Hardening composition

Abstract

Provided is a curable composition containing a hydrolyzable silyl group-containing polyoxyalkylene polymer (A), silica (B), a silane compound (C) having an alkyl group having at least 4 carbon atoms, and a compound (D) in which a silyl group of aminosilane is used alone or aminosilane and other alkoxysilane compounds are partially condensed.

Description

[Technical Field]

[0001] The present invention relates to a curable composition containing a hydrolyzable silyl group-containing polyoxyalkylene polymer. [Background technology]

[0002] Polymers having hydrolyzable silyl groups are known as moisture-reactive polymers, and their curable compositions are used in a wide range of industrial applications, including adhesives, sealants, coating materials, paints, and pressure-sensitive adhesives.

[0003] As the main chain skeleton of such a polymer having a hydrolyzable silyl group, various polymers are known, such as polyoxyalkylene polymers, saturated hydrocarbon polymers, (meth)acrylic acid ester copolymers, etc. Among them, polyoxyalkylene polymers have a wide range of applications due to their characteristics such as relatively low viscosity at room temperature, easy handling, and good elasticity of the cured product obtained after the reaction.

[0004] A curable composition containing a hydrolyzable silyl group-containing polyoxyalkylene polymer contains a plurality of additives to impart various physical properties. Patent Documents 1 and 2 disclose curable compositions containing a hydrolyzable silyl group-containing polyoxyalkylene polymer, silica, and a compound in which the silyl group of an aminosilane is partially condensed alone or with another alkoxysilane compound. Patent Documents 3 and 4 disclose curable compositions containing a hydrolyzable silyl group-containing polyoxyalkylene polymer, silica, and a long-chain alkylsilane. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2015-508419 [Patent Document 2] Japanese Patent Application Publication No. 2019-014885 [Patent Document 3] Special Publication No. 2013-525529 [Patent Document 4] Japanese Patent Application Laid-Open No. 2014-043519 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a curable composition that improves water-resistant adhesion to concrete without the need for a primer coating and gives a cured product with low water absorption. [Means for solving the problem]

[0007] As a result of extensive research into solving the above problems, the present inventors have completed the following invention.

[0008] That is, the present invention provides: (1) The present invention relates to a curable composition containing a hydrolyzable silyl group-containing polyoxyalkylene polymer (A), silica (B), a silane compound (C) containing an alkyl group having 4 or more carbon atoms, and a compound (D) obtained by partially condensing the silyl group of an aminosilane alone or an aminosilane with another alkoxysilane compound.

[0009] (2) The curable composition according to (1) further contains an epoxy silane (E).

[0010] (3) The curable composition according to (1) or (2), wherein the silane compound (C) containing an alkyl group having 4 or more carbon atoms is a silane compound containing an alkyl group having 7 or more carbon atoms.

[0011] (4) The hydrolyzable silyl group of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) is represented by the general formula (1): -Si(R 1 ) 3-a (X) a (1) (In the formula, R 1each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent consisting of a heteroatom-containing group or a halogen atom. Each X independently represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. (5) The curable composition according to (4), wherein a represents 3.

[0012] (6) The curable composition according to any one of (1) to (5), wherein the aminosilane has a hydrolyzable silyl group.

[0013] (7) The curable composition according to any one of (1) to (6), wherein the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) has a number average molecular weight of 3,000 to 50,000.

[0014] (8) The curable composition according to any one of (1) to (7), containing, relative to 100 parts by weight of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A), 10 to 300 parts by weight of silica (B), 0.5 to 20 parts by weight of a silane compound (C) containing an alkyl group having 4 or more carbon atoms, and 0.5 to 20 parts by weight of a compound (D) in which the silyl group of an aminosilane is used alone or in which the aminosilane is partially condensed with another alkoxysilane compound.

[0015] (9) A cured product obtained by curing the curable composition according to any one of (1) to (8).

[0016] (10) A waterproof coating material for concrete, comprising the curable composition according to any one of (1) to (8). [Effects of the Invention]

[0017] According to the present invention, it is possible to provide a hardenable composition that improves water-resistant adhesion to concrete without the need for a primer coating and gives a hardened product with low water absorption. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, an embodiment of the present invention will be described. The present invention relates to a curable composition containing (A) a hydrolyzable silyl group-containing polyoxyalkylene polymer, (B) silica, (C) a silane compound containing an alkyl group having 4 or more carbon atoms, and (D) a compound obtained by partially condensing the silyl group of an aminosilane alone or an aminosilane with another alkoxysilane compound.

[0019] The curable composition of the present invention contains the components (B), (C), and (D), and thereby exhibits improved water-resistant adhesion to concrete without the need for a primer. Furthermore, the cured product obtained from the curable composition exhibits low water absorption.

[0020] <<Hydrolyzable Silyl Group-Containing Polyoxyalkylene Polymer (A)>> The curable composition contains a "polyoxyalkylene polymer (A) having a hydrolyzable silyl group" (hereinafter also referred to as "polymer (A)").

[0021] The number average molecular weight of the polymer (A), as measured by GPC in terms of polystyrene, is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and particularly preferably 3,000 to 30,000. When the number average molecular weight is 1,000 or more, the amount of reactive silicon groups introduced can be appropriately controlled, which is advantageous in terms of production costs. Furthermore, when the number average molecular weight is 50,000 or less, the polymer has a low viscosity, which is advantageous in terms of workability.

[0022] The molecular weight of polymer (A) can also be expressed as an end-group converted molecular weight calculated by directly measuring the end-group concentration of an organic polymer precursor before the introduction of a hydrolyzable silyl group by titration analysis based on the principles of the hydroxyl value measurement method specified in JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and taking into account the structure of the organic polymer (the degree of branching determined by the polymerization initiator used).

[0023] The molecular weight distribution (Mw / Mn) of the polymer (A) is not particularly limited, but is preferably narrow to enable low viscosity, and is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.4 or less, and particularly preferably 1.3 or less. Furthermore, from the viewpoint of improving various mechanical properties such as durability and elongation of the cured product, 1.2 or less is preferred. The molecular weight distribution of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.

[0024] <Hydrolyzable silyl group> The hydrolyzable silyl group contained in the polymer (A) is preferably represented by the following general formula (1). -Si(R 1 ) 3-a (X) a (1) In formula (1), R 1 each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent consisting of a heteroatom-containing group or a halogen atom. Each X independently represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. R 1 Examples of the alkyl group include alkyl groups such as methyl and ethyl groups, cycloalkyl groups, aryl groups, aralkyl groups, halogenated methyl groups such as chloromethyl groups, and alkoxymethyl groups such as methoxymethyl groups. Preferred are methyl groups, chloromethyl groups, and methoxymethyl groups, and more preferred is methyl group.

[0025] Examples of X include a hydroxyl group, a halogen, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, etc. Among these, alkoxy groups such as a methoxy group and an ethoxy group are preferred because they are mildly hydrolyzable and easy to handle, and a methoxy group and an ethoxy group are more preferred.

[0026] a represents 1, 2, or 3, preferably 2 or 3, and more preferably 3.

