Moisture-curable resin composition

Abstract

Provided is a moisture-curable resin composition having better storage stability than conventional ones. [Solution] A moisture-curable resin composition containing an (meth)acrylic acid alkyl ester polymer (P) having a crosslinkable silyl group, an amine (A) having an amino group and / or a latent amino group but no crosslinkable silyl group, and a monoaminosilane (S) having a crosslinkable silyl group and only one amino group per molecule.

Description

[Technical field]

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

[0002] Conventionally, a composition containing a polymer having a crosslinkable silyl group and two different ketimines having different melting points has been known as a moisture-curable resin composition for a sealant (for example, Patent Document 1). This composition contains two different ketimines, and is intended to improve the surface uniformity and stain resistance of the cured product obtained by curing the composition. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2022-077120 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have examined the moisture-curable resin composition described in Patent Document 1 and found that, depending on the composition and storage conditions, the storage stability is not necessarily sufficient, and there are disadvantages such as a decrease in workability over time and a shortened storage period, and that there is room for further improvement in storage stability.

[0005] In view of the above circumstances, an object of the present invention is to provide a moisture-curable resin composition having better storage stability than conventional ones. [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 blending a monoaminosilane with a moisture-curable resin composition, and have arrived at the present invention. That is, the present inventors have found that the above problems can be solved by the following configuration.

[0007] [1] a (meth)acrylic acid alkyl ester polymer (P) having a crosslinkable silyl group; Latent amine (A) having a latent amino group and no crosslinkable silyl group and, Contains a crosslinkable silyl group and a monoaminosilane (S) having only one amino group per molecule, The monoaminosilane (S) is present in an amount of 10.4 to 30 parts by mass relative to 100 parts by mass of the polymer (P). Moisture-curable resin composition. [ 2 ] The monoaminosilane (S) is 100 mass % of the amine (A). Department 25 to 400 mass Department The moisture-curable resin composition according to [1] or [2], wherein the content of [ 3 ] Used as a composition for forming a sealant.[1] Or [2] The moisture-curable resin composition described above. [ 4 ] [1]~[ 3

[0023] A step of preparing a moisture-curable resin composition according to the present invention; and curing the moisture-curable resin composition. [ 5 ] [1]~[ 3 2. A sealant obtained by curing the moisture-curable resin composition according to claim 1. 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 having better storage stability than conventional ones. 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.

[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 a moisture-curable resin composition containing an (meth)acrylic acid alkyl ester polymer (P) having a crosslinkable silyl group, an amine (A) having an amino group and / or a latent amino group but no crosslinkable silyl group, and a monoaminosilane (S) having a crosslinkable silyl group and only one amino group per molecule.

[0011] It is believed that the composition of the present invention contains such ingredients and therefore has the desired effects. Although the reason for this is not clear, it is speculated to be roughly as follows. The (meth)acrylic acid alkyl ester polymer (P) having a crosslinkable silyl group has an ester bond in its molecule. The ester bond may react with the amine (A) present in the composition as a side reaction to form an amide bond. If a crosslinkable silyl group and a monoaminosilane (S) having only one amino group per molecule are present in a composition containing such a polymer (P), it competes with the amine (A) in the side reaction, preventing the polymer (P) from reacting with the amine (A), and improving storage stability.

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

[0013] <Polymer (P)> The composition of the present invention contains a (meth)acrylic acid alkyl ester polymer (P) having a crosslinkable silyl group. The polymer (P) contains a repeating unit of an alkyl (meth)acrylate. The alkyl group of the alkyl (meth)acrylate may be unsubstituted or may have a substituent. The polymer (P) may further contain repeating units other than the repeating units derived from the (meth)acrylic acid alkyl ester.

[0014] (Crosslinkable silyl group) The polymer (P) has a crosslinkable silyl group. The polymer (P) preferably has at least one crosslinkable silyl group in one molecule. The polymer (P) preferably has a crosslinkable silyl group at its terminal. The crosslinkable silyl group can undergo a condensation reaction, for example, in the presence of moisture or the like, by using a curing catalyst or the like.

