Multi-component curable composition and cured product

Abstract

To provide a curable composition and a cured product improved in durability.SOLUTION: A multi-component curable composition comprises: a main agent containing a (meth)acrylic copolymer (A1) and a polyoxyalkylene polymer (B) having alkoxysilyl groups; and a curing agent containing a curing catalyst. The (meth)acrylic copolymer (A1) is a block copolymer containing an X block and a Y block and has alkoxysilyl groups. The X block and the Y block are different in content of alkoxysilyl groups.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a multi-component curable composition and a cured product thereof. [Background technology]

[0002] Polymer molecules containing alkoxysilyl groups form siloxane bonds with other polymer molecules through hydrolysis of the alkoxysilyl groups. This crosslinking reaction is known to produce rubber-like cured products. Taking advantage of the above-mentioned characteristics, polymers containing alkoxysilyl groups are used in a wide range of applications, including sealants, adhesives, and paints.

[0003] An example of such a polymer is a polyoxyalkylene polymer having an alkoxysilyl group. A curable composition containing a polyoxyalkylene polymer having an alkoxysilyl group has good workability and an excellent balance of mechanical properties (e.g., elongation at break, strength at break). However, in the case of a polyoxyalkylene polymer, unless an antioxidant is used, the hydrogen atoms bonded to the tertiary carbon are easily oxidized. This causes a problem of poor weather resistance of the curable composition.

[0004] To solve this problem, a curable composition has been proposed in which a polyoxyalkylene polymer having an alkoxysilyl group is mixed with a (meth)acrylic copolymer having an alkoxysilyl group. For example, Patent Document 1 discloses a sealant composition containing a vinyl polymer (A) having an alkoxysilyl group, a polyoxyalkylene compound (B) having an alkoxysilyl group at its terminal, and a polypropylene glycol (C1) of a specific molecular weight or a vinyl polymer (C2) having no alkoxysilyl group. Patent Document 2 discloses a sealant composition containing (A) an oxyalkylene polymer having an alkoxysilyl group and (B) a specific vinyl polymer having a crosslinkable functional group. Patent Document 3 discloses a curable resin composition containing a specific vinyl polymer containing a (meth)acrylic acid ester monomer having a hydrolyzable silyl group as a constituent monomer, and a hydrolyzable silyl group-containing oxyalkylene polymer. Patent Document 4 discloses a curable composition containing a polyether polymer (I) having a number average molecular weight of 10,000 or more and a vinyl polymer (II) having at least one crosslinkable functional group at the polymer terminal. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-018748 [Patent Document 2] International Publication No. 2008 / 059872 Pamphlet [Patent Document 3] Japanese Patent Application Laid-Open No. 2014-118502 [Patent Document 4] International Publication No. 2005 / 095492 Pamphlet Summary of the Invention [Problem to be solved by the invention]

[0006]

[0006] It is known that one embodiment of such a curable composition is a multi-component curable composition. However, the inventors have conducted studies and found that when the curable compositions of the prior art described above are converted into multi-component curable compositions, there is still room for improvement in durability.

[0007] An object of one aspect of the present invention is to provide a curable composition and a cured product having improved durability and fatigue resistance. [Means for solving the problem]

[0008] The multi-component curable composition according to one embodiment of the present invention comprises: a base agent containing a (meth)acrylic copolymer (A1) and a polyoxyalkylene polymer (B) having an alkoxysilyl group; a curing agent containing a curing catalyst; A multi-component curable composition comprising: The (meth)acrylic copolymer (A1) has an X block and a Y block, The molecule of the (meth)acrylic copolymer (A1) contains an XY diblock structure or an XYX triblock structure, the number of repeating units derived from a (meth)acrylic acid ester monomer having an alkoxysilyl group contained in the X block is 1.0 or more on average, the content of repeating units derived from a (meth)acrylic acid ester monomer having an alkoxysilyl group contained in the Y block is 0 to 3 wt % based on the weight of all repeating units contained in the Y block; The (meth)acrylic copolymer (A1) has a molecular weight distribution (Mw / Mn) of 1.8 or less. [Effects of the Invention]

[0009] According to one aspect of the present invention, there are provided a multi-component curable composition and a cured product having improved durability. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, an example of an embodiment of the present invention will be described in detail, but the present invention is not limited to this.

[0011] Unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more and B or less." In this specification, "(meth)acrylic" means "acrylic" and / or "methacrylic."

[0012] One of the typical applications of (meth)acrylic copolymers having alkoxysilyl groups is construction sealants. When producing construction sealants using (meth)acrylic copolymers, multi-component curable compositions are usually used. A multi-component curable composition is a curable composition in which a base agent containing a (meth)acrylic copolymer and the like and a curing agent containing a curing catalyst and the like are separately prepared (e.g., a two-component curable composition). By mixing the base agent and the curing agent, siloxane bonds are formed between the alkoxysilyl groups, resulting in a cured product. Multi-component curable compositions tend to be particularly popular in the field of construction sealants because cured products of various colors can be obtained by adding colorants.

[0013] An example of a conventional (meth)acrylic copolymer having an alkoxysilyl group is the copolymer disclosed in JP 2007-302749 A. However, it has been found that a multi-component curable composition containing this copolymer leaves room for improvement in the durability and fatigue resistance of the resulting cured product. In one aspect of the present invention, this problem is solved by incorporating a (meth)acrylic copolymer (A1) into the base resin.

[0014] In this specification, "durability" refers to the resistance of a material to external physical and / or chemical influences. "Fatigue resistance" refers to the resistance of a material to the deterioration of mechanical properties that occurs when subjected to continuous or repeated mechanical stress. Both durability and fatigue resistance can be evaluated by the evaluation methods described in the Examples.

[0015] ≪1. Main ingredient≫ The main component of the multi-component curable composition according to one embodiment of the present invention contains a (meth)acrylic copolymer (A1) and a polyoxyalkylene polymer (B) having an alkoxysilyl group. Each component will be described in detail below.

[0016] [1.1. (Meth)acrylic copolymer (A1) and (meth)acrylic liquid copolymer (A2)] The (meth)acrylic copolymer (A1) has an X block and a Y block, and contains an XY diblock structure or an XYX triblock structure in the molecule. The overall molecular structure of the (meth)acrylic copolymer (A1) is not particularly limited as long as it contains an XY diblock structure or an XYX triblock structure, and may be, for example, an XYXY tetrablock structure.

[0017] Here, the term "XYX triblock structure" refers to what is commonly referred to by those skilled in the art as an "ABA triblock structure." The X / Y ratio in the (meth)acrylic copolymer (A1) is preferably from (5 / 95) to (60 / 40), more preferably from (15 / 85) to (40 / 60).

[0018] In one embodiment, the molecule of the (meth)acrylic copolymer (A1) has an XY diblock structure. In a molecule of the XY diblock structure, the X block can be a region of 40% or less, 30% or less, or 25% or less from one end of the molecule (all units contained in the molecule are taken as 100%). Here, the X block is the block on the side where alkoxysilyl groups are distributed in a relatively large amount.

[0019] In one embodiment, the molecule of the (meth)acrylic copolymer (A1) has an XYX triblock structure. In the molecule of the XYX triblock structure, the X blocks may be 40% or less, 30% or less, or 25% or less of the region from the terminal of the molecule (all units contained in the molecule are taken as 100%). Here, the X blocks are blocks located at both terminals of the molecule.

[0020] The (meth)acrylic copolymer (A1) also contains repeating units derived from (meth)acrylic ester monomers having an alkoxysilyl group. These repeating units derived from (meth)acrylic ester monomers having an alkoxysilyl group are contained in a relatively large amount in the X block. Specifically, the repeating units derived from (meth)acrylic ester monomers having an alkoxysilyl group contained in the X block are 1.0 or more on average. Meanwhile, the repeating units derived from (meth)acrylic ester monomers having an alkoxysilyl group contained in the Y block are 0 to 3 wt % based on the weight of all repeating units contained in the Y block.

[0021] Therefore, the repeating units derived from the (meth)acrylic acid ester monomer having an alkoxysilyl group are distributed in large quantities at least at one end of the (meth)acrylic copolymer (A1). In particular, when the (meth)acrylic copolymer (A1) has an XY diblock structure, the repeating units derived from the (meth)acrylic acid ester monomer having an alkoxysilyl group are localized at one end of the molecule. In addition, when the (meth)acrylic copolymer (A1) has an XYX triblock structure, the repeating units derived from the (meth)acrylic acid ester monomer having an alkoxysilyl group are localized at both ends of the molecule.

[0022] The number of repeating units derived from (meth)acrylic acid ester monomers having an alkoxysilyl group contained in the X block is, on average, 1.0 or more, preferably 1.1 or more, more preferably 1.3 or more, even more preferably 1.5 or more, and particularly preferably 1.7 or more. Similarly, the number of repeating units derived from (meth)acrylic acid ester monomers having an alkoxysilyl group contained in the X block is preferably greater than 3 wt%, more preferably 4.5 wt% or more, and even more preferably 5 wt% or more, based on the weight of all repeating units contained in the X block. The upper limit of the number of repeating units derived from (meth)acrylic acid ester monomers having an alkoxysilyl group contained in the Y block is preferably 2 wt% or less, more preferably 1 wt% or less, based on the weight of all repeating units contained in the Y block. The lower limit of the number of repeating units derived from (meth)acrylic acid ester monomers having an alkoxysilyl group contained in the Y block is preferably greater than 0 wt%, more preferably 0 wt% or more, based on the weight of all repeating units contained in the Y block.

[0023] Furthermore, the (meth)acrylic copolymer (A1) is an acrylic copolymer having a small ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn; molecular weight distribution). The molecular weight distribution of the (meth)acrylic copolymer (A1) is 1.5 or less. The molecular weight distribution of the (meth)acrylic copolymer (A1) is preferably 1.4 or less, 1.3 or less, or 1.2 or less. If the molecular weight distribution is too large, the viscosity of the polymer increases, which tends to reduce workability.

[0024] The weight-average molecular weight and number-average molecular weight can be measured, for example, by gel permeation chromatography (GPC). For GPC measurement, chloroform can be used as the mobile phase and a polystyrene gel column can be used as the stationary phase. These molecular weights can be calculated in terms of polystyrene.

[0025] The (meth)acrylic copolymer (A1) having such a narrow molecular weight distribution can be suitably produced, for example, by a production method utilizing living radical polymerization, and more suitably by the method described in Section [1.2].

[0026] ((Meth)acrylic copolymer (A2)) In one embodiment, the (meth)acrylic copolymer (A1) is a (meth)acrylic copolymer (A2). The (meth)acrylic copolymer (A2) is a preferred embodiment among the (meth)acrylic copolymers (A1) because it has a particularly low viscosity. The (meth)acrylic copolymer (A2) randomly contains repeating units derived from a (meth)acrylic acid ester monomer (α). The repeating units derived from the (meth)acrylic acid ester monomer (α) account for 5 to 20 wt % of the total weight of the repeating units contained in the (meth)acrylic copolymer (A2) (this content is critical). Here, the (meth)acrylic acid ester monomer (α) refers to a monomer having an alkyl group ester-bonded to (meth)acrylic acid, and the alkyl group has an alkoxy group having 1 to 5 carbon atoms. Preferably, the alkyl group ester-bonded to acrylic acid has 1 to 5 carbon atoms.

[0027] The content of the repeating unit derived from the (meth)acrylic acid ester monomer (α) is preferably 10 to 20% by weight based on the weight of all repeating units contained in the (meth)acrylic copolymer (A2).

[0028] The (meth)acrylic copolymer (A2) has particularly high compatibility with the polyoxyalkylene polymer (B), and therefore, a curable composition and a cured product with excellent properties can be obtained.

[0029] [1.1.1. (Meth)acrylic acid ester monomers] The (meth)acrylic copolymer (A1) contains structural units derived from (meth)acrylic acid ester monomers in its main chain. The (meth)acrylic acid ester monomers constituting the main chain are not particularly limited as long as they satisfy the above-mentioned requirements. Only one type of (meth)acrylic acid ester monomer may be used, or two or more types of (meth)acrylic acid ester monomers may be used in combination.

[0030] Examples of such (meth)acrylic acid ester monomers include the following. (Meth)acrylic acid ester monomer (α): A monomer having an alkyl group ester-bonded to (meth)acrylic acid, and the alkyl group having an alkoxy group having 1 to 5 carbon atoms. (Meth)acrylic acid ester monomer (β): A monomer in which the alkyl group ester-bonded to (meth)acrylic acid has 1 to 5 carbon atoms. (Meth)acrylic acid ester monomer (γ): A monomer in which the alkyl group ester-bonded to (meth)acrylic acid has 6 to 15 carbon atoms. (Meth)acrylic acid ester monomer (δ): A monomer in which the alkyl group ester-bonded to (meth)acrylic acid has 16 to 25 carbon atoms.

[0031] In the (meth)acrylic copolymer (A1), the content of repeating units derived from the (meth)acrylic acid ester monomer (α) is preferably 0 to 20 wt % based on the weight of all repeating units contained in the (meth)acrylic copolymer (A1). The total content of repeating units derived from the (meth)acrylic acid ester monomer (β) and the (meth)acrylic acid ester monomer (γ) is preferably 45 to 96 wt % based on the weight of all repeating units contained in the (meth)acrylic copolymer (A1). The content of repeating units derived from the (meth)acrylic acid ester monomer (δ) is preferably 4 to 35 wt % based on the weight of all repeating units contained in the (meth)acrylic copolymer (A1). By containing each (meth)acrylic acid ester monomer in such a composition, the (meth)acrylic copolymer (A1) can achieve good workability, mechanical properties, and weather resistance.

