Curable composition

Abstract

To provide a curable composition capable of exhibiting desired elongation, breaking strength, and stain resistance even after long-term storage.SOLUTION: The curable composition contains a modified polymer (A) having at least one crosslinkable silyl group, an aliphatic amine compound (B) having a melting point of 20°C or higher and lower than 100°C, a curing catalyst (C), a plasticizer (D), and a filler (E). The polymer (A) contains a modified polymer (A1) having a crosslinkable silyl group at a terminal of the main chain and having a polyoxyalkylene skeleton in the main chain, and a modified polymer (A2) having a crosslinkable silyl group at a terminal of the main chain and having a skeleton derived from a (meth)acrylate in the main chain. The amine compound (B) contains an aliphatic amine compound (B1) having an imino group and an amino group and having a melting point of 55°C or higher and 80°C or lower.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable composition, and more particularly to a curable composition that can be suitably used as a construction sealant. [Background technology]

[0002] Curable compositions are used for various purposes. For example, curable compositions are used as sealants for joints of exterior walls, etc. Various sealants capable of preventing surface contamination and coating contamination have been reported.

[0003] Patent Document 1 discloses a one-liquid non-staining sealant composition containing a modified silicone polymer having a methyldimethoxysilyl functional group at the end of a polypropylene oxide main chain, a copolymer of a methacrylic acid ester and / or an acrylic acid ester, 1,12-diaminododecane having a melting point of 60°C to 80°C, dioctyl phthalate (plasticizer), calcium carbonate (filler), etc. (see Patent Document 1, Claims, Examples 1-2, etc.). Patent Document 1 discloses that the sealant composition is excellent in stain prevention and weather resistance.

[0004] Patent Document 2 discloses a room temperature curable composition containing a polymer having a hydrolyzable silyl group at the end of a polypropylene oxide main chain (e.g., Exestar 2410 (product name) manufactured by Asahi Glass Co., Ltd.), stearylamine, polypropylene glycol, etc. (see claims, Examples 1 and 2, etc. of Patent Document 2). Patent Document 2 discloses that the room temperature curable composition is excellent in gloss, stain resistance, and elongation.

[0005] Patent Document 3 discloses a curable composition that includes a polymer having a hydrolyzable silyl group at the end of the main chain of a vinyl polymer, an amine compound having a group represented by -NH-R-NH2 (R is an aliphatic hydrocarbon group having 1 to 5 carbon atoms), a fluorine-containing nonionic surfactant, etc. (See the claims of Patent Document 3, etc.) Patent Document 3 discloses that the curable composition exhibits excellent antifouling properties and self-cleaning action continuously after curing.

[0006] Patent Document 4 discloses a sealant composition including a polymer having a trimethoxysilyl group at the end of the main chain of a (meth)acrylic acid ester polymer, an amine compound having an alkyl group having 20 or more carbon atoms and an amino group, a silane coupling agent having an amino group, a filler, etc. (See the claims of Patent Document 4, Examples 1 to 4, etc.) Patent Document 4 discloses that the composition has excellent stain resistance after exposure to outdoors.

[0007] Patent Document 5 discloses a sealant composition including a modified polymer having trimethoxysilyl groups at both ends of a poly(meth)acrylate main chain, a modified polymer having trimethoxysilyl groups at both ends of a polyoxypropylene main chain, an alkylamine having a melting point of 50° C. or higher and an alkyl group having 20 or more carbon atoms, an amine-based silane coupling agent having a triethoxysilyl group, a filler, a plasticizer, etc. (See Patent Document 5, Claims, Example 1, etc.). Patent Document 5 discloses that the composition has excellent stain resistance.

[0008] Patent Document 6 discloses a sealant composition including a modified polymer having a poly(meth)acrylate main chain and trimethoxysilyl groups at both ends of the main chain, a modified polymer having a polyoxypropylene main chain and trimethoxysilyl groups at both ends of the main chain, a monoamine having a monovalent hydrocarbon group with 20 or more carbon atoms, an amine having a monovalent hydrocarbon group with less than 20 carbon atoms, a silane coupling agent having an amino group, a filler, a plasticizer, etc. (see Patent Document 6, Claims, Examples 1 to 7, etc.). Patent Document 6 discloses that the composition has excellent stain resistance.

[0009] Patent Document 7 discloses a sealant composition including a modified polymer having a main chain of polypropylene oxide and a methyldimethoxysilyl group at the end of the main chain, a modified polymer having a main chain of a copolymer of methyl methacrylate and n-butyl acrylate and having a trimethoxysilyl group at a side chain of the main chain, an amine compound having a melting point of 55° C. or higher, an aminosilane compound, a filler, a plasticizer, etc. (See Patent Document 7, Claims, Examples 1 to 6, etc.) Patent Document 7 discloses that the composition has excellent adhesiveness and can maintain excellent rubber elasticity with excellent curing properties for a long period of time.

[0010] Patent Document 8 discloses a curable composition including a modified polymer having a main chain of polypropylene oxide and a methyldimethoxysilyl group at the end of the main chain, a modified polymer having a main chain of a copolymer of methyl methacrylate and n-butyl acrylate and having a trimethoxysilyl group at a side chain of the main chain, a monoamine compound having a melting point of 60° C. or less, a diamine compound having a melting point 5° C. or more higher than the melting point of the monoamine compound, a filler, a plasticizer, etc. (See Patent Document 8, Claims, Examples 1 to 5, etc.) Patent Document 8 discloses that the curable composition can maintain an excellent antifouling effect for a long period of time after curing.

[0011] Patent Document 9 discloses a curable composition that includes a modified polymer having a main chain of polypropylene oxide and a methyldimethoxysilyl group at the end of the main chain, a modified polymer having a main chain of a copolymer of methyl methacrylate and n-butyl acrylate and having a trimethoxysilyl group at a side chain of the main chain, a diamine compound having a melting point of 50° C. or less, a filler, a plasticizer, etc. (See the claims of Patent Document 9, Examples 1 to 3, etc.) Patent Document 9 discloses that the curable composition can maintain an excellent antifouling effect for a long period of time after curing.

[0012] Patent Document 10 discloses a curable composition including a modified polymer having a main chain of polypropylene oxide and a methyldimethoxysilyl group at the end of the main chain, a modified polymer having a main chain of a copolymer of methyl methacrylate and n-butyl acrylate and having a trimethoxysilyl group at a side chain of the main chain, a monoamine compound having a melting point of 65° C. or lower, a diamine compound having a melting point lower than the melting point of the monoamine compound, a filler, a plasticizer, etc. (See Patent Document 10, Claims, Examples 2-3, etc.) Patent Document 10 discloses that the curable composition can maintain an excellent antifouling effect for a long period of time after curing. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] Japanese Patent Application Publication No. 5-125271 [Patent Document 2] Patent No. 3335523 [Patent Document 3] Patent No. 5289755 [Patent Document 4] Patent No. 6668903 [Patent Document 5] JP 2019-151676 A [Patent Document 6] JP 2020-172621 A [Patent Document 7] JP 2021-161428 A [Patent Document 8] JP 2021-161429 A [Patent Document 9] JP 2021-161430 A [Patent Document 10] JP 2021-161431 A Summary of the Invention [Problem to be solved by the invention]

[0014] When the curable composition is used as a sealant, it may be used after being stored for a relatively long period of time (for example, stored at 50°C for 30 days) after the composition is produced. Such storage conditions are expected to be storage conditions at construction sites in summer. However, there is no description as to whether the compositions described in the above Patent Documents 1 to 10 can exhibit the desired elongation, breaking strength, stain resistance, and weather resistance even after such long-term storage. [Means for solving the problem]

[0015] As a result of intensive research, the present inventors have found that it is possible to obtain a curable composition containing two specific modified polymers (A1) and (A2), a specific aliphatic amine compound (B1), a curing catalyst (C), a plasticizer (D) and a filler (E). Furthermore, they have found that such a curable composition is suitable for use as a sealant, and have thus completed the present invention.

