Composition, curable composition, cured product, and storage method

Abstract

Provided is a composition having improved storage viscosity. A composition according to one mode of the present invention contains a (meth)acrylic copolymer (A') and epoxy compound (C). The molecule of the (meth)acrylic copolymer (A') includes a XY diblock structure or a XYX triblock structure within the molecule. The average number of repeating units derived from a (meth)acrylic acid ester monomer that has an alkoxysilyl group and that is included in an X-block, is 1.0 or more. Repeating units derived from a (meth)acrylic acid ester monomer that has an alkoxysilyl group and that is included in a Y-block account for 0-3 wt% with respect to the weight of all repeating units included in the Y-block. The molecule weight distribution (Mw / Mn) of the (meth)acrylic copolymer (A') is 1.8 or less.

Description

[Technical Field]

[0001] The present invention relates to a composition, a curable composition, a cured product, and a storage method. [Background technology]

[0002] Polymer molecules having 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. Utilizing this characteristic, polymers having alkoxysilyl groups are used in a wide range of applications, including sealants, adhesives, and paints.

[0003] Patent Document 1 discloses a method for producing an example of such a polymer, a (meth)acrylic copolymer having an alkoxysilyl group, by atom transfer radical polymerization. This method includes the following three steps:

[0004] (1) A first step of polymerizing an initiator having one halogen group in the molecule, a (meth)acrylic monomer (B) having a hydrolyzable silyl group, and a (meth)acrylic monomer (C) not having a hydrolyzable silyl group to synthesize a macroinitiator.

[0005] (2) A second step of adding a (meth)acrylic monomer (C) to synthesize an intermediate polymer.

[0006] (3) The third step is to add a (meth)acrylic monomer (B) to synthesize an intermediate polymer. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2018-162394 Summary of the Invention [Problem to be solved by the invention]

[0008] According to the production method described in Patent Document 1, a (meth)acrylic copolymer having an alkoxysilyl group can be produced with higher productivity than conventional production methods. However, the (meth)acrylic copolymer produced by this production method has room for improvement in the viscosity of the polymer. Specifically, there is a problem in that the viscosity of the copolymer increases after storage at high temperatures (storage viscosity).

[0009] One aspect of the present invention is to provide a composition having improved storage viscosity. [Means for solving the problem]

[0010] In order to solve the above problems, a composition according to one aspect of the present invention comprises: A composition comprising a (meth)acrylic copolymer (A') and an epoxy compound (C), The (meth)acrylic copolymer (A') has an X block and a Y block, The molecule of the (meth)acrylic copolymer (A') contains an XY diblock structure or an XYX triblock structure in the molecule, 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 (A') has a molecular weight distribution (Mw / Mn) of 1.8 or less. [Effects of the Invention]

[0011] According to one aspect of the present invention, a composition having improved storage viscosity can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, an example of an embodiment of the present invention will be described in detail, but the present invention is not limited to this.

[0013] 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."

[0014] A composition according to one aspect of the present invention includes a (meth)acrylic copolymer (A') and an epoxy compound (C). In one embodiment, the (meth)acrylic copolymer (A') is a (meth)acrylic copolymer (A'').

[0015] [1. (Meth)acrylic copolymer (A') and (meth)acrylic copolymer (A'')] A composition according to one embodiment of the present invention contains a (meth)acrylic copolymer (A'). The (meth)acrylic copolymer (A') 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 (A') 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.

[0016] 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 (A') is preferably from (5 / 95) to (60 / 40), more preferably from (15 / 85) to (40 / 60).

[0017] In one embodiment, the molecule of the (meth)acrylic copolymer (A') 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.

[0018] In one embodiment, the molecule of the (meth)acrylic copolymer (A') has an XYX triblock structure. In a molecule with an XYX triblock structure, the X blocks may be 40% or less, 30% or less, or 25% or less of the region from the ends of the molecule (all units contained in the molecule are taken as 100%). Here, the X blocks are blocks located at both ends of the molecule.

[0019] The (meth)acrylic copolymer (A') 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.