[0032] On the other hand, in the (meth)acrylic copolymer (A2) of the (meth)acrylic copolymer (A1), the content of repeating units derived from the (meth)acrylic acid ester monomer (α) is 5 to 20 wt%, and preferably 10 to 20 wt%, based on the weight of all repeating units contained in the (meth)acrylic copolymer (A2). The content of repeating units derived from the (meth)acrylic acid ester monomer (β) is preferably 45 to 70 wt%, and more preferably 50 to 70 wt%, based on the weight of all repeating units contained in the (meth)acrylic copolymer (A2). The content of repeating units derived from the (meth)acrylic acid ester monomer (γ) is preferably 0 to 25 wt%, and more preferably 10 to 25 wt%, based on the weight of all repeating units contained in the (meth)acrylic copolymer (A2). The content of the repeating units derived from the (meth)acrylic acid ester monomer (δ) is preferably 15 to 25 wt %, more preferably 15 to 20 wt %, based on the weight of all repeating units contained in the (meth)acrylic copolymer (A2). By containing each (meth)acrylic acid ester monomer in such a composition, the (meth)acrylic copolymer (A2) can obtain good workability, mechanical properties, and weather resistance.

[0033] When the content of the repeating unit derived from the (meth)acrylic acid ester monomer (β) is within the above range, the compatibility between the (meth)acrylic copolymer (A1) and the polyoxyalkylene polymer (B) can be sufficiently ensured. When the content of the repeating unit derived from the (meth)acrylic acid ester monomer (γ) is within the above range, an increase in viscosity at low temperatures can be prevented, a decrease in workability can be prevented, and the compatibility between the (meth)acrylic copolymer (A1) and the polyoxyalkylene polymer (B) can be sufficiently ensured. When the content of the repeating unit derived from the (meth)acrylic acid ester monomer (δ) is within the above range, the compatibility between the (meth)acrylic copolymer (A1) and the polyoxyalkylene polymer (B) can be sufficiently ensured, a increase in viscosity at low temperatures can be prevented, and a decrease in workability can be prevented.

[0034] The (meth)acrylic acid ester monomer is not particularly limited, and conventionally known ones can be used. Examples of the (meth)acrylic acid ester monomer (α) include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and isopropoxyethyl (meth)acrylate. Examples of the (meth)acrylic acid ester monomer (β) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate. Examples of the (meth)acrylic acid ester monomer (γ) include n-hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, and tetradecyl (meth)acrylate. Examples of the (meth)acrylic acid ester monomer (δ) include pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, icosyl (meth)acrylate, and docosyl (meth)acrylate.

[0035] Among the above-mentioned monomers, 2-methoxyethyl acrylate is preferred as the (meth)acrylic acid ester monomer (α). Butyl acrylate is preferred as the (meth)acrylic acid ester monomer (β). 2-ethylhexyl acrylate and dodecyl acrylate are preferred as the (meth)acrylic acid ester monomer (γ). Octadecyl acrylate is preferred as the (meth)acrylic acid ester monomer (δ). By selecting these monomers, the (meth)acrylic copolymer (A1) produced can achieve high levels of viscosity, compatibility with the polyoxyalkylene polymer (B), weather resistance, mechanical properties, and durability in a well-balanced manner.

[0036] In one embodiment, the (meth)acrylic copolymer (A1) does not contain a repeating unit derived from the (meth)acrylic acid ester monomer (γ). Such a (meth)acrylic copolymer (A1) has, for example, units derived from the preferred (meth)acrylic acid ester monomers (α), (β), and (δ) listed in the above paragraph. By not including the (meth)acrylic acid ester monomer (γ) in the raw materials, the types of raw material monomers used can be reduced, thereby reducing production costs and labor.

[0037] The repeating units derived from (meth)acrylic acid ester monomers contained in the (meth)acrylic copolymer (A1) preferably account for 70% by weight or more, more preferably 90% by weight or more, based on all repeating units contained in the (meth)acrylic copolymer (A1). When the content of repeating units derived from (meth)acrylic acid ester monomers is 70% or more, the produced (meth)acrylic copolymer (A1) can be sufficiently compatible with the polyoxyalkylene polymer (B), and can also exhibit good weather resistance, mechanical properties, and durability.

[0038] [1.1.2. (Meth)acrylic acid ester monomers having an alkoxysilyl group] The (meth)acrylic copolymer (A1) contains a repeating unit derived from a (meth)acrylic acid ester monomer having an alkoxysilyl group. In one embodiment, the alkoxysilyl group is represented by the following general formula (1): -[Si(R 1 ) 2-b (Y) b O] m -Si(R 2 ) 3-a (Y) a ···(1).

[0039] In the formula, R 1 and R 2 are independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a methoxymethyl group, or a triorganosiloxy group represented by (R')3SiO- (wherein R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's may be the same or different). 1 or R 2 When there are two or more R 1 or R 2 may be the same or different. Y is an alkoxy group having 1 to 20 carbon atoms (when there are two or more Y's, they may be the same or different). a is 0, 1, 2 or 3. b is 0, 1 or 2. m is an integer of 0 to 19. In addition, the relationship a+mb≧1 is satisfied.

[0040] Generally, the fewer the carbon atoms in an alkoxy group, the higher the reactivity. That is, the reactivity decreases in the order of methoxy group, ethoxy group, propoxy group, etc. Therefore, an appropriate alkoxy group can be selected depending on the production method and application of the (meth)acrylic copolymer (A1).

[0041] The specific structure of the (meth)acrylic acid ester monomer having an alkoxysilyl group is not particularly limited, and an example thereof is a monomer represented by the following general formula (2). H2C=CR 3 C(=O)O-(CH2)m -SiR 4 n (OR 5 ) 3-n ···(2).

[0042] In the formula, R 3 is hydrogen or a methyl group. 4 and R 5 R is one or more selected from the group consisting of hydrogen, a methyl group, and an ethyl group. 4 and / or R 5 If there are multiple R 4 and / or R 5 are independently selected. m is an integer from 0 to 10. n is an integer from 0 to 2.

[0043] Specific examples of the (meth)acrylic acid ester monomer having an alkoxysilyl group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

[0044] The number of alkoxysilyl groups introduced into the (meth)acrylic copolymer (A1) differs between the X block and the Y block, as specifically described above. When the (meth)acrylic copolymer (A1) has an XY diblock structure, the average number of alkoxysilyl groups introduced into the entire molecule is 1 or more, preferably 1.1 or more, more preferably 1.3 or more, even more preferably 1.5 or more, and particularly preferably 1.7 or more. When the (meth)acrylic copolymer (A1) has an XYX triblock structure or an XYXY tetrablock structure, the average number of alkoxysilyl groups introduced into the entire molecule is 2 or more, preferably 2.2 or more, more preferably 2.6 or more, even more preferably 3.0 or more, and particularly preferably 3.4 or more. The upper limit of the number of alkoxysilyl groups introduced into the (meth)acrylic copolymer (A1) is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 6.0 or less, and particularly preferably 5.0 or less. When the number of alkoxysilyl groups is within the above range, the physical properties of the curable composition and the cured product using the (meth)acrylic copolymer (A1) are good.

[0045] [1.1.3. Other physical properties] The number average molecular weight of the (meth)acrylic copolymer (A1) is not particularly limited, but is preferably 4,000 to 80,000, and more preferably 20,000 to 50,000. If the number average molecular weight is 4,000 or more, the properties of the (meth)acrylic copolymer (A1) can be fully exhibited. If the number average molecular weight is 80,000 or less, the viscosity does not become too high, and sufficient workability can be ensured. The number average molecular weight can be measured, for example, by gel permeation chromatography (GPC).

[0046] The (meth)acrylic copolymer (A1) can be produced, for example, by a production method utilizing a living radical polymerization method disclosed in JP 2018-162394 A. Examples of living radical polymerization methods include the following. Atom Transfer Radical Polymerization (ATRP) (see J. Am. Chem. Soc. 1995, 117, 5614; Macromolecules. 1995, 28, 1721) ·Sigle Electron Transfer Polymerization; SET-LRP (J. Am. Chem. Soc. 2006, 128, 14156; JPSChem 2007, 45, 1607) Reversible Chain Transfer Catalyzed Polymerization (RTCP) ("Living Radical Polymerization Controlled by Organic Catalysts," Polymer Review, 68, 223-231 (2011); See JP 2014-111798 Reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) Nitroxy radical method (NMP method) Organotellurium Polymerization (TERP) method Polymerization method using organoantimony compounds (SBRP method) Organobismuth polymerization method (BIRP) -Iodine transfer polymerization method.

[0047] When the production method disclosed in JP 2018-162394 A is employed, halogen atoms may remain at one or both ends of the (meth)acrylic copolymer (A1) molecule (extended terminals of the molecular chain during polymerization). In one embodiment, the (meth)acrylic copolymer (A1) has, on average, one or more halogen atoms per extended terminal of the molecular chain during polymerization.

[0048] 1.2. Method for producing (meth)acrylic copolymer (A1) In one embodiment, the (meth)acrylic copolymer (A1) can be produced by a production method including the following steps 1a and 2a, or the following steps 1b and 2b. In the following description, "containing 0% by weight of a (meth)acrylic acid ester monomer having an alkoxysilyl group" means "containing no (meth)acrylic acid ester monomer having an alkoxysilyl group." (Step 1a) A step of polymerizing a (meth)acrylic acid ester monomer mixture containing more than 3% by weight of a (meth)acrylic acid ester monomer having an alkoxysilyl group using a living polymerization initiator. (Step 2a) A step of adding a (meth)acrylic acid ester monomer mixture containing 0 to 3% by weight of a (meth)acrylic acid ester monomer having an alkoxysilyl group to the reaction system after Step 1a and polymerizing the mixture. (Step 1b) A step of polymerizing a (meth)acrylic acid ester monomer mixture containing 0 to 3% by weight of a (meth)acrylic acid ester monomer having an alkoxysilyl group using a living polymerization initiator. (Step 2b) A step of adding a (meth)acrylic acid ester monomer mixture containing more than 3% by weight of a (meth)acrylic acid ester monomer having an alkoxysilyl group to the reaction system after Step 1b and polymerizing the mixture.

[0049] Hereinafter, each step will be described in more detail for each structure of the (meth)acrylic copolymer (A1).

[0050] (When the copolymer has an XY diblock structure) The (meth)acrylic copolymer (A1), which is a molecule having an XY diblock structure, can be produced by the above-mentioned steps 1a and 2a, or steps 1b and 2b. In this case, steps 1a and 2b form an X block containing a relatively large amount of alkoxysilyl groups. On the other hand, steps 2a and 1b form a Y block containing a relatively small amount of alkoxysilyl groups.

[0051] In step 1a, a (meth)acrylic acid ester monomer having an alkoxysilyl group is polymerized using a living polymerization initiator. For example, an initiator having one halogen group in the molecule can be used as the living polymerization initiator. The amount of the (meth)acrylic acid ester monomer having an alkoxysilyl group can be 1 to 10 molar equivalents per molar equivalent of the initiator. If necessary, 1 to 100 molar equivalents of a (meth)acrylic acid ester monomer not having an alkoxysilyl group may also be polymerized together. The amount of the (meth)acrylic acid ester monomer having an alkoxysilyl group added to the reaction system in step 1a accounts for more than 3% by weight of the monomer mixture added to the reaction system in step 1a.

[0052] In step 2a, a (meth)acrylic acid ester monomer having no alkoxysilyl group is added to the reaction system after step 1a and polymerized. The amount of the (meth)acrylic acid ester monomer having no alkoxysilyl group added can be 2 to 600 molar equivalents per molar equivalent of the polymer obtained in step 1a. In step 2a, a (meth)acrylic acid ester monomer having an alkoxysilyl group may be added to the reaction system. The amount of the (meth)acrylic acid ester monomer having an alkoxysilyl group added to the reaction system in step 2a accounts for 0 to 3 wt % of the monomer mixture added to the reaction system in step 2a.

[0053] In step 1b, a (meth)acrylic acid ester monomer having no alkoxysilyl group is polymerized using a living polymerization initiator. The same living polymerization initiator as in step 1a can be used. The amount of the (meth)acrylic acid ester monomer having no alkoxysilyl group can be 2 to 600 molar equivalents per molar equivalent of the initiator. In step 1b, a (meth)acrylic acid ester monomer having an alkoxysilyl group may be added to the reaction system. The amount of the (meth)acrylic acid ester monomer having an alkoxysilyl group added to the reaction system in step 1b accounts for 0 to 3 wt % of the monomer mixture added to the reaction system in step 1b.

[0054] In step 2b, a (meth)acrylic acid ester monomer having an alkoxysilyl group is added to the reaction system after step 1b and polymerized. The amount of the (meth)acrylic acid ester monomer having an alkoxysilyl group can be 1 to 10 molar equivalents per molar equivalent of the polymer obtained in step 1b. If necessary, 1 to 100 molar equivalents of a (meth)acrylic acid ester monomer not having an alkoxysilyl group may also be polymerized together. The amount of the (meth)acrylic acid ester monomer having an alkoxysilyl group added to the reaction system in step 2b accounts for more than 3 wt% of the monomer mixture added to the reaction system in step 2b.

