. , Cuminaldehyde, or any mixture thereof.

  Of the compounds mentioned as the block amine compound (B), an oxazolidine compound is preferred because it is excellent in storage stability and antifoaming performance of the resulting curable composition, and moreover, by dehydration reaction between diethanolamine and isobutyraldehyde. The resulting oxazolidine compound is preferred. Furthermore, the hydroxyl group remaining in the molecule of the compound having an oxazolidine group obtained by dehydration reaction of diethanolamine and aldehydes is the same organic isocyanate compound (a) as mentioned in the synthesis of the urethane prepolymer (A). A urethane bond-containing oxazolidine compound obtained by urethanization with an isocyanate group is particularly preferred. In this case, as the organic isocyanate compound (a) to be used, an aliphatic diisocyanate is preferable, and hexamethylene diisocyanate is particularly preferable in that the viscosity of the latent curing agent to be obtained is low.

  Next, the additive (C) that is preferably added to the system composed of the urethane prepolymer (A) and the block amine compound (B) will be described. The additive (C) is blended into the curable composition and used for improving various performances such as curing acceleration and adhesion improvement. Specifically, a curing accelerating catalyst, a plasticizer, Examples include weathering stabilizers, fillers, thixotropic agents, adhesion improvers, storage stability improvers (dehydrating agents), colorants, organic solvents, and the like, depending on the application of the curable composition. One or two or more selected from can be used in combination.

  The curing accelerating catalyst is a compound that accelerates the curing reaction of the curable composition and is a hydrolysis accelerating catalyst that accelerates the hydrolysis reaction rate of the block amine compound (B) or the activity of active hydrogen or moisture regenerated by the hydrolysis reaction. Examples thereof include metal catalysts that increase the reaction rate between hydrogen and isocyanate groups.

  Specific examples of the hydrolysis promoting catalyst include organic carboxylic acid compounds, p-toluenesulfonyl isocyanate, a reaction product of p-toluenesulfonyl isocyanate and moisture, and the organic carboxylic acid compounds include formic acid, Aliphatic carboxylic acids such as acetic acid, propionic acid, caproic acid, oxalic acid, succinic acid, adipic acid, 2-ethylhexanoic acid, octenoic acid, lauric acid, oleic acid and stearic acid; unsaturated carboxylic acids such as maleic acid; Examples thereof include aromatic carboxylic acids such as phthalic acid, benzoic acid, and salicylic acid, and acid anhydrides thereof. Examples of p-toluenesulfonyl isocyanate include those marketed by Nippon Soda Co., Ltd. under the PTSI trade name. In addition, since p-toluenesulfonyl isocyanate reacts with the moisture content in a curable composition rapidly, and also has the effect of storage stability, it is especially preferable.

  The reaction product of p-toluenesulfonyl isocyanate and moisture may be obtained by reacting p-toluenesulfonyl isocyanate and moisture in advance before blending with the curable composition, or p-toluene. It may be produced by reacting with moisture contained in an additive to be described later during blending of the sulfonyl isocyanate into the curable composition or during storage after blending into the curable composition. Examples of the metal catalyst include tin octylate, tin naphthenate, zinc octylate, bismuth octylate, zirconium octylate and the like, and metals such as bismuth, zinc, zirconium, and tin, octyl acid, neodecanoic acid, stearic acid, naphthene. Salts of organic acids such as acids; salts of organic tin and organic acids such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin distearate, dibutyltin dioctoate, dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate; Examples thereof include metal chelate compounds such as tin bis (acetylacetonate), aluminum tris (acetylacetonate), acetylacetone primary cobalt, and ferric tris (acetylacetonate).

  The amount of the curing accelerating catalyst used is preferably 0.001 to 10 parts by mass, particularly 0.01 to 5 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A). If the amount used is less than 0.001 part by mass, there is no effect of accelerating curing, and if it exceeds 10 parts by mass, the storage stability decreases, such being undesirable.