[0016] This specification includes the following forms. 1. A modified polymer (A) having at least one crosslinkable silyl group, (B) an aliphatic amine compound having a melting point of 20°C or higher and lower than 100°C; Curing catalyst (C), Plasticizer (D) and Filler (E) Including, the modified polymer (A) having a crosslinkable silyl group includes a modified polymer (A1) having a crosslinkable silyl group at an end of the main chain and having a polyoxyalkylene skeleton in the main chain, and a modified polymer (A2) having a crosslinkable silyl group at an end of the main chain and having a skeleton derived from a (meth)acrylate in the main chain; A curable composition, characterized in that the aliphatic amine compound (B) contains an aliphatic amine compound (B1) having an imino group and an amino group and a melting point of 55°C or higher and lower than 75°C. 2. The curable composition according to the above item 1, wherein the aliphatic amine compound (B1) having an imino group and an amino group and having a melting point of 55° C. or higher and 80° C. or lower contains behenyl propylene diamine. 3. 3. The curable composition according to 1 or 2 above, further comprising an aliphatic amine compound (B2) having an imino group and an amino group, and having a melting point of 20°C or more and less than 55°C, and / or an aliphatic amine compound (B3) having a melting point of 20°C or more and less than 65°C. 4. 4. The curable composition according to any one of the above 1 to 3, comprising 5 to 200 parts by mass of the aliphatic amine compound (B2) and the aliphatic amine compound (B3) in total relative to 100 parts by mass of the aliphatic amine compound (B1). 5. 5. The curable composition according to any one of the above 1 to 4, comprising 0.1 to 10 parts by mass of an aliphatic amine compound (B) based on 100 parts by mass of the modified polymer (A). 6. The curable composition according to any one of the above items 1 to 5, wherein the modified polymer (A) further comprises, in addition to the modified polymer (A1) and the modified polymer (A2), a modified polymer (A3) having a skeleton derived from a (meth)acrylate having a crosslinkable silyl group pendantly attached (at a side chain). 7. 7. The curable composition according to any one of the above 1 to 6, wherein the modified polymer (A2) having a crosslinkable silyl group at its terminal and a skeleton derived from a (meth)acrylate includes a modified polymer having at least a skeleton derived from butyl acrylate. 8. 8. The curable composition according to any one of the above 1 to 7, wherein the modified polymer (A2) contains at least a modified polymer (A2-2) having a skeleton derived from a C13 to C19 aliphatic (meth)acrylate. 9. 9. The curable composition according to any one of the above 1 to 8, comprising 20 to 80 parts by mass of the modified polymer (A2) in 100 parts by mass of the modified polymer (A). 10. The curable composition according to any one of the above 1 to 9, further comprising a compound having an amino group and a silyl group (a silane coupling agent) and / or a silane coupling agent (F) having a ketimino group and a silyl group. 11. 11. The curable composition according to the above 10, wherein the silyl group of the silane coupling agent (F) is triethoxy or methyldiethoxy. Effect of the Invention

[0017] The curable composition according to an embodiment of the present invention comprises two specific modified polymers (A1) and (A2), a specific aliphatic amine compound (B1), a curing catalyst (C), a plasticizer (D), and a filler (E). The curable composition according to an embodiment of the present invention exhibits well-balanced properties of elongation, breaking strength, and stain resistance after curing, even when used after long-term storage at temperatures higher than room temperature (e.g., storage at 50°C for 30 days). [Brief description of the drawings]

[0018] [Figure 1] FIG. 1 shows a schematic diagram of an ISO type test specimen used for measuring elongation and breaking strength. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] In one aspect, the present invention provides a new curable composition, which comprises: A modified polymer (A) having at least one crosslinkable silyl group (hereinafter also referred to as "polymer (A)"); An aliphatic amine compound (B) having a melting point of 20°C or higher and lower than 100°C (hereinafter also referred to as "amine compound (B)"); Curing catalyst (C), Plasticizer (D) and Filler (E) Including, the modified polymer (A) having a crosslinkable silyl group includes a modified polymer (A1) (hereinafter also referred to as "polymer (A1)") having a crosslinkable silyl group at an end of the main chain and having a polyoxyalkylene skeleton in the main chain, and a modified polymer (A2) (hereinafter also referred to as "polymer (A2)") having a crosslinkable silyl group at an end of the main chain and having a poly(meth)acrylate skeleton in the main chain, The aliphatic amine compound (B) includes an aliphatic amine compound (B1) (hereinafter also referred to as "amine compound (B1)") which has an imino group and an amino group and has a melting point of 55°C or more and 80°C or less. The curable composition can be suitably used as a sealant.

[0020] In this specification, the term "modified polymer (A) having at least one crosslinkable silyl group" (polymer (A)) includes "modified polymer (A1) having a crosslinkable silyl group at an end of the main chain and having a polyoxyalkylene skeleton in the main chain" (polymer (A1)) and "modified polymer (A2) having a crosslinkable silyl group at an end of the main chain and having a poly(meth)acrylate skeleton in the main chain" (polymer (A2)), and is not particularly limited as long as the curable composition targeted by the present invention can be obtained.

[0021] In this specification, the term "crosslinkable silyl group" refers to a group that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can form a siloxane bond and crosslink by a reaction catalyzed by a curing catalyst. The term "hydrolyzable group" is not particularly limited as long as the curable composition of the present invention can be obtained, and may be a conventionally known hydrolyzable group. Specific examples of the hydrolyzable group include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. The crosslinkable group is preferably a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, or an alkenyloxy group, and is particularly preferably an alkoxy group because it is mildly hydrolyzable and easy to handle.

[0022] The crosslinkable silyl group may have a group other than the crosslinkable group as long as the curable composition targeted by the present invention can be obtained. Examples of the group other than the crosslinkable group include an alkyl group. More specifically, the crosslinkable silyl group is preferably a trialkoxysilyl group (such as a trimethoxysilyl group and a triethoxysilyl group) or an alkyldialkoxysilyl group (such as a methyldimethoxysilyl group, a methyldiethoxysilyl group, an ethyldimethoxysilyl group and an ethyldiethoxysilyl group).

[0023] The "polymer (A1)" is not particularly limited as long as it has a "crosslinkable silyl group" at the end of its main chain, has a skeleton made of polyoxyalkylene (or a skeleton derived from polyoxyalkylene) in its main chain, and can provide the curable composition of the present invention. In the polymer (A1), the "polyoxyalkylene skeleton" refers to a skeleton made of polyalkylene oxide (or alkylene oxide polymer) obtained by polymerization of alkylene oxide, and is not particularly limited as long as the curable composition targeted by the present invention can be obtained.

[0024] Polymer (A1) has at least one crosslinkable silyl group (in the main chain), more preferably has two or three crosslinkable silyl groups, and most preferably has two crosslinkable silyl groups. The average number of crosslinkable silyl groups contained in the polymer (A1) is preferably from 1.0 to 3.0, more preferably from 1.5 to 2.5, and even more preferably from 1.7 to 2.3.

[0025] Examples of "polyoxyalkylene" include polypropylene oxide, polyethylene oxide, propylene oxide-ethylene oxide copolymer, etc. Among these, polypropylene oxide is preferred because of its easy availability. The number average molecular weight of the polymer (A1) is preferably from 8,000 to 50,000, and more preferably from 20,000 to 50,000.

[0026] As the polymer (A1), a commercially available product can be used. Examples of such polymers (A1) include the EXCESTAR series (ES-S2410, ES-S4530 (trade name), etc.) manufactured by AGC Corporation, and SAX-220 (trade name) and SB820S (trade name) manufactured by Kaneka Corporation. The polymers (A1) can be used alone or in combination.

[0027] The "polymer (A2)" is not particularly limited as long as it has a "crosslinkable silyl group" at the end of the main chain, has a skeleton made of poly(meth)acrylate (or a skeleton derived from poly(meth)acrylate) in the main chain, and can obtain the curable composition targeted by the present invention. The term "poly(meth)acrylate backbone" refers to a backbone made of poly(meth)acrylate (or poly(meth)acrylic acid ester polymer) obtained by polymerization of (meth)acrylate (or (meth)acrylic acid ester), and is not particularly limited as long as the curable composition targeted by the present invention can be obtained.

[0028] Polymer (A2) has at least one crosslinkable silyl group (in the main chain), more preferably has two or three crosslinkable silyl groups, and most preferably has two crosslinkable silyl groups. The average number of crosslinkable silyl groups in the polymer (A2) is preferably from 1.0 to 3.0, more preferably from 1.5 to 2.5, and even more preferably from 1.7 to 2.3.

