Moisture-curable resin composition

Abstract

To provide a moisture-curable resin composition having an even and smooth surface after cured, and exhibiting excellent stain resistance irrespective of a construction period.SOLUTION: A moisture-curable resin composition contains: at least one kind of a polymer (A) having at least one cross-linkable silyl group in a molecule, and selected from the group consisting of a polyoxyalkylene-based polymer and a (meth)acrylic acid alkyl ester-based polymer; a ketimine (B) in which an amine generated when subjected to hydrolysis is an alkylamine having at least one primary amino group and a melting point (coagulation point) of less than 50°C; and a ketimine (C) in which an amine generated when subjected to hydrolysis is an alkylamine having at least one primary amino group and a melting point (coagulation point) of 50°C or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a moisture-curable resin composition. [Background technology]

[0002] 2. Description of the Related Art Conventionally, compositions containing a polymer having a crosslinkable silyl group and a ketimine have been known as moisture-curable resin compositions for sealing materials (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2005-290242 A Summary of the Invention [Problem to be solved by the invention]

[0004] In this situation, the present inventors have studied the curable composition (moisture-curable resin composition) described in Patent Document 1, and have found that the composition does not necessarily meet the level of stain resistance that is currently required depending on the time of application. In addition, the moisture-curable resin composition is also required to have a uniform and smooth surface after curing.

[0005] In view of the above-mentioned circumstances, the present invention has an object to provide a moisture-curable resin composition which has a uniform and smooth surface after curing and exhibits excellent stain resistance regardless of the time of application. [Means for solving the problem]

[0006] As a result of extensive investigations into the above problems, the present inventors have found that the above problems can be solved by using two specific ketimines in combination, and have completed the present invention. That is, the present inventors have found that the above problems can be solved by the following configuration.

[0007] (1) at least one polymer (A) selected from the group consisting of polyoxyalkylene polymers and (meth)acrylic acid alkyl ester polymers, each of which has at least one crosslinkable silyl group in one molecule; A ketimine (B) which produces an amine upon hydrolysis that is an alkylamine having at least one primary amino group in one molecule and a melting point (freezing point) of less than 50°C; and a ketimine (C) which produces an amine upon hydrolysis that is an alkylamine having at least one primary amino group in one molecule and a melting point (freezing point) of 50°C or higher. (2) The moisture-curable resin composition according to (1) above, wherein the total content of the ketimine (B) and the ketimine (C) is 0.5 to 10 parts by mass per 100 parts by mass of the polymer (A). (3) The moisture-curable resin composition according to (1) or (2) above, wherein the ratio (B / C) of the content of the ketimine (B) to the content of the ketimine (C) is 30 to 300 mass %. Effect of the Invention

[0008] As will be described below, according to the present invention, it is possible to provide a moisture-curable resin composition which has a uniform and smooth surface after curing and exhibits excellent stain resistance regardless of the time of application. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The moisture-curable resin composition of the present invention will be described below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present specification, each component may be used alone or in combination of two or more. When two or more components are used in combination, the content of the components refers to the total content unless otherwise specified. In this specification, (meth)acrylic means acrylic or methacrylic, and (meth)acrylate means acrylate or methacrylate. In this specification, being excellent in appearance, stain resistance and adhesion is also referred to as "having excellent effects of the present invention."

[0010] [Moisture-curable resin composition] The moisture-curable resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") is At least one polymer (A) selected from the group consisting of polyoxyalkylene polymers and (meth)acrylic acid alkyl ester polymers, having at least one crosslinkable silyl group in one molecule; A ketimine (B) which produces an amine upon hydrolysis that is an alkylamine having at least one primary amino group in one molecule and a melting point (freezing point) of less than 50°C; The moisture-curable resin composition contains a ketimine (C), which is an alkylamine having at least one primary amino group in one molecule and a melting point (freezing point) of 50°C or higher, and which produces an amine upon hydrolysis.