  Plasticizers are used to reduce the viscosity of curable compositions and improve workability, and to adjust the rubber elastic properties of cured products. Phthalate esters such as dioctyl phthalate, dibutyl phthalate, and butyl benzyl phthalate Low molecular weight plasticizers having a molecular weight of less than 1,000, such as aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate and butyl oleate; the above isocyanate group-containing urethane prepolymer (A) Compounds obtained by etherification or esterification of the same polyether polyols or polyether monools used in the synthesis of styrene; molecular weight not reacting with isocyanate groups such as poly-α-methylstyrene and polystyrenes such as polystyrene 1,000 The above high molecular weight plasticizers may be mentioned. These can be used alone or in combination of two or more.

The plasticizer is preferably blended in an amount of 1 to 200 parts by mass and further 2 to 50 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A).
Weathering stabilizers are used for the purpose of further improving heat resistance as well as weather resistance by preventing oxidation, photodegradation, and thermal degradation of cured products, hindered amine light stabilizers, hindered phenolic antioxidants, UV absorption Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (2,2,6,6-tetramethyl-1) decanedioate. (Octyloxy) -4-piperidyl) ester, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] Methyl] butyl malonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) seba 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, dimethyl succinate 1- (2-hydroxyethyl)- 4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4 -Diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N′- Bis (3-aminopropy ) Ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, etc. Low molecular weight hindered amine light stabilizers having a molecular weight of less than 1,000; high molecular weight hindered amine light stabilizers having a molecular weight of 1,000 or more such as trade names ADK STAB LA-63P and LA-68LD manufactured by Asahi Denka Kogyo Co., Ltd. It is done.

  As the hindered phenol-based antioxidant, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], which is generally commercially available from BASF Japan under the name of IRGANOX 1010, octadecyl- 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propioamide], 3,5-bis (1,1-dimethylethyl) benzenepropanoic acid, 4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, ethylene Bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy m- tolyl) propionate] and the like.

  Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole; 2- (4,6-diphenyl-1, 3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol and other triazine ultraviolet absorbers; benzophenone ultraviolet absorbers such as octabenzone; 2,4-di-tert-butylphenyl-3 Benzoate-based ultraviolet absorbers such as 5-di-tert-butyl-4-hydroxybenzoate.

  These can be used singly or in combination of two or more. Among these, a hindered amine light stabilizer and / or a hindered phenol antioxidant is preferred, and a hindered phenol antioxidant is particularly preferable in terms of a high effect of improving weather resistance. Antioxidants are preferred. It is preferable that the weathering stabilizer is blended in an amount of 0.01 to 30 parts by mass, and further 0.1 to 10 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A).

  The filler is used for the purpose of increasing the amount of the curable composition and reinforcing the physical properties of the cured product.Mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, silicic anhydride, quartz fine powder, aluminum Powder, zinc powder, synthetic silica such as precipitated silica, inorganic powder filler such as calcium carbonate, magnesium carbonate, alumina, calcium oxide, magnesium oxide; fiber filler such as glass fiber, carbon fiber; glass balloon, shirasu Inorganic fillers such as inorganic balloon fillers such as balloons, silica balloons and ceramic balloons; or fillers whose surfaces are treated with organic substances such as fatty acids; wood powder, walnut shell powder, rice husk powder, pulp powder Cotton chips, rubber powder, thermoplastic or thermosetting resin fine powder, polyethylene powder, etc. In addition to organic fillers such as organic balloon-like fillers such as body and saran microballoons, flame retardant imparting fillers such as magnesium hydroxide and aluminum hydroxide, etc. are also included, and the particle size is 0.01 to 1 1,000 μm is preferred. These can be used alone or in combination of two or more, and the amount used is preferably from 0.1 to 500 parts by mass, more preferably from 1 to 300 parts by mass, per 100 parts by mass of the urethane prepolymer (A).

  The thixotropic agent is used for the purpose of preventing sagging (slump) of the curable composition, and is an inorganic thixotropic agent such as hydrophilic or hydrophobic fine powder silica and fatty acid-treated calcium carbonate; organic bentonite, fatty acid amide Organic thixotropy imparting agents such as these can be mentioned, and these can be appropriately selected from these.

  The adhesion improver is used for the purpose of improving the adhesiveness of the curable composition, and can include various coupling agents such as silane, aluminum, and zircoaluminate or partially hydrolyzed condensates thereof. Of these, a silane coupling agent or a partially hydrolyzed condensate thereof is preferable because of its excellent adhesiveness.