[0029] An example of the "poly(meth)acrylate" in the polymer (A2) is a poly(meth)acrylate (or a (meth)acrylic acid ester polymer) obtained by polymerizing a (meth)acrylate (or a (meth)acrylic acid ester). Examples of such (meth)acrylates include the following compounds: (Meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, 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, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate; (meth)acrylic acid esters having an aromatic hydrocarbon group, such as phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, and biphenyl (meth)acrylate; (meth)acrylic acid esters having an alkoxy group, such as 2-methoxyethyl (meth)acrylate and 3-methoxybutyl (meth)acrylate; (Meth)acrylic acid esters having a hydroxy group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; (Meth)acrylic acid esters having an epoxy group, such as glycidyl (meth)acrylate; (meth)acrylic acid esters having an amino group and / or an imino group, such as 2-aminoethyl (meth)acrylate; (Meth)acrylic acid esters having a tertiary amine, such as diethylaminoethyl (meth)acrylate; (Meth)acrylic acid esters having halogens such as trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate. These (meth)acrylates may be used alone or in combination of two or more kinds.

[0030] Furthermore, the poly(meth)acrylate may contain, in addition to the repeating units, monomer units copolymerizable therewith. Such monomers may include, for example, monomer units containing a carboxy group, such as acrylic acid and methacrylic acid; monomer units containing an amide group, such as acrylamide, methacrylamide, N-methylol acrylamide, and N-methylol methacrylamide; and compounds having an ether bond, such as aminoethyl vinyl ether, polyoxyethylene acrylate, and polyoxyethylene methacrylate. Furthermore, it may contain monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, and the like.

[0031] Furthermore, the poly(meth)acrylate may contain a monomer unit having a reactive silyl group. Examples of monomer units having a reactive silyl group include (meth)acryloxymethyltrimethoxysilane, (meth)acryloxymethylmethyldimethoxysilane, (meth)acryloxymethyldimethylmethoxysilane, (meth)acryloxymethyltriethoxysilane, (meth)acryloxymethylmethyldiethoxysilane, (meth)acryloxymethyldimethylethoxysilane, 2-(meth)acryloxyethyltrimethoxysilane, 2-(meth)acryloxyethylmethyldimethoxysilane, 2-(meth)acryloxyethyl Dimethylmethoxysilane, 2-(meth)acryloxyethyltriethoxysilane, 2-(meth)acryloxyethylmethyldiethoxysilane, 2-(meth)acryloxyethyldimethylethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropyldimethylmethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropyl Dipropyl dimethyl ethoxy silane, 4-(meth)acryloxy butyl trimethoxy silane, 4-(meth)acryloxy butyl methyl dimethoxy silane, 4-(meth)acryloxy butyl dimethyl methoxy silane, 4-(meth)acryloxy butyl triethoxy silane, 4-(meth)acryloxy butyl methyl diethoxy silane, 4-(meth)acryloxy butyl dimethyl ethoxy silane, 5-(meth)acryloxy pentyl trimethoxy silane, 5-(meth)acryloxy pentyl methyl dimethoxy silane, 5-(meth)acryloxy pentyl aryloxypentyl dimethyl methoxy silane, 5-(meth)acryloxypentyl triethoxy silane, 5-(meth)acryloxypentyl methyl diethoxy silane, 5-(meth)acryloxypentyl dimethyl ethoxy silane, 6-(meth)acryloxyhexyl trimethoxy silane, 6-(meth)acryloxyhexyl methyl dimethoxy silane, 6-(meth)acryloxyhexyl dimethyl methoxy silane, 6-(meth)acryloxyhexyl triethoxy silane, 6-(meth)acryloxyhexyl methyl diethoxy silane,Examples include silanes containing a (meth)acryloyloxy group, such as 6-(meth)acryloxyhexyldimethylethoxysilane.

[0032] Examples of monomer units having a reactive silyl group include mercapto group-containing silanes such as mercaptomethyldimethylmethoxysilane, mercaptomethyldimethylethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and 4-mercaptobutylmethyldimethoxysilane.

[0033] The monomer composition of the above-mentioned poly(meth)acrylate can be appropriately selected as long as the curable composition targeted by the present invention can be obtained. The poly(meth)acrylate preferably contains a (meth)acrylic acid alkyl ester or a (meth)acrylic acid ester having an aromatic hydrocarbon group, and more preferably contains a (meth)acrylic acid alkyl ester. The poly(meth)acrylate preferably contains a (meth)acrylic acid alkyl ester or a (meth)acrylic acid ester having an aromatic hydrocarbon group, and more preferably contains a (meth)acrylic acid alkyl ester.

[0034] The polymer (A2) preferably contains at least a polymer (A2-1) having a skeleton derived from butyl acrylate. In this case, the curable composition can exhibit advantageous effects such as increased flexibility and improved elongation performance. The polymer (A2) preferably contains at least a polymer (A2-2) having a skeleton derived from a C13-19 aliphatic (meth)acrylate. In this case, the curable composition can advantageously exhibit the effect that it tends to have better stain resistance after storage stability due to a synergistic effect with the aliphatic amine compound (B) described below.

[0035] The number average molecular weight of the polymer (A2) is preferably from 3,000 to 100,000, more preferably from 13,000 to 50,000, and even more preferably from 20,000 to 35,000. When the number average molecular weight of the polymer (A2) is 3,000 or more, the physical properties (e.g., elongation, strength, etc.) of the cured product of the curable composition can be improved. When the number average molecular weight is 100,000 or less, workability can be ensured (or the curable composition can be applied more easily and efficiently).

[0036] The method for producing the acrylic polymer (A2) can be any known method, and is not particularly limited as long as the curable composition aimed at by the present invention can be obtained. For example, the method for producing the acrylic polymers (a2-2) to (a2-6) used in the examples described later is not particularly limited as long as they can be obtained, and known methods can be used as appropriate. For example, the method described in Japanese Patent No. 4829107 (Patent Document 11) can be referenced. For example, the above-mentioned monomers are polymerized by radical polymerization, and the terminal alkenyl functional groups present in the obtained polymer are reacted with a hydrosilane compound to obtain an acrylic polymer (A2) having a terminal silyl group.

[0037] For example, another known method can be appropriately used as a method for producing the acrylic polymers (a2-7) to (a2-8) used in the examples described later. For example, the method described in JP 2022-138640 A (Patent Document 12) can be referred to. For example, a method of reacting a mixture containing a (meth)acrylic monomer having a reactive silyl group and a (meth)acrylic monomer not having a silyl group in three stages has been proposed. In the first stage, a monomer having a reactive silyl group is present at a relatively high concentration, in the second stage, a monomer having a reactive silyl group is present at zero or a relatively low concentration, and in the third stage, a monomer having a reactive silyl group is additionally added and reacted to obtain an acrylic polymer (A2) having a silyl group at the end.

[0038] For example, as a method for producing the acrylic polymers (a2-9) to (a2-12) used in the examples described later, another known method can be appropriately used. For example, the method described in JP-A-2022-64209 (Patent Document 13) can be referred to. For example, a (meth)acrylic monomer having no silyl group, a (meth)acrylic monomer having a reactive silyl group, and a mercaptosilane having a reactive silyl group are mixed and reacted, and if necessary, a (meth)acrylic monomer having a reactive silyl group is added at the final stage of the reaction to obtain an acrylic polymer (A2) having a terminal silyl group.

[0039] The acrylic polymer (A) may be produced by living radical polymerization. The acrylic polymer (A) may be a random copolymer or a block copolymer.

[0040] As the polymer (A2), a commercially available product can be used. Examples of such a polymer (A2) include SA-410S (trade name) and SB802S (trade name) manufactured by Kaneka Corporation. The polymers (A2) can be used alone or in combination.

[0041] The polymers (A1) and (A2) each have at least one crosslinkable silyl group at the end of the main chain. Even if the polymers (A1) and (A2) have a crosslinkable silyl group at the side chain, they do not fall under the polymer (A3) described below. That is, the polymer (A3) described below excludes the polymers (A1) and (A2).

[0042] In an embodiment of the present invention, the polymer (A) may further include, in addition to the polymer (A1) and the polymer (A2), a modified polymer (A3) (hereinafter also referred to as "polymer (A3)") having a crosslinkable silyl group pendantly attached (at a side chain) and having a skeleton derived from a (meth)acrylate.

