Two-component curable composition and its use

Abstract

The present invention provides a two-component curable composition that yields a cured product with improved tear strength. [Solution] The two-component curable composition according to the present disclosure comprises a polyoxyalkylene polymer (A) having a specific reactive silicon group, an epoxy resin curing agent (B), and a (meth)acrylic acid ester copolymer (C), wherein the epoxy resin curing agent (B) and the (meth)acrylic acid ester copolymer (C) are contained in separate solutions, and the (meth)acrylic acid ester copolymer (C) comprises structural units derived from a (meth)acrylic acid ester monomer having a glycidyl structure and a (meth)acrylic acid ester monomer having a hydroxyl structure.

Description

[Technical Field]

[0001] The present invention relates to a two-component curable composition and a waterproofing material using the same. The present invention also relates to a method for manufacturing a waterproofing structure using a two-component curable composition. [Background technology]

[0002] Coating waterproofing is a waterproofing method that involves applying a solution or emulsion of synthetic rubber or synthetic resin, consisting of one or more components, to the substrate of a building to form a continuous waterproof layer of a predetermined thickness. As described in JIS A 6021, various materials are used in coating waterproofing, including urethane rubber, acrylic rubber, chloroprene rubber, rubber asphalt, FRP, and silicone rubber.

[0003] Incidentally, it is known that organic polymers containing reactive silicon groups can be crosslinked at room temperature through the formation of siloxane bonds accompanied by hydrolysis reactions of the reactive silicon groups due to moisture, etc., resulting in a rubbery cured product.

[0004] The use of a curable composition containing an organic polymer containing reactive silicon groups as a waterproof coating material has been investigated, for example, in Patent Document 1. Patent Document 1 discloses a curable composition for use in waterproofing methods, which contains an organic polymer (A) having silicon-containing groups, an epoxy resin (B), and an epoxy resin curing agent (C). Patent Document 1 also discloses that the main chain of the organic polymer (A) can be selected from oxyalkylene polymers and (meth)acrylic acid ester polymers, etc. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2014-227427 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, the prior art as described above had room for further improvement in terms of tear strength. One aspect of the present invention aims to realize a two-component curable composition capable of obtaining a cured product with improved tear strength.

Means for Solving the Problems

[0007] In order to solve the above problems, the two-component curable composition according to one aspect of the present invention is -Si(R) 3-a (X) a (1) (In the formula, R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a represents 2 or 3.) It contains a polyoxyalkylene polymer (A) having a reactive silicon group represented by, an epoxy resin curing agent (B), and a (meth)acrylate copolymer (C), and the epoxy resin curing agent (B) and the (meth)acrylate copolymer (C) are contained in separate solutions from each other. It is a two-component curable composition, and the (meth)acrylate copolymer (C) contains structural units derived from a (meth)acrylate monomer having a glycidyl structure and a (meth)acrylate monomer having a hydroxy structure.

Effects of the Invention

[0008] According to one aspect of the present invention, it is possible to provide a two-component curable composition capable of obtaining a cured product with improved tear strength.

Embodiments for Carrying Out the Invention

[0009] One embodiment of the present invention will be described in detail below. Note that (meth)acrylic acid represents acrylic acid and / or methacrylic acid. All the documents described in this specification are incorporated herein by reference.

[0010] 〔1. Two-component curable composition〕 A multi-component curable composition according to one embodiment of the present invention comprises a polyoxyalkylene polymer (A) having a reactive silicon group represented by general formula (1), an epoxy resin curing agent (B), and a (meth)acrylic acid ester copolymer (C), wherein the epoxy resin curing agent (B) and the (meth)acrylic acid ester copolymer (C) are contained in separate solutions, and the (meth)acrylic acid ester copolymer (C) comprises structural units derived from a (meth)acrylic acid ester monomer having a glycidyl structure and a (meth)acrylic acid ester monomer having a hydroxyl structure. In this specification, the solution containing the epoxy resin curing agent (B) is also referred to as the first agent, and the solution containing the (meth)acrylic acid ester copolymer (C) is also referred to as the second agent.

[0011] The inventors' independent research revealed that simply combining a polyoxyalkylene polymer (A) having reactive silicon groups with a conventional (meth)acrylic acid ester copolymer as a waterproof coating material left room for improvement in tear strength. For example, there was room for improvement from the viewpoint of making the waterproof coating material a walkable coating film. As a result of diligent research to solve the above problems, the inventors found that tear strength could be improved by using a (meth)acrylic acid ester copolymer (C) containing structural units derived from a (meth)acrylic acid ester monomer having a glycidyl structure and a (meth)acrylic acid ester monomer having a hydroxyl structure as the second agent.

[0012] Furthermore, it was found that the multi-component curable composition according to one embodiment of the present invention provides tackiness and weather resistance equivalent to or better than conventional compositions.

[0013] While inexpensive two-component urethane products (containing residual isocyanate) are commonly used in waterproof coating materials, according to one embodiment of the present invention, it is possible to provide a two-component curable composition that can provide a cured product with the above-mentioned advantages without using highly toxic isocyanate. This can contribute to achieving Sustainable Development Goals (SDGs) such as Goal 12 "Ensure sustainable consumption and production patterns" and Goal 11 "Make cities and human settlements inclusive, safe, resilient and inclusive, safe

[0014] Hereinafter, the polyoxyalkylene polymer having reactive silicon groups (A) will also be referred to as component (A), the epoxy resin curing agent (B) as component (B), and the (meth)acrylic acid ester copolymer (C) as component (C).

[0015] (1-1. Polyoxyalkylene polymer having reactive silicon groups (A)) The polyoxyalkylene polymer (A) has a reactive silicon group represented by general formula (1). -Si(R) 3-a (X) a (1) In the formula, R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a represents 2 or 3.

[0016] The hydrocarbon group R preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. Specific examples of R include methyl, ethyl, chloromethyl, methoxymethyl, and N,N-diethylaminomethyl groups, with methyl, ethyl, chloromethyl, and methoxymethyl groups being preferred, and methyl and methoxymethyl groups being more preferred. This configuration makes it easier to achieve both storage stability and reactivity.

[0017] Examples of X include hydroxyl groups, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. Among these, alkoxy groups such as methoxy and ethoxy groups are more preferred due to their mild hydrolysis and ease of handling, with methoxy and ethoxy groups being particularly preferred. From the viewpoint of room-temperature reactivity, a in general formula (1) is preferably 2 or 3, and more preferably 2.

[0018] The reactive silicon groups of component (A) include, but are not limited to, trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl, triacetoxysilyl, methyldimethoxysilyl, methyldiethoxysilyl, ethyldimethoxysilyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, and (N,N-diethylaminomethyl)diethoxysilyl. Among these, methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, (chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, and (N,N-diethylaminomethyl)dimethoxysilyl groups are preferred because they exhibit high activity and yield cured products with good mechanical properties. Since a highly rigid cured product can be obtained, a trimethoxysilyl group and a triethoxysilyl group are more preferred, and a trimethoxysilyl group is even more preferred.

[0019] Component (A) may have more than one reactive silicon group on average at one terminal site. Having more than one reactive silicon group on average at one terminal site means that component (A) contains a polyoxyalkylene having two or more reactive silicon groups at one terminal site as represented by the following general formula (4). That is, component (A) may contain only a polyoxyalkylene having two or more reactive silicon groups at one terminal site, or may contain both a polyoxyalkylene having two or more reactive silicon groups at one terminal site and a polyoxyalkylene having one reactive silicon group at one terminal site. Also, as the plurality of terminal sites of one molecule of polyoxyalkylene, there may be both a terminal site having two or more reactive silicon groups and a terminal site having one reactive silicon group. Furthermore, component (A) may contain a polyoxyalkylene that has, as a whole, more than one reactive silicon group on average at one terminal site but has a terminal site without a reactive silicon group.

[0020] The terminal site of component (A) is preferably represented by the general formula (4):

[0021] [Chemical formula]

[0022] (In formula (4), R 7 , R 9 are each independently a divalent linking group having 1 to 6 carbon atoms which may contain a hetero atom. R 8 , R 10 are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer from 1 to 10. R 11 are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X is each independently a hydroxyl group or a hydrolyzable group. c is an integer from 1 to 3.) R 7 、R 9This may be a divalent organic group having 1 to 6 carbon atoms, which may contain an oxygen atom, or it may be a hydrocarbon group. The hydrocarbon group preferably has 1 to 4 carbon atoms, more preferably 1 to 3, and even more preferably 1 or 2. 7 Specific examples include CH2OCH2, CH2O, and CH2, with CH2OCH2 being preferred. 9 Specific examples include CH2 and CH2CH2, with CH2 being preferred.

[0023] R 8 , R 10 The number of carbon atoms in the hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2. 8 , R 10 Specific examples include hydrogen atoms, methyl groups, and ethyl groups, preferably hydrogen atoms and methyl groups, and more preferably hydrogen atoms.

[0024] The terminal portion represented by general formula (4) is, in a particularly preferred embodiment, R 7 is CH2OCH2, and R 9 CH2 is, R 8 and R 10 Each of these is a hydrogen atom. n is preferably an integer from 1 to 5, more preferably an integer from 1 to 3, and even more preferably 1 or 2. However, n is not limited to a single value, and may be a mixture of multiple values.

[0025] The reactive silicon groups in component (A) preferably number more than 1.0 on average at each terminal site, more preferably 1.1 or more, even more preferably 1.5 or more, and even more preferably 2.0 or more. Furthermore, the number of reactive silicon groups in each terminal site preferably number 5.0 or less on average, and more preferably 3.0 or less.

[0026] The number of terminal sites containing more than one reactive silicon group in one molecule of component (A) is preferably 0.5 or more on average, more preferably 1.0 or more, even more preferably 1.1 or more, and even more preferably 1.5 or more. Furthermore, the number of such terminal sites is preferably 4.0 or less on average, and more preferably 3.0 or less.