  As this silane coupling agent, vinyltrimethoxysilane, vinylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-amino) Ethyl) -3-aminopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and other alkoxysilyl group-containing molecular weight of 500 or less, preferably 400 or less Compound or this It may include compounds having a molecular weight of 200 to 3,000 with one or more partially hydrolyzed condensate of the silane coupling agent. These can be used alone or in combination of two or more.

  A storage stability improver (dehydrating agent) is used for the purpose of improving the storage stability of a curable composition, and reacts with moisture present in the curable composition to act as a dehydrating agent. , Calcium oxide, p-toluenesulfonyl isocyanate and the like, and these can be used alone or in combination. Among these, p-toluenesulfonyl isocyanate is preferable in that the effect of improving storage stability is high. The usage-amount is 0.01-50 mass parts with respect to 100 mass parts of urethane prepolymer (A), Furthermore, 0.01-10 mass parts is preferable.

  The colorant is used for the purpose of coloring the curable composition and imparting design properties to the cured product, and includes inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black. . These can be used alone or in admixture of two or more.

  The organic solvent is used to lower the viscosity of the curable composition of the present invention and to improve the workability of extrusion and coating. An ester solvent such as ethyl acetate; a ketone solvent such as methyl ethyl ketone; n -An aliphatic solvent such as hexane; a naphthene solvent such as methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, or a mixture thereof; a compound that does not react with an isocyanate group in a conventionally known organic solvent such as an aromatic solvent such as toluene or xylene. Can be mentioned. Examples of suitable commercially available naphthenic solvents include Exon Mobil's Exol series D30, D40, D80, Shell Chemicals Japan's Shellsol series D40, D60, D70, and the like. These can be used alone or in admixture of two or more. Of these, naphthenic solvents are preferred because of their low toxicity and high viscosity-reducing effect of the urethane prepolymer (A). However, in order to suppress the emission of volatile substances and have no adverse effect on the environment, it is preferable to reduce the amount of the organic solvent used as little as possible, 10% by mass or less, and further 5% by mass of the entire curable composition. The following is preferable.

  In addition, the curable composition of the present invention has no work of mixing the main agent and the curing agent, and has excellent workability without occurrence of curing failure due to a mixing error, so that it is cured by bringing the curable composition into contact with moisture. It is particularly preferable to use it as a one-component moisture curable type, but it can also be used as a two-component curable type using water as a curing agent.

  Further, the curable composition of the present invention is cured without foaming even under severe conditions of high temperature and high humidity assuming the summer season, and the rubber elastic properties of the cured product are low hardness and high elongation to high hardness. It can be adjusted over a wide range to low elongation and has excellent adhesion, water resistance, weather resistance, and other durability, so it can be used for construction and civil engineering paints, waterproof coatings, and adhesives. Although it can be used for various applications such as a sealing material, it is most suitable to be used for a waterproof coating material because it is particularly excellent in tearing performance of a cured product.

  In addition, the materials to which the curable composition of the present invention is applied include cement-based materials such as mortar and concrete; natural stone materials such as marble; ceramic materials such as siding and tiles; various materials such as polypropylene and vinyl chloride A sheet-like or plate-like material made of a synthetic resin; a wood-based material such as wood or plywood is preferable because of its good adhesion.

  Next, the manufacturing method of the curable composition concerning the 3rd of this invention is demonstrated. As described in the method for producing the urethane prepolymer (A), a reaction apparatus or a mixing apparatus made of stainless steel is used to react the organic isocyanate compound (a) with the polymer diol (b) as described above. After charging at a molar ratio, the step (Ia) of heating and reacting at the reaction temperature as described above is performed to synthesize the urethane prepolymer (A).

  In this reaction step (Ia), the reaction can be carried out in the absence of a filler, or the filler is further added to the organic isocyanate compound (a) and the polymer diol (b), and in the presence of the filler. In addition to the step (I) for synthesizing the urethane prepolymer (A), the step (I ′) for obtaining the mixture (A ′) with the filler can be carried out, and the process can be shortened. Step (I ′) is preferred. Further, in the synthesis step (I) of the urethane prepolymer (A), as described above, the removal operation (Ib) of the unreacted organic isocyanate compound (a) can be carried out after the reaction. It is preferable that the step (Ib) is not performed because it can be manufactured at low cost. Separately from this, a step (II) of synthesizing the block amine compound (B) component is carried out using a reaction apparatus made of stainless steel or the like. Next, the product obtained in step (I) is added to the product obtained in step (I) or step (I ′), and more preferably, the additive (C) component selected as necessary is blended and mixed. There is a method of producing a curable composition by carrying out step (III), and then preferably degassing under reduced pressure. A commercially available block amine compound (B) can also be used.