[0011] Since the composition of the present invention has the above-mentioned structure, it is believed that the desired effects can be obtained. Although the reason is not clear, it is speculated to be as follows. As described above, the composition of the present invention contains the following two types of ketimines. (i) Ketimine (B), which produces an amine upon hydrolysis that is an alkylamine having at least one primary amino group in one molecule and a melting point (freezing point) of less than 50°C. (ii) Ketimine (C), which is an alkylamine that has at least one primary amino group in one molecule and a melting point (freezing point) of 50°C or higher when hydrolyzed. It is believed that both of the above-mentioned two types of ketimines bleed out from the inside of the cured product to the surface, are hydrolyzed by moisture, etc. to become the corresponding amine, and furthermore, the amino group of the amine reacts with carbon dioxide in the air to form a salt on the surface of the cured product. As a result, it is believed that the surface tack of the cured product is reduced, and dirt such as dust is less likely to adhere to the surface of the cured product. On the other hand, the way in which ketimines bleed out changes depending on the environment (especially temperature) during and after curing, so if only one type of ketimine is used, depending on the time of application, the bleed-out may be insufficient or, conversely, excessive (leading to tackiness) may occur. Therefore, depending on the time of application, the stain resistance may be insufficient. In this regard, as described above, the present invention uses two specific ketimines in combination, which achieves appropriate bleed-out over a wide temperature range, and as a result, it is presumed that the coating exhibits excellent stain resistance regardless of the time of application. In addition, amines tend to recrystallize easily, which can result in the surface of the cured product (especially when cured in a low temperature environment) becoming uneven (white particles appearing on the surface of the cured product). However, since ketimines are used in the present invention, recrystallization is less likely to occur, and it is presumed that as a result, the surface after curing becomes uniform and smooth.

[0012] Each component contained in the composition of the present invention will be described below.

[0013] [Polymer (A)] The polymer (A) is at least one polymer selected from the group consisting of polyoxyalkylene polymers and (meth)acrylic acid alkyl ester polymers, which has at least one crosslinkable silyl group in one molecule.

[0014] <Main chain> The main chain of the polymer (A) is at least one polymer selected from the group consisting of polyoxyalkylene polymers and (meth)acrylic acid alkyl ester polymers. Among them, polyoxyalkylene polymers are preferred because they provide better effects of the present invention.

[0015] (Polyoxyalkylene polymer) Examples of polyoxyalkylene polymers include polyoxyethylene and polyoxypropylene. Among them, polyoxypropylene is preferred because it provides superior effects of the present invention.

[0016] ((Meth)acrylic acid alkyl ester polymer) The (meth)acrylic acid alkyl ester polymer is not particularly limited as long as it contains a repeating unit of a (meth)acrylic acid alkyl ester. The alkyl group of the (meth)acrylic acid alkyl ester may be unsubstituted or may have a substituent. The (meth)acrylic acid alkyl ester polymer may further include a repeating unit other than the repeating unit of the (meth)acrylic acid alkyl ester. The repeating unit other than the repeating unit of the (meth)acrylic acid alkyl ester is not particularly limited. For example, a repeating unit of a compound having an ethylenic group may be mentioned.

[0017] <Crosslinkable silyl group> As described above, the polymer (A) has at least one crosslinkable silyl group in one molecule. The polymer (A) preferably has a crosslinkable silyl group at its terminal, and more preferably has a crosslinkable silyl group at its terminal, because this provides better effects of the present invention. The crosslinkable silyl group can undergo a condensation reaction, for example, in the presence of moisture or the like, using a curing catalyst or the like.

[0018] Examples of the crosslinkable silyl group include a hydrolyzable silyl group. The crosslinkable silyl group may include a silanol group formed by hydrolysis of the hydrolyzable silyl group. Examples of the crosslinkable silyl group (hydrolyzable silyl group) include a group in which at least one hydrolyzable group selected from the group consisting of 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 is bonded to a silicon atom.

[0019] (hydrolyzable group) The hydrolyzable group is preferably at least one selected from the group consisting of a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an aminooxy group, a mercapto group, and an alkenyloxy group, more preferably an alkoxy group, and even more preferably a methoxy group, for reasons of superior effects of the present invention.

[0020] In the hydrolyzable silyl group, 1 to 3 of the hydrolyzable groups can be bonded to one silicon atom. The hydrolyzable silyl group is preferably a trialkoxysilyl group, more preferably a trimethoxysilyl group, because the effects of the present invention are more excellent. When one or two of the hydrolyzable groups are bonded to one silicon atom, the groups that can be bonded to the silicon atom other than the hydrolyzable groups are not particularly limited, and examples thereof include hydrocarbon groups.