[0027] Component (A) may have reactive silicon groups in locations other than the terminal portion, but it is preferable to have them only in the terminal portion, as this makes it easier to obtain a rubbery cured product with high elongation and low elastic modulus.

[0028] The average number of reactive silicon groups per molecule of component (A) is preferably more than 1.0, more preferably 1.2 or more, even more preferably 1.3 or more, even more preferably 1.5 or more, and particularly preferably 1.7 or more. Furthermore, the average number of reactive silicon groups per molecule is preferably 6.0 or less, more preferably 5.5 or less, and even more preferably 5.0 or less. If the average number of reactive silicon groups per molecule is more than 1.0, a high-strength cured product is more likely to be obtained. If the average number of reactive silicon groups per molecule is 6.0 or less, a cured product with high elongation is more likely to be obtained.

[0029] <Main chain structure> There are no particular restrictions on the main chain skeleton of component (A), and examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer. Among these, polyoxypropylene is preferred.

[0030] The number-average molecular weight of component (A) is 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000, in terms of polystyrene-based molecular weight in GPC. A number-average molecular weight of 3,000 or more is preferable in terms of manufacturing cost because it prevents the amount of reactive silicon groups introduced from becoming too large. A number-average molecular weight of 100,000 or less is preferable in terms of workability because it prevents the viscosity from becoming too high.

[0031] The molecular weight of component (A) can also be expressed as the end-group-reduced molecular weight, which is determined by directly measuring the end-group concentration of the organic polymer precursor before the introduction of reactive silicon groups using 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 considering the structure of the organic polymer (degree of branching determined by the polymerization initiator used). Alternatively, the end-group-reduced molecular weight of component (A) can be determined by creating a calibration curve between the number-average molecular weight obtained by general GPC measurement of the organic polymer precursor and the above-mentioned end-group-reduced molecular weight, and then converting the number-average molecular weight obtained by GPC of component (A) to the end-group-reduced molecular weight.

[0032] The molecular weight distribution (Mw / Mn) of component (A) is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.2 or less. The molecular weight distribution of component (A) can be determined from the number-average molecular weight and weight-average molecular weight obtained by GPC measurement.

[0033] Furthermore, the main chain structure of component (A) may be linear or branched. In one embodiment of the present invention, component (A) preferably includes the following (i) and / or (ii): (i) A branched polyoxyalkylene polymer (A) having alkoxy group terminators (preferably dialkoxy group terminators); (ii) A linear polyoxyalkylene polymer (A) having alkoxy group termini (preferably dialkoxy group termini).

[0034] In (i) above, the average number of reactive silicon groups per molecule of component (A) is preferably more than 2.0, and more preferably 2.1 or more. Also, in (ii) above, the average number of reactive silicon groups per molecule of component (A) is preferably 1.7 or more, more preferably 1.8 or more, and even more preferably 1.9 or more.

[0035] An example of component (A) as described in (i) above is the polyoxyalkylene polymer (A-1) described in the Examples. Furthermore, an example of component (A) as described in (ii) above is the polyoxyalkylene polymer (A-3) described in the Examples.

[0036] In 100% by weight of component (A), component (A), which has a linear main chain structure and alkoxy group termini, is preferably present in an amount of 75% to 95% by weight, and more preferably in an amount of 80% to 90% by weight. This further improves the tear strength.

[0037] In one embodiment of the present invention, component (A) may further include (iii): (iii) A polyoxyalkylene polymer (A) having a linear chain with a reactive silicon group at only one end and an alkoxy group end (preferably a dialkoxy group end).

[0038] In (iii) above, the average number of reactive silicon groups per molecule of component (A) is preferably 0.4 or more, more preferably 0.5 or more, even more preferably 0.6 or more, and particularly preferably 0.7 or more. An example of a polyoxyalkylene polymer (A) as described in (iii) above is the polyoxyalkylene polymer (A-2) described in the examples.

[0039] The molecular weight (Mn) of the branched and alkoxy-terminated component (A) is not particularly limited, but is preferably large, preferably 10,000 or more, more preferably 15,000 or more, and even more preferably 17,000 or more. The weight ratio of the branched and alkoxy-terminated component (A) to the total component (A) is, for example, 2% to 40%, preferably 5% to 35%, more preferably 7% to 30%, and even more preferably 10% to 25%.

[0040] As component (A), commercially available products can also be used. Examples of such products include "KANEKA MS POLYMER (registered trademark)" and "KANEKA SILYL (registered trademark)" from Kaneka Corporation; "EXCESTAR (registered trademark)" from AGC Inc.; "GENIOSIL (registered trademark) STP-E" from Wacker Inc. (e.g., "STP-E10", "STP-E30", "STP-E15", "STP-E35"); and "Risun STP" from Risun Inc. (e.g., "FS-S16", "FS-16").

[0041] Component (A) may be included not only in the first agent but also in the second agent. If component (C) is solid at room temperature, and liquid component (A) is included in the second agent, then component (C) can be dissolved in component (A).

[0042] <Method for synthesizing polyoxyalkylene polymer (A)> Next, the method for synthesizing component (A) will be described. The introduction of reactive silicon groups into the main chain of component (A) can be carried out by known methods. For example, the following methods can be used.

[0043] Method I: An organic polymer having a functional group such as a hydroxyl group is reacted with a compound having an active group that is reactive to this functional group and an unsaturated group to obtain an organic polymer having an unsaturated group. Then, the obtained organic polymer having an unsaturated group is reacted with a hydrosilane compound having a reactive silicon group by hydrosilylation.

[0044] Method II: A compound having a mercapto group and a reactive silicon group is introduced into the unsaturated group site of an organic polymer having an unsaturated group, obtained in the same manner as in Method I, by a radical addition reaction in the presence of a radical initiator and / or a radical source.

[0045] Method III: An organic polymer having functional groups such as hydroxyl groups, epoxy groups, and isocyanate groups in its molecule is reacted with a compound having functional groups that are reactive to these functional groups and a reactive silicon group.

[0046] Methods for synthesizing component (A) are disclosed, for example, in Japanese Patent Publication No. 45-36319, Japanese Patent Publication No. 46-12154, Japanese Unexamined Patent Publication No. 50-156599, Japanese Unexamined Patent Publication No. 54-6096, Japanese Unexamined Patent Publication No. 55-13767, Japanese Unexamined Patent Publication No. 55-13468, Japanese Unexamined Patent Publication No. 57-164123, Japanese Unexamined Patent Publication No. 3-2450, U.S. Patent No. 3632557, U.S. Patent No. 4345053, U.S. Patent No. 4366307, U.S. Patent No. 4960844, etc. Furthermore, polyoxyalkylene polymers having a number average molecular weight of 6,000 or more, a molecular weight distribution (Mw / Mn) of 1.6 or less or 1.3 or less, and a narrow molecular weight distribution, as proposed in Japanese Patent Publication Nos. 61-197631, 61-215622, 61-215623, 61-218632, 3-72527, 3-47825, and 8-231707, are also preferred. Such polyoxyalkylene polymers having a number average molecular weight of 6,000 or more, and a molecular weight distribution (Mw / Mn) of 1.6 or less or 1.3 or less, and having a high molecular weight and a narrow molecular weight distribution, are also preferred. Such polyoxyalkylene polymers having a number average molecular weight of 6,000 or more, and a molecular weight distribution (Mw / Mn) of 1.6 or less, and having a reactive silicon group are also preferred.

[0047] A polyoxyalkylene polymer (A) having an average of more than 1.0 reactive silicon groups at one terminal site is preferably obtained by introducing two or more carbon-carbon unsaturated bonds to one terminal of a hydroxyl-terminated polymer obtained by polymerization, and then reacting it with a reactive silicon group-containing compound that reacts with carbon-carbon unsaturated bonds. A method for synthesizing such a polyoxyalkylene polymer (A) having an average of more than 1.0 reactive silicon groups at one terminal site is disclosed, for example, in International Publication No. 2023 / 068083.

[0048] (1-2. Epoxy resin hardener (B)) The epoxy resin curing agent (B) is preferably an epoxy resin curing agent represented by the following general formula (2):

[0049] [ka]

[0050] (In formula (2), Z is hydrogen, an N-containing alkyl group represented by the following general formula (3), or a linear or branched alkyl group having 2 or more carbon atoms, R 1 From R 4 Y and Y' are each independently linear or branched alkyl groups, and Y and Y' are each independently linear or branched alkylene groups.

[0051] [ka]

[0052] (In formula (3), X 2 R is a linear or branched alkylene group, 5 and R 6 Each of these is independently a linear or branched alkyl group. This configuration allows for improved tackiness of the cured product.

[0053] In formula (2), R 1 From R 4Each of these is independently a linear or branched alkyl group. 1 From R 4 The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. 1 From R 4 The alkyl group may be linear or branched, but it is preferably linear.

[0054] In formula (2), Y and Y' are each independently a linear or branched alkylene group. The number of carbon atoms in the alkylene groups Y and Y' is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5. The alkylene groups Y and Y' may be linear or branched, but linear is preferred.

[0055] R 5 and R 6 The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. 5 and R 6 The alkyl group may be linear or branched, but linear is preferred. When Z is a linear or branched alkyl group having 2 or more carbon atoms, the number of carbon atoms in the alkyl group is, for example, 2 to 10, preferably 1 to 5, and more preferably 1 to 3. The alkyl group may be linear or branched, but linear is preferred.

[0056] In formula (3), X 2 Each of these is independently a linear or branched alkylene group. 2 The number of carbon atoms in the alkylene group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5. 2 The alkylene group may be linear or branched, but linear is preferred.

[0057] Each alkyl group and each alkylene group of component (B) may be independently substituted with any substituent. Examples of such substituents include ethyl, propyl, ethylene, and propylene.

[0058] In one embodiment of the present invention, component (B) is a hydrogen atom or an N-containing alkyl group represented by general formula (3), and X 2 Y and Y' are linear alkylene groups with 3 carbon atoms, R 1 From R 6 It is preferable that the group is a methyl group.