[0055] In the above process, examples of the "(meth)acrylic acid ester monomer not having an alkoxysilyl group" include the (meth)acrylic acid ester monomers (α), (β), (γ), and (δ) described in Section [1.1.1.]. This also applies to the following description.

[0056] (When the copolymer has an XYX triblock structure) The (meth)acrylic copolymer (A1), which is a molecule having an XYX triblock structure, can be produced by the above-mentioned steps 1a and 2a followed by step 3a, in which steps 1a and 3a form an X block containing a relatively large amount of alkoxysilyl groups.

[0057] In step 3a, a (meth)acrylic acid ester monomer having an alkoxysilyl group is added to the reaction system after step 2a and polymerized. The amount of the (meth)acrylic acid ester monomer having an alkoxysilyl group added can be 1 to 10 molar equivalents per molar equivalent of the polymer obtained in step 2a. If necessary, 1 to 100 molar equivalents of a (meth)acrylic acid ester monomer not having an alkoxysilyl group may also be polymerized together. The amount of the (meth)acrylic acid ester monomer having an alkoxysilyl group added to the reaction system in step 3a accounts for more than 3% by weight of the monomer mixture added to the reaction system in that step.

[0058] The (meth)acrylic copolymer (A1), which is a molecule having a YXY triblock structure, can be produced by the above-mentioned steps 1b and 2b, followed by step 3b, in which step 2b forms an X block containing a relatively large amount of alkoxysilyl groups.

[0059] In step 3b, a (meth)acrylic acid ester monomer having no alkoxysilyl group is added to the reaction system after step 2b and polymerized. The amount of the (meth)acrylic acid ester monomer having no alkoxysilyl group added can be 2 to 600 molar equivalents per molar equivalent of the polymer obtained in step 2b. In step 3b, a (meth)acrylic acid ester monomer having an alkoxysilyl group may be added to the reaction system. The amount of the (meth)acrylic acid ester monomer having an alkoxysilyl group added to the reaction system in step 3b accounts for 0 to 3 wt% of the monomer mixture added to the reaction system in that step.

[0060] (When the copolymer has four or more blocks) By appropriately combining the above-mentioned steps 1a, 2a, 3a, 1b, 2b, and 3b, it is possible to produce a (meth)acrylic copolymer (A1) having four or more blocks, such as a (meth)acrylic copolymer (A1) having an XYXY tetrablock structure.

[0061] (Method for producing (meth)acrylic copolymer (A2)) In the above-mentioned production method, by appropriately adjusting the amount of (meth)acrylic acid ester monomer (α) added as a (meth)acrylic acid ester monomer having no alkoxysilyl group, it is possible to produce a (meth)acrylic copolymer (A2). Specifically, if the (meth)acrylic acid ester monomer having no alkoxysilyl group added to the reaction system in the above step contains 5 to 20 wt % of the (meth)acrylic acid ester monomer (α) based on the weight of all monomers, it is possible to produce the (meth)acrylic copolymer (A2).

[0062] The above-mentioned production method can be suitably carried out by adopting a living radical polymerization method, among which atom transfer radical polymerization, single electron transfer polymerization, and reversible transfer catalytic polymerization are preferred.

[0063] More preferred production methods include living radical polymerization of vinyl monomers using ATRP or SET-LRP with a transition metal or transition metal complex (composed of a transition metal compound and a ligand) as a catalyst, and RTCP, which does not use a transition metal as a catalyst.

[0064] Currently, there are two interpretations of the mechanism of living radical polymerization catalyzed by transition metal complexes: ATRP and SET-LRP. Based on ATRP, living radical polymerization consists of the equilibrium of the following two reactions (as an example, we will explain using a copper complex): (a) The monovalent copper complex abstracts the halogen at the end of the polymer to generate a radical, which then becomes a divalent copper complex. (b) The divalent copper complex adds a halogen to the radical at the polymer end to form a monovalent copper complex.

[0065] On the other hand, when interpreted based on SET LRP, living radical polymerization consists of the equilibrium of the following three reactions (explained using a copper complex as an example): (a) Zero-valent metallic copper or a copper complex abstracts a halogen atom from the polymer terminal to generate a radical, thereby becoming a divalent copper complex. (b) The divalent copper complex adds a halogen to the radical at the polymer end to become a zero-valent copper complex. (c) The monovalent copper complex disproportionates to give zero- and divalent copper complexes.

[0066] The above-mentioned production method can also be interpreted as any living radical polymerization system, but no particular distinction is made between them in this specification. Any living radical polymerization system using a transition metal or a transition metal complex as a catalyst is included in the scope of the present invention.

[0067] Furthermore, a synthetic method called Activators Regenerated by Electron Transfer (ARGET), which is an improved version of ATRP, has also been reported (Macromolecules. 2006, 39, 39). This method uses a reducing agent to reduce highly oxidized transition metal complexes, which can cause polymerization delays or terminations, and allows the polymerization reaction to proceed rapidly to a high conversion rate even under low catalyst conditions with a small amount of transition metal complex. This ARGET method can also be used in the present invention.

[0068] (Identification of the Structure of the (Meth)acrylic Copolymer (A1) by Production Method) In one embodiment, the (meth)acrylic copolymer (A1) is defined as a copolymer obtained by the above-mentioned production method, i.e., the (meth)acrylic copolymer (A1) may be a copolymer obtained by a production method including steps 1a and 2a, or steps 1b and 2b.

[0069] In the above-mentioned production method, a (meth)acrylic acid ester monomer having an alkoxysilyl group is introduced by copolymerization, and therefore it is almost impractical to specifically specify the position of the alkoxysilyl group in the resulting copolymer molecule.

[0070] Furthermore, in the above-mentioned production method, when the same type of (meth)acrylic acid ester monomer not having an alkoxysilyl group is added to the reaction system in steps 1a and 2a (or steps 1b and 2b), the main chain structure of the obtained copolymer will be the same for both the X block and the Y block. In such a copolymer, it is almost impractical to specifically identify the boundary between the X block and the Y block.

[0071] For these reasons, there are cases where the (meth)acrylic copolymer (A1) must be defined not as a specific structure of the copolymer molecule, but as a copolymer obtained by the above-mentioned production method.

[0072] Various chemicals that can be used in the production method according to one embodiment of the present invention will be described below. Each of these chemicals may be used alone or in combination of two or more. These chemicals may be added directly to the polymerization system, or may be generated within the polymerization system.

[0073] 1.2.1. Initiator As the initiator, a radical initiator having one halogen group in the molecule can be used. Examples of such initiators include ethyl 2-bromoisobutyrate, ethyl 2-bromobutyrate (also called ethyl α-bromobutyrate), ethyl bromoacetate, methyl bromoacetate, (1-bromoethyl)benzene, allyl bromide, methyl 2-bromopropionate, methyl chloroacetate, methyl 2-chloropropionate, and (1-chloroethyl)benzene.

[0074] From the viewpoint of easy availability, ethyl 2-bromobutyrate, (1-bromoethyl)benzene, and methyl chloroacetate are preferred, and from the viewpoint of reactivity and safety, ethyl 2-bromobutyrate is preferred.

[0075] Alternatively, an initiator having an alkoxysilyl group may be used as the initiator. Alternatively, an alkoxysilyl group may be introduced into the initiator before or after the polymerization reaction. By such a method, a (meth)acrylic copolymer (A1) having an alkoxysilyl group at least at the terminal can be produced.

[0076] [1.2.2. Polymerization catalyst] In the ATRP system, whether or not a reducing agent is used, a metal complex having a central metal of an element of Group 7, 8, 9, 10, or 11 of the periodic table can be used. Among these, metal complexes having a central metal of monovalent copper, divalent ruthenium, or divalent iron are particularly suitable.

[0077] Specific examples include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous acetate, and cuprous perchlorate. When using a copper compound as a polymerization catalyst, it is preferable to add an amine ligand to the polymerization system to enhance catalytic activity. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl2(PPh3)3) is also suitable as a catalyst. When using this catalyst, it is preferable to add an aluminum compound (such as trialkoxyaluminum) to the polymerization system to enhance catalytic activity. Furthermore, a tristriphenylphosphine complex of divalent iron chloride (FeCl2(PPh3)3) is also suitable as a catalyst.

[0078] Among the above catalysts, copper catalysts are preferred because they are inexpensive. To enhance catalytic activity and productivity, it is more preferred to use a polydentate amine in combination with a copper catalyst.

[0079] [1.2.3. Polydentate amines] Examples of polydentate amines that can be used as ligands include: Bidentate and polydentate amines: 2,2-bipyridine, 4,4'-di-(5-nonyl)-2,2'-bipyridine, N-(n-propyl)pyridylmethanimine, N-(n-octyl)pyridylmethanimine Tridentate and multidentate amines: N,N,N',N'',N''-pentamethyldiethylenetriamine, N-propyl-N,N-di(2-pyridylmethyl)amine Tetradentate and polydentate amines: hexamethyltris(2-aminoethyl)amine (Me6TREN), N,N-bis(2-dimethylaminoethyl)-N,N'-dimethylethylenediamine, 2,5,9,12-tetramethyl-2,5,9,12-tetraazatetradecane, 2,6,9,13-tetramethyl-2,6,9,13-tetraazatetradecane, 4,11-dimethyl-1,4,8,11-tetraazabicyclohexadecane, N',N''-dimethyl-N',N''-bis((pyridin-2-yl)methyl)ethane-1,2-diamine, tris[(2-pyridyl)methyl]amine, 2,5,8,12-tetramethyl-2,5,8,12-tetraazatetradecane Pentacoordinated polydentate amine: N,N,N',N'',N''',N'''',N''''-heptamethyltetraethylenetetramine Hexadentate polydentate amine: N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine · Polyamine: Polyethyleneimine.

[0080] [1.2.4. Bases] A base may be added to the polymerization system to neutralize the acid present or generated in the polymerization system and prevent the accumulation of the acid. Examples of bases include: Monoamines: Monoamines are compounds that have one base moiety per molecule. Examples of monoamines include primary amines (methylamine, aniline, lysine, etc.), secondary amines (dimethylamine, piperidine, etc.), tertiary amines (trimethylamine, triethylamine, etc.), aromatic amines (pyridine, pyrrole, etc.), and ammonia. Polyamines: Examples of polyamines include diamines (ethylenediamine, tetramethylethylenediamine, etc.), triamines (diethylenetriamine, pentamethyldiethylenetriamine, etc.), tetramines (triethylenetetramine, hexamethyltriethylenetetramine, hexamethylenetetramine, etc.), polyethyleneimine, etc. Inorganic Bases: Inorganic bases are elements or compounds of Groups 1 and 2 of the periodic table. Examples of elements of Groups 1 and 2 of the periodic table include lithium, sodium, and calcium. Examples of compounds of elements of Groups 1 and 2 of the periodic table include sodium methoxide, potassium ethoxide, methyllithium, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium bicarbonate, ammonium bicarbonate, trisodium phosphate, disodium hydrogen phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, sodium acetate, potassium acetate, sodium oxalate, potassium oxalate, sodium phenoxy, potassium phenoxy, sodium ascorbate, and potassium ascorbate.

[0081] 1.2.5. Reducing Agents In living radical polymerization using a copper complex as a catalyst, it is known that polymerization activity can be improved by using a reducing agent in combination (ARGET ATRP). In ARGET ATRP, it is believed that polymerization activity is improved by reducing and reducing highly oxidized transition metal complexes (produced by coupling between radicals, etc.), which cause delays or terminations in the polymerization reaction. This allows the transition metal catalyst, which would normally require hundreds to thousands of ppm, to be reduced to tens to hundreds of ppm. In a production method according to one embodiment of the present invention, a reducing agent can be used to achieve a reaction mechanism similar to that of ARGET ATRP. Examples of reducing agents include the following:

[0082] (A reducing agent that does not generate acid when reducing copper complexes) Metals: Examples of metals include alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (beryllium, magnesium, calcium, barium, etc.), main group metals (aluminum, zinc, etc.), and transition metals (copper, nickel, ruthenium, iron, etc.). These metals can also be used in the form of alloys (amalgams) with mercury. Metal Compounds: Examples of metal compounds include metal salts and metal complexes. Examples of ligands in metal complexes include carbon monoxide, olefins, nitrogen-containing compounds, oxygen-containing compounds, phosphorus-containing compounds, and sulfur-containing compounds. More specific examples include compounds of metals with ammonia / amines, titanium trichloride, titanium alkoxides, chromium chloride, chromium sulfate, chromium acetate, iron chloride, copper chloride, copper bromide, tin chloride, zinc acetate, zinc hydroxide, carbonyl complexes (Ni(CO)4, Co2CO8, etc.), olefin complexes ([Ni(cod)2], [RuCl2(cod)], [PtCl2(cod)], etc.; cod represents cyclooctadiene), and phosphine complexes ([RhCl(P(CH5)3)3], [RuCl2(P(CH5)3)2], [PtCl2(P(CH5)3)2], etc.). ·Organotin compounds: Specific examples include tin octoate, tin 2-ethylhexylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, and dioctyltin thiocarboxylate. Phosphorus or phosphorus compounds: Specific examples include phosphorus, trimethylphosphine, triethylphosphine, triphenylphosphine, trimethylphosphite, triethylphosphite, triphenylphosphite, hexamethylphosphorastriamide, and hexaethylphosphorastriamide. Sulfur or sulfur compounds: Specific examples include sulfur, rongalites, hydrosulfites, and thiourea dioxide. Rongalite refers to formaldehyde derivatives of sulfoxylates, and is represented by the general formula: MSO2·CHO (where M is Na or Zn). Specific examples of rongalite include sodium formaldehyde sulfoxylate and zinc formaldehyde sulfoxylate. Hydrosulfite refers to sodium hyposulfite and formaldehyde derivatives of sodium hyposulfite.