[0021] The crosslinkable silyl group may further have a siloxane bond in addition to the hydrolyzable silyl group. The siloxane bond may be divalent or higher. When the crosslinkable silyl group further has a siloxane bond, the siloxane bond may be bonded to the main chain. The siloxane bond is not particularly limited as long as it is -Si-O-. The organic group bonded to the silicon atom in the -Si-O- is not particularly limited. The siloxane bond may be a polysiloxane. In one preferred embodiment, the polysiloxane is divalent.

[0022] <Bond between main chain and crosslinkable silyl group> In the polymer (A), the crosslinkable silyl group can be bonded to the main chain directly or via an organic group. The organic group is not particularly limited.

[0023] <Molecular weight> The weight average molecular weight of the polymer (A) is preferably from 10,000 to 70,000, and more preferably from 20,000 to 60,000, because the effects of the present invention are more excellent. The weight average molecular weight is a value calculated as standard polystyrene based on a measurement value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0024] <Content> In the composition of the present invention, the content of the polymer (A) is preferably 10 to 50 mass % and more preferably 20 to 40 mass % based on the total mass of the composition, because the effects of the present invention are more excellent.

[0025] [Ketimine (B)] Ketimine (B) is a ketimine which produces an amine upon hydrolysis that is an alkylamine (hereinafter also referred to as "amine (B)") having at least one primary amino group in each molecule and having a melting point (freezing point) of less than 50°C.

[0026] <Amine (B)> The amine (B) is an alkylamine having at least one primary amino group in one molecule and a melting point (freezing point) of less than 50° C. The primary amino group means —NH2. The amine (B) is preferably an alkylamine having two or more primary amino groups in one molecule, because the effects of the present invention are more excellent.

[0027] (Alkyl group) The alkyl group of the amine (B) may be linear, branched, or cyclic, but is preferably linear because the effects of the present invention are more excellent. The amine (B) preferably has a structure having one or more primary amino groups at the terminal of a linear alkyl group because the effects of the present invention are more excellent.

[0028] (Melting Point) The melting point of the amine (B) is below 50°C. The melting point of the amine (B) is preferably 45° C. or lower because the effects of the present invention are more excellent. The lower limit of the melting point of the amine (B) is not particularly limited, but in order to obtain better effects of the present invention, it is preferably 5° C. or higher, and more preferably 20° C. or higher. In this specification, the melting point is the melting point at 1 atmospheric pressure.

[0029] (Preferred embodiment) When the amine (B) has one primary amino group (when it is a monoamine), the number of carbon atoms in the alkyl group of the amine (B) is preferably 10 to 17, and more preferably 12 to 16, for reasons such as better effects of the present invention. Furthermore, when the amine (B) has two primary amino groups (when it is a diamine), the amine (B) is preferably ethylenediamine, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-hexanediamine, 1,7-heptanediamine, 1,9-nonanediamine or 1,11-undecanediamine, and more preferably 1,4-diaminobutane, 1,6-hexanediamine, 1,7-heptanediamine, 1,9-nonanediamine or 1,11-undecanediamine, because the effects of the present invention are more excellent.

[0030] <Carbonyl compounds> When ketimine (B) is hydrolyzed, a carbonyl compound is usually produced together with amine (B).

[0031] The carbonyl compound is not particularly limited, but from the viewpoint of the superior effects of the present invention, R 1 C(=O)R 2 It is preferable that the compound is represented by the following formula: Here, R 1 and R 2 R each independently represents a hydrogen atom or a hydrocarbon group. 1 and R2 may be bonded to each other to form a ring. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of these groups. Among these, an aliphatic hydrocarbon group is preferred because it provides superior effects of the present invention. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Specific examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, alkynyl groups, etc. Among these, alkyl groups are preferred because they provide better effects of the present invention. The number of carbon atoms in the hydrocarbon group is not particularly limited, but is preferably 1 to 10 because the effects of the present invention are superior.