[0015] The crosslinkable silyl group may be, for example, a hydrolyzable silyl group. The crosslinkable silyl group may contain a silanol group formed by hydrolysis of the hydrolyzable silyl group. The crosslinkable silyl group (hydrolyzable silyl group) may be, for example, 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.

[0016] (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 amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. The hydrolyzable group is more preferably an alkoxy group, and even more preferably a methoxy group.

[0017] The hydrolyzable silyl group is preferably a trialkoxysilyl group, more preferably a trimethoxysilyl group. When the polymer (P) contains two or more kinds of polymers, one kind may be a polymer having a trialkoxysilyl group, and the other kind may be a polymer having a dialkoxysilyl group (preferably a dimethoxysilyl group). 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.

[0018] 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.

[0019] <Bond between main chain and crosslinkable silyl group> In the polymer (P), the crosslinkable silyl group can be bonded to the main chain directly or via an organic group. The organic group is not particularly limited.

[0020] (molecular weight) The weight average molecular weight of the polymer (P) is preferably from 20,000 to 100,000, and more preferably from 40,000 to 80,000. The weight average molecular weight is a value calculated as a standard polystyrene based on a measurement value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0021] (Content) In the composition of the present invention, the polymer (P) is preferably present in an amount of 10 to 90% by mass based on the total mass of the composition, and more preferably 15 to 80% by mass.

[0022] <Amine (A)> The composition of the present invention contains an amine (A) which has an amino group and / or a latent amino group and does not have a crosslinkable silyl group.

[0023] <Amine (A-1)> The amine (A) may be an amine (A-1) having an amino group and no crosslinkable silyl group. The amine (A-1) is preferably an alkylamine having at least one primary amino group in one molecule. The primary amino group means -NH2. The amine (A) may be an alkylamine having two or more primary amino groups in one molecule.

[0024] (Alkyl group) The alkyl group of the amine (A-1) may be linear, branched, or cyclic. The amine (A-1) may have, for example, a structure having one or more primary amino groups at the terminal of a cyclic linear alkyl group, or a structure having one or more primary amino groups at the terminal of a linear alkyl group.

[0025] (Preferred embodiment) The alkyl group of the amine (A) preferably has 3-40 carbon atoms, more preferably 5-30 carbon atoms, further preferably 10-25 carbon atoms, and even more preferably 15-20 carbon atoms. The amine (A) may be an amine that is solid at room temperature, such as stearylamine or cetylamine.

[0026] <Ketimine (K)> The amine (A) may be a ketimine (K). The ketimine (K) is a compound that generates an amine when hydrolyzed. The ketimine (K) is preferably a compound that generates an amine when hydrolyzed, which is an alkylamine having at least one primary amino group in one molecule. The alkylamine generated by the hydrolysis is preferably the same as the amine (A-1).

[0027] <Carbonyl compounds> When a ketimine (K) is hydrolyzed, a carbonyl compound (C) is usually produced along with an amine (A).

[0028] The carbonyl compound (C) is preferably a compound represented by R1C(=O)R2. Here, R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group, and R1 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 thereof, etc. Among these, an aliphatic hydrocarbon group is preferable. 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.

[0029] Specific examples of the carbonyl compound (C) 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.

[0030] <Manufacturing method> The ketimine (K) can be obtained, for example, by a method in which the amine (A) is subjected to a dehydration reaction with the above carbonyl compound (C).

[0031] <Content> In the composition of the present invention, the content of the amine (A) is 100 mass % of the polymer (P). Department 1 to 50 mass Department The content is preferably 2 to 40 mass %. DepartmentMore preferably, the weight ratio is 5 to 30 Department It is more preferable that:

[0032] <Silane (S)> The composition of the present invention contains a monoaminosilane (S) having a crosslinkable silyl group and only one amino group per molecule. The crosslinkable silyl group of the monoaminosilane (S) is preferably a hydrolyzable silyl group.

[0033] (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, more preferably a methoxy group.