[0059] Examples of component (B) include tris(3-(dimethylamino)propyl)amine ("JEFFADD® MW-760" manufactured by Huntsman Japan Co., Ltd.) and tetramethyliminobispropylamine ("JEFFCAT Z-130" manufactured by Huntsman Japan Co., Ltd.).

[0060] In 100% by weight of the two-component curable composition, component (B) is preferably present in an amount of 0.5% to 10% by weight, but may also be present in an amount of 1% to 10% by weight, or 1% to 5% by weight. This allows the composition to cure without the separation of component (C).

[0061] The aforementioned two-component curable composition may contain epoxy resin curing agents other than component (B) represented by general formula (2). By including epoxy resin curing agents other than component (B) represented by general formula (2) in addition to component (B) represented by general formula (2), rapid curing of the epoxy resin is achieved.

[0062] Other epoxy resin curing agents besides component (B) shown in general formula (2) are not particularly limited, but include, for example, N,N-diethyl-1,3-propanediamine (DEAPA) ("Reagent N,N-diethyl-1,3-propanediamine" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), a mixture of tris-2,4,6-(dimethylaminomethyl)phenol and bis(dimethylaminomethyl)phenol ("ANCAMINE® K54" manufactured by Evonik Japan Co., Ltd.), pentamethyldipropylenetriamine ("JEFFADD® MW-740" manufactured by Huntsman Japan Co., Ltd.), and 1-(bis(3-(dimethylamino)propyl)amino)-2-propanol ("JEFFADD®" manufactured by Huntsman Japan Co., Ltd.) Examples include MW-750), 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) (C3070 manufactured by Koei Chemical Co., Ltd.), a mixture of dimethylamino(methyl)phenol and phenol (ANCAMINE® 1110 manufactured by Evonik Japan Co., Ltd.), N,N,N,N-tetramethyl-1,6-hexanediaminodiamine (TOYOCAT-MR manufactured by Tosoh Corporation), hexahydro-1,3,5-tris(3-dimethylaminopropyl)-1,3,5-triazine (TOYOCAT-TRC manufactured by Tosoh Corporation), etc. From the viewpoint of low odor and low cost, N,N-diethyl-1,3-propanediamine (DEAPA) is preferred.

[0063] The content of epoxy resin curing agents other than component (B) represented by general formula (2) is preferably, for example, 0 to 7.0 parts by weight, more preferably 0 to 5.0 parts by weight, even more preferably 0 to 4.0 parts by weight, and particularly preferably 0 to 3.0 parts by weight, based on 100 parts by weight of the total of components (A) and (C).

[0064] (1-3. (meth)acrylic acid ester copolymer (C)) The (meth)acrylic acid ester copolymer (C) contains structural units derived from a (meth)acrylic acid ester monomer having a glycidyl structure. These structural units are included in the main chain of component (C). Specific examples of (meth)acrylic acid ester monomers having a glycidyl structure include, but are not limited to, glycidyl (meth)acrylate and 4-hydroxybutyl acrylate glycidyl ether.

[0065] The (meth)acrylic acid ester copolymer (C) further comprises structural units derived from a (meth)acrylic acid ester monomer having a hydroxyl structure. In this specification, "having a hydroxyl structure" means having a structure containing a hydroxyl group. This makes it possible to provide a multi-component curable composition that yields a cured product with further improved tear strength. The structural units are included in the main chain of component (C). In this specification, a (meth)acrylic acid ester monomer having a hydroxyl structure means a (meth)acrylic acid ester monomer that does not have a glycidyl structure or a benzotriazole structure and has a hydroxyl structure.

[0066] Specific examples of (meth)acrylic acid ester monomers having a hydroxyl structure include, but are not limited to, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0067] The (meth)acrylic acid ester copolymer (C) preferably further contains structural units derived from a (meth)acrylic acid ester monomer having a hindered amine structure and / or a (meth)acrylic acid ester monomer having a benzotriazole structure. This makes it possible to provide a two-component curable composition that yields a cured product with improved weather resistance. The structural units are included in the main chain of component (C).

[0068] Examples of (meth)acrylic acid ester monomers having a hindered amine structure include compounds represented by the following general formula (5).

[0069] [ka]

[0070] (In formula (5), R 14 R is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. 15 R is a hydrogen atom or a cyano group. 16 R is a hydrogen atom or an alkyl group having 1 or 2 carbon atoms. 17 Y is a hydrogen atom or an alkyl group having 1 or 2 carbon atoms. 2 (This indicates an oxygen atom or an imino group.) Specific examples of (meth)acrylic acid ester monomers having a hindered amine structure include, but are not limited to, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidyl methacrylate, 2,2,6,6-tetramethyl-4-iminopiperidyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, and 4-cyano-1,2,2,6,6-pentamethyl-4-piperidyl methacrylate.

[0071] Examples of (meth)acrylic acid ester monomers having a benzotriazole structure include compounds represented by the following general formula (6).

[0072] [ka]

[0073] (In formula (6), R 18 R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 19 R is an alkylene group having 1 to 6 carbon atoms. 20 X is a hydrogen atom or a methyl group. 3 (This indicates a hydrogen atom or a halogen atom.) Specific examples of (meth)acrylic acid ester monomers having a benzotriazole structure include, but are not limited to, 2-(2'-hydroxy-5'-(meth)acryloyloxyethylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-(meth)acryloyloxyethylphenyl)-5-chloro-2H-benzotriazole, 2-(2'-hydroxy-5'-(meth)acryloyloxypropylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-(meth)acryloyloxypropylphenyl)-5-chloro-2H-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-(meth)acryloyloxyethylphenyl)-2H-benzotriazole, and 2-(2'-hydroxy-3'-tert-butyl-5'-(meth)acryloyloxyethylphenyl)-5-chloro-2H-benzotriazole.

[0074] The component (C) more preferably contains structural units derived from a (meth)acrylic acid ester monomer having a glycidyl structure, a (meth)acrylic acid ester monomer having a hindered amine structure, and a (meth)acrylic acid ester monomer having a hydroxyl structure.

[0075] The (meth)acrylic acid ester copolymer (C) preferably contains 2% to 60% by weight, more preferably 5% to 50% by weight, and even more preferably 10% to 40% by weight of structural units derived from a (meth)acrylic acid ester monomer having a glycidyl structure in component (C). If the content of structural units derived from a (meth)acrylic acid ester monomer having a glycidyl structure in component (C) is 2% by weight or more, the improvement effect on tensile properties, tear strength, and tackiness is further enhanced. If the content of structural units derived from a (meth)acrylic acid ester monomer having a glycidyl structure in component (C) is 60% by weight or less, the storage stability of component (C) is further enhanced.

[0076] The component (C) preferably contains 1% to 40% by weight, more preferably 5% to 30% by weight, and even more preferably 10% to 20% by weight, structural units derived from (meth)acrylic acid ester monomers having a hydroxyl structure in component (C). If the content of structural units derived from (meth)acrylic acid ester monomers having a hydroxyl structure in component (C) is 1% by weight or more, the tear strength improvement effect is further enhanced. If the content of structural units derived from (meth)acrylic acid ester monomers having a hydroxyl structure in component (C) is 40% by weight or less, the storage stability of component (C) is further enhanced.

[0077] The aforementioned component (C) preferably contains 0.5% to 10% by weight of structural units derived from (meth)acrylic acid ester monomers having a hindered amine structure, more preferably 1% to 5% by weight, and even more preferably 2% to 5% by weight. If the content of structural units derived from (meth)acrylic acid ester monomers having a hindered amine structure in component (C) is 0.5% by weight or more, the weather resistance improvement effect is further enhanced. If the content of structural units derived from (meth)acrylic acid ester monomers having a hindered amine structure in component (C) is 10% by weight or less, the storage stability of component (C) is further enhanced.

[0078] The component (C) preferably contains 0.5% to 10% by weight of structural units derived from a (meth)acrylic acid ester monomer having a benzotriazole structure, more preferably 1% to 5% by weight, and even more preferably 2% to 5% by weight. If the content of structural units derived from a (meth)acrylic acid ester monomer having a benzotriazole structure in component (C) is 0.5% by weight or more, the weather resistance improvement effect is further enhanced. If the content of structural units derived from a (meth)acrylic acid ester monomer having a benzotriazole structure in component (C) is 10% by weight or less, the storage stability of component (C) is further enhanced.

[0079] The other monomers constituting the main chain of component (C) are not particularly limited, and various (meth)acrylic acid monomers can be used. In this specification, (meth)acrylic acid monomers mean a general term for (meth)acrylic acid, (meth)acrylic acid ester monomers, and other monomers having a structure derived from (meth)acrylic acid.

[0080] Specifically, (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, and 3-methoxyethyl (meth)acrylate. Examples include silbutyl, stearyl (meth)acrylate, isobornyl (meth)acrylate, ethylene oxide adducts of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, trifluoromethyl (meth)acrylate, bis(trifluoromethyl)methyl (meth)acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate.

[0081] Other usable (meth)acrylic acid monomers include, for example, (meth)acrylic acids such as acrylic acid and methacrylic acid; monomers containing an amide group such as N-methylolacrylamide and N-methylolmethacrylamide; and monomers containing a nitrogen group such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate.

[0082] As component (C), a polymer obtained by copolymerizing a (meth)acrylic acid monomer with a vinyl monomer copolymerizable therewith may also be used. The vinyl monomer is not particularly limited and includes, for example, styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and its salts; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, oc Examples include maleimide monomers such as cylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenyl monomers such as ethylene and propylene; conjugated diene monomers such as butadiene and isoprene; and vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. Multiple of these can be used as copolymerization components.