[0083] (A reducing agent (hydride reducing agent) that generates acid when reducing a copper complex) Metal hydrides: Specific examples include sodium hydride, germanium hydride, tungsten hydride, aluminum hydrides (diisobutylaluminum hydride, lithium aluminum hydride, sodium aluminum hydride, sodium triethoxyaluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, etc.), and organotin hydrides (triphenyltin hydride, tri-n-butyltin hydride, diphenyltin hydride, di-n-butyltin hydride, triethyltin hydride, trimethyltin hydride, etc.). Silicon hydrides: Specific examples include trichlorosilane, trimethylsilane, triethylsilane, diphenylsilane, phenylsilane, and polymethylhydrosiloxane. Boron hydrides. Specific examples include borane, diborane, sodium borohydride, sodium trimethoxyborohydride, sodium borohydride sulfide, sodium cyanide borohydride, lithium cyanide borohydride, lithium borohydride, lithium triethylborohydride, lithium tri-s-butylborohydride, lithium tri-t-butylborohydride, calcium borohydride, potassium borohydride, zinc borohydride, and tetra-n-butylammonium borohydride. Nitrogen-hydrogen compounds: Examples include hydrazine and diimide. Phosphorus or phosphorus compounds: Specific examples include phosphines and diazaphospholenes. Sulfur or sulfur compounds: A specific example is hydrogen sulfide. Organic compounds that exhibit reducing properties: Specific examples include alcohols, aldehydes, phenols, and organic acid compounds. Examples of alcohols include methanol, ethanol, propanol, and isopropanol. Examples of aldehydes include formaldehyde, acetaldehyde, benzaldehyde, and formic acid. Examples of phenols include phenol, hydroquinone, dibutylhydroxytoluene, and tocopherol. Examples of organic acid compounds include citric acid, oxalic acid, ascorbic acid, ascorbate, and ascorbic acid esters.

[0084] Alternatively, the reducing agent may be generated in the polymerization system by electrolytic reduction. In electrolytic reduction, electrons generated at the cathode directly (or after solvation) exhibit a reducing effect. In other words, the reducing agent may be generated by electrolysis.

[0085] 1.2.6. Solvents Examples of solvents include the following: However, ATRP can also be carried out without using a solvent. Highly polar aprotic solvents: dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone Carbonate solvents: ethylene carbonate, propylene carbonate Alcohol-based solvents: methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol Nitrile solvents: acetonitrile, propionitrile, benzonitrile Ketone solvents: acetone, methyl ethyl ketone, methyl isobutyl ketone Ether solvents: diethyl ether, tetrahydrofuran Halogenated hydrocarbon solvents: methylene chloride, chloroform Ester solvents: ethyl acetate, butyl acetate Hydrocarbon solvents: pentane, hexane, heptane, cyclohexane, octane, decane, benzene, toluene, xylene ·Other solvents: ionic liquids, water, supercritical fluids.

[0086] In ATRP (ARGET) systems using a reducing agent, it is preferable that the transition metal or transition metal compound, polydentate amine, base, reducing agent, monomer, and initiator are uniformly contained in the polymerization system from the viewpoints of reaction control, polymerization reaction rate, ease of charging, and risk of scale-up. Therefore, it is preferable to select a solvent that can dissolve these substances.

[0087] [1.3. Polyoxyalkylene polymer (B)] [1.3.1. Alkoxysilyl group] The structure of the alkoxysilyl group contained in the polyoxyalkylene polymer (B) is not particularly limited. Examples of the alkoxysilyl group include the alkoxysilyl group represented by general formula (1) described in Section [1.1.2.]. When the polyoxyalkylene polymer (B) contains multiple alkoxysilyl groups in one molecule, these alkoxysilyl groups may have different structures. Alternatively, the alkoxysilyl groups contained in the polyoxyalkylene polymer (B) may have different structures depending on the molecule.

[0088] In one embodiment, the alkoxysilyl group contained in the polyoxyalkylene polymer (B) is represented by the following formula (3). -Si(R 6 ) 3-a (X) a ···(3).

[0089] In the formula, R 6 and X may be different for each alkoxysilyl group. Therefore, the polyoxyalkylene polymer (B) may have a plurality of different alkoxysilyl groups represented by formula (3) in one molecule. Alternatively, the alkoxysilyl groups represented by formula (3) contained in the polyoxyalkylene polymer (B) may be different depending on the molecule.

[0090] R 6 R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 6 When R is a substituted hydrocarbon group, the substituent may be a heteroatom-containing group. Examples of heteroatoms include oxygen, nitrogen, sulfur, phosphorus, and halogen atoms (fluorine, chlorine, bromine, and iodine). Examples of heteroatom-containing groups include hydroxy, carboxy, ether, ester, amino, amide, sulfo, phospho, halogen, and halogenated hydrocarbon groups. When two or more R are present in the alkoxysilyl group of formula (3), 6 If included, they may be the same or different.

[0091] X is a hydroxyl group or a hydrolyzable group. The hydrolyzable group is not particularly limited and may be any 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 amido group, an aminooxy group, a mercapto group, and an alkenyloxy group. a is 1, 2, or 3. When two or more Xs are contained in the alkoxysilyl group of formula (3), they may be the same or different.

[0092] Specific examples of the alkoxysilyl group represented by formula (3) include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group. Among these, the trimethoxysilyl group and the dimethoxymethylsilyl group are preferred because they have the advantage of being easily reacted quickly.

[0093] The lower limit of the number of alkoxysilyl groups contained in the polyoxyalkylene polymer (B) is preferably 0.5 or more per molecule, more preferably 1.0 or more, and even more preferably 1.5 or more. The upper limit of the number of alkoxysilyl groups contained in the polyoxyalkylene polymer (B) is preferably 6.0 or less per molecule, more preferably 3.0 or less, even more preferably 2.5 or less, and particularly preferably 1.8 or less. When the number of alkoxysilyl groups is within the above range, the curable composition can be provided with good curability.

[0094] The alkoxysilyl group in the polyoxyalkylene polymer (B) is preferably located at at least one end of the molecule, and more preferably at both ends of the molecule. When the alkoxysilyl group is located at the end of the molecule, good rubber elasticity can be imparted to the cured product. A polyoxyalkylene polymer (B) having an alkoxysilyl group located at one end of the molecule and a polyoxyalkylene polymer (B) having alkoxysilyl groups located at both ends of the molecule may be used in combination.

[0095] [1.3.2. Main chain of polyoxyalkylene polymer (B)] The main chain structure of the polyoxyalkylene polymer (B) may be linear or branched. It may also be a mixture of molecules having these structures. Among these, a main chain derived from one or more selected from the group consisting of polyoxypropylene diols and polyoxypropylene triols is particularly preferred.

[0096] An example of the main chain of the polyoxyalkylene polymer (B) is substantially a group represented by the general formula (4): -R 7 -O-" (wherein R 7 is a divalent alkylene group.) Here, the term "substantially" means that the repeating unit represented by general formula (4) accounts for 50% by weight or more (preferably 80% by weight or more) of the total weight of the polyoxyalkylene polymer (B).

[0097] R in general formula (4) 7 is not particularly limited as long as it is a divalent alkylene group. 7 is preferably an alkylene group having 1 to 14 carbon atoms, and more preferably a linear or branched alkylene group having 2 to 4 carbon atoms.

[0098] The repeating unit represented by general formula (4) is not particularly limited. Specific examples include -CHO-, -CHCHO-, -CHCH(CH)O-, -CHCH(CH)O-, -CHC(CH)O-, and -CHCHCHCHO-. Among these, the main chain of the polyoxyalkylene polymer (B) is preferably polypropylene oxide consisting of -CHCH(CH)O-.

[0099] The polyoxyalkylene polymer (B) may contain a urethane bond or a urea bond in the main chain structure.

[0100] The number average molecular weight of the polyoxyalkylene polymer (B) is not particularly limited. The number average molecular weight is preferably 10,000 to 40,000. The number average molecular weight can be measured, for example, by gel permeation chromatography.

[0101] [1.3.3. Production method of polyoxyalkylene polymer (B)] The molecular structure of the polyoxyalkylene polymer (B) varies depending on the intended use and desired properties. For example, the compounds described in JP-A-63-112642 can be used as the polyoxyalkylene polymer (B). Such polyoxyalkylene polymer (B) can be synthesized by a conventional polymerization method (anionic polymerization using caustic alkali). Furthermore, it can also be synthesized by a method using a cesium metal catalyst, a porphyrin / aluminum complex catalyst (see JP-A-61-197631, JP-A-61-215622, JP-A-61-215623, and JP-A-61-218632, etc.), a composite metal cyanide complex catalyst (see JP-B-46-27250, JP-B-59-15336, etc.), or a catalyst made of a polyphosphazene salt (see JP-A-10-273512, etc.). As the composite metal cyanide complex catalyst, zinc hexacyanocobaltate is particularly preferred.

[0102] By employing a method using a catalyst comprising a porphyrin / aluminum complex catalyst, a composite metal cyanide complex catalyst, or a polyphosphazene salt, it is possible to obtain a polyoxyalkylene polymer having a molecular weight distribution (Mw / Mn) of 1.6 or less (preferably 1.5 or less, more preferably 1.4 or less, and even more preferably 1.3 or less). The use of a polyoxyalkylene polymer (B) having a narrow molecular weight distribution is preferred because it allows the viscosity of the curable composition to be reduced while maintaining a low modulus and high elongation of the cured product.

[0103] In addition, a double metal cyanide complex having an organic ligand is also preferably used for the polymerization of the polyoxyalkylene polymer (B). The organic ligand is preferably an ether-based ligand or an alcohol-based ligand. Examples of ether-based ligands include ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), and triethylene glycol dimethyl ether. Specific examples of alcohol-based ligands include tert-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, and ethylene glycol mono-tert-butyl ether. Among double metal cyanide complexes having an organic ligand, a catalyst in which the organic ligand is glyme or tert-butyl alcohol and the double metal cyanide complex is zinc hexacyanocobaltate is preferred. Furthermore, a catalyst in which the organic ligand is tert-butyl alcohol and the double metal cyanide complex is zinc hexacyanocobaltate is more preferred.

[0104] By using such a catalyst, a precursor polymer having a hydroxyl group at the end of the main chain can be obtained by ring-opening addition of an alkylene oxide (ethylene oxide, propylene oxide, etc.). The method for introducing an alkoxysilyl group into this precursor polymer will be explained in Section [1.3.4.].

[0105] [1.3.4. Method for introducing alkoxysilyl groups] The method for introducing alkoxysilyl groups into polyoxyalkylene polymers can be any conventionally known method. For example, JP-A-3-72527 can be referred to for the introduction of alkoxysilyl groups into oxyalkylene polymers obtained using a composite metal cyanide complex catalyst. Furthermore, JP-A-11-60723 can be referred to for the introduction of alkoxysilyl groups into oxyalkylene polymers obtained using a polyphosphazene salt and active hydrogen as catalysts.

[0106] Other implementation methods include the following: Method 1: An oxyalkylene polymer having a terminal functional group such as a hydroxyl group is reacted with an organic compound having an active group and an unsaturated group that is reactive with the functional group to obtain an oxyalkylene polymer having an unsaturated group. Alternatively, an oxyalkylene polymer having a terminal functional group such as a hydroxyl group is copolymerized with an unsaturated group-containing epoxy compound to obtain an oxyalkylene polymer having an unsaturated group. The resulting reaction product is then reacted with a hydrosilane having an alkoxysilyl group to perform hydrosilylation. Method 2: An unsaturated group-containing oxyalkylene polymer obtained in the same manner as in Method 1 is reacted with a compound having a mercapto group and an alkoxysilyl group. Method 3: An oxyalkylene polymer having a terminal Y functional group is reacted with a compound having a Y' functional group and an alkoxysilyl group. Here, the Y functional group is a hydroxyl group, epoxy group, isocyanate group, etc. The Y' functional group is a functional group that is reactive with the Y functional group.

[0107] Examples of compounds having a Y′ functional group and an alkoxysilyl group that can be used in Method 3 include amino group-containing silanes (γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, 3-amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyltrimethoxysilane, 4-amino-3-methylpropyltrimethoxysilane, 4-amino-3-methylpropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane; further, partial Michael addition products of amino group-containing silanes with maleic esters or acrylate compounds, etc.), mercapto group-containing silanes (γ-mercaptopropyltrimethoxysilane, ... Examples of suitable silanes include hydroxypropyltrimethoxysilane, hydroxypropyltrimethoxysilane, hydroxypropyltriethoxy ...

[0108] 2. Hardener The curing agent of the multi-component curable composition according to one embodiment of the present invention contains a curing catalyst. Each component that can be contained in the curing agent will be described in detail below.