[0034] The hydrolyzable silyl group may be, for example, one in which 1 to 3 hydrolyzable groups are bonded to a silicon atom. The hydrolyzable silyl group is preferably one in which 3 hydrolyzable groups are bonded to a silicon atom. When one or two hydrolyzable groups are bonded to a silicon atom, the other groups bonded to the silicon atom may be, for example, alkyl groups, such as methyl and ethyl groups. The hydrolyzable silyl group is preferably an alkoxysilyl group, and more preferably a trimethoxysilyl group.

[0035] (organic group) The hydrolyzable silyl group and the amino group can be bonded via an organic group. The organic group may be, for example, an aliphatic hydrocarbon group (linear or branched) or an aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include alkylene groups having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, and a trimethylene group.

[0036] The silane (S) having a hydrolyzable silyl group and an amino group may be, for example, an aminoalkyltrialkoxysilane such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltrimethoxysilane, and 4-aminobutyltriethoxysilane, with 3-aminopropyltriethoxysilane being preferred.

[0037] (Content) In the composition of the present invention, the monoaminosilane (S) is Department 2 to 30 mass Department The content is preferably 3 to 25 mass %. Department More preferably, the weight ratio is 4 to 20 Department More preferably, the weight ratio is 5 to 15 Department It is even more preferred that:

[0038] (Content) In the composition of the present invention, the monoaminosilane (S) is a silane having a molecular weight of 1000 parts by mass of the above-mentioned amine (A). Department 25 to 400 mass Department The content is preferably 30 to 350 mass %. Department More preferably, the weight ratio is 35 to 300. Department More preferably, the weight ratio is 40 to 250. Department More preferably, the weight ratio is 50 to 200. Department It is most preferable that:

[0039] [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), catalysts (curing catalysts), thixotropic agents, dehydrating agents, and antioxidants.

[0040] <Filling agent> The compositions of the present invention may contain a filler. 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.

[0041] (Content) In the composition of the present invention, the content of the filler is preferably 100% by mass of the above-mentioned polymer (P) because the effects of the present invention are more excellent. Department 50 to 400 mass Department It is preferable that the weight ratio is 100 to 300. Department may be also possible.

[0042] <Plasticizer> The composition of the present invention may contain a plasticizer. The plasticizer is preferably a polymer having a weight average molecular weight of 400 to 11000. Specific examples include phthalates such as dioctyl phthalate, dibutyl phthalate, and butyl benzyl phthalate, polyalkylene oxides such as polypropylene glycol, and acrylic polymers. Among these, acrylic polymers are preferred. The acrylic polymers preferably do not contain a hydrolyzable silyl group.

[0043] (Content) In the composition of the present invention, the content of the plasticizer is 100% by mass of the polymer (P). Department 20 to 400 mass Department It is preferable that the weight ratio is 30 to 300. Department More preferably, the weight ratio is 50 to 200. Department It is more preferable that: <Catalyst> The composition of the present invention may contain a catalyst (curing catalyst). The curing catalyst is a compound capable of hydrolyzing and / or condensing the crosslinkable silyl group.

[0044] The curing catalyst may include a tin catalyst.

[0045] Examples of tin catalysts include metal carboxylates such as tin octoate, tin butanoate, tin caprylate, and tin oleate; organic tin compounds such as dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dioctyltin dilaurate, diphenyltin diacetate, dibutyltin oxide, reaction products of dibutyltin oxide and phthalic acid esters, dibutyltin dimethoxide, and dibutyltin(triethoxysiloxy); tin chelate compounds such as dibutyltin diacetylacetonate; tin oxides such as dibutyltin oxide and dioctyltin oxide; and diisononyl phthalate (DINP)-modified tin.

[0046] (Content) In the composition of the present invention, the content of the curing catalyst is Department 0.05 to 5 mass Department is preferably 0.1 to 3 mass Department It is more preferable that:

[0047] [Manufacturing method] The composition of the present invention can be produced, for example, by mixing the above-mentioned components.