[0032] Specific examples of the carbonyl compound include methyl isopropyl ketone (MIPK), methyl t-butyl ketone (MTBK), methyl isobutyl ketone (MIBK), methyl cyclohexyl ketone, methyl cyclohexanone, etc. Among these, methyl isobutyl ketone (MIBK) is preferred because it provides superior effects of the present invention.

[0033] <Manufacturing method> The method for producing the ketimine (B) is not particularly limited, and examples thereof include a method in which the amine (B) is subjected to a dehydration reaction with the carbonyl compound.

[0034] <Content> In the composition of the present invention, the content of the ketimine (B) is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the above-mentioned polymer (A), because the effects of the present invention are more excellent.

[0035] [Ketimine (C)] Ketimine (C) is a ketimine which produces an amine upon hydrolysis that is an alkylamine (hereinafter also referred to as "amine (C)") having at least one primary amino group in each molecule and having a melting point (freezing point) of 50°C or higher.

[0036] <Amine (C)> The amine (C) is an alkylamine having at least one primary amino group in one molecule and a melting point (freezing point) of 50° C. or higher. The amine (C) is preferably an alkylamine having two or more primary amino groups in one molecule, because the effects of the present invention are more excellent.

[0037] (Alkyl group) The alkyl group of the amine (C) may be linear, branched or cyclic, but is preferably linear because it provides better effects of the present invention.

[0038] (Melting Point) The melting point of the amine (C) is 50° C. or higher. The melting point of the amine (C) is preferably 55° C. or higher because the effects of the present invention are more excellent. The upper limit of the melting point of the amine (C) is not particularly limited, but it is preferably 70° C. or lower because the effects of the present invention are more excellent.

[0039] (Preferred embodiment) When the amine (C) has one primary amino group (when it is a monoamine), the number of carbon atoms in the alkyl group of the amine (C) is preferably 18 to 22, and more preferably 20 to 21, for reasons such as better effects of the present invention. Furthermore, when the amine (C) has two primary amino groups (when it is a diamine), the amine (C) is preferably 1,8-octanediamine, 1,10-decanediamine, or 1,12-dodecanediamine, and more preferably 1,10-decanediamine or 1,12-dodecanediamine, for reasons such as better effects of the present invention.

[0040] <Carbonyl compounds> When a ketimine (C) is hydrolyzed, a carbonyl compound is usually produced along with an amine (C). Specific examples and preferred embodiments of the carbonyl compound are the same as those of the carbonyl compound described in the ketimine (B).

[0041] <Manufacturing method> The method for producing the ketimine (C) is not particularly limited, and examples thereof include a method in which the amine (C) is subjected to a dehydration reaction with the above carbonyl compound.

[0042] <Content> In the composition of the present invention, the content of the ketimine (C) is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the above-mentioned polymer (A), because the effects of the present invention are more excellent.

[0043] [B+C] In the composition of the present invention, the total content of the ketimine (B) and the ketimine (C) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the above-mentioned polymer (A), for reasons of better effects of the present invention, etc.

[0044] [B / C] The ratio (B / C) of the content of ketimine (B) to the content of ketimine (C) is preferably 30 to 300 mass%, more preferably 50 to 150 mass%, and even more preferably 80 to 120 mass%, for reasons such as better effects of the present invention.

[0045] [Optional ingredients] The composition of the present invention may contain components (optional components) other than the above-mentioned components. Examples of such optional components include fillers, plasticizers, solvents (thickening agents), silane coupling agents, catalysts (curing catalysts), thixotropic agents, dehydrating agents, and antioxidants.

[0046] When the composition of the present invention contains an amine, the content is preferably 1.5 mass% or less, more preferably 0.5 mass% or less, based on the total composition, because the effects of the present invention are more excellent. When the composition of the present invention contains an amine, the content is preferably 5 mass% or less, more preferably 2 mass% or less, based on 100 mass% of the above-mentioned polymer (A), because the effects of the present invention are more excellent. However, when the composition of the present invention contains an amine as a silane coupling agent described later, the amine content does not include the amine that is the silane coupling agent. This is because the silane coupling agent is unlikely to bleed out and is unlikely to become solid, and therefore has little effect on the appearance.