[0027] Specific examples of the hydrolyzable silyl group include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a (chloromethyl)dimethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, an (N,N-diethylaminomethyl)dimethoxysilyl group, etc. Among these, a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, and a (methoxymethyl)dimethoxysilyl group are preferred.

[0028] The number of hydrolyzable silyl groups contained in one molecule of polymer (A) is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 1.2 or more on average, and the upper limit is preferably 4 or less, more preferably 3 or less.

[0029] Furthermore, a polymer having multiple hydrolyzable silyl groups in one terminal structure can also be used as the polymer (A). A representative example is a terminal structure represented by the following general formula (2):

[0030] [ka]

[0031] In formula (2), R 2 represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms. 3 represents hydrogen or an alkyl group having 1 to 6 carbon atoms. 4 represents a direct bond or a divalent bonding group having 1 to 6 carbon atoms. 5 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. n is an integer of 1 to 10. The oxygen atom at the left end represents an oxygen atom in a repeating unit located at the end of a polymer skeleton formed by linking multiple repeating units, or an oxygen atom bonded to a repeating unit located at the end of the polymer skeleton. R 1 , X, and a are the same as described above for formula (1).

[0032] R 2 is preferably a hydrocarbon group having 1 to 3 carbon atoms, more preferably a hydrocarbon group having 1 to 2 carbon atoms. The hydrocarbon group is preferably an alkylene group. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group. A methylene group is particularly preferred.

[0033] R 3 is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, more preferably hydrogen or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. 3 As the alkyl group, hydrogen, a methyl group, and an ethyl group are preferred, hydrogen and a methyl group are more preferred, and hydrogen is even more preferred.

[0034] R 4 R may be a divalent organic group having 1 to 6 carbon atoms. The organic group is preferably a hydrocarbon group or a hydrocarbon group containing an oxygen atom. The number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. 4 As the alkyl group, -CH2OCH2-, -CH2O- and -CH2- are preferred, and -CH2OCH2- is more preferred.

[0035] R 5 is preferably hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, more preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and even more preferably hydrogen or a hydrocarbon group having 1 to 2 carbon atoms. Particularly preferred are hydrogen and a methyl group, and most preferred is hydrogen.

[0036] <Main chain structure> The main chain structure of the polymer (A) may be linear or may have a branched chain.

[0037] The main chain of the polymer (A) is -R 6 It is preferable that the polymer has a repeating unit represented by -O-. 6represents preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and more preferably a linear or branched alkylene group having 2 to 4 carbon atoms. 6 Specific examples of the repeating unit represented by -O- include -CH2O-, -CH2CH2O-, -CH2CH(CH3)O-, -CH2C(CH3)(CH3)O-, and -CH2CH2CH2CH2O-.

[0038] The polymer (A) may have any one of the various main chain skeletons described above, or may be a mixture of two or more polymers having different main chain skeletons.

[0039] <Synthesis method> Preferred methods for synthesizing the polymer (A) include: (i) a method in which a hydroxyl-terminated polyoxyalkylene polymer is obtained by polymerizing an epoxy compound with a hydroxyl group-containing initiator using a double metal cyanide complex catalyst, and then the hydroxyl groups of the obtained hydroxyl-terminated polyoxyalkylene polymer are converted to carbon-carbon unsaturated groups, followed by addition of a hydrosilane compound by a hydrosilylation reaction; (ii) a method in which a hydroxyl-terminated polyoxyalkylene polymer is obtained by polymerizing an epoxy compound with a hydroxyl group-containing initiator using a double metal cyanide complex catalyst, and then the obtained hydroxyl-terminated polyoxyalkylene polymer is reacted with a compound having both a group reactive with a hydroxyl group and a hydrolyzable silyl group; and (iii) a method in which a hydroxyl-terminated polyoxyalkylene polymer is reacted with an excess polyisocyanate compound to form a polymer having isocyanate groups at its terminals, and then the polymer is reacted with a compound having both a group reactive with an isocyanate group and a hydrolyzable silyl group.

[0040] Examples of initiators having a hydroxyl group that can be used in methods (i) and (ii) include compounds or polymers having one or more hydroxyl groups, such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, low-molecular-weight polypropylene glycol, polyoxypropylene triol, allyl alcohol, methanol, ethanol, propanol, butanol, pentanol, hexanol, polypropylene monoallyl ether, and polypropylene monoalkyl ether.

[0041] Examples of epoxy compounds used in methods (i) and (ii) include alkylene oxides such as ethylene oxide and propylene oxide; glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether; etc. Among these, propylene oxide is preferred.

[0042] Examples of the carbon-carbon unsaturated group used in method (i) include a vinyl group, an allyl group, a methallyl group, a propargyl group, etc. Among these, an allyl group is preferred.

[0043] As a method for converting the hydroxyl groups (i) into carbon-carbon unsaturated groups, it is preferable to use a method in which an alkali metal salt is reacted with a hydroxyl-terminated polymer, and then a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted therewith.

[0044] Examples of the halogenated hydrocarbon compound used in method (i) include vinyl chloride, allyl chloride, methallyl chloride, propargyl chloride, vinyl bromide, allyl bromide, methallyl bromide, propargyl bromide, vinyl iodide, allyl iodide, methallyl iodide, and propargyl iodide.

[0045] Examples of the hydrosilane compound used in method (i) include trimethoxysilane, triethoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, dimethoxymethylsilane, (chloromethyl)dimethoxysilane, (methoxymethyl)dimethoxysilane, and (N,N-diethylaminomethyl)dimethoxysilane.

[0046] The hydrosilylation reaction used in method (i) is accelerated by a hydrosilylation catalyst. Known catalysts can be used. Examples include platinum supported on alumina, silica, carbon black, or other carriers; chloroplatinic acid; chloroplatinic acid complexes composed of chloroplatinic acid and alcohols, aldehydes, or ketones; platinum-olefin complexes [e.g., Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2]; platinum-vinylsiloxane complexes [Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4]; platinum-phosphine complexes [Ph(PPh3)4, Pt(PBu3)4]; and platinum-phosphite complexes [Pt{P(OPh)3}4].

[0047] Examples of compounds having both a group reactive with a hydroxyl group and a hydrolyzable silyl group that can be used in method (ii) include isocyanate silanes such as 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyltriethoxysilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane, and isocyanatemethyldimethoxymethylsilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, and 3-mercaptopropyltriethoxysilane; and epoxy silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropyltriethoxysilane.

[0048] Examples of polyisocyanate compounds that can be used in method (iii) include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate.

[0049] Compounds having both a group reactive with an isocyanate group and a hydrolyzable silyl group that can be used in the method (iii) include γ-aminopropyltrimethoxysilane, γ-aminopropyldimethoxymethylsilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyldimethoxymethylsilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, γ-(N-phenyl)aminopropyltrimethoxysilane, γ-(N-phenyl)aminopropyltriethoxysilane, Examples thereof include amino group-containing silanes such as propyldimethoxymethylsilane, N-ethylaminoisobutyltrimethoxysilane, N-ethylaminoisobutyldimethoxymethylsilane, N-cyclohexylaminomethyltrimethoxysilane, and N-cyclohexylaminomethyldimethoxymethylsilane; hydroxy group-containing silanes such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyldimethoxymethylsilane; and mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyldimethoxymethylsilane.