[0043] In "Polymer (A3)", the "crosslinkable silyl group" and the "poly(meth)acrylate backbone" are as described in the columns for "Polymer (A1)" and "Polymer (A2)". The polymer (A3) differs from the polymer (A2) in that a "crosslinkable silyl group" is present in the side chain and is bonded to the main chain in a pendant form. The polymer (A3) is not particularly limited as long as it has crosslinkable silyl groups pendant (at side chains) and has a skeleton derived from a (meth)acrylate in its main chain, and the curable composition targeted by the present application can be obtained. When the polymer (A3) is contained, the weather resistance of the cured product of the curable composition can be improved compared to that of the polymer (A1), and since the viscosity of the polymer (A3) is lower than that of the polymer (A2), the workability of the curable composition can be improved. That is, in order to achieve both weather resistance and workability, the polymer (A3) can be used to reduce the amount of the polymer (A2) added while maintaining the weather resistance, thereby ensuring the workability.

[0044] The monomer composition of the poly(meth)acrylate of the polymer (A3) can be appropriately selected as long as the curable composition aimed at by the present invention can be obtained. The poly(meth)acrylate preferably contains a (meth)acrylic acid alkyl ester or a (meth)acrylic acid ester having an aromatic hydrocarbon group, and more preferably contains a (meth)acrylic acid alkyl ester.

[0045] The polymer (A3) preferably contains at least a polymer having (as a main component) a skeleton derived from butyl acrylate. In this case, the curable composition can exhibit advantageous effects such as increased flexibility and improved elongation performance. The polymer (A3) preferably contains at least a polymer having a skeleton derived from a long-chain alkyl (for example, an alkyl having 13 to 19 carbon atoms, preferably an alkyl having 15 to 18 carbon atoms) such as stearyl acrylate. In this case, the curable composition can provide an advantageous effect of reducing the contamination of a sealant composition using a composition stored at 50°C.

[0046] The number average molecular weight of the polymer (A3) is preferably from 500 to 100,000, more preferably from 1,000 to 50,000, and even more preferably from 2,000 to 17,000.

[0047] As the polymer (A3), a commercially available product can be used. Examples of such a polymer (A3) include US6100 (trade name) and US-6150 (trade name) of the ARUFON series manufactured by Toa Gosei Co., Ltd. The polymers (A3) can be used alone or in combination.

[0048] The average number of crosslinkable silyl groups contained in the total of the polymers (A1) to (A3) is preferably from 1.0 to 4.0, more preferably from 1.3 to 3.0, and even more preferably from 1.5 to 2.5.

[0049] The polymer having a (meth)acrylate skeleton contained in the polymers (A2) and (A3) is preferably contained in a mass ratio of 20 to 80, more preferably a mass ratio of 25 to 75, even more preferably a mass ratio of 40 to 70, and even more preferably a mass ratio of 45 to 60, based on the polymer (A) being 100. When the polymer having a (meth)acrylate skeleton is contained in a mass ratio of 20 to 80, relative to 100 of the polymer (A), the curable composition according to an embodiment of the present invention can exhibit an advantageous effect of being more excellent in weather resistance.

[0050] In 100 parts by mass of polymer (A), it is preferable to contain 80 to 20 parts by mass of modified polymer (A1), more preferably 75 to 25 parts by mass of modified polymer (A1), even more preferably 60 to 30 parts by mass of modified polymer (A1), and even more preferably 55 to 40 parts by mass of modified polymer (A1). When 80 to 20 parts by mass of the modified polymer (A1) is contained in 100 parts by mass of the polymer (A), the curable composition according to the embodiment of the present invention can exhibit the advantageous effect of being superior in the above-mentioned effects of the invention and superior in workability. It is preferable that 100 parts by mass of polymer (A) contains 20 to 80 parts by mass of modified polymer (A2), more preferably 25 to 75 parts by mass of modified polymer (A2), even more preferably 40 to 70 parts by mass of modified polymer (A2), and even more preferably 45 to 60 parts by mass of modified polymer (A2). When 20 to 80 parts by mass of the modified polymer (A2) is contained in 100 parts by mass of the polymer (A), the curable composition according to the embodiment of the present invention can exhibit the advantageous effect of being superior in the above-mentioned effects of the invention and superior in weather resistance.

[0051] The polymer (A) may contain a polymer (A3), and the weight ratio of the polymers (A1) to (A3) (polymer (A1) / (polymer (A2)+(A3))) is preferably 80 / 20 to 20 / 80, more preferably 75 / 25 to 25 / 75, even more preferably 60 / 40 to 30 / 70, and still more preferably 55 / 45 to 40 / 60. When the weight ratio of the polymers (A1) to (A3) (polymer (A1) / (polymer (A2)+(A3))) is 80 / 20 to 20 / 80, the curable composition according to an embodiment of the present invention can exhibit advantageous effects such as superior weather resistance and workability.

[0052] The curable composition according to the embodiment of the present invention preferably contains 15 to 65 mass% of the polymer (A), based on 100 mass% of the entire curable composition, more preferably contains 18 to 50 mass%, even more preferably contains 22 to 45 mass%, and even more preferably contains 26 to 40 mass%. When the polymer (A) is contained in an amount of 15 to 65 mass % relative to 100 mass % of the entire curable composition, the curable composition according to the embodiment of the present invention can exhibit advantageous effects such as being more excellent in strength and elongation.

[0053] The curable composition according to an embodiment of the present invention contains an aliphatic amine compound (B) (hereinafter referred to as "amine compound (B)") having a melting point of 20°C or more and less than 100°C, and it is preferable that the amine compound (B) contains an aliphatic amine compound (B1) (hereinafter also referred to as "amine compound (B1)") having an imino group and an amino group and having a melting point of 55°C or more and 80°C or less. In this specification, the term "amine compound (B)" refers to a compound in which at least one carbon atom in an aliphatic hydrocarbon is substituted with a nitrogen atom and has a melting point of 20°C or higher and lower than 100°C, and is not particularly limited as long as the curable composition targeted by the present invention can be obtained. Regarding the amine compound (B), an "aliphatic hydrocarbon compound" is a compound consisting of carbon and hydrogen, which may be saturated or unsaturated, chain or cyclic, straight-chain or branched, but does not include aromatic hydrocarbons.

[0054] In this specification, the term "amine compound (B1)" refers to a compound having an amino group and an imino group and having a melting point of 55°C or more and 80°C or less, and is not particularly limited as long as the curable composition targeted by the present invention can be obtained. In this specification, the term "amino group" refers to a monovalent group represented by -NH2, which can be obtained by replacing a carbon atom bonded to one carbon atom in the above-mentioned aliphatic hydrocarbon with a nitrogen atom. The term "imino group" refers to a divalent group represented by -NH-, which can be obtained by replacing a carbon atom bonded to two carbon atoms in the above-mentioned aliphatic hydrocarbon with a nitrogen atom.

[0055] The amine compound (B1) preferably includes a compound represented by the following formula (B1-1): Formula (B1-1): R12-NH-R11-NH2 [In formula (B1-1), R11 represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms. R12 represents a monovalent aliphatic hydrocarbon group having 20 to 24 carbon atoms.] When the curable composition according to the embodiment of the present invention contains the amine compound (B1-1), it has an advantageous effect that the contamination property of a sealant composition obtained by using the curable composition stored (or kept) at 50°C can be further reduced (or the contamination resistance can be further improved).

[0056] Examples of the "divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms" represented by R11 in the above formula (B1-1) include linear or branched alkylene groups having 1 to 5 carbon atoms (e.g., methylene, ethylene, trimethylene, tetramethylene, pentamethylene, 1-methylethylene, 2-methylethylene, 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 2-ethyltrimethylene, etc.), linear or branched alkenylene groups having 2 to 5 carbon atoms (e.g., vinylene, propenylene, butenylene, pentylene, Examples of the alkynylene group include a linear or branched alkynylene group having 2 to 5 carbon atoms (e.g., an ethynylene group, a 1-propynylene group, a 1-butynylene group, a 1-pentynylene group, a 1-hexynylene group, a 2-butynylene group, a 2-pentynylene group, a 1-methylethynylene group, a 3-methyl-1-propynylene group, a 3-methyl-1-butynylene group, etc.). R11 has a hydrophobic structure sandwiched between two polar groups, an amino group and an imino group, and is a structure that exerts the polarizability of the present amine compound (B1-1). Therefore, R11 is preferably a linear or branched alkylene group having 1 to 5 carbon atoms, and particularly preferably a trimethylene group.