[0109] [2.1. Curing catalyst] The curing catalyst forms siloxane bonds between the alkoxysilyl groups contained in the (meth)acrylic copolymer (A1) and the polyoxyalkylene polymer (B), crosslinking and curing the resin. Examples of curing catalysts include tin-based curing catalysts. Specific examples of tin-based curing catalysts include dialkyltin carboxylates (dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethyl maleate, dibutyltin diethyl maleate, dibutyltin dibutyl maleate, dibutyltin diisooctyl maleate, dibutyltin ditridecyl maleate, dibutyltin dibenzyl maleate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethyl maleate, dioctyltin diisooctyl maleate, etc.); dialkyltin oxides (dibutyltin oxide, dioctyltin oxide, a mixture of dibutyltin oxide and a phthalate ester, etc.); tetravalent tin compounds (dialkyltin oxide, dialkyltin diacetate, etc.) and low molecular weight compounds having an alkoxysilyl group. Examples of the reactants include reaction products with silicon compounds (tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, etc.); divalent tin compounds (tin octoate, tin naphthenate, tin stearate, etc.); monoalkyltin compounds (monobutyltin compounds (monobutyltin trisoctoate, monobutyltin triisopropoxide, etc.), monooctyltin compounds, etc.); reaction products or mixtures of amine compounds and organotin compounds (reaction products or mixtures of laurylamine and tin octoate, etc.); chelate compounds (dibutyltin bisacetylacetonate, dioctyltin bisacetylcetonate, dibutyltin bisethylacetonate, dioctyltin bisethylacetonate, etc.); and tin alcoholates (dibutyltin dimethylate, dibutyltin diethylate, dioctyltin dimethylate, dioctyltin diethylate, etc.).

[0110] Among these, chelate compounds (such as dibutyltin bisacetylacetonate) and tin alcoholates are preferred because of their high activity as silanol condensation catalysts, and dibutyltin dilaurate is preferred because it causes little coloration when added to a curable composition, is inexpensive, and is easily available.

[0111] ≪3. Other agents≫ The multi-component curable composition according to one embodiment of the present invention may contain other agents in addition to the base agent and the curing agent. Examples of such agents include colorants. The multi-component curable composition according to one embodiment of the present invention may be composed of two types of agents, three types of agents, or four or more types of agents.

[0112] ≪4. Curable composition≫ The main component of the multi-component curable composition according to one embodiment of the present invention contains a (meth)acrylic copolymer (A1) and a polyoxyalkylene polymer (B).

[0113] In one embodiment, the blending ratio of each component, in parts by weight, is (meth)acrylic copolymer (A1):polyoxyalkylene polymer (B)=100:(5 to 1900). Preferably, the blending ratio of each component, in parts by weight, is (meth)acrylic copolymer (A1):polyoxyalkylene polymer (B)=100:(100 to 240). When the blending ratio is within the above range, there is an advantage that the resulting cured product has excellent weather resistance.

[0114] [4.1. Other additives] The multi-component curable composition according to one embodiment of the present invention may contain various additives. By incorporating these additives, various physical properties of the multi-component curable composition and the cured product can be adjusted. Examples of additives include the following. These additives may be used alone or in combination of two or more. These additives may be incorporated into the base agent, the curing agent, or other agents.

[0115] [4.1.1 Adhesion promoter] An adhesion promoter may be added to the multi-component curable composition according to one embodiment of the present invention. There are no particular limitations on the agent to contain the adhesion promoter. However, since there is a possibility that the adhesion promoter may react with the curing catalyst, it is preferable to add the adhesion promoter to the base resin. Adding an adhesion promoter can reduce the risk of the sealant peeling off from the adherend, such as a siding board (this peeling occurs when the joint width or the like changes due to external forces). Furthermore, there may be cases where the need to use a primer to improve adhesion is eliminated. In this case, simplification of the application process is expected.

[0116] Examples of adhesion promoters include silane coupling agents. Specific examples of silane coupling agents include isocyanate group-containing silanes (γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, etc.); amino group-containing silanes (γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, silane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, etc.; mercapto group-containing silanes (γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc.); carboxysilanes (β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, N-(β-carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane, etc.); vinyl-type unsaturated group-containing silanes (vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acroyloxypropylmethyltriethoxysilane, etc.); halogen-containing silanes (γ-chloropropyltrimethoxysilane, etc.); isocyanurate silanes (tris(trimethoxysilyl)isocyanurate, etc.).In addition, derivatives obtained by modifying silane coupling agents, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and silylated polyesters, can also be used as silane coupling agents.

[0117] The amount of the adhesion promoter is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the total amount of the (meth)acrylic copolymer (A1) and the polyoxyalkylene polymer (B).

[0118] [4.1.2 Plasticizers] A multi-component curable composition according to one embodiment of the present invention may contain a plasticizer. The combined use of a plasticizer and a filler (described below) increases the elongation of the cured product and allows for the incorporation of a large amount of filler. The agent containing the plasticizer is not particularly limited. The inclusion of a plasticizer in the base agent can reduce the viscosity of the base agent. The inclusion of a plasticizer in the curing agent makes it easier for the curing catalyst to mix with the base agent. Therefore, it is preferable to include a plasticizer in both the base agent and the curing agent.

[0119] Examples of plasticizers include phthalate esters (dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, etc.); non-aromatic dibasic acid esters (dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, etc.); aliphatic esters (butyl oleate, methyl acetylricinoleate, etc.); esters of polyalkylene glycols (diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol ester, etc.); phosphate esters (tricresyl phosphate, tributyl phosphate, etc.); trimellitic acid esters; polystyrenes (polystyrene, poly-α-methylstyrene, etc.); polybutadiene; polybutene; polyisobutylene; butadiene-acrylonitrile; polychloroprene; chlorinated paraffins; hydrocarbon oils (aqua, etc.); alkyldiphenyl, partially hydrogenated terphenyl, etc.); process oils; polyethers (polyether polyols (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.), and derivatives of polyether polyols in which the hydroxyl groups have been converted to ester groups, ether groups, etc.); epoxy plasticizers (epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof, etc.); polyester plasticizers obtained from dibasic acids and dihydric alcohols (polyesters obtained from sebacic acid, adipic acid, azelaic acid, phthalic acid, etc., and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc.); vinyl polymers (obtained by polymerizing vinyl monomers such as acrylic plasticizers by various methods).

[0120] Specific examples of epoxy plasticizers include epoxidized soybean oil, epoxidized linseed oil, di-(2-ethylhexyl) 4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, and epoxy butyl stearate. Among the above-mentioned epoxy plasticizers, E-PS is preferred. Using a compound having an epoxy group as a plasticizer can improve the recovery of the cured product.

[0121] Acrylic plasticizers can be prepared by high-temperature continuous polymerization without using solvents or chain transfer agents (see U.S. Pat. No. 4,414,370, Japanese Patent Application Laid-Open No. 59-6207, Japanese Patent Publication No. 5-58005, Japanese Patent Application Laid-Open No. 1-313522, and U.S. Pat. No. 5,010,166). Specific examples of acrylic plasticizers include ARUFON UP-1000, UP-1020, and UP-1110 (all manufactured by Toagosei Co., Ltd.), and JDX-P1000, JDX-P1010, and JDX-P1020 (all manufactured by Johnson Polymer Co., Ltd.). Alternatively, acrylic reactive plasticizers having an alkoxysilyl group may be used. Specific examples of such plasticizers include ARFUON US-6100.

[0122] The amount of the plasticizer to be added is preferably 5 to 800 parts by weight, more preferably 10 to 600 parts by weight, and even more preferably 10 to 500 parts by weight, per 100 parts by weight of the total amount of the (meth)acrylic copolymer (A) and the polyoxyalkylene polymer (B).

[0123] [4.1.3. Filler] A multi-component curable composition according to one embodiment of the present invention may contain a filler. The agent to contain the filler is not particularly limited. However, since the filler is generally compounded in a large amount, it is difficult to uniformly mix the filler with the (meth)acrylic copolymer (A1) and the polyoxyalkylene polymer (B) at the construction site. Therefore, it is preferable to contain the filler in the main component. Examples of fillers include wood flour; reinforcing fillers (pulp, cotton chips, asbestos, mica, walnut shell flour, rice husk flour, graphite, white clay, silica (fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrated silicic acid, etc.), carbon black, etc.); fillers (heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, red iron oxide, fine aluminum powder, flint powder, zinc oxide, activated zinc white, zinc powder, zinc carbonate, shirasu balloons, etc.); and fibrous fillers (asbestos, glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber, etc.).

[0124] The amount of the filler to be added is preferably 5 to 5,000 parts by weight, more preferably 10 to 2,500 parts by weight, and particularly preferably 15 to 1,500 parts by weight, per 100 parts by weight of the total amount of the (meth)acrylic copolymer (A1) and the polyoxyalkylene polymer (B).

[0125] [4.1.4. Physical property adjusters] The multi-component curable composition according to one embodiment of the present invention may contain a physical property modifier that adjusts the tensile properties of the cured product. The use of the physical property modifier can increase the hardness of the cured product, or conversely, decrease the hardness of the cured product to increase elongation. The agent to be used as the physical property modifier is not particularly limited. However, since there is a possibility that the physical property modifier may react with the curing catalyst, it is preferable to include the physical property modifier in the base resin.

[0126] Examples of physical property adjusters include alkylalkoxysilanes (methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, etc.); alkylisopropenoxysilanes (dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, etc.); alkoxysilanes having functional groups (vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.); silicone varnishes; and polysiloxanes.

[0127] The amount of the physical property adjuster to be added is preferably 0.1 to 80 parts by weight, more preferably 0.1 to 50 parts by weight, per 100 parts by weight of the total amount of the (meth)acrylic copolymer (A1) and the polyoxyalkylene polymer (B).

[0128] [4.1.5. Thixotropic agents (anti-sagging agents)] A multi-component curable composition according to one embodiment of the present invention may contain a thixotropy-imparting agent (anti-sagging agent) to prevent sagging and improve workability. The agent to be used as the thixotropy-imparting agent is not particularly limited. However, since it would be complicated to uniformly mix the (meth)acrylic copolymer (A1), the polyoxyalkylene polymer (B), and the thixotropy-imparting agent at the construction site, it is preferable to include the thixotropy-imparting agent in the main agent.

[0129] Examples of the thixotropy-imparting agent include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps (calcium stearate, aluminum stearate, barium stearate, etc.).

[0130] The amount of the thixotropy-imparting agent is preferably 0.1 to 50 parts by weight, more preferably 0.2 to 25 parts by weight, per 100 parts by weight of the total amount of the (meth)acrylic copolymer (A1) and the polyoxyalkylene polymer (B).

[0131] [4.1.6. Photocurable substance] A multi-component curable composition according to one embodiment of the present invention may contain a photocurable substance. A photocurable substance is a substance that undergoes a chemical change in a short period of time under the action of light, resulting in a change in physical properties (such as curing). The inclusion of a photocurable substance can reduce the tackiness (residual tack) of the cured surface. A typical photocurable substance can be cured by leaving it at room temperature for one day in a sunny location indoors (e.g., near a window). The agent containing the photocurable substance is not particularly limited. However, because the photocurable substance may react with the curing catalyst, it is preferable to include the photocurable substance in the base resin. Many photocurable substances are known, including organic monomers, oligomers, resins, and compositions containing these, and the type is not particularly limited. Examples of photocurable substances include unsaturated acrylic compounds, polyvinyl cinnamates, and azide resins.

[0132] Specific examples of unsaturated acrylic compounds include (meth)acrylic acid esters of low molecular weight alcohols (ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, neopentyl alcohol, etc.); (meth)acrylic acid esters of alcohols obtained by modifying acids (bisphenol A, isocyanuric acid) or low molecular weight alcohols with ethylene oxide, propylene oxide, etc.; (meth)acrylic acid esters (polyether polyols whose main chain is a polyether and has a hydroxyl group at the end, and polyols whose main chain is a polyether, obtained by radical polymerization of vinyl monomers in such polyols). polymer polyols obtained by reacting an epoxy resin (such as bisphenol A or novolac) with (meth)acrylic acid; and urethane acrylate oligomers having urethane bonds and (meth)acrylic groups in the molecular chain, which are obtained by reacting a polyol, polyisocyanate, hydroxyl group-containing (meth)acrylate, etc.

[0133] The amount of the photocurable substance to be added is preferably 0.01 to 30 parts by weight per 100 parts by weight of the total amount of the (meth)acrylic copolymer (A1) and the polyoxyalkylene polymer (B).

[0134] 4.1.7. Air-oxidation-curable substances The multi-component curable composition according to one embodiment of the present invention may contain an air-oxidation curable substance. An air-oxidation curable substance refers to a compound having an unsaturated group that can be crosslinked and cured by oxygen in the air. By including an air-oxidation curable substance, the stickiness (residual tack) of the surface of the cured product can be reduced. A typical air-oxidation curable substance can be cured, for example, by leaving it in air indoors for one day. The agent to be included with the air-oxidation curable substance is not particularly limited. However, since there is a possibility that the air-oxidation curable substance may react with the curing catalyst, it is preferable to include the air-oxidation curable substance in the base resin.

[0135] Examples of air-oxidatively curable substances include drying oils (tung oil, linseed oil, etc.); various alkyd resins obtained by modifying drying oils; substances obtained by modifying acrylic polymers, silicone resins, etc. with drying oils; 1,2-polybutadiene; 1,4-polybutadiene; polymers or copolymers of C5-C8 dienes; and various modified polymers or copolymers of C5-C8 dienes (malein-modified products, boiled oil-modified products, etc.). Of the above, tung oil, liquid diene polymers, and modified products thereof are preferred.

[0136] The amount of the air-oxidation-curable substance to be blended is preferably 0.01 to 30 parts by weight per 100 parts by weight of the total amount of the (meth)acrylic copolymer (A1) and the polyoxyalkylene polymer (B).