  In addition, (A) component and (B) component react when exposed to moisture and cause thickening and hydrolysis. Therefore, reaction synthesis, stirring, and mixing are performed in a sealed state or in a nitrogen gas atmosphere so as not to contact moisture. It is preferable to carry out in a state where moisture such as is blocked. Since the produced curable composition also reacts when exposed to moisture and thickens and hardens, it is preferably stored in a container that can block moisture, and sealed and stored. The container is not particularly limited, but a metal drum such as stainless steel or iron, a square can, a cylindrical can; a metal or synthetic resin pail can or bag-like container; laminated paper or synthetic Various examples include resin-made cartridge-like containers.

  Hereinafter, the present invention will be described in more detail with reference to examples and the like, taking a one-component moisture-curing waterproofing film as an example of the curable composition, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Urethane Bond-Containing Oxazolidine Compound O-1 420 g of diethanolamine (molecular weight 105) was passed through a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, ester tube and heating / cooling device while flowing nitrogen gas. 177 g of toluene and 317 g of isobutyraldehyde (molecular weight 72.1) were charged, heated with stirring, and reflux dehydration was performed at 110 to 150 ° C. while removing by-product water (71.9 g) from the system. It was. After no water distilling was observed, the mixture was further heated under reduced pressure (50 to 70 hPa) to remove toluene and unreacted isobutyraldehyde, and N-hydroxyethyl-2-isopropyloxazolidine as an intermediate reaction product Got. Next, 336 g of hexamethylene diisocyanate (molecular weight 168) was further added to 636 g of the obtained N-hydroxyethyl-2-isopropyloxazolidine, heated at 80 ° C. for 8 hours, and the NCO content actually measured by titration was reduced to 0.0 mass%. At this point, the reaction was terminated, and a urethane bond-containing oxazolidine compound O-1 having two oxazolidine rings in the molecule was obtained. The obtained urethane bond-containing oxazolidine compound O-1 was liquid at room temperature.

(Manufacture and testing of one-component moisture-curing waterproofing membrane)
Example 1
While flowing nitrogen gas into a reactor equipped with a stirrer, thermometer, nitrogen seal tube and heating and cooling device, 902 g of polyoxypropylene diol (Asahi Glass Co., Ltd., Exenol 3021, number average molecular weight 3,220), dioctyl phthalate 88 g And 126 g of naphthenic solvent (Exxon Mobil Corp., Exol D40) and dried in a dryer at 100 to 110 ° C. in advance with stirring to make heavy calcium carbonate having a water content of 0.05% by mass or less. 1,260 g, titanium oxide 20 g, and carbon black 2 g were sequentially charged and kneaded for 1 hour until uniform. Next, 98 g of toluene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate T-80, molecular weight 174.2) and 0.4 g of zirconium octylate as a reaction catalyst were charged, heated to 120 to 125 ° C., and reacted for 3 hours. Then, it cooled to room temperature. The reaction molar ratio (number of moles of isocyanate group as raw material / number of moles of hydroxyl group) at this time is 2.0. Next, 10 g of hindered phenol-based antioxidant (manufactured by BASF Japan (former Ciba Japan), IRGANOX1010), 1 g of p-toluenesulfonyl isocyanate and 86 g of urethane bond-containing oxazolidine compound O-1 are charged until uniform. Further, after kneading for 30 minutes, degassed under reduced pressure at 50 to 100 hPa, and filled and sealed in a tin can container, thereby producing a one-part moisture-curing waterproofing film S-1.
The obtained one-component moisture-curable waterproofing membrane S-1 was a gray liquid that was viscous at room temperature and had a viscosity at 25 ° C. of 4,200 mPa · s measured using a B-type rotational viscometer.