[0047] <Filling agent> The composition of the present invention preferably contains a filler because the effects of the present invention are more excellent. Examples of the filler include fillers that are generally used in moisture-curable resin compositions, and specific examples include calcium carbonate, talc, silica, and carbon black. The filler is preferably calcium carbonate because it provides better effects of the present invention. Specific examples of calcium carbonate include colloidal calcium carbonate, heavy calcium carbonate, and light calcium carbonate.

[0048] (Content) In the composition of the present invention, the content of the filler is preferably 50 to 400 parts by mass, and more preferably 100 to 300 parts by mass, per 100 parts by mass of the above-mentioned polymer (A), because the effects of the present invention are more excellent.

[0049] <Plasticizer> The composition of the present invention preferably contains a plasticizer because the effects of the present invention are more excellent. Examples of the plasticizer include fillers used in moisture-curable resin compositions, and specific examples include phthalates such as dioctyl phthalate and diisononyl phthalate; non-aromatic dibasic acid esters such as diisononyl adipate; aliphatic monocarboxylic acid esters; esters of polyalkylene glycol; phosphate esters; trimellitic acid esters; chlorinated paraffins; process oils; polyether polyols such as polyethylene glycol and polypropylene glycol; epoxidized soybean oil; polyester, etc. Among these, polyether polyols are preferred, and polypropylene glycol is more preferred, because the effects of the present invention are superior.

[0050] (Content) In the composition of the present invention, the content of the plasticizer is preferably 5 to 100 parts by mass, and more preferably 10 to 50 parts by mass, per 100 parts by mass of the above-mentioned polymer (A), because the effects of the present invention are more excellent.

[0051] <Silane coupling agent> The composition of the present invention preferably contains a silane coupling agent because the effects of the present invention are more excellent. The silane coupling agent is not particularly limited, but is preferably a compound having a hydrolyzable silyl group and an amino group and / or an imino group, because this provides a better effect of the present invention.

[0052] (Hydrolyzable silyl group) A hydrolyzable silyl group is a group in which a hydrolyzable bond is attached to a silicon atom. Specific examples of the hydrolyzable group are the same as the hydrolyzable groups of the crosslinkable silyl group described above. The hydrolyzable group is preferably an alkoxy group, and more preferably a methoxy group, because the effects of the present invention are more excellent.

[0053] Examples of the hydrolyzable silyl group include those in which 1 to 3 hydrolyzable groups are bonded to a silicon atom. From the viewpoint of obtaining superior effects of the present invention, those in which 3 hydrolyzable groups are bonded to a silicon atom are preferred. When one or two hydrolyzable groups are bonded to a silicon atom, the remaining groups are not particularly limited. For example, the remaining groups include alkyl groups. For example, the alkyl groups include methyl groups and ethyl groups. The hydrolyzable silyl group is preferably an alkoxysilyl group, and more preferably a trimethoxysilyl group, because the effects of the present invention are more excellent.

[0054] (Amino group and / or imino group) The silane coupling agent preferably has an amino group and / or an imino group, and more preferably has an amino group and an imino group, because the effects of the present invention are more excellent.

[0055] (organic group) The hydrolyzable silyl group and the amino group and / or imino group can be bonded via an organic group. The organic group is not particularly limited. For example, an aliphatic hydrocarbon group (chain or branched) or an aromatic hydrocarbon group can be mentioned. For example, an aliphatic hydrocarbon group can be an alkylene group having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, or a trimethylene group.

[0056] (Content) In the composition of the present invention, the content of the silane coupling agent is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the above-mentioned polymer (A), because the effects of the present invention are more excellent.

[0057] <Catalyst> The composition of the present invention preferably contains a catalyst (curing catalyst) for the reason that the effects of the present invention are more excellent. The curing catalyst is not particularly limited as long as it is a compound capable of hydrolyzing and / or condensing the crosslinkable silyl group.

[0058] The curing catalyst preferably contains a tin catalyst because the effects of the present invention are more excellent.