[0050] Furthermore, a polyoxyalkylene polymer having multiple hydrolyzable silyl groups in one terminal structure, such as that represented by the formula (2), can also be used as the polymer (A). Examples of a method for synthesizing such a polyoxyalkylene polymer include a method in which a double metal cyanide complex catalyst is used to polymerize an epoxy compound with a hydroxyl group-containing initiator to obtain a hydroxyl-terminated polyoxyalkylene polymer, followed by reacting the hydroxyl groups of the obtained hydroxyl-terminated polyoxyalkylene polymer with an alkali metal salt, reacting with allyl glycidyl ether, and further reacting the resulting hydroxyl terminals with an alkali metal salt, followed by reacting with a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond to obtain a polyoxyalkylene polymer having multiple carbon-carbon unsaturated groups in one terminal structure, followed by adding a hydrosilane compound by hydrosilylation.

[0051] <<Silica (B)>> The curable composition according to this embodiment contains silica (B). By containing silica (B), the water-resistant adhesion of the curable composition to concrete can be improved.

[0052] Examples of silica (B) include wet silica such as precipitated silica, dry silica such as fumed silica, crystalline silica, fused silica, silicic acid anhydride, silicic acid hydrate, etc. Among these, crystalline silica is preferred.

[0053] The specific surface area of ​​silica (B) (BET adsorption method) is 0.1 to 10 m 2 / g is preferred, and 0.5 to 5m 2 / g is more preferred.

[0054] The median diameter (D50) of the silica (B) is preferably from 1 to 50 μm, more preferably from 2 to 30 μm, and even more preferably from 5 to 20 μm.

[0055] The amount of silica (B) is preferably 10 to 400 parts by weight, more preferably 30 to 300 parts by weight, and even more preferably 50 to 250 parts by weight, per 100 parts by weight of polymer (A). When the amount of silica (B) is 10 parts by weight or more, the water-resistant adhesion of the curable composition to concrete can be further improved. Furthermore, when the amount of silica (B) is 400 parts by weight or less, the mechanical properties of the cured product obtained from the curable composition can be improved.

[0056] <<Silane compounds (C) containing alkyl groups with 4 or more carbon atoms>> The curable composition according to this embodiment contains a "silane compound (C) containing an alkyl group having 4 or more carbon atoms" (hereinafter also referred to as "silane compound (C)"). By containing the silane compound (C), the water-resistant adhesion of the curable composition to concrete can be improved, and a cured product with low water absorption can be obtained.

[0057] The silane compound (C) contains an alkyl group having 4 or more carbon atoms on the silicon atom. The alkyl group is preferably an alkyl group having 6 or more carbon atoms, more preferably an alkyl group having 7 or more carbon atoms, and even more preferably an alkyl group having 8 or more carbon atoms. The upper limit of the number of carbon atoms in the alkyl group is not particularly limited, but may be, for example, 20 or less, and preferably 18 or less. The alkyl group in the silane compound (C) may be branched, but is preferably a linear alkyl group.

[0058] Specific examples of alkyl groups having 4 or more carbon atoms include, for example, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, cetyl group, ocdadecyl group, eicosyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, eicosenyl group, octadecadienyl group, 9,12,15-octadecatrienyl group, and 9,11,13-octadecatrienyl group. Of these, butyl, pentyl, hexyl, heptyl, octyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and octadecyl groups are preferred, and octyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and octadecyl groups are more preferred.

[0059] The silane compound (C) preferably has a hydrolyzable silyl group, such as those already exemplified as the hydrolyzable silyl groups of the polymer (A).

[0060] Specific examples of the silane compound (C) include n-butyltrimethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltriethoxysilane, n-hexyltriethoxysilane, n-heptyltriethoxysilane, n-octyltriethoxysilane, n-dodecyltriethoxysilane, n-octadecyltriethoxysilane, and n-butylmethyldimethoxysilane, n-pentylmethyldimethoxysilane, n-hexylmethyldimethoxysilane, n-heptylmethyldimethoxysilane, n-octylmethyldimethoxysilane, n-dodecylmethyldimethoxysilane, n-octadecylmethyldimethoxysilane, n-octylmethyldiethoxysilane, 1,8-bis(trimethoxysilyl)octane, 1,12-bis(trimethoxysilyl)dodecane, 1,8-bis(triethoxysilyl)octane, 1,12-bis(triethoxysilyl)dodecane, 1,8-bis(methyldimethoxysilyl)octane, and the like. Among these, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltrimethoxysilane, n-heptyltriethoxysilane, n-octyltriethoxysilane, n-dodecyltriethoxysilane, n-octadecyltriethoxysilane, n-heptylmethyldimethoxysilane, n-octylmethyldimethoxysilane, n-dodecylmethyldimethoxysilane, and n-octadecylmethyldimethoxysilane are preferred, and n-octyltrimethoxysilane, n-decyltrimethoxysilane, n-dodecyltrimethoxysilane, and n-octadecyltrimethoxysilane are more preferred.

[0061] The amount of silane compound (C) is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, and even more preferably 5 to 12 parts by weight, per 100 parts by weight of polymer (A). When the amount of silane compound (C) is 0.5 parts by weight or more, the water-resistant adhesion of the curable composition to concrete is further improved, and the water absorption rate of the cured product obtained from the curable composition can be further reduced. Furthermore, when the amount of silane compound (C) is 20 parts by weight or less, the curability of the curable composition can be improved.

[0062] <<Compound (D) obtained by partially condensing the silyl group of aminosilane alone or aminosilane with other alkoxysilane compounds>> The curable composition according to this embodiment contains a compound (D) obtained by partially condensing the silyl group of an aminosilane alone or an aminosilane with another alkoxysilane compound (hereinafter also referred to as a silane compound (D)). By including the silane compound (D), the water-resistant adhesion of the curable composition to concrete can be improved.

[0063] The silane compound (D) includes either one or both of a "silane compound (D1) obtained by partial condensation of the silyl group of an aminosilane alone" (hereinafter also referred to as "silane compound (D1)") and a "silane compound (D2) obtained by partial condensation of an aminosilane compound with another alkoxysilane compound" (hereinafter also referred to as "silane compound (D2)"). The aminosilane in the silane compound (D1) may be one type or two or more types in combination. The aminosilane in the silane compound (D1) is preferably an aminosilane having a hydrolyzable silyl group. The hydrolyzable silyl group is preferably represented by the above-mentioned formula (1). The silane compound (D1) is preferably a partial condensation product of the hydrolyzable silyl groups of an aminosilane compound having a hydrolyzable silyl group. The aminosilane in the silane compound (D2) may be used alone or in combination of two or more. The aminosilane in the silane compound (D2) is preferably an aminosilane having a hydrolyzable silyl group. The hydrolyzable silyl group is preferably represented by the above-mentioned formula (1). The other alkoxysilane compounds in the silane compound (D2) may be used alone or in combination of two or more. The silane compound (D2) is preferably a compound obtained by partially condensing the hydrolyzable silyl group of an aminosilane compound having a hydrolyzable silyl group with the alkoxy group of the other alkoxysilane compound.