Example 2
In Example 1, a one-component moisture-curable waterproofing membrane S-2 was produced in the same manner except that the plasticizer dioctyl phthalate was not used.
The obtained one-component moisture-curing waterproofing membrane S-2 was a gray liquid that was viscous at room temperature and had a viscosity at 25 ° C. of 9,600 mPa · s.

Example 3
In Example 1, a one-component moisture-curing waterproofing membrane S-3 was produced in the same manner except that 108 g of toluene diisocyanate was used and the reaction molar ratio was 2.2.
The obtained one-component moisture-curable coating film waterproofing material S-3 was a gray liquid that was viscous at room temperature and had a viscosity at 25 ° C. of 5,200 mPa · s.

Comparative Examples 1-3
In each of Examples 1-3, instead of reacting at 120 to 125 ° C. for 3 hours, a one-component moisture-curing waterproofing film comparative material S-1 Comparative S-3 was produced respectively.
The obtained one-component moisture-curable waterproofing membrane has a viscosity at 25 ° C. of 5,500 mPa · s for comparison S-1, 6,700 mPa · s for comparison S-2, and 5,400 mPa for comparison S-3. -Each s was a viscous gray liquid at room temperature.

Comparative Examples 4-6
In each of Examples 1 to 3, 724 g of polyoxypropylene diol and 178 g of polyoxypropylene triol were used, 102 g of toluene diisocyanate was used in Comparative Examples 4 and 5, and 112 g in Comparative Example 6, respectively. Instead of reacting at 3 [deg.] C. for 3 hours, 1-component moisture-curing waterproofing film comparative materials S-4 to S-6 were produced in the same manner except that the reaction was performed at 75 to 80 [deg.] C. for 3 hours.
The obtained one-component moisture-curing waterproofing membrane has a viscosity at 25 ° C. of 5,400 mPa · s for comparison S-4, 7,200 mPa · s for comparison S-5, and 4,600 mPa for comparison S-6. -Each s was a viscous gray liquid at room temperature.

Tables 1 to 3 show the results of testing by the following test methods using the one-component moisture-curing waterproofing membranes obtained in Examples 1 to 3 and Comparative Examples 1 to 6, together with preparation compositions and reaction conditions. It describes.
Although only the polyoxypropylene diol shown in Table 2 and the urethane prepolymer does not have an allophanate bond, the elongation is excellent, but the tensile strength and particularly the tearing performance are inferior. Examples of ordinary urethane prepolymers shown are polyoxypropylene diol and polyoxypropylene triol, and those in which the urethane prepolymer does not have an allophanate bond have a higher tensile strength and temperature dependency, especially tearing performance. In contrast to the inferior results, in the examples of the present invention shown in Table 1, the urethane prepolymer has an allophanate bond despite using only polyoxypropylene diol. Excellent in all of tensile performance, tear performance and temperature dependence, especially tear strength is 14 N / mm It shows the above indicates that the curable composition of the present invention is superior.

(Test method)
1) Confirmation test for presence of isocyanate group and allophanate bond in prepolymer About 0.2 g of the obtained 1-component moisture-curing waterproofing membrane was collected, dissolved in 10 ml of cyclohexane, and then centrifuged. The obtained supernatant was used as a sample. This sample was subjected to FTIR, and in the obtained infrared absorption spectrum, one having strong absorption in the vicinity of 2270 cm ⁻¹ was determined to have an isocyanate group in the (urethane) prepolymer.

Moreover, what is observed pair of absorption around 1720 cm ^-1 and near 1690 cm ^-1 in the same infrared absorption spectrum, the (urethane) determines that there allophanate bond in the prepolymer, which takes a pair of absorption is not observed No allophanate binding was determined.

2) Test according to JIS A 6021 2-1) Tensile performance Carefully pour the foam so as not to entrain the foam so as to have a thickness of about 2 mm in a mold that has been subjected to a release treatment. After leaving in a room of 50 ° C. and 50% relative humidity for 4 days, it was demolded, and further allowed to stand for 3 days under the same conditions and cured to prepare a cured sheet as a test specimen.
Using the prepared specimen, the test piece was tested in dumbbell shape No. 3 as defined in JIS K 6251 according to JIS A 6021 (2000) “Waterproofing material for architectural coatings” and “6.3 Tensile performance”. Tensile strength, elongation at break and tensile product were determined. The numerical value in [] in a table | surface shows the numerical value prescribed | regulated to JISA6021.