[0057] Examples of the "monovalent aliphatic hydrocarbon group having 20 to 24 carbon atoms" represented by R12 in the above formula (B1-1) include alkyl groups such as behenyl group, eicosyl group (or eicosane group), henicosyl group (or henicosane group, henticosane group), docosyl group (or docosane group), tricosyl group (or tricosane group), and tetracosyl group (or tetracosane group); alkenyl groups such as docosaenyl group (or docosaene group); and isomers thereof. Formula (B1-1) is a polarizable structure having a polar group and a hydrophobic group, and R12 is a structure that can further emphasize the hydrophobicity. Therefore, R12 is preferably a linear alkyl group having 20 to 24 carbon atoms, and particularly preferably a behenyl group.

[0058] More specifically, examples of the amine compound (B1) include behenyl propylene diamine (melting point: 60° C.), eicosane propylene diamine, tetracosane propylene diamine, and the like, with behenyl propylene diamine being particularly preferred. The amine compounds (B1) can be used alone or in combination. As the amine compound (B1), a commercially available product can be used.

[0059] The curable composition according to an embodiment of the present invention may further contain an aliphatic amine compound (B2) having an imino group and an amino group and having a melting point of 20° C. or more and less than 55° C. (hereinafter also referred to as "amine compound (B2)"), and / or an aliphatic amine compound (B3) having a melting point of 20° C. or more and less than 65° C. (hereinafter also referred to as "amine compound (B3)"). In this specification, the term "amine compound (B2)" refers to a compound having an amino group and an imino group and having a melting point of 20° C. or more and less than 55° C., and is not particularly limited as long as the curable composition targeted by the present invention can be obtained. The "amino group" and "imino group" are as defined above.

[0060] The amine compound (B2) preferably includes a compound represented by the following formula (B2-1): Formula (B2-1): R22-NH-R21-NH2 [In formula (B2-1), R21 represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms. R22 represents a monovalent aliphatic hydrocarbon group having 14 to 19 carbon atoms.] When the curable composition according to the embodiment of the present invention contains the amine compound (B2-1), it exhibits the advantageous effect of being more excellent in stain resistance.

[0061] In the above formula (B2-1), examples of the "divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms" represented by R21 include linear or branched alkylene groups having 1 to 5 carbon atoms (e.g., methylene, ethylene, trimethylene, tetramethylene, pentamethylene, 1-methylethylene, 2-methylethylene, 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 2-ethyltrimethylene, etc.), linear or branched alkenylene groups having 2 to 5 carbon atoms (e.g., vinylene, propenylene, butenylene, pentylene, Examples of the alkynylene group include a linear or branched alkynylene group having 2 to 5 carbon atoms (e.g., an ethynylene group, a 1-propynylene group, a 1-butynylene group, a 1-pentynylene group, a 1-hexynylene group, a 2-butynylene group, a 2-pentynylene group, a 1-methylethynylene group, a 3-methyl-1-propynylene group, a 3-methyl-1-butynylene group, etc.). R21 has a hydrophobic structure sandwiched between two polar groups, an amino group and an imino group, and is a structure that allows the amine compound (B2-1) to exhibit polarity. Therefore, R21 is preferably a linear or branched alkylene group having 1 to 5 carbon atoms, and particularly preferably a trimethylene group.

[0062] In the above formula (B2-1), examples of the "monovalent aliphatic hydrocarbon group having 14 to 18 carbon atoms" represented by R22 include alkyl groups such as a stearyl group, a myristyl group, and a palmityl group; and alkenyl groups such as an oleyl group. Formula (B2-1) is a polarizable structure having a polar group and a hydrophobic group, in which R22 is preferably a linear or branched alkyl group having 14 to 18 carbon atoms, and particularly preferably a stearyl group.

[0063] More specifically, examples of the amine compound (B2) include tallow alkyl propylene diamine, hardened tallow alkyl propylene diamine, oleyl propylene diamine, etc. More specifically, examples include Duomin CD (C8-18 alkyl-NH-C3H6-NH2) (melting point: 15-30°C), Duomin T (C14-18 alkyl-NH-C3H6-NH2) (melting point: 30-40°C), Duomin HT (C14-18 alkyl-NH-C3H6-NH2) (melting point: 30-50°C), Nissan Amine DOB-R (C18H35-NH-C3H6-NH2; oleyl propylene diamine) (melting point: about 20°C), and hardened tallow propylene diamine (Nissan Amine DT-H, freezing point: 40-42°C), all manufactured by Lion Corporation. The amine compounds (B2) can be used alone or in combination. As the amine compound (B2), a commercially available product can be used.

[0064] In this specification, the term "amine compound (B3)" refers to an aliphatic amine compound having a melting point of 20°C or higher and lower than 65°C, excluding the above-mentioned amine compounds (B1) and (B2), and is not particularly limited as long as the curable composition targeted by the present invention can be obtained. When the curable composition according to the embodiment of the present invention contains the amine compound (B3), it can exhibit the advantageous effect of having more excellent stain resistance.

[0065] Examples of such amine compounds (B3) include aliphatic amine compounds such as diamine compounds such as 1,12-dodecanediamine, 1,10-decanediamine (melting point: 59 to 64°C), 1,8-octanediamine, 1,14-tetradecanediamine, and 1,16-hexadecanediamine, and monoamine compounds such as behenylamine (melting point: 55 to 65°C), laurylamine (melting point: 28°C), and stearylamine (melting point: 53°C). These amine compounds can be produced according to a conventionally known method. Commercially available products may also be used. The amine compounds (B3) can be used alone or in combination.

[0066] The curable composition of the embodiment of the present invention preferably contains 0.1 to 10 parts by mass of the aliphatic amine compound (B), more preferably contains 0.3 to 5 parts by mass of the aliphatic amine compound (B), and further preferably contains 0.5 to 3 parts by mass of the aliphatic amine compound (B), relative to 100 parts by mass of the curable composition. When the curable composition according to the embodiment of the present invention contains 0.1 to 10 parts by mass of the aliphatic amine compound (B) relative to 100 parts by mass of the polymer (A), the curable composition can exhibit an advantageous effect of being more excellent in stain resistance.

[0067] The curable composition according to an embodiment of the present invention may contain 5 to 200 parts by mass, 10 to 100 parts by mass, 20 to 70 parts by mass, or 30 to 60 parts by mass of the total of the aliphatic amine compound (B2) and the aliphatic amine compound (B3) relative to 100 parts by mass of the aliphatic amine compound (B1). The curable composition according to the embodiment of the present invention, when containing 5 to 200 parts by mass of the aliphatic amine compound (B2) and the aliphatic amine compound (B3) in total relative to 100 parts by mass of the aliphatic amine compound (B1), can exhibit an advantageous effect of better stain resistance after standing at 50°C for 14 days.

[0068] The curable composition according to the embodiment of the present invention contains a curing catalyst (C). The curing catalyst is not particularly limited as long as the curable composition according to the present invention can be obtained, and any known curing catalyst used in curable compositions can be used. Examples of the curing catalyst include tin-based catalysts such as tin dioctylate, dibutyltin dilaurate, dibutyltin bisacetylacetonate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin oxide, dibutyltin bisethoxysilicate, and dioctyltin oxide; titanium-based catalysts such as tetraisopropyl titanate, tetra-n-butyl titanate, and partial hydrolysis condensates thereof, titanium diisopropyl bisacetylacetate, and titanium diisopropyl bisethylethylacetoacetate.

[0069] The curable composition according to the embodiment of the present invention preferably contains 0.05 to 3 parts by mass of the curing catalyst (C) relative to 100 parts by mass of the curable composition, more preferably contains 0.08 to 2.5 parts by mass of the curing catalyst (C), even more preferably contains 0.1 to 1.5 parts by mass of the curing catalyst (C), and even more preferably contains 0.15 to 1 part by mass of the curing catalyst (C). The curable composition according to the embodiment of the present invention, when containing 0.05 to 3 parts by mass of the curing catalyst (C) per 100 parts by mass of the polymer (A), can exhibit the advantageous effect of having workability (or application workability) that allows appropriate curing while ensuring time for application and spatula smoothing.