[0064] The silane compound (D) is preferably a compound obtained by partial condensation of the hydrolyzable silyl groups of an aminosilane compound having a hydrolyzable silyl group represented by the above-mentioned formula (1), or a compound obtained by partial condensation of the hydrolyzable silyl group of an aminosilane compound having a hydrolyzable silyl group represented by the above-mentioned formula (1) with an alkoxy group of the other alkoxysilane compound.

[0065] Examples of the aminosilane include N-2-aminoethyl-3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-1-aminomethyltriethoxysilane, Nn-butyl-3-aminopropyltrimethoxysilane, etc. As the aminosilane, one of these may be used, or two or more may be used in combination.

[0066] Examples of the other alkoxysilane compounds include (a) methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and methyltriacetone. (b) silicate compounds such as tetramethyl orthosilicate (tetramethoxysilane or methyl silicate), tetraethyl orthosilicate (tetraethoxysilane or ethyl silicate), tetrapropyl orthosilicate, and tetrabutyl orthosilicate; (c) 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxysilane), (d) Epoxy group-containing silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; (e) vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and methacryloyloxymethyltrimethoxysilane; Examples of the other alkoxysilane compounds include mercapto group-containing silanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane; (f) isocyanurate silanes such as 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate; and (g) partial hydrolysis condensates thereof. As the other alkoxysilane compounds, one of these compounds may be used, or two or more of them may be used in combination.

[0067] Commercially available silane compounds (D) include, for example, X-40-2651 (manufactured by Shin-Etsu Chemical Co., Ltd.), MS3301 (manufactured by JNC Corporation), MS3302 (manufactured by JNC Corporation), Dynasylan 1146, Dynasylan VPS SIVO 260, and Dynasylan VPS SIVO 280 (manufactured by Evonik).

[0068] The amount of silane compound (D) is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of polymer (A). When the amount of silane compound (D) is 0.5 parts by weight or more, the water-resistant adhesion of the curable composition to concrete can be further improved. Furthermore, when the amount of silane compound (D) is 20 parts by weight or less, the mechanical properties of the cured product obtained from the curable composition can be improved.

[0069] <<Epoxysilane (E)>> The curable composition according to this embodiment may contain an epoxy silane (E). By including the epoxy silane (E), the water-resistant adhesion of the curable composition to concrete can be further improved, and a cured product with low water absorption can be obtained.

[0070] The epoxy silane (E) is not particularly limited as long as it is a silane coupling agent having an epoxy group, and specific examples thereof include γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, epoxy group-modified silicone resin, silyl group-modified epoxy resin, copolymers of epoxy resin and silicone resin, and the like.

[0071] Of these, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane are preferred.

[0072] Commercially available epoxy silanes (E) include γ-glycidoxypropylmethyldiethoxysilane (KBE402, manufactured by Shin-Etsu Chemical Co., Ltd.), γ-glycidoxypropyltrimethoxysilane (Dynasylan GLYMO, manufactured by Evonik), SH6040 (manufactured by Dow Corning Toray Co., Ltd.), SILQUESTA-187, and TSL8350 (all manufactured by Momentive Performance Materials Japan).

[0073] The amount of epoxy silane (E) to be added is not particularly limited, but is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of polymer (A).

[0074] <<Other additives>> The curable composition according to the present embodiment may contain additives other than the polymer (A), silica (B), silane compound (C), silane compound (D), and epoxy silane (E), such as a silanol condensation catalyst, a filler other than component (B), an adhesion promoter other than components (D) and (E), a plasticizer, an anti-sagging agent, an antioxidant, a light stabilizer, an ultraviolet absorber, a physical property adjuster, a tackifier resin, a photocurable substance, an oxygen-curable substance, an epoxy resin, or other resin. Furthermore, the curable composition according to this embodiment may contain various additives as needed to adjust the physical properties of the curable composition or the cured product, such as a surface property improver, a foaming agent, a curability regulator, a flame retardant, a silicate, a radical inhibitor, a metal deactivator, an antiozonant, a phosphorus-based peroxide decomposer, a lubricant, a pigment, and a mildew inhibitor.

[0075] <Silanol condensation catalyst> A silanol condensation catalyst may be blended into the curable composition for the purpose of accelerating the hydrolysis and condensation reaction of the hydrolyzable silyl groups of the polymer (A) and chain-extending or crosslinking the polymer.

[0076] Examples of silanol condensation catalysts include organotin compounds, metal carboxylates, amine compounds, carboxylic acids, and alkoxy metals.

[0077] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dioctyltin bis(acetylacetonate), dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin diketanoate, dioctyltin oxide, a reaction product of dibutyltin oxide with a silicate compound, a reaction product of dioctyltin oxide with a silicate compound, and a reaction product of dibutyltin oxide with a phthalate ester.

[0078] Specific examples of metal carboxylates include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, etc. The carboxylic acid group can be a combination of the following carboxylic acids with various metals.

[0079] Specific examples of the amine compound include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.

[0080] Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

[0081] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis(acetylacetonate) and diisopropoxytitanium bis(ethylacetoacetate), aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0082] Other silanol condensation catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0083] Two or more different silanol condensation catalysts may be used in combination.

[0084] The amount of the silanol condensation catalyst used is preferably from 0.001 to 20 parts by weight, more preferably from 0.01 to 15 parts by weight, and particularly preferably from 0.01 to 10 parts by weight, relative to 100 parts by weight of the polymer (A).

[0085] <Filler> The curable composition according to this embodiment may contain various fillers other than silica (B), such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber, and filament.

[0086] The amount of the filler used is preferably 1 to 300 parts by weight, particularly preferably 10 to 250 parts by weight, per 100 parts by weight of the polymer (A).

[0087] Organic or inorganic balloons may be added to reduce the weight (specific gravity) of the composition. Balloons are hollow spherical fillers, and examples of materials for the balloons include inorganic materials such as glass and shirasu, and organic materials such as phenolic resin, urea resin, polystyrene, and saran. The amount of balloons used is preferably 0.1 to 100 parts by weight, particularly preferably 1 to 20 parts by weight, per 100 parts by weight of polymer (A).

[0088] <Adhesion promoter> To the curable composition according to this embodiment, an adhesion promoter other than the silane compound (D) and the epoxy silane (E) can be added.

[0089] As the adhesion promoter, a silane coupling agent or a reaction product of a silane coupling agent can be added.

[0090] Specific examples of silane coupling agents include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; isocyanate group-containing silanes such as γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, α-isocyanatemethyltrimethoxysilane, and α-isocyanatemethyldimethoxymethylsilane; and mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane.

[0091] The adhesion promoters may be used alone or in combination of two or more kinds. Also, reaction products of various silane coupling agents may be used.

[0092] The amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A).