[0137] 4.1.8. Antioxidants and light stabilizers The multi-component curable composition according to one embodiment of the present invention may contain an antioxidant and / or light stabilizer. The antioxidant and / or light stabilizer may be any suitable agent. However, the antioxidant and / or light stabilizer may be a solid substance. In this case, it is preferable to incorporate the antioxidant and / or light stabilizer into the base resin, since uniformly mixing the (meth)acrylic copolymer (A1) and polyoxyalkylene polymer (B) with the antioxidant and / or light stabilizer at the construction site would be cumbersome. Various antioxidants and light stabilizers are known. Examples include those described in [Kenichi Saruwatari et al., "Antioxidant Handbook," Taiseisha, 1976] and [Zenjiro Osawa, editor, "Degradation and Stabilization of Polymeric Materials," CMC, 1990, pp. 235-242].

[0138] Examples of antioxidants include thioether-based antioxidants such as ADK STAB PEP-36 and ADK STAB AO-23 (all manufactured by Asahi Denka Kogyo Co., Ltd.); phosphorus-based antioxidants such as Irgafos 38, Irgafos 168, and Irgafos P-EPQ (all manufactured by Ciba Specialty Chemicals); and hindered phenol-based antioxidants. Of the above, hindered phenol-based antioxidants are preferred.

[0139] Specific examples of hindered phenol antioxidants include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, mono (or di or tri) (α-methylbenzyl) phenol, 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), and 2,5-di-t-butylhydroquinone. , 2,5-di-t-amylhydroquinone, triethylene glycol-bis-[3-(3-t-butyl-5-methyl-4 hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene ethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis(3,5-di-t-butyl-4-hydroxybenzyl) Ethyl benzylphosphonate) calcium, tris-(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-bis[(octylthio)methyl]o-cresol, N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine, tris(2,4-di-t-butylphenyl)phosphite, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)-benzotriazole, methyl-3-[3-t-butyl Examples of suitable hydroxybenzoates include 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and 2,4-di-t-butylphenyl-4-hydroxybenzoate.

[0140] Examples of commercially available antioxidants include Nocrac 200, Nocrac M-17, Nocrac SP, Nocrac SP-N, Nocrac NS-5, Nocrac NS-6, Nocrac NS-30, Nocrac 300, Nocrac NS-7, and Nocrac DAH (all manufactured by Ouchi Shinko Chemical Industry Co., Ltd.); Adeka Stab AO-30, Adeka Stab AO-40, Adeka Stab AO-50, Adeka Stab AO-60, Adeka Stab AO-616, Adeka Stab AO-635, Adeka Stab AO-658, Adeka Stab AO-80, Adeka Stab AO-15, Adeka Stab AO-18, Adeka Stab 328, and Adeka Stab AO-37 (all manufactured by Asahi Denka Kogyo); IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all manufactured by Chiba Specialty Chemicals); Sumilizer GM, Sumilizer GA-80, Sumilizer GS (all manufactured by Sumitomo Chemical).

[0141] Examples of light stabilizers include ultraviolet absorbers (benzotriazole compounds such as Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, and Tinuvin 213 (all manufactured by Ciba Specialty Chemicals); triazine light stabilizers such as Tinuvin 1577; benzophenone compounds such as CHIMASSORB81; benzoate compounds such as Tinuvin 120 (manufactured by Ciba Specialty Chemicals); and hindered amine compounds). Of the above, hindered amine compounds are preferred.

[0142] Specific examples of the hindered amine compound include dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}], N,N'-bis(3aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, and succinic acid bis(2,2,6,6-tetramethyl-4-piperidinyl)ester.

[0143] Examples of commercially available light stabilizers include Tinuvin 622LD, Tinuvin 144, CHIMASSORB944LD, and CHIMASSORB119FL (all manufactured by Chiba Specialty Chemicals), Adeka STAB LA-52, Adeka STAB LA-57, Adeka STAB LA-62, Adeka STAB LA-67, Adeka STAB LA-63, Adeka STAB LA-68, Adeka STAB LA-82, and Adeka STAB LA-87 (all manufactured by Asahi Denka Kogyo Co., Ltd.), and Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744, and Sanol LS-440 (all manufactured by Sankyo Co., Ltd.).

[0144] An antioxidant and a light stabilizer may be used in combination. By using these in combination, the effects of each agent may be further improved, and the heat resistance, weather resistance, etc. of the cured product may be improved. For example, to improve weather resistance, an ultraviolet absorber and a hindered amine-based compound (HALS) may be combined. This combination is preferable because it can further improve the effects of each agent.

[0145] The amount of the antioxidant and / or light stabilizer to be added is preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the total amount of the (meth)acrylic copolymer (A1) and the polyoxyalkylene polymer (B).

[0146] 4.2. Uses of the curable composition The uses of the multi-component curable composition and cured product according to one embodiment of the present invention are not particularly limited. Examples include architectural and industrial sealants (high-durability architectural elastic sealants used in working joints, as well as sealants for siding boards, double-glazing sealants, and vehicle sealants), electrical and electronic component materials (such as solar cell backside sealants), electrical insulating materials (such as insulating coatings for electric wires and cables), pressure-sensitive adhesives, adhesives, elastic adhesives, contact adhesives, tile adhesives, reactive hot melt adhesives, paints, powder paints, coating materials, foams, sealants for can lids, and other sealants, electrical and electronic potting agents, films, gaskets, casting materials, various molding materials, artificial marble, rust-preventing and waterproofing sealants for cut sections of wire-reinforced glass and laminated glass, vibration-proofing, vibration-damping, soundproofing, and seismic isolation materials (used in automobiles, ships, home appliances, etc.), liquid sealants (used in automobile parts, electrical parts, various machine parts, etc.), and waterproofing agents.

[0147] Among the above, the multi-component curable composition and cured product according to one embodiment of the present invention are preferably used in applications requiring durability and fatigue resistance, such as construction sealants.

[0148] Another reason why multi-component curable compositions are suitable for architectural sealant applications is their readiness for coloring. A colorant can be added to a multi-component curable composition when mixing the base agent and curing agent. This makes it possible to provide sealants in a wide variety of colors to match the color of the siding board. Therefore, multi-component curable compositions can easily meet market demands for multiple colors and are suitable for applications such as low-rise buildings. A colorant that is a paste made by mixing, for example, a pigment, a plasticizer, and optionally a filler, is preferred for its ease of use.

[0149] Furthermore, a retarder can be added to the multi-component curable composition when mixing the base resin and curing agent, allowing for fine adjustment of the curing speed at the work site.

[0150] 5. Method for producing curable composition A method for producing a multi-component curable composition according to one embodiment of the present invention includes the following steps (a) and (b). Step (a): A step of mixing a (meth)acrylic copolymer (A1) and a polyoxyalkylene polymer (B) to obtain a base material. Step (b): A step of preparing a curing agent containing a curing catalyst.

[0151] The method for producing the (meth)acrylic copolymer (A1) is as explained in Section [1.2.]. The structure of the (meth)acrylic copolymer (A1) is as explained in Section [1.1.]. The structure of the polyoxyalkylene polymer (B) is as explained in Sections [1.3.1.] and [1.3.2.]. The method for producing the polyoxyalkylene polymer (B) is as explained in Sections [1.3.3.] and [1.3.4.]. The (meth)acrylic copolymer (A1) and the polyoxyalkylene polymer (B) can be mixed by a method commonly used in this technical field.

[0152] In one embodiment, the polyoxyalkylene polymer (B) mixed in step (b) is produced by a production method including the following steps. 1. A step of ring-opening addition of an alkylene oxide in the presence of a composite metal cyanide complex catalyst having a glyme as a ligand to obtain a precursor polymer (B'') having a hydroxyl group at the end of the main chain. 2. A step of reacting the precursor polymer (B'') with a compound having a carbon-carbon unsaturated group to obtain a precursor polymer (B') having an unsaturated group at the molecular end. 3. The precursor polymer (B') is provided with a hydrogen-silicon bond and a group of the formula "-Si(R 6 ) 3-a (X) a " to obtain a polyoxyalkylene polymer (B). The alkoxysilyl group is as described in Section [1.3.1].

[0153] In another embodiment, the polyoxyalkylene polymer (B) mixed in step (b) is produced by a production method including the following steps: 1. A step of ring-opening addition of an alkylene oxide in the presence of a composite metal cyanide complex catalyst having t-butyl alcohol as a ligand to obtain a precursor polymer (B'') having a hydroxyl group at the end of the main chain. 2. A step of reacting the precursor polymer (B'') with a compound having a carbon-carbon unsaturated group to obtain a precursor polymer (B') having an unsaturated group at the molecular end. 3. The precursor polymer (B') is provided with a hydrogen-silicon bond and a group of the formula "-Si(R 6 ) 3-a (X) a " to obtain a polyoxyalkylene polymer (B). The alkoxysilyl group is as described in Section [1.3.1].

[0154] 〔summary〕 The present invention includes the following aspects. <1> a base agent containing a (meth)acrylic copolymer (A1) and a polyoxyalkylene polymer (B) having an alkoxysilyl group; a curing agent containing a curing catalyst; A multi-component curable composition comprising: The (meth)acrylic copolymer (A1) has an X block and a Y block, The molecule of the (meth)acrylic copolymer (A1) contains an XY diblock structure or an XYX triblock structure, the number of repeating units derived from a (meth)acrylic acid ester monomer having an alkoxysilyl group contained in the X block is 1.0 or more on average, the content of repeating units derived from a (meth)acrylic acid ester monomer having an alkoxysilyl group contained in the Y block is 0 to 3 wt % based on the weight of all repeating units contained in the Y block; The (meth)acrylic copolymer (A1) has a molecular weight distribution (Mw / Mn) of 1.8 or less. Multi-component curable composition. <2> The (meth)acrylic copolymer (A1) is a (meth)acrylic copolymer (A2) that satisfies the following conditions: <1> The multi-component curable composition according to claim 1, Randomly containing repeating units derived from a (meth)acrylic acid ester monomer (α); The (meth)acrylic acid ester monomer (α) has an alkyl group which is ester-bonded to (meth)acrylic acid, and the alkyl group has an alkoxy group having 1 to 5 carbon atoms; The repeating units derived from the (meth)acrylic acid ester monomer (α) account for 5 to 20% by weight based on the weight of all repeating units contained in the (meth)acrylic copolymer (A2). <3> The (meth)acrylic acid ester monomer (α) is 2-methoxyethyl (meth)acrylate. <2> The multi-component curable composition according to claim 1. <4> the content of repeating units derived from a (meth)acrylic acid ester monomer having an alkoxysilyl group contained in the X block is more than 3% by weight based on the weight of all repeating units contained in the X block; <1> ~ <3> The multi-component curable composition according to any one of the preceding claims. <5> The (meth)acrylic copolymer (A1) contains, based on the weight of all repeating units, A total of 45 to 96% by weight of repeating units derived from the (meth)acrylic acid ester monomer (β) and the (meth)acrylic acid ester monomer (γ), 4 to 35% by weight of a repeating unit derived from a (meth)acrylic acid ester monomer (δ), It contains The (meth)acrylic acid ester monomer (β) has an alkyl group ester-bonded to (meth)acrylic acid and having 1 to 5 carbon atoms, The (meth)acrylic acid ester monomer (γ) has an alkyl group ester-bonded to (meth)acrylic acid and having 6 to 15 carbon atoms, The (meth)acrylic acid ester monomer (δ) has 16 to 25 carbon atoms in the alkyl ester bonded to the (meth)acrylic acid. <1> ~ <4> The multi-component curable composition according to any one of the preceding claims. <6> The (meth)acrylic copolymer (A1) does not contain a repeating unit derived from the (meth)acrylic acid ester monomer (γ). <5> The multi-component curable composition according to claim 1. <7> The (meth)acrylic copolymer (A1) has a molecular weight distribution (Mw / Mn) of 1.5 or less. <1> ~ <6> The multi-component curable composition according to any one of the preceding claims. <8> The polyoxyalkylene polymer (B) having an alkoxysilyl group has an alkoxysilyl group represented by the following formula: <1> ~ <7> The multi-component curable composition according to any one of the preceding claims. -Si(R 6 ) 3-a (X) a (In the formula, R in one alkoxysilyl group 6 When a plurality of are included, they may be the same or different, R 6may vary for each alkoxysilyl group, and represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms (if substituted, it may be substituted with a heteroatom-containing group), When one alkoxysilyl group contains a plurality of Xs, they may be the same or different. X may be different for each alkoxysilyl group and represents a hydroxyl group or a hydrolyzable group; a is 1, 2 or 3) <9> The number average molecular weight of the polyoxyalkylene polymer (B) having an alkoxysilyl group is 10,000 to 40,000. <1> ~ <8> The multi-component curable composition according to any one of the preceding claims. <10> The polyoxyalkylene polymer (B) having an alkoxysilyl group has, on average, 0.5 to 6.0 alkoxysilyl groups per molecule. <1> ~ <9> The multi-component curable composition according to any one of the preceding claims. <11> <1> ~ <10> A cured product obtained by curing the multi-component curable composition according to any one of the above items. <12> It is a construction sealant. <11> The cured product according to claim 1. <13> A method for producing a multi-component curable composition, comprising the following steps (a) and (b): Step (a): A step of mixing the (meth)acrylic copolymer (A1) and the polyoxyalkylene polymer (B) to obtain a base material; Step (b): preparing a curing agent containing a curing catalyst; The (meth)acrylic copolymer (A1) has an X block and a Y block, The molecule of the (meth)acrylic copolymer (A1) contains an XY diblock structure or an XYX triblock structure, the number of repeating units derived from a (meth)acrylic acid ester monomer having an alkoxysilyl group contained in the X block is 1.0 or more on average, the content of repeating units derived from a (meth)acrylic acid ester monomer having an alkoxysilyl group contained in the Y block is 0 to 3 wt % based on the weight of all repeating units contained in the Y block; The (meth)acrylic copolymer (A1) has a molecular weight distribution (Mw / Mn) of 1.8 or less. Manufacturing method. <14> The polyoxyalkylene polymer (B) can be obtained by a production method including the following steps: <13> The manufacturing method described in 1. A step of ring-opening addition of an alkylene oxide in the presence of a double metal cyanide complex catalyst having a glyme as a ligand to obtain a precursor polymer (B'') having a hydroxyl group at the end of the main chain; 2. A step of reacting the precursor polymer (B'') with a compound having a carbon-carbon unsaturated group to obtain a precursor polymer (B') having an unsaturated group at the molecular terminal; 3. A step of reacting the precursor polymer (B') with a compound having a hydrogen-silicon bond and an alkoxysilyl group represented by the following formula to obtain the polyoxyalkylene polymer (B); -Si(R 6 ) 3-a (X) a (In the formula, R 6 When a plurality of are included, they may be the same or different, R 6 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms (if substituted, it may be substituted with a heteroatom-containing group), When a plurality of X's are present, they may be the same or different, X represents a hydroxyl group or a hydrolyzable group; a is 1, 2 or 3). <15> The polyoxyalkylene polymer (B) is obtained by a production method according to claim 13, comprising the following steps: 1. A step of ring-opening addition of an alkylene oxide in the presence of a double metal cyanide complex catalyst having t-butyl alcohol as a ligand to obtain a precursor polymer (B'') having a hydroxyl group at the end of the main chain; 2. A step of reacting the precursor polymer (B'') with a compound having a carbon-carbon unsaturated group to obtain a precursor polymer (B') having an unsaturated group at the molecular terminal; 3. A step of reacting the precursor polymer (B') with a compound having a hydrogen-silicon bond and an alkoxysilyl group represented by the following formula to obtain the polyoxyalkylene polymer (B); -Si(R 6 ) 3-a (X) a (In the formula, R 6 When a plurality of are included, they may be the same or different, R 6 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms (if substituted, it may be substituted with a heteroatom-containing group), When a plurality of X's are present, they may be the same or different, X represents a hydroxyl group or a hydrolyzable group; a is 1, 2 or 3).