[0070] The curable composition according to the embodiment of the present invention contains a plasticizer (D). The plasticizer is not particularly limited as long as the curable composition according to the present invention can be obtained, and any known plasticizer used in curable compositions can be used. Examples of the plasticizer include acrylic acid ester plasticizers such as non-functional acrylic polymers, phthalic acid diesters, epoxidized hexahydrophthalic acid diesters, alkylene dicarboxylate diesters, alkylbenzenes, polyalkylene glycols, and the like.

[0071] The curable composition of the embodiment of the present invention preferably contains 3 to 40 parts by mass of the plasticizer (D) per 100 parts by mass of the curable composition, more preferably contains 6 to 35 parts by mass of the plasticizer (D), even more preferably contains 8 to 30 parts by mass of the plasticizer (D), and even more preferably contains 10 to 25 parts by mass of the plasticizer (D). When the curable composition according to the embodiment of the present invention contains 3 to 40 parts by mass of the plasticizer (D) relative to 100 parts by mass of the polymer (A), the curable composition can exhibit an advantageous effect of being more excellent in coating workability.

[0072] The curable composition according to the embodiment of the present invention contains a filler (E). The filler (E) is not particularly limited as long as the curable composition according to the present invention can be obtained, and any known filler (E) used in a curable composition can be used. Examples of the filler include ground calcium carbonate, fatty acid-treated calcium carbonate, fume silica, precipitated silica, carbon black, talc, and titanium oxide.

[0073] The curable composition of the embodiment of the present invention preferably contains 5 to 65 parts by mass of the filler (E) relative to 100 parts by mass of the curable composition, more preferably contains 10 to 60 parts by mass of the filler (E), even more preferably contains 20 to 55 parts by mass of the plasticizer (D), and even more preferably contains 30 to 50 parts by mass of the filler (E). When the curable composition according to the embodiment of the present invention contains 5 to 65 parts by mass of the filler (E) per 100 parts by mass of the polymer (A), it can exhibit an advantageous effect of being more excellent in the property of being less likely to cause sagging (sagging resistance).

[0074] The curable composition according to the embodiment of the present invention may further include a silane coupling agent (F) having an amino group and a silyl group and / or a silane coupling agent (F) having a ketimino group and a silyl group (hereinafter also referred to as "silane coupling agent"). As long as the curable composition according to the present invention can be obtained, the silane coupling agent (F) is not particularly limited, and any known silane coupling agent (F) used in curable compositions may be used. The silyl group of the silane coupling agent (F) preferably contains triethoxy or methyldiethoxy. Examples of the silane coupling agent (F) include N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and the like.

[0075] The curable composition of the embodiment of the present invention preferably contains 0.1 to 5 parts by mass of the silane coupling agent (F) relative to 100 parts by mass of the curable composition, more preferably contains 0.5 to 3 parts by mass of the silane coupling agent (F), and even more preferably contains 0.8 to 2 parts by mass of the silane coupling agent (F). When the curable composition according to the embodiment of the present invention contains 0.1 to 5 parts by mass of the silane coupling agent (F) relative to 100 parts by mass of the polymer (A), the curable composition can exhibit an advantageous effect of exhibiting superior adhesion to a base.

[0076] The curable composition according to the embodiment of the present invention may contain various additives used in ordinary curable compositions in addition to the above-mentioned components. Examples of such additives include colorants, organic solvents, adhesion agents, antioxidants, thixotropic agents, moisture retaining agents, ultraviolet absorbers and / or light stabilizers, antioxidants, stain resistance improvers, storage stability improvers, etc.

[0077] Examples of colorants include red iron oxide, titanium oxide, carbon black, other color pigments, dyes, and the like. Examples of the organic solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, butanol, acetone, methyl ethyl ketone, ligroin, ethyl acetate, tetrahydrofuran, n-hexane, heptane, and isoparaffin-based high boiling point solvents. The adhesive agent may be, for example, an epoxy compound.

[0078] Examples of the antioxidant include hindered phenols, mercaptans, sulfides, dithiocarboxylates, thioureas, thiophosphates, and thioaldehydes. Examples of the thixotropic agent include colloidal silica, organic bentonite, fatty acid amide, polyamide wax, and hydrogenated castor oil. Examples of the moisture retaining agent include water and hydrates of inorganic salts. Examples of ultraviolet absorbents and light stabilizers include benzotriazoles and hindered amines. Examples of the antioxidant include hindered phenols. As the stain resistance improver, a fluorine compound can be mentioned as an example. An example of the storage stability improver is vinylsilane.

[0079] The curable composition of the embodiment of the present invention may contain 0.01 to 5 parts by mass of various additives, may contain 0.1 to 3 parts by mass of various additives, or may contain 0.2 to 2 parts by mass of various additives, relative to 100 parts by mass of the curable composition.

[0080] The curable composition according to the embodiment of the present invention may be a one-liquid composition containing all the necessary components from the above-mentioned polymer (A), or may be a two-liquid composition consisting of a main material containing the above-mentioned polymer (A), an amine compound (B), etc., and a curing material containing a curing catalyst (C), etc., or may be a three-liquid composition containing a separate component other than (A) to (E), such as a colorant, when such a component is contained. The curable composition according to the embodiment of the present invention has excellent stability even when used as a one-liquid composition.

[0081] The curable composition according to the embodiment of the present invention can be cured at ordinary temperatures, preferably within the range of 5 to 50°C.

[0082] The curable composition according to an embodiment of the present invention can be used for various applications, such as sealing materials for construction, sealing materials for automobiles, electrical appliances, and civil engineering, as well as other adhesives, paints, coating materials, potting materials, molded articles, and the like. The curable composition according to the embodiment of the present invention can be suitably used as a building sealant. It is effective in some cases as a building sealant, and can be suitably used as a sealant for, for example, a matte finish exterior wall, an orange peel finish exterior wall, or a sandstone finish exterior wall. EXAMPLES

[0083] The present invention will be specifically and in detail explained below with reference to examples and comparative examples. However, these examples are merely one embodiment of the present invention, and the present invention is not limited to these examples in any way. In the description of the examples, unless otherwise specified, parts by weight and percentages by weight are based on the parts not taking into account the solvent.

[0084] The components used in this example are shown below. (A) A modified polymer having at least one crosslinkable silyl group (A1) A modified polymer having a crosslinkable silyl group at the end and a polyoxyalkylene skeleton. (a1-1) A modified polymer having a methyldimethoxysilyl group at the end and a polyoxypropylene skeleton in the main chain (Exestar ES-S4530 (product name) manufactured by AGC Corporation) (a1-2) A modified polymer having a trimethoxysilyl group at the end and a polyoxypropylene skeleton in the main chain (SAX-220 (trade name) manufactured by Kaneka Corporation)

[0085] (A2) A modified polymer having a crosslinkable silyl group at the end and a poly(meth)acrylate skeleton. (a2-1) A modified polymer having a methyldimethoxysilyl group at the end and a poly(meth)acrylate skeleton in the main chain (SA410S (product name) manufactured by Kaneka Corporation) (a2-2) Modified polymer having a methyldimethoxy crosslinkable silyl group at the end and a poly(meth)acrylate skeleton in the main chain (ethyl acrylate / butyl acrylate / stearyl acrylate=7.5 / 75 / 17.5 (molar ratio)), Mn=28000, average number of functional groups f=2 (a2-3) A modified polymer having a methyldimethoxy crosslinkable silyl group at the end and a poly(meth)acrylate skeleton in the main chain (butyl acrylate=100%)

[0086] (a2-4) Modified polymer having a trimethoxysilyl group at the end and a poly(meth)acrylate skeleton in the main chain (methyl methacrylate / butyl acrylate / stearyl acrylate=5 / 80 / 15), Mn=36000, average number of functional groups f=2 (a2-5) Modified polymer having a triethoxysilyl group at the end and a poly(meth)acrylate skeleton in the main chain (ethyl acrylate / butyl acrylate / stearyl acrylate=7.5 / 75 / 17.5), Mn=30,000, average number of functional groups f=2 (a2-6) Modified polymer having a methyldiethoxysilyl group at the end and a poly(meth)acrylate skeleton in the main chain (methyl methacrylate / butyl acrylate / stearyl acrylate=5 / 80 / 15), Mn=25000, average number of functional groups f=2 (2a-7) Modified polymer having a poly(meth)acrylate skeleton in the main chain, having a terminal based on trimethoxysilylpropyl meth(acrylate) and a trimethoxysilyl group in a side chain or at another terminal (ethyl acrylate / butyl acrylate / stearyl acrylate=7.5 / 75 / 17.5), Mn=24000, average number of functional groups f=2