[0083] Component (C) may have a reactive silicon group represented by general formula (1) as described in component (A). In component (C), a in general formula (1) is preferably 2 or 3, and more preferably 2, from the viewpoint of room temperature reactivity. The method for introducing the reactive silicon group into component (C) is not particularly limited, and for example, the following method can be used. Method (iv): A compound having a polymerizable unsaturated group and a reactive silicon group is copolymerized with the monomer described above. Using this method, the reactive silicon group tends to be randomly introduced into the main chain of the polymer. Method (v): A mercaptosilane compound having a reactive silicon group is used as a chain transfer agent to polymerize a (meth)acrylic acid ester polymer. This method allows the reactive silicon group to be introduced to the polymer ends. Method (vi): A compound having a polymerizable unsaturated group and a reactive functional group (V group) is copolymerized, and then reacted with a compound having a reactive silicon group and a functional group that reacts with the V group. Specifically, examples include copolymerizing 2-hydroxyethyl acrylate and then reacting it with an isocyanate silane having a reactive silicon group, or copolymerizing glycidyl acrylate and then reacting it with an aminosilane compound having a reactive silicon group. Method (vii): The terminal functional groups of (meth)acrylic acid ester polymers synthesized by living radical polymerization are modified to introduce reactive silicon groups. (meth)acrylic acid ester polymers obtained by living radical polymerization readily accept the introduction of functional groups at the polymer ends, and by modifying them, reactive silicon groups can be introduced at the polymer ends.

[0084] For example, compounds having a polymerizable unsaturated group and a reactive silicon group used in method (iv) include (meth)acrylate 3-(trimethoxysilyl)propyl, (meth)acrylate 3-(triethoxysilyl)propyl, (meth)acrylate 3-(methyldimethoxysilyl)propyl, (meth)acrylate 2-(trimethoxysilyl)ethyl, (meth)acrylate 2-(methyldimethoxysilyl)ethyl, (meth)acrylate (trimethoxysilyl)methyl, (meth)acrylate (triethoxysilyl)methyl, (meth)acrylate (methyldimethoxysilyl)methyl, and (meth)acrylate 3-((methoxymethyl)dimethoxysilyl)propyl. From the viewpoint of availability, (meth)acrylate 3-(methyldimethoxysilyl)propyl and (meth)acrylate 3-(trimethoxysilyl)propyl are particularly preferred.

[0085] The number-average molecular weight of component (C) is not particularly limited, but is preferably 500 to 50,000, more preferably 500 to 30,000, and particularly preferably 1,000 to 10,000, based on polystyrene-equivalent molecular weight measured by GPC.

[0086] The glass transition temperature of component (C) is not particularly limited, but is preferably 50°C or higher, more preferably 60°C or higher, even more preferably 80°C or higher, and particularly preferably 100°C or higher. If the glass transition temperature of component (C), which is an acrylic resin, is within the above range, the surface tackiness and stain resistance will be improved when the curable composition is used as a coating film. The upper limit of the glass transition temperature is not particularly limited, but from the viewpoint of handling, for example, 180°C or lower is preferred.

[0087] In the aforementioned two-component curable composition, the content of component (C) is preferably 5% to 60% by weight, and more preferably 30% to 50% by weight, of the total 100% by weight of the liquid components (A) and (C), from the viewpoint of achieving manageable viscosity and high concentration. Alternatively, if the aforementioned two-component curable composition contains a liquid component (F) described later, the content of component (C) is preferably 5% to 60% by weight, and more preferably 30% to 50% by weight, of the total 100% by weight of the liquid components (F) and (C).

[0088] (1-4. Aminosilane (D)) The two-component curable composition preferably further contains aminosilane (D). The inclusion of aminosilane (D) in the two-component curable composition makes it easier to achieve both improved tear strength of the cured product and reduced costs. Hereinafter, aminosilane (D) will also be referred to as component (D).

[0089] Examples of component (D) include 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane. These may be used individually or in combination of two or more. Commercially available products such as Silkquest A-1120 (manufactured by Momentive Performance Materials Japan LLC), Silkquest A-1110 (manufactured by Momentive Performance Materials Japan LLC), KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd.), KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KBM-903 (manufactured by Shin-Etsu Chemical Co., Ltd.) may also be used.

[0090] In 100% by weight of the two-component curable composition, component (D) is preferably present in an amount of 1% to 5% by weight, and more preferably in an amount of 1% to 3% by weight. Within the above range of component (D) content, it is easier to achieve both improved tear strength of the cured product and reduced costs. Component (D) is preferably contained in a separate solution from component (C), specifically in the first agent.

[0091] (1-5. Hydroxyl group-containing polyoxyalkylene polymer (F)) The two-component curable composition preferably further contains a hydroxyl group-containing polyoxyalkylene polymer (F). In the two-component curable composition, the hydroxyl group-containing polyoxyalkylene polymer (F) functions as a plasticizer. By including the hydroxyl group-containing polyoxyalkylene polymer (F) in the two-component curable composition, it is possible to reduce the viscosity and cost of the composition, as well as adjust the properties such as hardness and elastic modulus of the cured product obtained from the composition. Hereinafter, the hydroxyl group-containing polyoxyalkylene polymer (F) will also be referred to as component (F).

[0092] Component (F) may be included in the first agent, in the second agent, or in both the first and second agents. Since component (F) is used as a plasticizer for component (A), it is preferable that it does not contain any groups that can be crosslinked at room temperature, such as the reactive silicon groups present in component (A). If component (C) is solid at room temperature, and liquid component (F) is included in the second agent, component (C) can be dissolved in component (F).

[0093] The main chain of component (F) preferably has 60% or more, more preferably 80% or more, of the monomer units constituting the main chain having repeating units represented by general formula (8): -R f -O- (8) (In formula (8), R f (Although it is a divalent hydrocarbon group, it is most preferable when the majority of it is an alkylene group having 3 or 4 carbon atoms.) R fSpecific examples include -CH(CH3)CH2-, -CH(C2H5)CH2-, -C(CH3)2CH2-, -CH2CH2CH2CH2-, etc. The molecular chain of component (F) may consist of only one type of repeating unit, or it may consist of two or more types of repeating units. f -CH(CH3)CH2- is particularly preferred.

[0094] Component (F) is not particularly limited, but specific examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer. Among these, polyoxypropylene is preferred from the viewpoint of suppressing bleeding that occurs over time.

[0095] Since component (F) acts as a plasticizer for component (A), its number-average molecular weight must be smaller than that of component (A). The number-average molecular weight of component (F) is preferably 300 or more, more preferably 800 or more, and even more preferably 1,000 or more. The upper limit is preferably 15,000 or less, more preferably 10,000 or less, even more preferably 8,000 or less, and particularly preferably 5,000 or less. When the number-average molecular weight of component (F) is 300 or more, it has the effect of being less volatile. Also, when the number-average molecular weight of component (F) is 15,000 or less, it has the effect of making the two-component curable composition easier to reduce viscosity. The number-average molecular weight of component (F) is the molecular weight corresponding to the number-average molecular weight obtained by end-group analysis.

[0096] A smaller molecular weight distribution of component (F) is preferable, as it results in lower viscosity. For example, the molecular weight distribution of component (F) should be such that Mw / Mn is 1.6 or less, preferably 1.5 or less. The molecular weight distribution (Mw / Mn) of component (F) is measured using GPC (polystyrene equivalent).

[0097] The content of component (F) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and even more preferably 20 parts by weight or more, based on 100 parts by weight of the total of components (A) and (C). The upper limit is preferably 150 parts by weight or less, more preferably 100 parts by weight or less, and even more preferably 50 parts by weight or less. When the content of component (F) is 5 parts by weight or more, its effect as a plasticizer can be fully exhibited. Furthermore, when the content of component (F) is 150 parts by weight or less, an appropriate mechanical strength can be obtained in the cured product. Note that component (F) can also be blended during polymer production.

[0098] Component (F) may be produced by a conventional polymerization method using caustic alkali, but it may also be produced by a polymerization method using a complex metal cyanide complex such as zinc hexacyanocobaltate as a catalyst.

[0099] (1-6. Inorganic fillers) The aforementioned two-component curable composition preferably further contains an inorganic filler. Since the inorganic filler is an inexpensive material, it enables cost reduction.

[0100] The inorganic fillers are not particularly limited, but examples include calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, diatomaceous earth, calcined clay, clay, talc, barite, anhydrous gypsum, titanium dioxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc oxide, mica, zinc oxide, lead white, lithopone, zinc sulfide, shirasu balloons, glass microballoons, etc. Among these, calcium carbonate is preferred from the viewpoint of being less expensive, a smaller particle size is preferred from the viewpoint of tensile properties, and heavy calcium carbonate without surface treatment is preferred from the viewpoint of suppressing deterioration of physical properties after water resistance testing. Titanium dioxide is also preferred from the viewpoint of weather resistance, and rutile-type titanium dioxide is more preferred. These inorganic fillers may be used individually or in combination of two or more types.

[0101] The inorganic filler content is preferably 20 to 300 parts by weight, more preferably 20 to 250 parts by weight, even more preferably 25 to 200 parts by weight, particularly preferably 30 to 180 parts by weight, and especially preferably 28 to 200 parts by weight, based on 100 parts by weight of the total of components (A) and (C). If the inorganic filler content is within the above range, it is easier to achieve both low viscosity and low cost for the two-component curable composition.

[0102] The inorganic filler may be included in the first agent, in the second agent, or in both the first and second agents.

[0103] (1-7.Curing catalyst) The two-component curable composition preferably further contains a curing catalyst. The curing catalyst is not particularly limited, as long as it can be used as a condensation catalyst; any catalyst may be used.