[0020] 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 (A'). In particular, when the (meth)acrylic copolymer (A') 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 (A') 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.

[0021] The number of repeating units derived from (meth)acrylic acid ester monomers having an alkoxysilyl group contained in the X block is preferably 1.5 or more, more preferably 1.7 or more, on average. Similarly, the number of repeating units derived from (meth)acrylic acid ester monomers having an alkoxysilyl group contained in the X block is preferably more 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 more than 0 wt%, more preferably 0 wt% or more, based on the weight of all repeating units contained in the Y block.

[0022] Furthermore, the (meth)acrylic copolymer (A') 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 (A') is 1.8 or less. The molecular weight distribution of the (meth)acrylic copolymer (A') is preferably 1.7 or less, more preferably 1.6 or less, even more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less. If the molecular weight distribution is too large, the viscosity of the polymer increases, tending to reduce workability.

[0023] 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.

[0024] The (meth)acrylic copolymer (A') 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 [2].

[0025] ((Meth)acrylic copolymer (A'')) In one embodiment, the (meth)acrylic copolymer (A') is a (meth)acrylic copolymer (A"). The (meth)acrylic copolymer (A") is a particularly preferred embodiment in that it has a reduced viscosity (initial viscosity) immediately after production. The (meth)acrylic copolymer (A") 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 % based on the weight of all repeating units contained in the (meth)acrylic copolymer (A"). 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.

[0026] 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 (A″).

[0027] When repeating units derived from the (meth)acrylic acid ester monomer (α) are randomly contained and their content is within the above-mentioned range, the initial viscosity of the (meth)acrylic copolymer (A″) can be reduced. The initial viscosity of the (meth)acrylic copolymer (A″) is preferably 200 Pa·s or less, more preferably 150 Pa·s or less, and more preferably 130 Pa·s or less. The initial viscosity can be measured using an appropriate viscometer. In this specification, the term “initial viscosity” refers to the viscosity of the (meth)acrylic copolymer (A″) stored at room temperature for up to six months after production of the (meth)acrylic copolymer (A″).

[0028] Furthermore, when the content of the repeating unit derived from the (meth)acrylic acid ester monomer (α) is within the above range, the compatibility between the (meth)acrylic polymer (A) and the polyoxyalkylene polymer (B) is high, and therefore, a curable composition and a cured product with good properties can be obtained.

[0029] [1.1. (Meth)acrylic acid ester monomers] The (meth)acrylic copolymer (A') 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 (A'), the content of repeating units derived from the (meth)acrylic acid ester monomer (α) is preferably 0 to 20% by weight, based on the weight of all repeating units contained in the (meth)acrylic copolymer (A'). The total content of repeating units derived from the (meth)acrylic acid ester monomer (β) and the (meth)acrylic acid monomer (γ) is preferably 45 to 96% by weight, based on the weight of all repeating units contained in the (meth)acrylic copolymer (A'). The content of repeating units derived from the (meth)acrylic acid ester monomer (δ) is preferably 4 to 35% by weight, based on the weight of all repeating units contained in the (meth)acrylic copolymer (A'). By containing each (meth)acrylic acid ester monomer in such a composition, the (meth)acrylic copolymer (A') can achieve good workability, mechanical properties, and weather resistance.