[0093] <Plasticizer> A plasticizer can be added to the curable composition according to this embodiment. Specific examples of the plasticizer include phthalate ester compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalate ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; and aliphatic polyhydric esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and acetyl tributyl citrate. Examples include carboxylic acid ester compounds; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkylsulfonic acid phenyl esters; phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oils; epoxidized soybean oil, epoxy benzyl stearate, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, epoxy butyl stearate and other epoxy plasticizers.

[0094] Furthermore, polymer plasticizers can be used. Specific examples of polymer plasticizers include vinyl polymers, polyester plasticizers, polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more, and polyethers such as derivatives in which the hydroxy groups of these polyether polyols are converted to ester groups, ether groups, etc., polystyrenes, polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, etc.

[0095] The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight, relative to 100 parts by weight of the polymer (A). The plasticizers may be used alone or in combination of two or more kinds.

[0096] <Anti-sagging agent> If necessary, an anti-sagging agent may be added to the curable composition according to this embodiment to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.

[0097] The amount of the anti-sagging agent used is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the polymer (A).

[0098] <Antioxidants> An antioxidant (antiaging agent) can be used in the curable composition according to this embodiment. The use of an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.

[0099] The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymer (A).

[0100] <Light stabilizer> A light stabilizer can be used in the curable composition according to this embodiment. The use of a light stabilizer can prevent photooxidative degradation of the cured product. Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, with hindered amine-based compounds being particularly preferred.

[0101] The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymer (A).

[0102] <UV absorber> An ultraviolet absorber can be used in the curable composition according to this embodiment. The use of an ultraviolet absorber can improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, and metal chelate-based compounds. Benzotriazole-based compounds are particularly preferred, and examples thereof include those commercially available under the names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (all manufactured by BASF).

[0103] The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymer (A).

[0104] <Physical property adjusters> The curable composition of the present invention may optionally contain a physical property modifier to adjust the tensile properties of the resulting cured product. The physical property modifier is not particularly limited, but examples include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, and trimethylmethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnishes; and polysiloxanes. The use of such a physical property modifier can increase the hardness of the curable composition of this embodiment upon curing, or, conversely, decrease the hardness and increase the elongation at break. The physical property modifiers may be used alone or in combination of two or more.

[0105] In particular, compounds that hydrolyze to form a compound having a monovalent silanol group in the molecule have the effect of reducing the modulus of the cured product without increasing the stickiness of the surface of the cured product. Compounds that form trimethylsilanol are particularly preferred. Examples of compounds that hydrolyze to form a compound having a monovalent silanol group in the molecule include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol and that form silane monools on hydrolysis. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

[0106] The amount of the physical property adjuster used is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, per 100 parts by weight of the polymer (A).

[0107] <Tackifying resin> In the present invention, a tackifying resin can be added for the purpose of improving adhesion or cohesion to a substrate or for other reasons. There are no particular limitations on the tackifying resin, and any commonly used resin can be used.

[0108] Specific examples include terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low-molecular-weight polystyrene resins, styrene copolymer resins, styrene block copolymers and hydrogenated products thereof, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These may be used alone or in combination of two or more.

[0109] The amount of the tackifier resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and even more preferably 5 to 30 parts by weight, relative to 100 parts by weight of the polymer (A).

[0110] <Photocurable substance> A photocurable material can be used in the curable composition according to this embodiment. When a photocurable material is used, a film of the photocurable material is formed on the surface of the cured product, improving the stickiness and weather resistance of the cured product. Many compounds of this type are known, including organic monomers, oligomers, resins, and compositions containing them. Representative examples include unsaturated acrylic compounds, such as monomers, oligomers, or mixtures thereof, having one or more acrylic or methacrylic unsaturated groups, polyvinyl cinnamates, and azido resins.

[0111] The photocurable substance is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer (A).

[0112] <Oxygen curing substance> An oxygen-curable substance can be used in the curable composition according to this embodiment. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air. Upon reacting with oxygen in the air, they form a cured film near the surface of the cured product, preventing surface stickiness and preventing the adhesion of dirt and dust to the surface of the cured product. Specific examples of oxygen-curable substances include drying oils such as tung oil and linseed oil, and various alkyd resins obtained by modifying these compounds; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and polymers of C5-C8 dienes obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. These substances may be used alone or in combination of two or more.

[0113] The amount of the oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A). As described in JP-A-3-160053, the oxygen-curable substance is preferably used in combination with a photo-curable substance.

[0114] <Epoxy resin> The curable composition according to this embodiment can be used in combination with an epoxy resin. Compositions containing an epoxy resin are particularly suitable as adhesives, especially adhesives for exterior wall tiles. Examples of epoxy resins include bisphenol A epoxy resins and novolac epoxy resins.

[0115] The ratio of these epoxy resins to the polymer (A) is preferably in the range of (A) / epoxy resin = 100 / 1 to 1 / 100 by weight. When the ratio of (A) / epoxy resin is 1 / 100 or more, the impact strength and toughness of the cured epoxy resin product are likely to be improved, and when the ratio of (A) / epoxy resin is 100 / 1 or less, the strength of the cured product can be improved.

[0116] When an epoxy resin is added, a curing agent for curing the epoxy resin can be used in combination with the curable composition according to this embodiment. There are no particular limitations on the epoxy resin curing agent that can be used, and any commonly used epoxy resin curing agent can be used.

[0117] When a curing agent for epoxy resin is used, the amount used is preferably in the range of 0.1 to 300 parts by weight per 100 parts by weight of the epoxy resin.

[0118] <<Preparation of Curable Composition>> The curable composition of the present invention can be prepared as a one-component composition in which all ingredients are mixed in advance and stored in a sealed container, and then cured by moisture in the air after application. Alternatively, it can be prepared as a two-component composition in which ingredients such as a curing catalyst, filler, plasticizer, and water are separately mixed as a curing agent, and the ingredients are mixed with the organic polymer composition before use. From the viewpoint of workability, the one-component composition is preferred.

[0119] When the curable composition is a one-component type, all of the components are blended in advance, and therefore it is preferable to dehydrate and dry the components containing water before use, or to dehydrate them by reducing the pressure during blending and kneading. In addition to the dehydration and drying method, the storage stability can be further improved by adding a dehydrating agent, particularly an alkoxysilane compound such as n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, or γ-glycidoxypropyltrimethoxysilane.

[0120] The amount of the dehydrating agent, particularly a silicon compound capable of reacting with water such as vinyltrimethoxysilane, used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A).

[0121] <<Application>> The curable composition according to this embodiment can be used as a sealant, adhesive, waterproof coating material, pressure-sensitive adhesive, paint, and mold release agent. It is particularly preferably used as a sealant, adhesive, or waterproof coating material, and more preferably as a waterproof coating material. It is particularly preferably used as a waterproof coating material for concrete. A waterproof coating material for concrete refers to a material for forming a coating film formed on the surface of concrete for waterproofing purposes. The curable composition according to this embodiment can be applied directly to the surface of concrete without applying a primer. [Example]

[0122] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0123] (number average molecular weight) The number average molecular weight in the examples is a GPC molecular weight measured under the following conditions. Liquid delivery system: Tosoh HLC-8220GPC Column: Tosoh TSKgel SuperH series Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0124] (Average number of silyl groups introduced) The average number of silyl groups introduced per terminal or per molecule of the polymers shown in the examples was calculated by NMR measurement.