[0104] Examples of curing catalysts include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin dimethyl malate, dibutyltin diethyl malate, dibutyltin dibutyl malate, dibutyltin diisooctyl malate, dibutyltin ditridecyl malate, dibutyltin dibenzyl malate, dibutyltin maleate, dioctyl tin diacetate, dioctyl tin distearate, dioctyl tin dilaurate, dioctyl tin diethyl malate, and dioctyl tin dilaurate. Dialkyltin dicarboxylates such as dibutyltin diisooctylmalate; dialkyltin alkoxides such as dibutyltin dimethoxide and dibutyltin diphenoxide; intramolecular coordinating derivatives of dialkyltin such as dibutyltin diacetylacetonate and dibutyltin diethylacetoacetate; reaction products of dialkyltin oxides such as dibutyltin oxide and dioctyltin oxide with ester compounds such as dioctyl phthalate, diisodecyl phthalate, and methyl maleate; dialkyltin oxide, Tin compounds obtained by reacting rubonic acid and alcohol compounds; reaction products of dialkyltin oxides and silicate compounds, such as dibutyltin bistriethoxysilicate and dioctyltin bistriethoxysilicate; tetravalent tin compounds such as oxy derivatives (stanoxane compounds) of these dialkyltin compounds; divalent tin compounds such as tin octoate, tin naphthenate, tin stearate, and tin felzaticate, or reaction products and mixtures thereof with amine compounds such as laurylamine described later; monobutyltin Monoalkyltin compounds such as trisoctoate, monobutyltin triisopropoxide, and monooctyltin compounds; titanates such as tetrabutyl titanate, tetrapropyl titanate, tetra(2-ethylhexyl) titanate, and isopropoxytitanium bis(ethylacetoacetate); organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate;Metal salts of carboxylic acids (such as 2-ethylhexanoic acid, neodecanoic acid, versatic acid, oleic acid, naphthenic acid, etc.) such as bismuth carboxylate, iron carboxylate, titanium carboxylate, lead carboxylate, vanadium carboxylate, zirconium carboxylate, calcium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, cerium carboxylate, nickel carboxylate, cobalt carboxylate, zinc carboxylate, and aluminum carboxylate, or reaction products and mixtures of these with amine compounds such as laurylamine described below; chelate compounds such as zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, dibutoxyzirconium diacetylacetonate, zirconium acetylacetonate bis(ethylacetoacetate), and titanium tetraacetylacetonate; methylamine, ethylamine, propylamine, isopodium Aliphatic primary amines such as propylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, and cyclohexylamine; Aliphatic secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dioctylamine, di(2-ethylhexyl)amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, and butylstearylamine; Aliphatic tertiary amines such as triamylamine, trihexylamine, and trioctylamine; Aliphatic unsaturated amines such as triallylamine and oleylamine; Aromatic amines such as laurylaniline, stearylaniline, and triphenylamine;Other amines include monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo(5,4,0)undecene-7(DBU), and other amine compounds, or salts of these amine compounds with carboxylic acids, etc.; reaction products and mixtures of amine compounds such as laurylamine and organotin compounds such as tin octoate; low molecular weight polyamide resins obtained from excess polyamine and polybasic acid; excess polyamine and Reaction products with epoxy compounds include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane, N-(β-aminoethyl)aminopropyltriethoxysilane, N-(β-aminoethyl)aminopropylmethyldiethoxysilane, N-(β-aminoethyl)aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, and the like. Furthermore, silanol condensation catalysts such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and other silane coupling agents having amino groups, which are modified derivatives of these;Furthermore, examples include known silanol condensation catalysts such as fatty acids like ferruzatic acids, acidic catalysts such as organic acidic phosphate ester compounds, and basic catalysts. These curing catalysts may be used individually or in combination of two or more. Dioctyl tin is particularly preferred. Note that ferruzatic acid is a mixture of neodecanoic acid and decanoic acid having a t-butyl group.

[0105] The content of the curing catalyst is preferably, for example, 0.1 parts by weight or more and 5 parts by weight or less, more preferably 0.2 parts by weight or more and 4 parts by weight or less, and even more preferably 0.3 parts by weight or more and 3 parts by weight or less, based on 100 parts by weight of the total of components (A) and (C). If the content of the curing catalyst is within the above range, it is easier to achieve both curability and cost reduction.

[0106] (1-8. Dehydrating agent) The two-component curable composition preferably further contains a dehydrating agent. The inclusion of a dehydrating agent provides excellent storage stability to the two-component curable composition.

[0107] The dehydrating agent is not particularly limited, but examples include vinylsilane, tosyl isocyanate, vinyltrimethoxysilane, calcium oxide, zeolite, p-toluenesulfonyl isocyanate, and 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine. In particular, vinylsilane is preferred as a dehydrating agent because it offers an excellent balance of cost and performance. These dehydrating agents may be used individually or in combination of two or more.

[0108] The amount of dehydrating agent is preferably 0.1 parts by weight or more and 10 parts by weight or less, more preferably 0.3 parts by weight or more and 3.0 parts by weight or less, and even more preferably 0.5 parts by weight or more and 2.0 parts by weight or less, per 100 parts by weight of the total of components (A) and (C). If the amount of dehydrating agent is 0.1 parts by weight or more per 100 parts by weight of the total of components (A) and (C), it is possible to prevent excessive reaction of component (A), which reacts in the presence of water. Furthermore, if the amount of dehydrating agent is 3.0 parts by weight or less per 100 parts by weight of the total of components (A) and (C), it is easier to achieve both storage stability and cost reduction.

[0109] (1-9. Other ingredients) In addition to the above, the two-component curable composition may also contain additives such as fillers, adhesion promoters, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, tackifying resins, low molecular weight plasticizers, and other resins. Furthermore, various additives may be added to the two-component curable composition as needed for the purpose of adjusting the physical properties of the curable composition or cured product. Examples of such additives include solvents, diluents, photocurable substances, oxygen-curable substances, surface modifiers, silicates, curing modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, antifungal agents, flame retardants, and foaming agents.

[0110] <Filler> Various fillers other than inorganic fillers can be added to the two-component curable composition. Examples of fillers include PVC powder and PMMA powder. The amount of filler used is preferably 0.5 parts by weight or more and 100 parts by weight or less, and more preferably 1 part by weight or more and 60 parts by weight or less, per 100 parts by weight of the total of components (A) and (C). Organic balloons may be added for the purpose of reducing the weight (specific gravity) of the two-component curable composition.

[0111] <Adhesion-enhancing agent> Adhesion-imparting agents may be added to the aforementioned two-component curable composition. Examples of adhesion-imparting agents include silane coupling agents and their reaction products.

[0112] 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; γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, and γ-I Examples include isocyanate group-containing silanes such as socyanate-propylmethyldimethoxysilane, α-isocyanate-methyltrimethoxysilane, and α-isocyanate-methyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; and epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0113] The above adhesion-improving agents may be used individually or in mixture of two or more types. Reaction products of various silane coupling agents can also be used. The amount of silane coupling agent used is preferably 0.1 parts by weight to 20 parts by weight, and particularly preferably 0.5 parts by weight to 10 parts by weight, per 100 parts by weight of the total of components (A) and (C).

[0114] <Drip-preventing agent> The two-component curable composition may contain, if necessary, an anti-sagging agent to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, but examples include silica, 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 individually or in combination of two or more. The amount of anti-sagging agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of the total of components (A) and (C).

[0115] <Antioxidant> An antioxidant (anti-aging agent) may be used in the aforementioned two-component curable composition. Using an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenol, monophenol, bisphenol, and polyphenol compounds. Specific examples of antioxidants are also described in Japanese Patent Publication No. 4-283259 and Japanese Patent Publication No. 9-194731. The amount of antioxidant used is preferably 0.1 parts by weight or more and 10 parts by weight or less, and particularly preferably 0.2 parts by weight or more and 5 parts by weight or less, per 100 parts by weight of the total of components (A) and (C).

[0116] <Light stabilizer> A light stabilizer may be used in the aforementioned two-component curable composition. Using a light stabilizer can prevent photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazole, hindered amine, and benzoate compounds, but hindered amine compounds are particularly preferred. The amount of light stabilizer used is preferably 0.1 parts by weight to 10 parts by weight, and particularly preferably 0.2 parts by weight to 5 parts by weight, per 100 parts by weight of the total of components (A) and (C).

[0117] <UV absorber> A UV absorber can be used in the aforementioned two-component curable composition. Using a UV absorber can improve the surface weather resistance of the cured product. Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, but benzotriazole-based compounds are particularly preferred, including Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (all manufactured by BASF). The amount of UV absorber used is preferably 0.1 parts by weight or more and 10 parts by weight or less, and particularly preferably 0.2 parts by weight or more and 5 parts by weight or less, per 100 parts by weight of the total of components (A) and (C).

[0118] <Adhesive-granting resin> The aforementioned two-component curable composition may contain a tackifying resin to enhance adhesion and bonding to the substrate, or as needed. There are no particular restrictions on the tackifying resin used; commonly used resins can be used.

[0119] Specific examples include terpene resins, aromatically 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 their hydrogenated products, 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 individually or in combination of two or more.

[0120] The amount of tackifying resin used is preferably 2 parts by weight or more and 100 parts by weight or less, more preferably 5 parts by weight or more and 50 parts by weight or less, and even more preferably 5 parts by weight or more and 30 parts by weight or less, based on 100 parts by weight of the total of components (A) and (C).

[0121] <Low molecular weight plasticizer> A low molecular weight plasticizer can be added to the aforementioned two-component curable composition. Specifically, preferred low molecular weight plasticizers include diisonoyl phthalate, 2-ethoxyethanol, bis(2-ethylhexyl) phthalate, and diisodecyl phthalate. These low molecular weight plasticizers may be used individually or in combination of two or more. If component (C) is solid at room temperature, a liquid low molecular weight plasticizer can be dissolved in the low molecular weight plasticizer if it is contained in the second agent.

[0122] The content of the low molecular weight plasticizer in the two-component curable composition is not particularly limited, but is preferably, for example, 5 to 150 parts by weight, more preferably 20 to 100 parts by weight, and even more preferably 30 to 80 parts by weight, based on 100 parts by weight of the total of components (A) and (C). With this configuration, it is easy to achieve both low viscosity in the two-component curable composition and high tear strength in the cured product.