2-2) Tear performance Using the specimen prepared in the above tensile performance test, the test piece was changed to JIS K 6252 according to JIS A 6021 (2000) “Waterproofing material for architectural coatings” and “6.4 Tear performance”. The test was conducted with the specified angle type without incision, and the tear strength was determined. The numerical value in [] in a table | surface shows the numerical value prescribed | regulated to JISA6021.

2-3) Temperature Dependence Using the specimen prepared in the tensile performance test, the test piece is JIS K 6021 (2000) “Building waterproofing coating material” and “6.5 Temperature dependence”. The dumbbell-shaped No. 3 specified in 6251 was tested, and the elongation between grips at the time of breaking was determined. The test temperature was 60 ° C. The numerical value in [] in a table | surface shows the numerical value prescribed | regulated to JISA6021.

Claims (13)

An organic isocyanate compound (a) and the polymer diol (b) and reacting the obtained is isocyanate group-containing urethane prepolymer (A), a curable composition containing a blocked amine compound (B), the isocyanate group-containing urethane prepolymer (a) is closed allophanate bond in the molecule, tear strength of more than 14N / mm in the test cured product obtained by a curable composition cured by moisture prescribed in JIS a 6021 is, 2.3 N / mm ² or more tensile strength, elongation at break of more than 450%, the curable composition characterized by have a tensile product of more than 280N / mm. After the reaction of the isocyanate group-containing urethane prepolymer (A) having an allophanate bond in the molecule with the organic isocyanate compound (a) and the polymer diol (b), the removal operation of the unreacted organic isocyanate compound (a) is performed. The curable composition according to claim 1, which is obtained without any treatment. The curable composition according to claim 1 or 2 , wherein the organic isocyanate compound (a) is an aromatic diisocyanate. The curable composition according to claim 3 , wherein the aromatic diisocyanate is toluene diisocyanate. The curable composition according to any one of claims 1 to 4 , wherein the polymer diol (b) is a polyoxyalkylene diol having a number average molecular weight of 2,000 or more. The curable composition according to any one of claims 1 to 5 , wherein the block amine compound (B) is an oxazolidine compound. Further, one or more selected from the group consisting of curing accelerators, plasticizers, weathering stabilizers, fillers, thixotropic agents, adhesion improvers, storage stability improvers, colorants and organic solvents. The curable composition according to any one of claims 1 to 6 , wherein the additive (C) is blended. The curable composition according to claim 7 , wherein the additive (C) is p-toluenesulfonyl isocyanate. The curable composition according to claim 7 , wherein the additive (C) is a naphthenic solvent. A waterproofing coating material comprising an isocyanate group-containing urethane prepolymer (A) obtained by reacting an organic isocyanate compound (a) with a polymer diol (b), and a block amine compound (B), isocyanate group-containing urethane prepolymer (a) is closed allophanate bond in the molecule, tear strength of more than 14N / mm in the tests the cured product defined in JIS a 6021 by the coating film waterproof material cured by moisture is, 2.3 N / mm ² or more tensile strength, elongation at break of more than 450%, waterproofing membrane material, characterized in that have a tensile product of more than 280N / mm. The organic isocyanate compound (a) a polymeric diol (b) and the 100-180 Ru at temperatures of ℃ step (I-a) an isocyanate group-containing urethane prepolymer having an allophanate bond in a molecule to implement the (A ) and the step of synthesizing (I), step (isocyanate group-containing urethane prepolymer obtained in I) (a) and blocked amine compound (B) are mixed step (III) and hardening composition that have a A cured product obtained by curing the curable composition with moisture in a test specified in JIS A 6021 has a tear strength of 14 N / mm or more and a tensile strength of 2.3 N / mm ² or more. A method characterized by having a strength, an elongation at break of 450% or more, and a tensile product of 280 N / mm or more . The curable composition according to claim 11 , wherein in the synthesis step (I), the step (Ib) for removing the unreacted organic isocyanate compound (a) is not performed after the reaction step (Ia). Manufacturing method. The manufacturing method of the curable composition of Claim 11 or 12 which reacts in presence of a filler in the said reaction process (Ia).