[0032] On the other hand, in the (meth)acrylic copolymer (A'), the content of repeating units derived from the (meth)acrylic acid ester monomer (α) in the (meth)acrylic copolymer (A") is 5 to 20% by weight, and preferably 10 to 20% by weight, based on the weight of all repeating units contained in the (meth)acrylic copolymer (A"). The content of repeating units derived from the (meth)acrylic acid ester monomer (β) is preferably 45 to 70% by weight, and more preferably 50 to 70% by weight, based on the weight of all repeating units contained in the (meth)acrylic copolymer (A"). The content of repeating units derived from the (meth)acrylic acid ester monomer (γ) is preferably 0 to 25% by weight, and more preferably 10 to 25% by weight, based on the weight of all repeating units contained in the (meth)acrylic copolymer (A"). The content of the repeating units derived from the (meth)acrylic acid ester monomer (δ) is preferably 15 to 25% by weight, more preferably 15 to 20% by weight, based on the weight of all repeating units contained in the (meth)acrylic copolymer (A''). By containing each (meth)acrylic acid ester monomer in such a composition, the (meth)acrylic copolymer (A'') 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 polymer (A') 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, and a decrease in workability can be prevented. Furthermore, when the content of the repeating unit derived from the (meth)acrylic acid ester monomer (γ) is within the above range, the compatibility between the (meth)acrylic polymer (A') 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 polymer (A') and the polyoxyalkylene polymer (B) can be sufficiently ensured. Furthermore, when the content of the repeating unit derived from the (meth)acrylic acid ester monomer (δ) is within the above range, an 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, the (meth)acrylic acid ester monomer (α) is preferably one or more selected from the group consisting of 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and isopropoxyethyl (meth)acrylate, with 2-methoxyethyl acrylate being more preferred. The (meth)acrylic acid ester monomer (β) is preferably butyl acrylate. The (meth)acrylic acid ester monomer (γ) is preferably 2-ethylhexyl acrylate and dodecyl acrylate. The (meth)acrylic acid ester monomer (δ) is preferably one or more selected from the group consisting of pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, eicosyl (meth)acrylate, and docosyl (meth)acrylate, with octadecyl acrylate being more preferred. By selecting these monomers, the (meth)acrylic copolymer (A') 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 (A') does not contain a repeating unit derived from the (meth)acrylic acid monomer (γ). Such a (meth)acrylic copolymer (A') 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 (A') preferably account for 70% by weight or more, and more preferably 90% by weight or more, based on all repeating units contained in the (meth)acrylic copolymer (A'). If the content of repeating units derived from (meth)acrylic acid ester monomers is 70% or more, the produced (meth)acrylic copolymer (A') can be sufficiently compatible with the polyoxyalkylene polymer (B), and can also exhibit good weather resistance, mechanical properties, and durability.

[0038] [1.2. (Meth)acrylic acid ester monomers having an alkoxysilyl group] The (meth)acrylic copolymer (A') 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 2may 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 (A').

[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 (meth)acrylic acid ester monomers having an alkoxysilyl group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane.

[0044] The number of alkoxysilyl groups introduced into the (meth)acrylic copolymer (A') differs between the X block and the Y block, as specifically described above. When the (meth)acrylic copolymer (A') 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, and more preferably 1.2 or more. When the (meth)acrylic copolymer (A') 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, and more preferably 2.4 or more. The upper limit of the number of alkoxysilyl groups introduced into the (meth)acrylic copolymer (A') is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 6.0 or less, and particularly preferably 4.0 or less. When the number of alkoxysilyl groups is within the above range, the physical properties of the curable composition and cured product using the (meth)acrylic copolymer (A') are good.

[0045] [1.3. Other physical properties] The number average molecular weight of the (meth)acrylic copolymer (A') 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 (A') 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 (A') can be produced, for example, by a production method utilizing a living radical polymerization method disclosed in Patent Document 1. 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) (see "Living Radical Polymerization Controlled by Organic Catalysts," Polymer Review, Vol. 68, pp. 223-231 (2011); JP Patent Publication No. 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 Patent Document 1 is employed, halogen atoms may remain at one or both ends of the molecule of the (meth)acrylic copolymer (A') (the elongated ends of the molecular chain during polymerization). In one embodiment, the (meth)acrylic copolymer (A') has, on average, one or more halogen atoms per elongated end of the molecular chain during polymerization.

[0048] 2. Method for producing (meth)acrylic copolymer (A') and (meth)acrylic copolymer (A'') In one embodiment, the (meth)acrylic copolymer (A') 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."

[0049] (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.

[0050] (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.

[0051] (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.

[0052] (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.

[0053] In one embodiment, the living polymerization initiator is a living radical polymerization initiator. As the living radical polymerization initiator, a known substance can be used.

[0054] Hereinafter, each step will be described in more detail for each structure of the (meth)acrylic copolymer (A').