[0087] (2a-8) Modified polymer having a poly(meth)acrylate skeleton in the main chain, having a terminal based on methyldimethoxysilylpropyl(meth)acrylate and having a methyldimethoxysilyl group in a side chain or at another terminal (ethyl acrylate / butyl acrylate / stearyl acrylate=7.5 / 75 / 17.5), Mn=30,000, average number of functional groups f=2 (2a-9) Modified polymer having a poly(meth)acrylate skeleton in the main chain, having a terminal based on methyldimethoxysilylpropylthiol and a methyldimethoxysilyl group in a side chain or at another terminal (ethyl acrylate / butyl acrylate / stearyl acrylate=7.5 / 75 / 17.5), Mn=30,000, average number of functional groups f=2 (2a-10) Modified polymer having a poly(meth)acrylate skeleton in the main chain, having a terminal based on trimethoxysilylpropylthiol and a trimethoxysilyl group in a side chain or at another terminal (methyl methacrylate / butyl acrylate / 2-ethylhexyl acrylate=5 / 80 / 15), Mn=30,000, average number of functional groups f=2 (2a-11) Modified polymer having a poly(meth)acrylate skeleton in the main chain, having a terminal based on methyldimethoxysilylpropylthiol and having a trimethoxysilyl group in a side chain or at another terminal (methyl methacrylate / butyl acrylate / 2-ethylhexyl acrylate=5 / 80 / 15), Mn=30,000, average number of functional groups f=2 (2a-12) Modified polymer having a poly(meth)acrylate skeleton in the main chain, having a terminal based on trimethoxysilylpropylthiol and a methyldimethoxysilyl group in a side chain or at another terminal (ethyl methacrylate / butyl acrylate / 2-ethylhexyl acrylate=7.5 / 75 / 17.5), Mn=30,000, average number of functional groups f=2

[0088] (A3) A modified polymer having a crosslinkable silyl group in a side chain and a poly(meth)acrylate skeleton. (a3-1) A modified polymer having a trimethoxysilyl group in a side chain and a poly(meth)acrylate skeleton consisting of methyl methacrylate and n-butyl acrylate in a main chain, weight average molecular weight 2,500, average number of silyl groups per molecule: 1 ARUFON US-6100 (trade name) manufactured by Toa Gosei Co., Ltd. was used. ARUFON US-6100 (trade name) contains 20% by mass of modified polymer (a3-1) and 80% by mass of a polymer having a poly(meth)acrylate skeleton in the main chain composed of unmodified methyl methacrylate and n-butyl acrylate. This unmodified (non-functional) polymer is shown as (d3). (a3-2) A modified polymer having a trimethoxysilyl group in the side chain and a poly(meth)acrylate skeleton in the main chain consisting of a copolymer of methyl methacrylate and n-butyl acrylate (content of methyl methacrylate component: 25% by weight, content of n-butyl acrylate component: 75% by weight), weight average molecular weight: 7,000, average number of silyl groups per molecule: 1 ARUFON US-6150 (trade name) manufactured by Toa Gosei Co., Ltd. was used. ARUFON US-6150 (trade name) contains 30% by mass of modified polymer (a3-2) and 70% by mass of a polymer having a poly(meth)acrylate skeleton in the main chain composed of unmodified methyl methacrylate and n-butyl acrylate. This unmodified (non-functional) polymer is shown as (d4).

[0089] (B) Aliphatic amine compounds having a melting point of 20°C or higher and lower than 100°C (B1) An aliphatic amine compound having an imino group and an amino group and a melting point of 55°C or higher and 80°C or lower (b1-1) Behenyl propylene diamine (Nissan Amine DV manufactured by NOF Corporation, melting point: 60°C) (B2) An aliphatic amine compound having an imino group and an amino group and a melting point of 20°C or higher and lower than 55°C (b2-1) Hardened beef tallow propylene diamine (Nissanamine DT-H manufactured by NOF Corp., melting point: 40-42°C)

[0090] (B3) Aliphatic amine compounds having a melting point of 20°C or higher and lower than 65°C (excluding (B1) and (B2)) (b3-1) Decanediamine (melting point: 59-64°C) (b3-2) Behenylamine (Nissanamine VB-S manufactured by NOF Corp., melting point: 55-65°C) (b3-3) Laurylamine (Nissan Amine BB manufactured by NOF Corp., melting point: 28°C) (b3-4) Stearylamine (Nissan Amine AB manufactured by NOF Corp., melting point: 53°C)

[0091] (C) Curing catalyst (c1) Dibutyltin bis(triethoxysilicate) (Neostan U-303 (trade name) manufactured by Nitto Kasei Co., Ltd.) (D) Plasticizer (d1) Non-functional acrylic polymer, weight average molecular weight 2,500 (UP-1110 (product name) manufactured by Toa Gosei Co., Ltd.) (d2) Polypropylene glycol (EXENOL 3020 (product name) manufactured by AGC Corporation) (d3) Non-functional acrylic polymer (a polymer having a poly(meth)acrylate skeleton consisting of non-functional methyl methacrylate and n-butyl acrylate in the main chain, contained in ARUFON US-6100 (trade name) manufactured by Toa Gosei Co., Ltd.) (d4) Non-functional acrylic polymer (a polymer having a poly(meth)acrylate skeleton consisting of non-functional methyl methacrylate and n-butyl acrylate in the main chain, contained in ARUFON US-6150 (trade name) manufactured by Toa Gosei Co., Ltd.)

[0092] (E) Filler (e1) Calcium carbonate (Calcine 500 (product name) manufactured by Maruo Calcium Co., Ltd.) (F) Silane coupling agent having an amino group or a ketimino group (f1) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (KBM-603 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.) (f2) 3-aminopropyltriethoxysilane (KBE-903 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.) (f3) 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine (KBE-9103P (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.) (X)Other (x1) Vinylsilane (KBE-1003 (product name) manufactured by Shin-Etsu Chemical Co., Ltd.) (x2) UV absorber (BASF Japan's Tinuvin 326 (product name)) (x3) Fluorine compound (Seimi Chemical's Surflon KH-40 (product name))

[0093] Number average molecular weight (Mn) and weight average molecular weight (Mw) The number average molecular weight (Mn) and weight average molecular weight (Mw) of each polymer were measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene under the following conditions. Equipment: GPC-8220 (Tosoh) Column: TSKgel G7000HXL / 7.8mmID x 1 + TSKgel GMHXL / 7.8mmID x 2 + TSKgel G2500HXL / 7.8mmID x 1 (all manufactured by Tosoh) Solvent: Tetrahydrofuran Flow rate: 1.0ml / min Concentration: 1.5mg / mL Injection volume: 300μL Column temperature: 40℃

[0094] These components were mixed in the ratios shown in Tables 2 to 5 to prepare curable compositions of Examples 1 to 25 and Comparative Examples 1 to 11. The stain resistance, weather resistance, initial elongation (%), initial breaking strength (MPa), elongation after heating (%), and breaking strength after heating (MPa) of each of the cured products of the above-mentioned curable compositions were measured and evaluated by the following methods. The results are shown in Tables 2 to 5.