[0125] (Synthesis Example 1) Using polyoxypropylene glycol with a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (P-1) with a number-average molecular weight of 27,500 and a molecular weight distribution (Mw / Mn) of 1.26, bearing hydroxyl groups at both ends. Subsequently, 1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution relative to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene (P-1). After removing the methanol by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether relative to the hydroxyl groups of the polymer (P-1) was added and the reaction was carried out at 130°C for 2 hours. Subsequently, 0.28 molar equivalent of sodium methoxide in methanol was added to remove the methanol, and 1.8 molar equivalents of allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. The resulting crude polyoxypropylene was mixed with n-hexane and water and stirred, then centrifuged to remove the water. The hexane was then devolatilized under reduced pressure from the resulting hexane solution to remove the metal salts from the polymer. This yielded polyoxypropylene (Q-1) with multiple terminal carbon-carbon unsaturated bonds. It was found that polymer (Q-1) had an average of 2.0 terminal carbon-carbon unsaturated bonds.

[0126] To 500 g of the resulting (Q-1), 50 μl of a platinum divinyldisiloxane complex solution (a 3 wt. % platinum equivalent isopropanol solution) was added, and 9.6 g of dimethoxymethylsilane was slowly added dropwise while stirring. The resulting mixture was reacted at 100°C for 2 hours, after which unreacted dimethoxymethylsilane was distilled off under reduced pressure to yield polyoxypropylene (A-1) with a number-average molecular weight of 28,200 and multiple dimethoxymethylsilyl groups at its terminals. It was found that polymer (A-1) contained an average of 1.7 dimethoxymethylsilyl groups at each terminal, with an average of 3.4 per molecule.

[0127] (Synthesis Example 2) Using polyoxypropylene glycol with a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (P-2) with a number-average molecular weight of 14,300 and a molecular weight distribution (Mw / Mn) of 1.21, bearing hydroxyl groups at both ends. To the resulting hydroxyl-terminated polyoxypropylene (P-2), 1.2 molar equivalents of sodium methoxide were added as a 28% methanol solution. After removing the methanol by vacuum devolatilization, an additional 1.5 molar equivalents of allyl chloride was added to the hydroxyl groups of the polymer (P-2) to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by vacuum devolatilization. The resulting crude polyoxypropylene was mixed and stirred with n-hexane and water, followed by centrifugation to remove the water. The resulting hexane solution was then devolatilized under reduced pressure to remove metal salts from the polymer. This resulted in the production of polyoxypropylene (Q-2) having allyl groups at the termini. 500 g of this polymer (Q-2) was mixed with 50 μl of a platinum divinyldisiloxane complex solution (a 3 wt. % platinum equivalent isopropanol solution), and 13.5 g of trimethoxysilane was slowly added dropwise while stirring. After reacting at 100°C for 2 hours, unreacted trimethoxysilane was removed under reduced pressure to produce polyoxypropylene (A-2) having trimethoxysilyl groups at the termini and a number-average molecular weight of 14,600. It was found that polymer (A-2) contained an average of 0.8 trimethoxysilyl groups at each terminus, with an average of 1.5 per molecule.

[0128] Example 1 A mixture of 100 parts by weight of the polymer (A-1) described in Synthesis Example 1, 75 parts by weight of DINP (diisononyl phthalate, manufactured by ExxonMobil), and Sibelite M3000 (median diameter (D50) 17 μm, specific surface area (BET adsorption method) 1.5 m) was used. 2 / g silica), 100 parts by weight, Imerseal 36S (Imerys: heavy calcium carbonate) 200 parts by weight, Eversorb HP1 (Everlight Chemical: light stabilizer) 1.7 parts by weight, Eversorb HP4 (Everlight Chemical: light stabilizer) 3 parts by weight, Irganox 245FF (BASF: bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]), 1 part by weight, Dynasylan VTMO (Evonik: vinyltrimethoxysilane), 3.2 parts by weight, Dynasylan 1146 (Evonik: diaminosilane-containing silane oligomer), 9 parts by weight, Dynasylan OCTMO (Evonik: trimethoxyoctylsilane), TIB KAT223 (TIB Four parts by weight of dioctyltin diketanoate (manufactured by MICRO CHEMICALS Co., Ltd.) was added and thoroughly mixed with a spatula, and then the mixture was uniformly mixed and degassed using a planetary mixer to obtain a curable composition. The water-resistant adhesion of the curable composition was evaluated and the water absorption rate was measured as described below. The results are shown in Table 1.

[0129] (Water-resistant adhesion evaluation) The resulting curable composition was applied to a concrete substrate (manufactured by ROCHOLL: conforming to ISO 13640 Method 1, 71 x 12 x 25 mm) and cured at 23°C and 50% relative humidity for 7 days, followed by immersion in water for 7 days. After removal from the water, a 90° hand peel test was performed on the cured product, and the adhesion was evaluated based on the cohesive failure rate at the adhesive interface (Water-Resistant Adhesion Evaluation 1). After removing from the water as described above, the sample was further cured at 23°C and 50% relative humidity for 3 days, and then a hand peel test was carried out in the same manner to evaluate the adhesiveness (Water-Resistant Adhesion Evaluation 2). The results are shown in Table 1. The evaluation criteria are as follows: A: Cohesive failure rate 80% or more B: Cohesive failure rate 50% or more but less than 80% C: Cohesive failure rate 5% or more but less than 50% D: 100% interface failure

[0130] (Water absorption rate) The resulting curable composition was used to create a 2 mm thick sheet, which was then cured at 23°C for 3 days and then at 50°C for 4 days. Two 5 x 5 cm samples were cut from the resulting sheet, their weights were measured, and they were then immersed in water at 23°C for 4 weeks. The samples were removed from the water, the surface moisture was removed with paper, and the weight was then measured to determine the water absorption [(weight of the sample after immersion in water - weight of the sample before immersion in water) / weight of the sample before immersion in water x 100], and the average water absorption of the two samples was calculated.

[0131] Example 2 The same evaluation as in Example 1 was carried out, except that the amount of Dynasylan OCTMO added was changed to 7 parts by weight and 2 parts by weight of Dynasylan GLYMO (manufactured by Evonik: 3-(2,3-epoxypropoxy)propyl)trimethoxysilane) was added. The results are shown in Table 1.

[0132] Example 3 The same evaluation as in Example 1 was carried out, except that polymer (A-2) described in Synthesis Example 2 was used instead of polymer (A-1), the amount of Dynasylan OCTMO added was changed to 7 parts by weight, the amount of TIB KAT223 added to 0.5 parts by weight, and 2 parts by weight of Dynasylan GLYMO was added. The results are shown in Table 1.