[0059] The tin catalyst is not particularly limited. For example, metal carboxylates such as tin octanoate, tin butanoate, tin caprylate, and tin oleate; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dioctyltin dilaurate, diphenyltin diacetate, dibutyltin oxide, reaction products of dibutyltin oxide and phthalic acid ester, dibutyltin dimethoxide, and dibutyltin (triethoxysiloxy)-like organic tin compounds; tin chelate compounds such as dibutyltin diacetylacetonate; tin oxides such as dibutyltin oxide and dioctyltin oxide, and diisononyl phthalate (DINP)-modified tin.

[0060] (Content) In the composition of the present invention, the content of the curing catalyst is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the above-mentioned polymer (A), because the effects of the present invention are more excellent.

[0061] [Manufacturing method] The method for producing the composition of the present invention is not particularly limited, and examples thereof include a method in which the above-mentioned components are mixed together.

[0062] [Application] There are no particular limitations on the substrate to which the composition of the present invention can be applied, and examples thereof include glass, plastic, rubber, wood, metal, asphalt, stone, and porous materials. The composition of the present invention is particularly useful as a sealant for exterior walls (for example, siding boards) and the like. The composition of the present invention is cured, for example, by moisture in the air. EXAMPLES

[0063] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0064] [Synthesis of ketimines] The ketimine was synthesized as follows.

[0065] <Synthesis 1> Ketimine was obtained by dehydrating 1,6-hexanediamine (melting point: 42°C) with methyl isobutyl ketone. The obtained ketimine is also called compound 1. Compound 1 corresponds to the above-mentioned ketimine (B) because it produces 1,6-hexanediamine (an alkylamine having two primary amino groups and a melting point of 42°C) when hydrolyzed.

[0066] <Synthesis 2> Ketimine was obtained by dehydrating cetylamine (melting point: 44°C) with methyl isobutyl ketone. The obtained ketimine is also called compound 2. Compound 2 corresponds to the above-mentioned ketimine (B) because it produces cetylamine (an alkylamine having one primary amino group and a melting point of 44°C) when hydrolyzed.

[0067] <Synthesis 3> Ketimine was obtained by dehydrating 1,10-decanediamine (melting point: 62°C) with methyl isobutyl ketone. The obtained ketimine is also called compound 3. Compound 3 corresponds to the above-mentioned ketimine (C) because it produces 1,10-decanediamine (an alkylamine having two primary amino groups and a melting point of 62°C) when hydrolyzed.

[0068] <Synthesis 4> Stearylamine (melting point: 53°C) and methyl isobutyl ketone were subjected to a dehydration reaction to obtain ketimine. The obtained ketimine is also called compound 4. Compound 4 corresponds to the above-mentioned ketimine (C) because it produces stearylamine (an alkylamine having one primary amino group and a melting point of 53°C) when hydrolyzed.

[0069] [Preparation of moisture-curable resin composition] Each moisture-curable resin composition was prepared by mixing the components shown in Table 1 below in the ratios (parts by mass) shown in the same table.

[0070] 〔evaluation〕 The obtained moisture-curable resin compositions were evaluated as follows.

[0071] <Appearance> Each of the obtained moisture-curable resin compositions was applied onto a substrate and allowed to stand for 2 weeks in an environment of 0° C. Then, the surface of the cured product was visually observed and the appearance was evaluated according to the following criteria. The results are shown in Table 1. ◯: The surface of the cured product is uniform and smooth. ×: The surface of the cured product is uneven and has irregularities (white grains of crystallized amine are present on the surface of the cured product).

[0072] <Stain resistance> Each of the obtained moisture-curable resin compositions was applied onto a substrate and left to stand in an environment of 5°C, 23°C, and 40°C. Then, the surface tack strength of the cured product after 24 hours and one week was measured using a tack checker (product name Tackiness Checker HTC-1, manufactured by Toyo Seiki Co., Ltd.). Then, the surface tack was evaluated according to the following criteria. The results are shown in Table 1. ◎ or ○ can be said to be excellent in contamination resistance, and ◎ can be said to be more excellent in contamination resistance. In addition, ◎ or ○ can be said to be excellent in contamination resistance regardless of the construction time at all of 5°C (5°C curing), 23°C (23°C curing), and 40°C (40°C curing). ◎: Surface tack strength is 1.0N or less ○: Surface tack strength is over 1.0N and 1.5N or less △: Surface tack strength is over 1.5N and 2.0N or less ×: Surface tack strength is over 2.0N

[0073] [Table 1]

[0074] Details of each component in Table 1 are as follows.