[0155] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention. [Example]

[0156] [Production Example 1: Production of (meth)acrylic copolymer (A2)] (preparation) A 2000 mL three-neck flask was prepared. The (meth)acrylic acid ester monomers (α), (β), and (δ) were placed in the flask and mixed in the proportions shown in Table 1. Specifically, 700 g of n-butyl acrylate, 110 g of 2-methoxyethyl acrylate, and 190 g of octadecyl acrylate (total: 1000 g) were mixed. This mixture is referred to as the "(meth)acrylic acid ester monomer mixture."

[0157] Next, another stirring vessel was prepared. 52.7 mg of copper bromide (CuBr2), 54.4 mg of hexamethyltris(2-aminoethyl)amine (Me6TREN), and 1.82 g of methanol were charged into the vessel, and the mixture was stirred under a nitrogen stream until a homogeneous solution was obtained. This homogeneous solution is referred to as the "copper solution." The copper content in the copper solution was equivalent to 15 ppm relative to the total amount of the (meth)acrylic acid ester monomer mixture.

[0158] In addition, another stirring vessel was prepared. 30.8 mL of methanol, 1.0 g of ascorbic acid, and 1.6 mL of triethylamine were charged into this vessel and stirred under a nitrogen stream to obtain a homogeneous solution. This homogeneous solution is referred to as the "ascorbic acid solution."

[0159] (1st step) 5.38 g of ethyl α-bromobutyrate (initiator; 0.028 mol), 200 g of a (meth)acrylic acid ester monomer mixture (20 wt % of the total), 11.53 g of 3-(dimethoxymethylsilyl)propyl methacrylate (0.050 mol; 1.80 molar equivalents relative to the initiator), 107.68 g of methanol (manufactured by Wako Pure Chemical Industries, Ltd.), and the entire copper solution were charged into a stirrer and stirred under a nitrogen stream for 30 minutes to obtain a homogeneous solution. The stirrer used here was a jacket temperature-controlled stirrer, and the jacket temperature was set to 45°C.

[0160] Next, when the temperature in the polymerization system reached 40°C or higher, the ascorbic acid solution was continuously added dropwise to initiate the polymerization reaction. The rate at which the ascorbic acid solution was added was set to 144 mg of ascorbic acid per hour.

[0161] When the temperature in the polymerization system was monitored, it rose simultaneously with the start of the dropwise addition of ascorbic acid, reached a maximum temperature, and then gradually decreased. When the temperature difference between the temperature in the polymerization system and the jacket temperature reached 1°C, a small amount of the reaction solution in the polymerization system was sampled and analyzed by gas chromatography. The results showed that 90% by weight of the (meth)acrylic acid ester monomer mixture initially charged had been consumed.

[0162] (2nd process) Next, the remaining (80 wt. % of the total amount) of the (meth)acrylic acid ester monomer mixture that was not added in the first step was continuously added dropwise to the polymerization system over a period of 90 minutes. The ascorbic acid solution was added dropwise at a rate of 48 mg of ascorbic acid per hour. Sampling was also performed sequentially and analyzed by gas chromatography. The polymerization was continued until 88 wt. % of the total amount of the (meth)acrylic acid ester monomer mixture added to the polymerization system was consumed.

[0163] (3rd step) Next, 12.69 g (0.055 mol; 1.98 molar equivalents relative to the initiator) of 3-(dimethoxymethylsilyl)propyl methacrylate was added to the polymerization system. The continuous dropwise addition of the ascorbic acid solution was continued until 98 wt% of the total amount of the (meth)acrylic acid ester monomer mixture added to the polymerization system was consumed. Thereafter, the dropwise addition of the ascorbic acid solution was stopped, and the polymerization was terminated.

[0164] The jacket temperature was changed to 80°C, and the solvent was then devolatilized. A diaphragm pump was used first, and then a vacuum pump was used. After devolatilization was completed, the jacket temperature was cooled to 60°C or lower.

[0165] (purification) 1000 g of butyl acetate was added to a jacket temperature-controlled stirrer and mixed with the polymer after devolatilization until a homogeneous solution was obtained. An adsorbent was added to the homogeneous solution and stirred for 1 hour. The adsorbents used were 10 g of Kyoward 500SH (Kyowa Chemical Industry Co., Ltd.) and 10 g of Kyoward 700SEN-S (Kyowa Chemical Industry Co., Ltd.).

[0166] After stirring, the resulting mixture was filtered through a filter equipped with a bag filter cloth. This resulted in a clear polymer solution. 1.5 g of an antioxidant (Sumilizer GS; manufactured by Sumitomo Chemical) was added to the solution and mixed until homogeneous. The solvent was then removed from the solution to obtain a (meth)acrylic copolymer (A2). A diaphragm pump was used first to remove the volatilization, followed by a vacuum pump.

[0167] [Production Example 2: Production of (meth)acrylic copolymer (A1)] A polymer was produced in the same manner as in Production Example 1, except that the composition of the raw material monomers was changed as shown in Table 1 below. Specifically, a mixture consisting of 706.6 g of n-butyl acrylate, 107.5 g of ethyl acrylate, and 185.9 g of octadecyl acrylate (total: 1000 g) was used as the (meth)acrylic acid ester monomer mixture. The amount of ethyl α-bromobutyrate used was 5.82 g (initiator; 0.030 mol). Furthermore, the amounts of 3-(dimethoxymethylsilyl)propyl methacrylate added in the first and third steps were changed to 13.87 g (0.060 mol; 2.0 molar equivalents relative to the initiator) and 15.25 g (0.066 mol; 2.2 molar equivalents relative to the initiator), respectively.

[0168] The polymer produced in Production Example 2 does not contain the (meth)acrylic acid ester monomer (α) as a raw material, and therefore corresponds to the (meth)acrylic copolymer (A1) but does not correspond to the (meth)acrylic copolymer (A2).

[0169] [Production Example 3] A (meth)acrylic copolymer was produced by the production method described below. This copolymer does not fall under the category of the (meth)acrylic copolymer (A1) of the present invention, since the alkoxysilyl groups are located only at the molecular terminals and the entire molecule does not contain X blocks.

[0170] (preparation) (Meth)acrylic acid ester monomers (α), (β), and (δ) were mixed in the proportions shown in Table 1. Specifically, 707 g of n-butyl acrylate, 107 g of ethyl acrylate, and 186 g of octadecyl acrylate (total: 1000 g) were mixed. This mixture is referred to as the "(meth)acrylic acid ester monomer mixture."

[0171] (polymerization) The inside of a stainless steel reactor equipped with a stirrer was deoxygenated. 5.8 g of cuprous bromide and 200 g of the (meth)acrylic acid ester monomer mixture were charged into the reactor and heated with stirring. Next, 90 g of acetonitrile and 10.7 g of initiator (diethyl 2,5-dibromoadipate) were added and mixed. The temperature of the mixture was adjusted to approximately 65°C, and pentamethyldiethylenetriamine was added to initiate the polymerization reaction. The remaining 800 g of the (meth)acrylic acid ester monomer mixture was then gradually added, and the polymerization reaction was allowed to proceed. During the polymerization reaction, pentamethyldiethylenetriamine was added as needed to adjust the polymerization rate. The total amount of pentamethyldiethylenetriamine used throughout the polymerization reaction was 1.7 g. As the polymerization progressed, the temperature of the reaction system tended to rise due to the heat of reaction, but the temperature of the reaction system was maintained at approximately 80-90°C. When the monomer conversion rate (polymerization reaction rate) reached 95%, the volatile matter was removed by devolatilization under reduced pressure to obtain a polymer concentrate. The time required to reach this stage was 4 hours.

[0172] To the obtained polymer concentrate, 200 g of 1,7-octadiene, 360 g of acetonitrile, and 3.1 g of pentamethyldiethylenetriamine were added. Next, the reaction system was heated and stirred for several hours while adjusting the temperature to about 70 to 90°C, thereby reacting 1,7-octadiene with the terminals of the polymer.

[0173] (purification) At the end of the reaction, an oxygen-nitrogen mixed gas was introduced into the gas phase of the reaction vessel. Next, the reaction solution was heated and stirred for several hours while maintaining the reaction temperature at approximately 70-90°C, thereby bringing the polymerization catalyst contained in the reaction solution into contact with oxygen. Next, acetonitrile and unreacted 1,7-octadiene were removed by devolatilization under reduced pressure, yielding a polymer concentrate.

[0174] The polymer concentrate was diluted with 1000 g of butyl acetate, and then 10 g of a filter aid (Radiolite #800, manufactured by Showa Chemical Industry Co., Ltd.) was added and stirred, and the insoluble catalyst components were removed by filtration.

[0175] The filtrate was placed in a stainless steel reactor equipped with a stirrer, and 5 g of adsorbents (Kyoward 700SEN-S and Kyoward 500SH) were added. Next, an oxygen-nitrogen mixed gas was introduced into the gas phase of the reactor, and the mixture was heated and stirred at approximately 100°C for 30 minutes. Next, insoluble components (such as adsorbents) were removed by filtration, yielding a clear filtrate. This procedure was repeated once, and the filtrate was concentrated to yield a crude polymer.

[0176] To the crude polymer, 1.5 g of a heat stabilizer (Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd.) and 5 g each of adsorbents (Kyoward 700SEN-S and Kyoward 500SH) were added. The system was heated and subjected to vacuum degassing at a high temperature of approximately 180-200°C for 2-4 hours, thereby purifying the crude polymer by adsorption. Next, 5 g and 20 g of adsorbents (Kyoward 700SEN and Kyoward 500SH), respectively, were added. Next, the gas phase in the reaction vessel was substituted with an oxygen-nitrogen mixed gas atmosphere, and the mixture was heated and stirred at a high temperature of approximately 180-200°C for 2-6 hours to continue the adsorption purification. Next, the polymer was diluted with 1000 g of butyl acetate and then filtered to remove the adsorbent. The filtrate was concentrated to obtain a polymer bearing alkenyl groups at both ends. The average number of alkenyl groups introduced into the polymer was 2.0 per molecule.

[0177] (Introduction of alkoxysilyl groups) The resulting polymer was mixed with 20 g of methyldimethoxysilane (DMS), 3 g of methyl orthoformate, and 0.13 g of an isopropanol solution (3.0 wt%) of bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst, and the mixture was heated and stirred at approximately 100°C. After approximately one hour, volatiles (unreacted DMS, etc.) were removed by distillation under reduced pressure to obtain a (meth)acrylic copolymer. The average number of alkoxysilyl groups introduced into the polymer was 2.0 per molecule.

[0178] [Table 1]

[0179] [Methods for measuring physical properties] [Preparation of evaluation samples] The base resin, curing agent, and colorant were prepared according to the compositions shown in Table 2 below. They were mixed at a weight ratio of 340:10:10 (base resin:curing agent:colorant). The resulting mixture was poured into a mold and degassed under reduced pressure. It was then heat-cured at 50°C for 20 hours to obtain a sheet-like cured product with rubber elasticity.