[0123] (1-10.Applications) The aforementioned two-component curable composition can be used in a variety of applications, including waterproofing materials, building elastic sealing materials, siding board sealing materials, double-glazed glass sealing materials, vehicle sealing materials, and other building and industrial sealing materials; electrical and electronic component materials such as back-surface sealants for solar cells; electrical insulating materials such as insulating coatings for wires and cables; adhesives, elastic adhesives, contact adhesives, tile adhesives, reactive hot-melt adhesives, structural adhesives, heat dissipation adhesives; paints, powder coatings, coating materials, foams, sealing materials such as can lids, heat dissipation sheets, electrical and electronic potting agents, films, gaskets, marine deck caulking, casting materials, various molding materials, artificial marble, and sealing materials for rust prevention and waterproofing of wired glass or laminated glass edges (cut sections); vibration isolation, vibration damping, sound insulation, and seismic isolation materials used in automobiles, ships, home appliances, etc.; and liquid sealing materials used in automobile parts, electrical components, and various machine parts.

[0124] [2. Cured product] A cured product according to one embodiment of the present invention is formed by curing the above-described two-component curable composition. That is, the cured product is formed by curing the above-described two-component curable composition. In one embodiment of the present invention, the cured product is formed by curing the above-described two-component curable composition at room temperature without heating.

[0125] The tensile elongation of the cured product is preferably 200% or more, more preferably 300% or more, even more preferably 350% or more, and particularly preferably 400% or more. A tensile elongation of 300% or more of the cured product provides the effect of being resistant to tearing. The greater the tensile elongation of the cured product, the better, and there is no particular upper limit, but for example, it is 900% or less. The tensile elongation of the cured product can be measured by the method described in the examples below.

[0126] The tensile strength of the cured product is preferably 1.8 MPa or higher, more preferably 1.9 MPa or higher, even more preferably 2.0 MPa or higher, and particularly preferably 2.5 MPa or higher. A tensile strength of 1.8 MPa or higher provides the effect of being resistant to tearing. A higher tensile strength of the cured product is preferable, and there is no particular upper limit, but for example, it is 10 MPa or lower. The tensile strength of the cured product can be measured by the method described in the examples below.

[0127] The tear strength of the cured material is preferably 9 N / mm or more, more preferably 10 N / mm or more, even more preferably 11 N / mm or more, and particularly preferably 12 N / mm or more. A tear strength of 9 N / mm or more of the cured material provides the effect of being difficult to tear. A higher tear strength of the cured material is better, and there is no particular upper limit, but for example, it is 40 N / mm or less. The tear strength of the cured material can be measured by the method described in the examples below.

[0128] [3. Waterproof material] In one embodiment, the curable composition of the present invention can be used as a waterproofing material. Because this waterproofing material forms a seamless coating film and offers high reliability in waterproofing, it is particularly useful as a breathable coating waterproofing material for roofs that require high waterproofing performance. For example, in underground waterproofing materials such as underground parking lots where weather resistance is not required, it is cost-effective to use a two-component curable composition waterproofing material containing a (meth)acrylic acid ester copolymer (C) that does not contain structural units derived from (meth)acrylic acid ester monomers having a hindered amine structure and / or (meth)acrylic acid ester monomers having a benzotriazole structure. Furthermore, for waterproofing materials on outdoor ceilings, rooftops, verandas, water channels, garages, etc., it is preferable to use a two-component curable composition waterproofing material containing a (meth)acrylic acid ester copolymer (C) that contains structural units derived from (meth)acrylic acid ester monomers having a hindered amine structure and / or (meth)acrylic acid ester monomers having a benzotriazole structure.

[0129] Waterproofing materials can be used as both a waterproofing layer and a topcoat layer. The curable composition according to one embodiment of the present invention combines the performance of both a waterproofing layer and a topcoat layer. The waterproofing layer has the physical properties of the JIS A6021 urethane rubber high-elongation type standard, which has the longest track record, and the topcoat layer needs weather resistance to suppress deterioration due to sunlight and rainwater. However, with current technology, there is no material that can achieve both the JIS A6021 urethane rubber high-elongation type standard and weather resistance for the waterproofing layer, so a structure in which the waterproofing layer and topcoat layer are laminated is used.

[0130] In one embodiment of the present invention, the curable composition can be applied as a topcoat and laminated onto a conventionally known waterproof layer. That is, the curable composition according to one embodiment of the present invention has an application as a topcoat material. By laminating the curable composition as a topcoat on top of an inexpensive waterproof material or a waterproof material with excellent adhesion on the lower layer of the waterproof layer, a waterproof material with excellent cost-effectiveness or workability can be obtained.

[0131] Furthermore, in another embodiment of the curable composition of the present invention, it can also be used as a waterproofing layer. When the curable composition is used as a waterproofing layer, it has excellent weather resistance and other properties, so there is no need to laminate another topcoat layer. That is, the curable composition of the present invention may be a topcoat-free waterproof coating material in which no other layer is laminated on a waterproofing layer containing the above-described two-component curable composition. In this specification, "waterproof coating material" means that the above-described two-component curable composition has been applied to a substrate and cured. Also, "topcoat-free" means that no topcoat has been applied on the waterproof coating material. Furthermore, a waterproof coating material in which a topcoat-free waterproof coating layer containing the above-described two-component curable composition is laminated on a waterproof coating layer that does not contain the above-described two-component curable composition is also included in one embodiment of the present invention.

[0132] The aforementioned waterproofing material may contain, in addition to the cured product described above, any other components that waterproofing materials generally contain. Such components may be one type or two or more types. Furthermore, the content of such components is not particularly limited and can be appropriately determined by those skilled in the art as long as the effects of the present invention are achieved.

[0133] [4. Method for manufacturing waterproof structures] A method for manufacturing a waterproof structure according to one embodiment of the present invention includes the step of applying the above-described two-component curable composition to a building substrate. Since the two-component curable composition can provide a cured product with improved tackiness, the application process to the substrate can be carried out quickly. Furthermore, since the two-component curable composition can provide a cured product with excellent tensile properties and tear strength, applying the two-component curable composition to a building substrate can provide a waterproof structure with excellent waterproofing function.

[0134] The method for applying the two-component curable composition to the substrate of a building is not particularly limited, but examples include applying the two-component curable composition directly to the substrate of the building, or applying it after a primer has been applied to the substrate.

[0135] A method for manufacturing a waterproof structure according to one embodiment of the present invention involves not applying a topcoat to the coating film obtained by curing the above-mentioned two-component curable composition. By not applying a topcoat to the coating film obtained by curing the two-component curable composition, it is possible to shorten the construction period and reduce labor costs by eliminating the topcoat process. This makes it possible to obtain the above-mentioned topcoat-free coating waterproof material.

[0136] A method for manufacturing a waterproof structure according to one embodiment of the present invention involves applying a waterproof layer with a thickness of 1 to 4 mm, without applying the aforementioned topcoat on top of the waterproof layer. The waterproof layer may be the aforementioned topcoat-free coating waterproof material. In other words, the process involves forming a waterproof layer with a thickness of 1 to 4 mm, without laminating any other layer on top of the waterproof layer. Here, the waterproof layer is subjected to conditions of 63°C, 50% relative humidity, and 125 mW / cm² illuminance. 2 In a weathering test in which a cycle of holding the material for 1 hour and 58 minutes followed by spraying it with a shower of pure water for 2 minutes is repeated, the time until cracks are observed can exceed 1000 hours. By not applying a topcoat to such a waterproof layer, weather resistance, construction time reduction, and labor cost reduction can be improved. The specific method of the weathering test is described in the examples.

[0137] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0138] One embodiment of the present invention may include the following configuration: <1> General formula (1) -Si(R) 3-a (X) a (1) (In the formula, R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a indicates 2 or 3.) A two-component curable composition comprising a polyoxyalkylene polymer (A) having a reactive silicon group represented by , an epoxy resin curing agent (B), and a (meth)acrylic acid ester copolymer (C), wherein the epoxy resin curing agent (B) and the (meth)acrylic acid ester copolymer (C) are contained in separate solutions, and the (meth)acrylic acid ester copolymer (C) comprises structural units derived from a (meth)acrylic acid ester monomer having a glycidyl structure and a (meth)acrylic acid ester monomer having a hydroxyl structure. <2> The two-component curable composition contains 0.5% to 5% by weight of the epoxy resin curing agent (B) in 100% by weight. <1> The two-component curable composition described above. <3> The two-component curable composition contains 1% to 5% by weight of the epoxy resin curing agent (B) in 100% by weight. <1> The two-component curable composition described above. <4> The (meth)acrylic acid ester copolymer (C) further comprises structural units derived from a (meth)acrylic acid ester monomer having a hindered amine structure and / or a (meth)acrylic acid ester monomer having a benzotriazole structure. <1> from <3> A two-component curable composition as described in any one of the following. <5> <1> from <4> A topcoat-free waterproof coating material comprising a two-component curable composition described in any one of the above. <6> <1> from <4> A topcoat waterproof coating material comprising a two-component curable composition described in any one of the above. [Examples]

[0139] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0140] 〔material〕 The materials used in the examples and comparative examples are as follows:

[0141] <Polyoxyalkylene polymer (A)> Polyoxyalkylene polymers (A-1), (A-2), and (A-3) having reactive silicon groups, prepared based on the synthesis examples below, were used.

[0142] <Epoxy resin curing agent (B)> Tris(3-(dimethylamino)propyl)amine (JEFFADD® MW-760, manufactured by Huntsman Japan Co., Ltd.) N,N-diethyl-1,3-propanediamine (DEAPA) (Reagent N,N-diethyl-1,3-propanediamine manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) <(meth)acrylic acid ester copolymer (C)> (Meth)acrylic acid ester copolymers (C-1) to (C-7), prepared based on the synthesis example below, were used.