[0075] Polymer A: SAX220 (polyoxypropylene having trimethoxysilyl groups at both ends, manufactured by Kaneka Corporation) (corresponding to the above-mentioned polymer (A)) Filler 1: Calfine 200 (calcium carbonate, manufactured by Maruo Calcium Co., Ltd.) Filler 2: Super S (calcium carbonate, manufactured by Maruo Calcium Co., Ltd.) Plasticizer: Exenol 3020 (polypropylene glycol, manufactured by AGC) Solvent: Mineral spirits (manufactured by Nippon Oil Corporation) Silane coupling agent: KBM-603 (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) Catalyst: MSCAT-02 (tin catalyst, manufactured by Nippon Chemical Industries Co., Ltd.) Ketimine B1: the above compound 1 Ketimine B2: the above compound 2 Ketimine C1: the above compound 3 Ketimine C2: the above compound 4 Amine 1: 1,6-Hexanediamine Amine 2: 1,10-decanediamine

[0076] In Table 1, the upper number in parentheses in the ketimine column indicates the name of the amine compound produced when the ketimine is hydrolyzed, and the lower number indicates its melting point [°C].

[0077] As can be seen from Table 1, in Examples 1 to 6 containing the polymer (A), the ketimine (B), and the ketimine (C), the surfaces after curing were all uniform and smooth. In addition, all of the examples showed excellent stain resistance regardless of the time of application. Comparing Examples 1 to 3 (comparison between embodiments in which only the mass parts of ketimine (B) and ketimine (C) are different), Example 1 in which the above-mentioned B / C is 50 to 150 mass% showed superior stain resistance (cured at 5°C or 40°C). Furthermore, comparing Example 1 with Examples 4 to 6 (comparison between embodiments in which only the types of ketimine (B) and ketimine (C) are different), Examples 1 and 4 to 5, in which the difference between the melting point of the amine (C) and the melting point of the amine (B) is 10°C or more, showed better stain resistance (after 24 hours of curing at 5°C or 24 hours of curing at 40°C). Among them, Examples 1 and 5, in which the difference between the melting point of the amine (C) and the melting point of the amine (B) is 15°C or more, showed even better stain resistance (after 24 hours of curing at 40°C). Among them, Example 1, in which the difference between the melting point of the amine (C) and the melting point of the amine (B) is 20°C or more, showed particularly excellent stain resistance (after 24 hours of curing at 5°C).

[0078] On the other hand, Comparative Examples 1 and 2, which contained only ketimine (B), had insufficient stain resistance when cured at high temperatures. Comparative Examples 3 and 4, which contained only ketimine (C), had insufficient stain resistance when cured at low temperatures. Comparative Example 5, which did not contain either ketimine (B) or ketimine (C), had insufficient stain resistance at any temperature when cured. Comparative Examples 6 to 8, which used amines instead of ketimine (B) and ketimine (C), had non-uniform surfaces after curing.

Claims

1. At least one polymer (A) selected from the group consisting of polyoxyalkylene polymers and (meth)acrylic acid alkyl ester polymers, each of which has at least one crosslinkable silyl group in one molecule; A ketimine (B) which produces an amine upon hydrolysis that is an alkylamine having at least one primary amino group in one molecule and a melting point (freezing point) of less than 50°C; and a ketimine (C) which is an alkylamine having at least one primary amino group in one molecule and a melting point (freezing point) of 50° C. or higher, The moisture-curable resin composition, wherein the ratio (B / C) of the content of the ketimine (B) to the content of the ketimine (C) is 30 to 300 mass%.

2. The moisture-curable resin composition according to claim 1, wherein the total content of the ketimine (B) and the ketimine (C) is 0.5 to 10 parts by mass relative to 100 parts by mass of the polymer (A).

3. The melting point of the amine produced when the ketimine (B) is hydrolyzed is 20° C. or higher, 3. The moisture-curable resin composition according to claim 1, wherein the melting point of the amine generated when the ketimine (C) is hydrolyzed is 70°C or lower.

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