[0133] (Comparative Example 1) The same evaluation as in Example 2 was carried out except that Socal U1S2 (precipitated calcium carbonate manufactured by Imerys) was added instead of Sibelite M3000. The results are shown in Table 1.

[0134] (Comparative Example 2) The same evaluation as in Example 1 was carried out, except that Dynasylan 1146 was not added and the amount of Dynasylan GLYMO added was changed to 5.2 parts by weight. The results are shown in Table 1.

[0135] (Comparative Example 3) Except for not adding Dynasylan OCTMO, the same evaluation as in Example 1 was carried out. The results are shown in Table 1.

[0136] [Table 1]

[0137] Table 1 shows that Comparative Examples 1 to 3, which do not contain any one of silica (B), silane compound (C), and silane compound (D), all showed 100% interfacial failure in the water-resistant adhesion evaluation, whereas Examples 1 to 3, which contain all of silica (B), silane compound (C), and silane compound (D), showed cohesive failure and improved water-resistant adhesion. It can also be seen that Examples 1 to 3 have water absorption rates equivalent to or lower than Comparative Examples 1 to 3.

[0138] Example 4 To 100 parts by weight of the polymer (A-1) described in Synthesis Example 1, 75 parts by weight of DINP, 150 parts by weight of Sibelite M3000, 150 parts by weight of Imerseal 36S, 1.7 parts by weight of Eversorb HP-1, 3 parts by weight of Eversorb HP-4, 1 part by weight of Irganox 245FF, 5 parts by weight of Dynasylan VTMO, 5.2 parts by weight of Dynasylan 1146, 7 parts by weight of Dynasylan OCTMO, and 4 parts by weight of TIB KAT223 were added, thoroughly mixed with a spatula, and then uniformly mixed and degassed using a planetary mixer to obtain a curable composition. The obtained curable composition was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0139] Example 5 The same evaluation as in Example 4 was carried out, except that the amount of Dynasylan 1146 added was changed to 3.2 parts by weight and the amount of Dynasylan OCTMO added was changed to 9 parts by weight. The results are shown in Table 2.

[0140] Comparative Example 4 The same evaluation as in Example 4 was carried out except that Dynasylan 1146 was changed to Dynasylan DAMO (manufactured by Evonik: N-(3-(trimethoxysilyl)propylethylenediamine)). The results are shown in Table 2.

[0141] (Comparative Example 5) The same evaluation as in Example 5 was carried out except that Dynasylan DAMO was used instead of Dynasylan 1146. The results are shown in Table 2.

[0142] [Table 2]

[0143] Table 2 shows that Comparative Examples 4 and 5, in which silane compound (D) was replaced with aminosilane, showed 100% interfacial failure in the water-resistant adhesion evaluation, whereas Examples 4 and 5, which contained silica (B), silane compound (C), and silane compound (D), showed cohesive failure, indicating improved water-resistant adhesion. It can also be seen that Examples 4 and 5 had lower water absorption than Comparative Examples 4 and 5.

[0144] (Synthesis Example 3) To 500 g of (Q-1) obtained in Synthesis Example 1, 50 μl of a platinum divinyldisiloxane complex solution (a 3 wt. % platinum equivalent isopropanol solution) was added, and 9.5 g of trimethoxysilane was slowly added dropwise while stirring. The resulting mixture was reacted at 100°C for 2 hours, after which unreacted trimethoxysilane was distilled off under reduced pressure to obtain polyoxypropylene (A-3) with a number-average molecular weight of 28,000 and multiple trimethoxysilyl groups at its terminals. It was found that polymer (A-3) contained an average of 1.7 trimethoxysilyl groups at each terminal, with an average of 3.4 per molecule.

[0145] (Synthesis Example 4) To the hydroxyl-terminated polyoxypropylene (P-2) obtained in Synthesis Example 2, 1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution relative to the hydroxyl groups. After removing the methanol by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added relative to the hydroxyl groups of the polymer (P-2) and the reaction was carried out at 130°C for 2 hours. Subsequently, 0.28 molar equivalent of a methanol solution of sodium methoxide was added to remove the methanol, and 1.8 molar equivalents of allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. The resulting crude polyoxypropylene was mixed and stirred with n-hexane and water, after which the water was removed by centrifugation. The hexane was then devolatilized under reduced pressure from the resulting hexane solution to remove metal salts from the polymer. This process yielded polyoxypropylene (Q-3) having multiple terminal carbon-carbon unsaturated bonds. It was found that polymer (Q-3) had an average of 2.0 carbon-carbon unsaturated bonds introduced into each terminal.

[0146] To 500 g of the resulting (Q-3), 50 μl of a platinum divinyldisiloxane complex solution (a 3 wt. % platinum equivalent isopropanol solution) was added, and 18.2 g of dimethoxymethylsilane was slowly added dropwise while stirring. The resulting mixture was reacted at 100°C for 2 hours, after which unreacted dimethoxymethylsilane was distilled off under reduced pressure to yield polyoxypropylene (A-4) with a number-average molecular weight of 14,500 and multiple dimethoxymethylsilyl groups at its terminals. Polymer (A-4) was found to have an average of 1.6 dimethoxymethylsilyl groups at each terminal, with an average of 3.2 per molecule.

[0147] Example 6 To 100 parts by weight of the polymer (A-3) described in Synthesis Example 3, 75 parts by weight of DINP, 100 parts by weight of Sibelite M3000, 200 parts by weight of Imerseal 36S, 1.7 parts by weight of Tinuvin 770 (manufactured by BASF: light stabilizer), 3 parts by weight of Tinuvin 326 (manufactured by BASF: light stabilizer), 1 part by weight of Irganox245FF, 5 parts by weight of Dynasylan VTMO, 3.2 parts by weight of Dynasylan 1146, 7 parts by weight of Dynasylan OCTMO, 2 parts by weight of Dynasylan GLYMO, 0.4 parts by weight of TIB KAT223 were added, and then thoroughly mixed with a spatula, and then uniformly mixed and degassed using a planetary mixer to obtain a curable composition. Using the obtained curable composition, the water-resistant adhesion evaluation was carried out in the same manner as in Example 1. The water absorption of the curable composition was measured as described below, and the results are shown in Table 3.

[0148] (Water absorption rate) The resulting curable composition was used to create a 2 mm thick sheet, which was then cured at 23°C for 3 days and then at 50°C for 4 days. Two 5 x 5 cm samples were cut from the resulting sheet, their weights were measured, and they were then immersed in water at 50°C for 4 days. The samples were removed from the water, the surface moisture was removed with paper, and the weight was then measured to determine the water absorption [(weight of the sample after immersion in water - weight of the sample before immersion in water) / weight of the sample before immersion in water x 100], and the average water absorption of the two samples was calculated.

[0149] (Comparative Example 6) The same evaluation as in Example 6 was carried out except that Dynasylan OCTMO and Dynasylan GLYMO were not added. The results are shown in Table 3.

[0150] (Comparative Example 7) The same evaluation as in Example 6 was carried out, except that Dynasylan OCTMO and Dynasylan GLYMO were not added and the amount of TIB KAT223 added was changed to 4 parts by weight. The results are shown in Table 3.