[0095] Stain resistance A The curable composition was stored in a high barrier cartridge (High Barrier Cartridge (product name) manufactured by Showa Marutsutsu Co., Ltd.) at 23° C. for 14 days. The stain resistance was evaluated in accordance with JSIA 003:2011 “Accelerated staining test method for finishing coating materials applied to architectural sealants” published by the Japan Sealant Industry Association. However, type B test specimens were used, and no barrier primer or finishing coating material was used. The curing conditions for the hardener composition were 23° C. and 50% RH for 7 days. The test was carried out in the following manner. The test specimen and Sakurajima volcanic ash were left to stand at 50°C for 14 days. After that, the joints of the test specimen were horizontalized, volcanic ash was sprinkled evenly on the test specimen, and it was left to stand for 5 minutes. The joints of the test specimen were verticalized, and the specimen was brushed several times, after which the dirt on the surface of the test specimen was visually observed. The sample gray scale described in JIS L 0805 was compared with the surface of the test specimen, and the stains were scored from 1 to 5. The evaluation criteria are as follows: 5: Very good as it is free of contamination and volcanic ash. 4: Good 3: Insufficient 2: Bad 1: Very bad due to contamination and heavy volcanic ash adhesion

[0096] Stain resistance B The curable composition was stored in a high barrier cartridge (High Barrier Cartridge (product name) manufactured by Showa Marutsutsu Co., Ltd.) at 23° C. for 14 days. A type B specimen was obtained using the same method as described for stain resistance A. The curable composition was cured at 23° C. and 50% RH for 7 days. The Sakurajima volcanic ash and its specimens were placed on an outdoor exposure platform facing south (with a 30° inclination) and exposed outdoors for three months. Then, Sakurajima volcanic ash was scattered on the surface of the test specimen using the same method as that described for contamination resistance A, and contamination resistance B was evaluated. The evaluation criteria were the same.

[0097] Stain resistance C Type B specimens were obtained using a method similar to that described for stain resistance A, except that the curable composition was stored in a high barrier cartridge at 50° C. for 30 days. The curable composition was aged at 23° C. and 50% RH for 7 days. The Sakurajima volcanic ash and its specimens were placed on an outdoor exposure platform facing south (with a 30° inclination) and exposed outdoors for three months. Then, Sakurajima volcanic ash was spread on the surface of the test specimen using the same method as that described for contamination resistance A, and contamination resistance C was evaluated. The evaluation criteria were the same.

[0098] weather resistance The curable composition was cast onto an anodized aluminum plate (width 40 mm × length 40 mm × thickness 3 mm) described in JIS A 6063. The cast size was width 40 mm × length 30 mm × thickness 5 mm. It was cured for 14 days under conditions of 23°C and 50% RH to obtain a test specimen. The test specimen was set in Iwasaki Electric's iSuper UV SUV-W262 (trade name) and irradiated with light for 500 hours. Water was sprayed for 120 seconds every 95 minutes of light irradiation. The light irradiation conditions are shown in Table 1 below.

[0099] [Table 1] The test specimen was visually observed and the evaluation criteria were as follows: 〇: No cracks △: Slight cracks (fine cracks of 0.5 mm or less may exist.) ×: Clear cracks present

[0100] Elongation and breaking strength The elongation and (maximum) breaking strength were evaluated in accordance with "5.3 Tensile property test" described in JIS A 1439. An ISO-type test specimen as shown in FIG. 1 was prepared using an anodized aluminum plate as specified in JIS A 5052P. After cleaning the adhesive surface of the adherend with IPA (isopropyl alcohol), a primer (Primer UD-EX (product name) manufactured by Sunstar Engineering Co., Ltd.) was applied (two double applications), and the open time was 1 hour at 23°C and 65% RH. The pour size of the hardenable composition was 10 mm wide x 8 mm deep x 50 mm long. The initial elongation and initial breaking strength were measured after the hardenable composition was cast and then cured at 23° C. and 50% RH for 14 days. The elongation and breaking strength after heating were measured after the hardenable composition was cast, cured at 23°C and 50% RH for 14 days, and then cured at 120°C for 10 days. Then, measurements were performed at a tensile speed of 50 mm / min, and the 50% tensile stress (M50), maximum tensile stress (Tmax), and elongation at maximum load (Emax) were obtained and the state of failure was recorded. The number of test specimens was N=3.

[0101] [Table 2]

[0102] [Table 3]

[0103] [Table 4]

[0104] [Table 5]

[0105] The curable compositions of Examples 1 to 25 contain (A1) a modified polymer having a polyoxyalkylene skeleton in its main chain and a crosslinkable silyl group at an end of the main chain, (A2) a modified polymer having a (meth)acrylate skeleton in its main chain and a crosslinkable silyl group at an end of the main chain, and (B1) an aliphatic amine compound having an amino group and an imino group and a melting point of 55°C or more and 80°C or less, and therefore have excellent, well-balanced stain resistance, weather resistance, elongation, and breaking strength.

[0106] The curable compositions of Comparative Examples 1 to 11 do not contain any one of (A1) a modified polymer having a polyoxyalkylene skeleton in its main chain and a crosslinkable silyl group at an end of the main chain, (A2) a modified polymer having a (meth)acrylate skeleton in its main chain and a crosslinkable silyl group at an end of the main chain, and (B1) an aliphatic amine compound having an amino group and an imino group and a melting point of 55°C or more and 80°C or less, and therefore are inferior in any of stain resistance, weather resistance, elongation, and breaking strength. [Industrial Applicability]

[0107] The curable composition according to an embodiment of the present invention comprises two specific modified polymers (A1) and (A2), a specific aliphatic amine compound (B1), a curing catalyst (C), a plasticizer (D), and a filler (E). The curable composition according to an embodiment of the present invention exhibits well-balanced properties of elongation, breaking strength, and stain resistance after curing, even when used after long-term storage at temperatures higher than room temperature (e.g., storage at 50°C for 30 days).

Claims

1. A modified polymer (A) having at least one crosslinkable silyl group; (B) an aliphatic amine compound having a melting point of 20° C. or higher and lower than 100° C.; curing catalyst (C), Plasticizer (D) and Filler (E) Including, the modified polymer (A) having a crosslinkable silyl group includes a modified polymer (A1) having a crosslinkable silyl group at an end of a main chain and having a polyoxyalkylene skeleton in the main chain, and a modified polymer (A2) having a crosslinkable silyl group at an end of a main chain and having a skeleton derived from a (meth)acrylate in the main chain; The modified polymer (A2) contains at least a polymer (A2-2) having a skeleton derived from a C13-19 aliphatic (meth)acrylate, The modified polymer (A2) is contained in 20 to 80 parts by mass in 100 parts by mass of the modified polymer (A), The aliphatic amine compound (B) includes an aliphatic amine compound (B1) having an imino group and an amino group and a melting point of 55° C. or more and 80° C. or less, The modified polymer (A) may further include, in addition to the modified polymer (A1) and the modified polymer (A2), a modified polymer (A3) having a crosslinkable silyl group in a side chain and a skeleton derived from a (meth)acrylate in a main chain, The curable composition further comprises the modified polymer (A), the content and mass ratio of which in the modified polymer (A) satisfies at least one of the following (i) and (ii): (i) 40 to 80 parts by mass of the modified polymer (A2) is contained in 100 parts by mass of the modified polymer (A); and (ii) The mass ratio of the modified polymers (A1) to (A3) (modified polymer (A1) / (modified polymer (A2)+modified polymer (A3)) is 60 / 40 to 20 / 80.

2. 2. The curable composition according to claim 1, wherein the aliphatic amine compound (B1) having an imino group and an amino group and a melting point of 55° C. or higher and 80° C. or lower comprises behenyl propylene diamine.

3. The curable composition according to claim 1 or 2, further comprising an aliphatic amine compound (B2) having an imino group and an amino group and having a melting point of 20° C. or more and less than 55° C., and / or an aliphatic amine compound (B3) having a melting point of 20° C. or more and less than 65° C.

4. The curable composition according to claim 3, comprising 5 to 200 parts by mass of the aliphatic amine compound (B2) and the aliphatic amine compound (B3) in total relative to 100 parts by mass of the aliphatic amine compound (B1).

5. 3. The curable composition according to claim 1, comprising 0.1 to 10 parts by mass of an aliphatic amine compound (B) relative to 100 parts by mass of the modified polymer (A).

6. The curable composition according to claim 1 or 2, wherein the modified polymer (A2) having a crosslinkable silyl group at a terminal and a skeleton derived from a (meth)acrylate includes at least a modified polymer (A2-1) having a skeleton derived from butyl acrylate.

7. The curable composition according to claim 1 or 2, further comprising (F) a silane coupling agent having an amino group and a silyl group and / or a silane coupling agent having a ketimino group and a silyl group.

8. 8. The curable composition according to claim 7, wherein the silyl group of the silane coupling agent (F) is triethoxy or methyldiethoxy.

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