[0143] <Diluent> Solvent (EXXSOL D80 manufactured by Ando Parachemy Co., Ltd.) <Aminosilane (D)> N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Silquest A-1120, manufactured by Momentive Performance Materials Japan LLC) <Dehydrating agent> Vinylsilane (A-171, manufactured by Momentive Performance Materials Japan LLC) <Curing catalyst> Tin catalyst (NEOSTANN U-810 manufactured by Nitto Chemical Co., Ltd.) <Hydroxyalkylene polymer containing hydroxyl groups (F)> Polypropylene glycol resin ("Actcol 21-56K" manufactured by Mitsui Chemicals, Inc.) Polypropylene glycol resin ("Actcol P-23K" manufactured by Mitsui Chemicals, Inc.) Polypropylene glycol resin (Actcall D-1000 manufactured by Mitsui Chemicals, Inc.) <Inorganic filler> Calcium carbonate ("Nanox #30" manufactured by Maruo Calcium Co., Ltd.) Titanium dioxide ("Sulfuric acid-processed titanium dioxide (rutile type) R-820" manufactured by Ishihara Sangyo Co., Ltd.) Carbon black (Asahi Thermal, manufactured by Asahi Carbon Co., Ltd.) <Drip-preventing agent> Silica (AEROSIL® R974, manufactured by Evonik Industries, Ltd.) Amide wax (CRAYVALLAC® SL manufactured by Arkema Corporation) [Measurement and evaluation methods] Measurements and evaluations in the examples and comparative examples were performed using the following methods.

[0144] (Tensile properties) Tensile elongation and tensile strength tests were performed using a Shimadzu Autograph (AGS-J) at 23°C and 50% RH. The evaluation was conducted in accordance with JIS A 6021, high-elongation urethane type (formerly Class 1). Test specimens punched into a dumbbell shape to the size of JIS No. 3 were used. Tensile elongation and tensile strength tests were performed at 500 mm / min. In the examples, if the tensile strength was at least greater than that of the comparative example, it was evaluated as having superior tensile properties.

[0145] (Tear strength) Tear strength was measured using a Shimadzu Autograph (AGS-J) at 23°C and 50% RH. The evaluation was conducted in accordance with JIS A 6021, high-elongation urethane type (formerly Class 1). Test specimens were punched out using an angle-shaped dumbbell without cuts as specified in JIS K 6252.

[0146] (Tuck-type) Tackiness is an evaluation that determines whether it is possible to walk on the sheet in order to apply the next topcoat. Tackiness was evaluated according to the following criteria, and a rating of B or higher was considered to be at a walkable level. AA: When I put my weight on it and pressed my palm against the seat, it didn't feel sticky at all. A: When I press my palm against the sheet, it doesn't feel sticky at all. B: When you press your palm against the sheet, it feels slightly sticky (the sheet peels off when you move your hand upwards). C: When you press your palm against the sheet, it feels a little sticky (the sheet peels off after you lift your hand and wait a while). D: When you press your palm against the sheet, it becomes sticky (the sheet doesn't peel off even when you lift your hand).

[0147] (weather resistance) The sheet was installed on a Daipla Metal Weather CW-R8PL-A manufactured by Daipla Wintes Co., Ltd., and a weather resistance test was conducted under the following conditions: Illuminance: 125 mW / cm² 2 The black panel temperature was set to 63°C and the humidity to 50% RH. Irradiation alone was performed for 1 hour and 58 minutes, after which a shower of pure water was sprayed for 2 minutes while continuing irradiation. This constituted one cycle, and this cycle was repeated until cracks were observed. The presence or absence of cracks was checked every 70 hours. The time until cracks were observed was measured as the crack time.

[0148] [Synthesis Example 1] An example of the synthesis of polyoxyalkylene polymer (A-1) is shown below.

[0149] Using a 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 polyoxypropylene (P-1) with a number-average molecular weight of 24,600 (end-group equivalent molecular weight of 17,400) and a molecular weight distribution Mw / Mn = 1.31, with hydroxyl groups at the ends. 1.2 molar equivalents of sodium methoxide in a 28% methanol solution were added to the hydroxyl groups of the obtained polyoxypropylene (P-1). After removing methanol by vacuum defoliation, an additional 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of polyoxypropylene (P-1) to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by vacuum defoliation. The obtained unpurified polyoxypropylene was mixed with n-hexane and water and stirred. Water was removed by centrifugation, and the metal salts in the polymer were removed by vacuum defoliation of the hexane from the resulting hexane solution. From the above steps, polyoxypropylene (Q-1) having allyl groups at its termini was obtained. To 500 g of this polyoxypropylene (Q-1), 50 μL of platinum divinyldisiloxane complex solution (3% by weight isopropanol solution in terms of platinum) was added, and 6.4 g of methyldimethoxysilane was slowly added dropwise while stirring. After reacting at 100°C for 2 hours, the unreacted methyldimethoxysilane was removed by distillation under reduced pressure to obtain polyoxyalkylene polymer (A-1), a polyoxypropylene with a number average molecular weight of 26,200 and methyldimethoxysilyl groups at its termini. It was found that polyoxyalkylene polymer (A-1) has an average of 0.7 methyldimethoxysilyl groups at each termini and an average of 2.2 groups per molecule.

[0150] [Synthesis Example 2] The following shows an example of the synthesis of a polyoxyalkylene polymer (A-2).

[0151] Using butanol as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate-grime complex catalyst to obtain polyoxypropylene (P-2) with a number-average molecular weight of 7,800 (end-group equivalent molecular weight of 5,000) and a molecular weight distribution Mw / Mn = 1.48, with a hydroxyl group at one end. Subsequently, 1.2 molar equivalents of sodium methoxide in a 28% methanol solution were added to the hydroxyl groups of this polyoxypropylene (P-2). After removing methanol by vacuum defoliation, 2.0 molar equivalents of allyl chloride were added to the hydroxyl groups of polyoxypropylene (P-2) to convert the terminal hydroxyl groups to allyl groups, and the unreacted allyl chloride was removed by vacuum defoliation. The obtained unpurified polyoxypropylene was mixed with n-hexane and water and stirred, then the water was removed by centrifugation, and the metal salts in the polymer were removed by vacuum defoliation of the hexane from the resulting hexane solution. From the above steps, polyoxypropylene (Q-2) having an allyl group at only one end was obtained. To 500 g of the obtained polyoxypropylene (Q-2), 50 μL of platinum divinyldisiloxane complex (a 2-propanol solution with 3% by weight of platinum) was added, and 9.5 g of methyldimethoxysilane was slowly added dropwise while stirring. After reacting the mixed solution at 100°C for 2 hours, the unreacted methyldimethoxysilane was removed under reduced pressure to obtain polyoxyalkylene polymer (A-2), which is polyoxypropylene having a methyldimethoxysilyl group at only one end. It was found that polyoxyalkylene polymer (A-2) has an average of 0.8 methyldimethoxysilyl groups at only one end.

[0152] [Synthesis Example 3] The following shows an example of the synthesis of a polyoxyalkylene polymer (A-3).

[0153] Using polyoxypropylene glycol with a number-average molecular weight of approximately 4,800 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate grime complex catalyst to obtain polyoxypropylene (P-3) with a number-average molecular weight of 28,000 (end-group equivalent molecular weight of 18,000) and a molecular weight distribution Mw / Mn = 1.21, having hydroxyl groups at both ends. Subsequently, 1.0 molar equivalent of sodium methoxide in a 28% methanol solution was added to the hydroxyl groups of this polyoxypropylene (P-3). After removing methanol by vacuum defoliation, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl groups of polyoxypropylene (P-3) and the reaction was carried out at 130°C for 2 hours. Then, methanol was removed by adding 0.28 molar equivalents of sodium methoxide in a methanol solution, and further 1.79 molar equivalents of allyl chloride were added to convert the terminal hydroxyl groups to allyl groups. The obtained unpurified polyoxypropylene was mixed with n-hexane and water and stirred. After removing the water by centrifugation, the hexane in the resulting hexane solution was deflorated under reduced pressure to remove the metal salts from the polymer. This process yielded polyoxypropylene (Q-3) having multiple carbon-carbon unsaturated bonds at its ends. It was found that polyoxypropylene (Q-3) had an average of 2.0 carbon-carbon unsaturated bonds at each end.

[0154] To 500 g of the obtained polyoxypropylene (Q-3), 50 μL of a platinum divinyldisiloxane complex solution (3% by weight of isopropanol solution in terms of platinum) was added, and 9.6 g of methyldimethoxysilane was slowly added dropwise while stirring. After reacting the mixed solution at 100°C for 2 hours, the unreacted methyldimethoxysilane was removed by distillation under reduced pressure to obtain polyoxyalkylene polymer (A-3), a polyoxypropylene with a number average molecular weight of 28,500 and multiple methyldimethoxysilyl groups at its terminals. It was found that polyoxyalkylene polymer (A-3) has an average of 1.7 methyldimethoxysilyl groups at each terminal and an average of 3.4 groups per molecule.

[0155] [Synthesis Example 4] The following is an example of the synthesis of (meth)acrylic acid ester copolymer (C-1).

[0156] To 48 g of isobutyl alcohol heated to 105°C, a solution containing 8 g of methyl methacrylate, 8 g of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 15 g of stearyl methacrylate, 41 g of isobornyl methacrylate, 20 g of glycidyl methacrylate, 1 g of γ-methacryloxypropylmethyldimethoxysilane, and 7.0 g of azobis-2-methylbutyronitrile (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-59) dissolved in 25 g of isobutyl alcohol was added dropwise over 4 hours. This yielded an isobutyl alcohol solution of (meth)acrylic acid ester copolymer (C-1). It was found that (meth)acrylic acid ester copolymer (C-1) has an average of one methyldimethoxysilyl group per molecule.

[0157] [Synthesis Examples 5 to 7] (C-6) was obtained from (meth)acrylic acid ester copolymer (C-2) using the same method as in Synthesis Example 4, except that the monomer composition listed in Table 1 was used. The units of the numerical values ​​in the specific compositions in Table 1 are in grams. Note that for component (C) where the number average molecular weight is not listed, it means that the number average molecular weight has not been measured.