[0151] [Table 3]

[0152] Table 3 shows that compared to Comparative Examples 6 and 7, which do not contain silane compound (C), Example 6, which contains all of silica (B), silane compound (C), and silane compound (D), has improved water-resistant adhesion and a lower water absorption rate than Comparative Example 6.

[0153] (Synthesis Example 5) Using polyoxypropylene triol with a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain terminal hydroxyl-containing polyoxypropylene (P-3) with a number-average molecular weight of 24,600 and a molecular weight distribution (Mw / Mn) of 1.31. To the resulting hydroxyl-terminated polyoxypropylene (P-3), 1.2 molar equivalents of sodium methoxide were added as a 28% methanol solution. After removing the methanol by vacuum devolatilization, 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene to convert the terminal hydroxyl groups to allyl groups. The resulting crude polyoxypropylene was mixed and stirred with n-hexane and water, after which the water was removed by centrifugation. The metal salts in the polymer were removed by vacuum devolatilization of the hexane from the resulting hexane solution. This yielded terminal allyl-containing polyoxypropylene (Q-4). To 500 g of this polymer (Q-4), 50 μl of a platinum divinyldisiloxane complex solution (3 wt % platinum equivalent isopropanol solution) was added, and 6.9 g of trimethoxysilane was slowly added dropwise while stirring. The resulting mixture was reacted at 90°C for 2 hours, after which unreacted trimethoxysilane was distilled off under reduced pressure to obtain polyoxypropylene (A-5) with trimethoxysilyl groups and a number-average molecular weight of 26,200. Polymer (A-5) was found to have an average of 0.7 trimethoxysilyl groups at each end and an average of 2.1 trimethoxysilyl groups per molecule.

[0154] (Synthesis Example 6) Using polyoxypropylene triol with a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain terminal hydroxyl-containing polyoxypropylene (P-4) with a number-average molecular weight of 16,400 and a molecular weight distribution (Mw / Mn) of 1.31. To the resulting hydroxyl-terminated polyoxypropylene (P-4), 1.2 molar equivalents of sodium methoxide were added as a 28% methanol solution. After removing the methanol by vacuum devolatilization, an additional 1.5 molar equivalents of allyl chloride was added to the hydroxyl groups of the polymer (P-4) to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was then removed by vacuum devolatilization. The resulting crude polyoxypropylene was mixed and stirred with n-hexane and water, followed by centrifugation to remove the water. The resulting hexane solution was then devolatilized under reduced pressure to remove metal salts from the polymer. This resulted in the production of polyoxypropylene (Q-5) with allyl groups at the termini. 500 g of this polymer (Q-5) was mixed with 50 μl of a platinum divinyldisiloxane complex solution (a 3 wt. % platinum equivalent isopropanol solution), and 10.9 g of trimethoxysilane was slowly added dropwise while stirring. After reacting at 100°C for 2 hours, unreacted trimethoxysilane was removed under reduced pressure to yield polyoxypropylene (A-6) with a number-average molecular weight of approximately 16,400 and trimethoxysilyl groups at the termini. Polymer (A-6) was found to contain an average of 0.7 trimethoxysilyl groups at each terminus, with an average of 2.2 per molecule.

[0155] (Synthesis Example 7) To the hydroxyl-terminated polyoxypropylene (P-1) obtained in Synthesis Example 1, 1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution relative to the hydroxyl groups. After distilling off the methanol by vacuum devolatilization, 1.79 molar equivalent of allyl chloride relative to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene was added to convert the terminal hydroxyl groups to allyl groups. The resulting crude polyoxypropylene was mixed and stirred with n-hexane and water, then the water was removed by centrifugation. The hexane was then devolatilized under reduced pressure from the resulting hexane solution to remove metal salts from the polymer. This yielded polyoxypropylene (Q-6) having allyl groups at its termini. 50 μl of a platinum divinyldisiloxane complex solution (a 3 wt. % isopropanol solution calculated as platinum) was added to 500 g of this polymer (Q-6), and 5.4 g of trimethoxysilane was slowly added dropwise with stirring. The mixture was reacted at 90°C for 2 hours, and then unreacted trimethoxysilane was removed by distillation under reduced pressure to obtain polyoxypropylene (A-7) having trimethoxysilyl groups and a number-average molecular weight of 28,500. It was found that polymer (A-7) had an average of 0.8 trimethoxysilyl groups at each end and an average of 1.6 trimethoxysilyl groups per molecule.

[0156] Examples 7 to 9 To 100 parts by weight of the polymer shown in Table 4, 75 parts by weight of DINP, 100 parts by weight of Sibelite M3000, 200 parts by weight of Imerseal 36S, 1.7 parts by weight of Tinuvin 770 (BASF: light stabilizer), 3 parts by weight of Tinuvin 326 (BASF: light stabilizer), 1 part by weight of Irganox 245FF, 5 parts by weight of Dynasylan VTMO, 3.2 parts by weight of Dynasylan 1146, 7 parts by weight of Dynasylan OCTMO, 2 parts by weight of Dynasylan GLYMO, and 0.5 parts by weight of TIB KAT223 were added, thoroughly mixed with a spatula, and then uniformly mixed and degassed using a planetary mixer to obtain a curable composition. The obtained curable composition was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0157] [Table 4]

[0158] Table 4 shows that Examples 7 to 9, which contain all of silica (B), silane compound (C), and silane compound (D), have good water-resistant adhesion and low water absorption.

Claims

1. 100 parts by weight of hydrolyzable silyl group-containing polyoxyalkylene polymer (A), Silica (B) 10 to 300 parts by weight, 5 to 12 parts by weight of a silane compound (C) containing an alkyl group having 4 or more carbon atoms, and A curable composition for a waterproof coating material for concrete, comprising 1 to 10 parts by weight of a compound (D) obtained by partially condensing a silyl group of an aminosilane alone or an aminosilane with another alkoxysilane compound.

2. The curable composition according to claim 1 , further comprising an epoxy silane (E).

3. The curable composition according to claim 1 or 2, wherein the silane compound (C) containing an alkyl group having 4 or more carbon atoms is a silane compound containing an alkyl group having 7 or more carbon atoms.

4. The hydrolyzable silyl group of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) is represented by the general formula (1): -Si(R １ ) ３－ａ (X) ａ (1) (In the formula, R １ each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent consisting of a heteroatom-containing group or a halogen atom; each X independently represents a hydroxyl group or a hydrolyzable group; and a represents 1, 2, or 3. The curable composition according to any one of claims 1 to 3, wherein

5. The curable composition according to claim 4, wherein a is 3.

6. The curable composition according to any one of claims 1 to 5, wherein the aminosilane has a hydrolyzable silyl group.

7. The curable composition according to any one of claims 1 to 6, wherein the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) has a number average molecular weight of 3,000 to 50,000.

8. A cured product which is a waterproof coating film formed on the surface of concrete, obtained by curing the curable composition according to any one of claims 1 to 7.

9. A waterproof coating material for concrete, comprising the curable composition according to any one of claims 1 to 7.

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