[0180] [Table 2]

[0181] [Mechanical properties] The prepared curable composition was filled into an H-shaped aluminum substrate according to the method for preparing a tensile adhesion test specimen specified in JIS A 1439:2016. The curing conditions were 23°C for 7 days and 50°C for 7 days. The aluminum used as the substrate was anodized aluminum measuring 50 x 50 x 5 mm in accordance with JIS H4000. Before filling with the curable composition, the substrate was cleaned with methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.). MP-2000 (manufactured by Cemedine Co., Ltd.) was used as a primer.

[0182] The H-shaped sample thus obtained was subjected to a tensile test at a tension speed of 50 mm / min in a thermostatic chamber at 23°C and humidity of 50±5% according to the tensile adhesion test method specified in JIS A 1439:2016. Specifically, the stress at 50% elongation, stress at 100% elongation, stress at break, and elongation at break were measured.

[0183] The resulting cured product was then aged (left to stand at 100°C for 3 weeks). The mechanical properties of the aged cured product were also measured in the same manner. The rate of change in each mechanical property before and after aging was calculated using the following formula. This test is considered an accelerated deterioration test, and the smaller the change in properties, the better (i.e., the closer the rate of change to 100%, the better). Change rate (%) = (measured value after curing / measured value before curing) x 100.

[0184] [Durability and fatigue resistance] The prepared multi-component curable compositions were subjected to durability and fatigue resistance tests as specified in JIS A 1439:2016, "Test Methods for Construction Sealant Materials." Detailed test conditions were 10030 for the durability test and CR100 for the fatigue resistance test. The fatigue resistance test was also performed under conditions where the compression heating temperature was changed to 120°C (hereinafter referred to as "CR120"). Furthermore, during the durability test 10030, the sealant was subjected to the first 100°C 30% compression heating, followed by one day of curing at 23°C and 50±5% humidity. The recovery rate of the joint width was evaluated as the recovery rate.

[0185] [Examples 1 and 2 and Comparative Example 1] In Examples 1 and 2, cured products were prepared using the (meth)acrylic copolymers obtained in Production Examples 1 and 2, respectively, and the various physical properties described above were measured. In Comparative Example 1, a cured product was prepared using the (meth)acrylic copolymer obtained in Production Example 3, and the various physical properties described above were measured. The measurement results of the mechanical properties are shown in Table 3.

[0186] [Table 3]

[0187] 〔result〕 In the durability and fatigue resistance tests, the appearance of the interface between the substrate and the curable composition, excluding both ends, was evaluated. The evaluation results were graded A as the most preferable, and graded D as the less preferable.

[0188] The detailed results of the durability test (10030) were as follows: The curable composition of Example 1 showed no change in appearance before and after the test, and the recovery rate was 41%. The curable composition of Example 2 showed no change in appearance before and after the test, and the recovery rate was 41%. The curable composition of Comparative Example 1 had slight bubbles at the interface with the substrate, and the recovery rate was 32%.

[0189] Detailed results of the fatigue resistance test (CR100) are as follows (two samples were used for each Example and Comparative Example in this test). For both samples of the curable composition according to Example 1, there was no change in appearance before and after the test. The curable composition according to Example 2 also showed results similar to those of the curable composition according to Example 1. For both samples of the curable composition according to Comparative Example 1, air bubbles occurred intermittently along the interface with the substrate, up to a distance of about 1 cm.

[0190] The detailed results of the fatigue resistance test (CR120) are as follows (two samples were used for each Example and Comparative Example in this test). Of the curable compositions according to Example 1, the first sample had intermittent bubbles of about 2 cm along the interface with the substrate. Of the curable compositions according to Example 1, the second sample had four small bubbles at the interface with the substrate. Of the curable compositions according to Comparative Example 1, the first sample had a crack of 8 cm in length and 1.5-2 mm in depth along the interface with the substrate. Of the curable compositions according to Comparative Example 1, the second sample had a crack of 15 cm in length and 1.5 mm in depth along the interface with the substrate.

[0191] As described above, the cured products of Examples 1 and 2 had improved durability and fatigue resistance compared to the cured product of Comparative Example 1. This suggests that the cured product according to one aspect of the present invention has improved durability and fatigue resistance compared to conventional cured products.

[0192] Furthermore, the cured products of Examples 1 and 2 had similar levels to the cured product of Comparative Example 1 in terms of the rate of change in stress at 50% or 100% elongation. [Industrial Applicability]

[0193] The present invention can be used for sealing materials and the like.

Claims

1. a base material containing a (meth)acrylic copolymer (A1) and a polyoxyalkylene polymer (B) having an alkoxysilyl group; a curing agent containing a curing catalyst; A multi-component curable composition comprising: The (meth)acrylic copolymer (A1) has an X block and a Y block, The molecule of the (meth)acrylic copolymer (A1) contains an XY diblock structure or an XYX triblock structure, the number of repeating units derived from a (meth)acrylic acid ester monomer having an alkoxysilyl group contained in the X block is 1.0 to 10.0 on average; the content of repeating units derived from (meth)acrylic acid ester monomers having an alkoxysilyl group contained in the X block is more than 3 wt % based on the weight of all repeating units contained in the X block; The (meth)acrylic copolymer (A1) has repeating units derived from the following monomers (i) and (ii): (i) at least one of a (meth)acrylic acid ester monomer (β) and a (meth)acrylic acid ester monomer (γ); (ii) (meth)acrylic acid ester monomer (δ); where: The (meth)acrylic acid ester monomer (β) has an alkyl group ester-bonded to (meth)acrylic acid and having 1 to 5 carbon atoms, The (meth)acrylic acid ester monomer (γ) has an alkyl group ester-bonded to (meth)acrylic acid and having 6 to 15 carbon atoms, The (meth)acrylic acid ester monomer (δ) has an alkyl group ester-bonded to (meth)acrylic acid having 16 to 25 carbon atoms; the content of repeating units derived from (meth)acrylic acid ester monomers having an alkoxysilyl group contained in the Y block is 0 to 3 wt % based on the weight of all repeating units contained in the Y block, the (meth)acrylic copolymer (A1) has a molecular weight distribution (Mw / Mn) of 1.8 or less; The polyoxyalkylene polymer (B) having an alkoxysilyl group has, on average, 0.5 to 6.0 alkoxysilyl groups per molecule, The content of each component in the base resin is, in parts by weight, the (meth)acrylic copolymer (A1):the polyoxyalkylene polymer (B) having an alkoxysilyl group=100:(5 to 1900), The base agent is a multi-component curable composition further comprising one or more components selected from the following group: (i) Filler; (ii) plasticizers; (iii) thixotropic agents; (iv) stabilizers; (v) Pigments.

2. The multi-component curable composition according to claim 1, wherein the (meth)acrylic copolymer (A1) is a (meth)acrylic copolymer (A2) that satisfies the following conditions: Randomly containing repeating units derived from a (meth)acrylic acid ester monomer (α); The (meth)acrylic acid ester monomer (α) has an alkyl group which is ester-bonded to (meth)acrylic acid, and the alkyl group has an alkoxy group having 1 to 5 carbon atoms; The repeating units derived from the (meth)acrylic acid ester monomer (α) account for 5 to 20% by weight based on the weight of all repeating units contained in the (meth)acrylic copolymer (A2).

3. 3. The multi-component curable composition according to claim 2, wherein the (meth)acrylic acid ester monomer (α) is 2-methoxyethyl (meth)acrylate.

4. The multi-component curable composition according to claim 2 or 3, wherein the (meth)acrylic copolymer (A2) does not contain a repeating unit derived from the (meth)acrylic acid ester monomer (γ).

5. The multi-component curable composition according to any one of claims 1 to 4, wherein the (meth)acrylic copolymer (A1) has a molecular weight distribution (Mw / Mn) of 1.5 or less.

6. The multi-component curable composition according to any one of claims 1 to 5, wherein the polyoxyalkylene polymer (B) having an alkoxysilyl group has an alkoxysilyl group represented by the following formula: -Si(R ６ ) ３－ａ (X) ａ (In the formula, One alkoxysilyl group has R ６ When a plurality of are included, they may be the same or different, R ６ may vary for each alkoxysilyl group and represent a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms (if substituted, it may be substituted with a heteroatom-containing group), When one alkoxysilyl group contains a plurality of X, they may be the same or different. X may be different for each alkoxysilyl group and represents a hydroxyl group or a hydrolyzable group (provided that at least one of X is an alkoxy group); a is 1, 2 or 3).

7. 7. The multi-component curable composition according to claim 1, wherein the polyoxyalkylene polymer (B) having an alkoxysilyl group has a number average molecular weight of 10,000 to 40,000.

8. The multi-component curable composition according to any one of claims 1 to 7, wherein the curing agent comprises a co-catalyst and / or a plasticizer.

9. A cured product obtained by curing the multi-component curable composition according to any one of claims 1 to 8.

10. The cured product according to claim 9, which is a construction sealant.

11. A method for producing a multi-component curable composition, comprising the following steps (a) and (b): Step (a): A step of mixing the (meth)acrylic copolymer (A1), the polyoxyalkylene polymer (B), and the third component to obtain a base material; Step (b): preparing a curing agent containing a curing catalyst; The (meth)acrylic copolymer (A1) has an X block and a Y block, The molecule of the (meth)acrylic copolymer (A1) contains an XY diblock structure or an XYX triblock structure, the number of repeating units derived from a (meth)acrylic acid ester monomer having an alkoxysilyl group contained in the X block is 1.0 to 10.0 on average; the content of repeating units derived from (meth)acrylic acid ester monomers having an alkoxysilyl group contained in the X block is more than 3 wt % based on the weight of all repeating units contained in the X block; the content of repeating units derived from (meth)acrylic acid ester monomers having an alkoxysilyl group contained in the Y block is 0 to 3 wt % based on the weight of all repeating units contained in the Y block, the (meth)acrylic copolymer (A1) has a molecular weight distribution (Mw / Mn) of 1.8 or less; The (meth)acrylic copolymer (A1) has repeating units derived from the following monomers (i) and (ii): (i) at least one of a (meth)acrylic acid ester monomer (β) and a (meth)acrylic acid ester monomer (γ); (ii) (meth)acrylic acid ester monomer (δ); where: The (meth)acrylic acid ester monomer (β) has an alkyl group ester-bonded to (meth)acrylic acid and having 1 to 5 carbon atoms, The (meth)acrylic acid ester monomer (γ) has an alkyl group ester-bonded to (meth)acrylic acid and having 6 to 15 carbon atoms, The (meth)acrylic acid ester monomer (δ) has an alkyl group ester-bonded to (meth)acrylic acid having 16 to 25 carbon atoms; The polyoxyalkylene polymer (B) having an alkoxysilyl group has, on average, 0.5 to 6.0 alkoxysilyl groups per molecule, The content of each component in the base resin is, in parts by weight, the (meth)acrylic copolymer (A1):the polyoxyalkylene polymer (B) having an alkoxysilyl group=100:(5 to 1900), The third component comprises one or more components selected from the following group: (i) Filler; (ii) plasticizers; (iii) thixotropic agents; (iv) stabilizers; (v) Pigments.

12. The polyoxyalkylene polymer (B) having an alkoxysilyl group is obtained by a production method comprising the following steps according to claim 11:

1. A step of ring-opening addition of an alkylene oxide in the presence of a double metal cyanide complex catalyst having a glyme as a ligand to obtain a precursor polymer (B″) having a hydroxyl group at the end of the main chain; 2. A step of reacting the precursor polymer (B″) with a compound having a carbon-carbon unsaturated group to obtain a precursor polymer (B′) having an unsaturated group at the molecular terminal; 3. A step of reacting the precursor polymer (B') with a compound having a hydrogen-silicon bond and an alkoxysilyl group represented by the following formula to obtain the polyoxyalkylene polymer (B); -Si(R ６ ) ３－ａ (X) ａ (In the formula, R ６ When a plurality of are included, they may be the same or different, R ６ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms (if substituted, it may be substituted with a heteroatom-containing group); When a plurality of X's are contained, they may be the same or different, X represents a hydroxyl group or a hydrolyzable group (provided that at least one of X is an alkoxy group); a is 1, 2 or 3).

13. The polyoxyalkylene polymer (B) having an alkoxysilyl group is obtained by a production method comprising the following steps according to claim 11:

1. A step of ring-opening addition of an alkylene oxide in the presence of a double metal cyanide complex catalyst having t-butyl alcohol as a ligand to obtain a precursor polymer (B″) having a hydroxyl group at the end of the main chain; 2. A step of reacting the precursor polymer (B″) with a compound having a carbon-carbon unsaturated group to obtain a precursor polymer (B′) having an unsaturated group at the molecular terminal; 3. A step of reacting the precursor polymer (B') with a compound having a hydrogen-silicon bond and an alkoxysilyl group represented by the following formula to obtain the polyoxyalkylene polymer (B); -Si(R ６ ) ３－ａ (X) ａ (In the formula, R ６ When a plurality of are included, they may be the same or different, R ６ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms (if substituted, it may be substituted with a heteroatom-containing group); When a plurality of X's are contained, they may be the same or different, X represents a hydroxyl group or a hydrolyzable group (provided that at least one of X is an alkoxy group); a is 1, 2 or 3).

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