[0048] [Application] Substrates to which the compositions of the present invention can be applied may be, for example, 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

[0049] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0050] [Synthesis of ketimines] Stearylamine (Melting point: 53°C, CH3(CH2) 17 Ketimine (K-1) was synthesized by the dehydration reaction of NH2) with methyl isobutyl ketone (MIBK).

[0051] [Preparation of moisture-curable resin composition] The components shown in Tables 1 and 2 below are mixed in the proportions (by mass) shown in the tables. Department ) were mixed to prepare each moisture-curable resin composition.

[0052] 〔evaluation〕 The viscosity of each of the obtained moisture-curable resin compositions was measured as follows.

[0053] <Viscosity> Each moisture-curable resin composition obtained was sealed in a glass container and allowed to stand in an environment of 80°C for 28 days. The viscosity (Pa·S) of each moisture-curable resin composition was measured initially, and after 3 or 7 days, and after 28 days. Viscosity was measured using an E-type viscometer (Toki Sangyo Co., Ltd., standard cone rotor) at a rotation speed of 1 rpm or 0.5 rpm and 23°C (unit: Pa·s). RC represents the rate of change (percentage) relative to the initial viscosity.

[0054] [Table 1]

[0055] [Table 2]

[0056] Details of each component in Tables 1 and 2 are as follows.

[0057] Polymer (P-1): Polyoxypropylene having trimethoxysilyl groups at both ends (product name SAX220, Polymer (P) do not (manufactured by Kaneka Corporation) Polymer (P-2): A modified polymer having a methyldimethoxysilyl group at the end and a poly(meth)acrylate skeleton in the main chain (product name SA410S, corresponding to Polymer (P), manufactured by Kaneka Corporation) Polymer (P-3): SB803S (a mixture of SA410S and SAX220 in a mass ratio of 70:30) Stearylamine-MIBK ketimine: The above-mentioned compound corresponds to ketimine (K). Diaminosilane (product name: KBM-603, having the following structure, manufactured by Shin-Etsu Chemical Co., Ltd.) (CH3O)3SiC3H6NHC2H4NH2 Epoxy silane: (Product name: KBM-403, having the following structure, manufactured by Shin-Etsu Chemical Co., Ltd.) JPEG0007625116000003.jpg1467·Monoaminosilane (product name: KBM-903, having the following structure, manufactured by Shin-Etsu Chemical Co., Ltd.) (CH3O)3SiC3H6NH2 NBDA: Norbornanediamine ("bis(aminomethyl)norbornane (mixture of isomers) having the following structure, manufactured by Tokyo Chemical Industry Co., Ltd.) TIFF0007625116000004.tif2056·Plasticizer: Non-functional acrylic plasticizer (product name ARUFON (registered trademark) UP-1110, manufactured by Toagosei Co., Ltd.) Moisture remover: Vinyl silane coupling agent (product name SILQUEST A-171, manufactured by Nippon Shokugyo Co., Ltd.)

[0058] As can be seen from Table 1, Example 1, which contains a polymer (P), an amine (A), and a monoaminosilane (S), exhibited a suppressed increase in viscosity over time compared to Comparative Examples 1 to 9, and had particularly excellent storage stability.

Claims

1. a (meth)acrylic acid alkyl ester polymer (P) having a crosslinkable silyl group; A latent amine (A) having a latent amino group and no crosslinkable silyl group; Contains a crosslinkable silyl group and a monoaminosilane (S) having only one amino group per molecule, The moisture-curable resin composition, wherein the monoaminosilane (S) is present in an amount of 10.4 to 15 parts by mass per 100 parts by mass of the polymer (P).

2. The moisture-curable resin composition according to claim 1, wherein the monoaminosilane (S) is present in an amount of 25 to 400 parts by mass per 100 parts by mass of the latent amine (A).

3. The moisture-curable resin composition according to claim 1 , which is used as a composition for forming a sealant.

4. A step of preparing the moisture-curable resin composition according to claim 1; and curing the moisture-curable resin composition.

5. A sealant obtained by curing the moisture-curable resin composition according to claim 1.

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