[0158] [Table 1]

[0159] The abbreviations in the table indicate the following compounds. MMA: Methyl methacrylate RHALS: 1,2,2,6,6-Pentamethyl-4-piperidyl methacrylate (ADEKA Corporation's reactive hindered amine-based light stabilizer "ADEKA Stab LA-82") SMA: Stearyl methacrylate HEMA: 2-hydroxyethyl methacrylate IBXMA: Isobornyl methacrylate GMA: Glycidyl methacrylate DSMA: γ-methacryloxypropylmethyldimethoxysilane (i.e., 3-(methyldimethoxysilyl)propyl methacrylate) [Comparative Example 1] The first agent was prepared by adding the amounts listed in Table 2, with (A-1) and (A-2) as components (A), JEFFADD® MW-760 and DEAPA as components (B), EXXSOL D80 as a diluent, Silke A-1120 as component (D), A-171 as a vinylsilane coupling agent, and Sn catalyst: NEOSTANN U-810 as a curing catalyst, and stirring by hand.

[0160] A solution of component (F) and component (C) (C-1) in isobutyl alcohol was blended in a solid content ratio (by weight) of 36:35, and the isobutyl alcohol was removed under reduced pressure and heating to obtain a clear, viscous liquid. The obtained liquid was mixed with component (A) (A-3), A-171 as a vinylsilane coupling agent, and calcium carbonate (Nanox #30) and titanium dioxide (R-820) as inorganic fillers in the amounts shown in Table 2. The mixture was stirred by hand and then passed through a ceramic triple-roll system three times to prepare a second agent.

[0161] Next, the first and second agents were added to disposable cups in the amounts listed in Table 2 and stirred by hand. Then, the mixture was mixed and degassed using a Super Mixer (Sinky Co., Ltd., ARE-250). Specifically, mixing and degassing was performed by stirring at 500 rpm for 20 seconds, 1500 rpm for 20 seconds, and 2000 rpm for 40 seconds, followed by degassing at 1500 rpm for 40 seconds. The degassed mixture was then poured into a mold (a mold consisting of a Teflon® sheet surrounded by a 2 mm thick backer) and the thickness was uniformly spread to 2 mm using a spatula. These operations were carried out to be completed within 10 minutes.

[0162] Subsequently, curing was performed under conditions of 23°C and 50% RH. Tensile properties, tear strength, tackiness, and weather resistance were evaluated for the cured material (sheet) obtained after 7 days of curing. The results are shown in Table 2.

[0163] [Examples 1 to 3, Comparative Examples 2 and 3] Curable compositions and cured products were prepared using the same procedure as in Comparative Example 1, except that the amounts of each component were changed as shown in Tables 2 and 3. The tensile properties, tear strength, tackiness, and weather resistance of the obtained cured products were evaluated. The results are shown in Tables 2 and 3.

[0164] [Example 4] The first agent was prepared by adding (A-1) and (A-3) as components (A), and titanium dioxide (R-820) in the amounts shown in Table 2, stirring by hand, and then passing the mixture through a ceramic three-roll system three times. Finally, the first agent was prepared by adding JEFFADD® MW-760 as component (B), EXXSOL D80 as a diluent, Silke A-1120 as component (D), A-171 as a vinylsilane coupling agent, and Sn catalyst: NEOSTANN U-810 as a curing catalyst, in the amounts shown in Table 2, and stirring by hand.

[0165] A solution of component (F) and (C-3) as component (C) in isobutyl alcohol was blended in a solid content ratio (by weight) of 36:35, and the isobutyl alcohol was removed under reduced pressure and heating to obtain a clear, viscous liquid. The obtained liquid was mixed with (A-3) as component (A), A-171 as a vinylsilane coupling agent, and calcium carbonate (Nanox #30) and carbon (Asahi Thermal) as inorganic fillers in the amounts shown in Table 2, and stirred by hand. The mixture was then passed through a ceramic three-roll system three times to prepare a second agent.

[0166] [Example 5] The first agent was prepared by adding the amounts of components (A) (A-1) and (A-3), titanium dioxide (R-820), and anti-sagging agent (CRAYVALLAC SL) as shown in Table 2, stirring by hand, passing the mixture through a ceramic three-roll machine three times, and then heating and dehydrating under reduced pressure in a stirrer (model 5XDMV-01-r, model number 13-A16, manufactured by Dalton) at 110°C for 2 hours at 90 rpm, followed by cooling to below 50°C. The first agent was then prepared by adding the amounts of component (B) JEFFADD® MW-760, diluent EXXSOL D80, component (D) Silke A-1120, vinylsilane coupling agent A-171, and curing catalyst Sn catalyst: NEOSTANN U-810 as shown in Table 2, stirring by hand.

[0167] A solution of component (F) and (C-3) as component (C) in isobutyl alcohol was blended in a solid content ratio (by weight) of 36:35, and the isobutyl alcohol was removed under reduced pressure and heating to obtain a clear, viscous liquid. The obtained liquid was mixed with (A-3) as component (A), A-171 as a vinylsilane coupling agent, and calcium carbonate (Nanox #30) and carbon black (Asahi Thermal) as inorganic fillers in the amounts shown in Table 2, and stirred by hand. The mixture was then passed through a ceramic triple roll three times to prepare a second agent.

[0168] [Example 6] The first agent was prepared by adding the amounts of components (A) (A-1) and (A-3) and titanium dioxide (R-820) as shown in Table 3, stirring by hand, and then passing the mixture through a ceramic three-roll system three times. After adding the amount of anti-sagging agent (R974) as shown in Table 3, the mixture was stirred in a stirrer (model 5XDMV-01-r, model number 13-A16, manufactured by Dalton) at 23°C, 90 rpm, and 10 minutes. Then, the amounts of component (B) JEFFADD (registered trademark) MW-760, the diluent EXXSOL D80, component (D) Silke A-1120, the vinylsilane coupling agent A-171, and the curing catalyst Sn catalyst: NEOSTANN U-810 as shown in Table 3, and stirring by hand.

[0169] A solution of component (F) and (C-3) as component (C) in isobutyl alcohol was blended in a solid content ratio (by weight) of 36:35, and the isobutyl alcohol was removed under reduced pressure and heating to obtain a clear, viscous liquid. The obtained liquid was mixed with (A-3) as component (A), A-171 as a vinylsilane coupling agent, and calcium carbonate (Nanox #30) and carbon black (Asahi Thermal) as inorganic fillers in the amounts listed in Table 3, and stirred by hand. The mixture was then passed through a ceramic three-roll system three times, and the amount of anti-sagging agent (R974) listed in Table 3 was added. The mixture was then mixed in a stirrer (model 5XDMV-01-r, model number 13-A16, manufactured by Dalton) at 23°C, 90 rpm, for 10 minutes to prepare the second agent.

[0170] For the preparation of sheets in Examples 4 to 6, the first and second agents were added to disposable cups in the amounts listed in Tables 2 and 3, respectively, and stirred by hand. The mixture was then mixed and degassed using a Super Mixer (Sinky Co., Ltd., ARE-250). Specifically, mixing and degassing were performed by stirring at 500 rpm for 20 seconds, 1500 rpm for 20 seconds, and 2000 rpm for 40 seconds, followed by degassing at 1500 rpm for 40 seconds. The degassed mixture was then poured into a mold (a mold consisting of a Teflon® sheet surrounded by a 2 mm thick backer) and the thickness was uniformly spread to 2 mm using a spatula. These operations were completed within 10 minutes.

[0171] Subsequently, curing was performed under conditions of 23°C and 50% RH. Tensile properties, tear strength, tackiness, and weather resistance were evaluated for the cured material (sheet) obtained after 7 days of curing. The results are shown in Tables 2 and 3.

[0172] [Evaluation Results] Tables 2 and 3 show the compositions and evaluation results of the examples and comparative examples. The units of the numerical values ​​showing the compositions in Tables 2 and 3 are grams.

[0173] [Table 2]

[0174] [Table 3]

[0175] Tables 2 and 3 show that the curable compositions of Examples 1 to 6, which used (meth)acrylic acid ester copolymers (C) having glycidyl and hydroxyl structures, exhibited greater tear strength when cured compared to the comparative examples. In other words, one embodiment of the present invention demonstrates that a curable composition can be provided that yields a cured product with improved tear strength. On the other hand, the cured compositions of Comparative Examples 1 to 3, which used (meth)acrylic acid ester copolymers (C) without glycidyl or hydroxyl structures, showed inferior tear strength compared to Examples 1 to 6. [Industrial applicability]

[0176] A multi-component curable composition according to one aspect of the present invention can provide a cured product with excellent tear strength and can therefore be used in waterproofing materials and the like.

Claims

1. General formula (1) -Si(R) ３－ａ (X) ａ (1) (In the formula, R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a represents 2 or 3.) A two-component curable composition comprising a polyoxyalkylene polymer (A) having reactive silicon groups as shown, an epoxy resin curing agent (B), and a (meth)acrylic acid ester copolymer (C), wherein the epoxy resin curing agent (B) and the (meth)acrylic acid ester copolymer (C) are contained in separate solutions, A two-component curable composition wherein the (meth)acrylic acid ester copolymer (C) contains structural units derived from a (meth)acrylic acid ester monomer having a glycidyl structure and a (meth)acrylic acid ester monomer having a hydroxyl structure.

2. The two-component curable composition according to claim 1, wherein the epoxy resin curing agent (B) is contained in an amount of 0.5% by weight or more and 5% by weight or less in 100% by weight of the two-component curable composition.

3. The two-component curable composition according to claim 1, wherein the epoxy resin curing agent (B) is contained in an amount of 1% to 5% by weight of 100% by weight of the two-component curable composition.

4. The two-component curable composition according to any one of claims 1 to 3, wherein the (meth)acrylic acid ester copolymer (C) further comprises structural units derived from a (meth)acrylic acid ester monomer having a hindered amine structure and / or a (meth)acrylic acid ester monomer having a benzotriazole structure.

5. A topcoat-free waterproof coating material comprising the two-component curable composition described in any one of claims 1 to 3.

6. A topcoat waterproofing material comprising the two-component curable composition described in any one of claims 1 to 3.