[0055] (When the copolymer has an XY diblock structure) The (meth)acrylic acid copolymer (A'), 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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 1 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.

[0060] In the above process, examples of the "(meth)acrylic acid ester monomer having no alkoxysilyl group" include the (meth)acrylic acid ester monomers (α), (β), (γ), and (δ) described in Section [1]. This also applies to the following description.

[0061] (When the copolymer has an XYX triblock structure) The (meth)acrylic acid copolymer (A'), which is a molecule having an XYX triblock structure, can be produced by carrying out the additional polymerization step (a) after the above-mentioned steps 1a and 2a, whereby an X block containing a relatively large amount of alkoxysilyl groups is formed by the steps 1a and 2a.

[0062] In the additional polymerization step (a), 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 the additional polymerization step (a) accounts for more than 3% by weight of the monomer mixture added to the reaction system in that step.

[0063] The (meth)acrylic acid copolymer (A'), which is a molecule having a YXY triblock structure, can be produced by carrying out the additional polymerization step (b) after the above-mentioned steps 1b and 2b, in which the X block containing a relatively large amount of alkoxysilyl groups is formed in step 2b.

[0064] In the additional polymerization step (b), 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 the additional polymerization step (b), 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 the additional polymerization step (b) accounts for 0 to 3 wt% of the monomer mixture added to the reaction system in that step.

[0065] (When the copolymer has four or more blocks) By appropriately combining the above-mentioned steps 1a, 2a, the additional polymerization step (a), 1b, 2b, and the additional polymerization step (b), a (meth)acrylic copolymer (A') having four or more blocks can be produced. For example, a (meth)acrylic copolymer (A') having an XYXY tetrablock structure can be produced.

[0066] (Method of producing (meth)acrylic copolymer (A'')) In the above-mentioned production method, by appropriately adjusting the amount of the (meth)acrylic acid ester monomer (α) added as a (meth)acrylic acid ester monomer having no alkoxysilyl group, the (meth)acrylic copolymer (A″) can be produced. 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% by weight of the (meth)acrylic acid ester monomer (α) based on the weight of all monomers, the (meth)acrylic copolymer (A″) can be produced.

[0067] 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.

[0068] 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.

[0069] 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):

[0070] (a) The monovalent copper complex abstracts the halogen at the end of the polymer to generate a radical, thereby becoming a divalent copper complex.

[0071] (b) The divalent copper complex adds a halogen to the radical at the polymer end to form a monovalent copper complex.

[0072] On the other hand, when interpreted based on SET LRP, living radical polymerization consists of the equilibrium of the following three reactions (as an example, we will explain using a copper complex):

[0073] (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.

[0074] (b) The divalent copper complex adds a halogen to the radical at the polymer end to become a zero-valent copper complex.

[0075] (c) The monovalent copper complex disproportionates to give zero- and divalent copper complexes.

[0076] The above-mentioned production method can also be interpreted as either living radical polymerization system, but the present invention does not particularly distinguish between the two. Any living radical polymerization system using a transition metal or transition metal compound and a ligand as a catalyst is included in the scope of the present invention.

[0077] 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.

[0078] (Identification of the structure of the (meth)acrylic copolymer (A') by the production method) In one embodiment, the (meth)acrylic copolymer (A') is defined as a copolymer obtained by the above-mentioned production method. That is, the (meth)acrylic copolymer (A') may be a copolymer obtained by a production method including steps 1a and 2a, or steps 1b and 2b.

[0079] 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.

[0080] 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.

[0081] For these reasons, there are cases where the (meth)acrylic copolymer (A') must be defined not as a specific structure of the copolymer molecule, but as a copolymer obtained by the above-mentioned production method.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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 (A') having an alkoxysilyl group at least at the terminal can be produced.

[0086] [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.

[0087] 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.

[0088] 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.

[0089] [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.

[0090] [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.

[0091] 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:

[0092] (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.

[0093] (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.

[0094] Alternatively, the reducing agent may be generated in the polymerization system by electrolytic reduction, in which electrons generated at the cathode directly (or after solvation) exhibit a reducing effect. In other words, the reducing agent may be generated by electrolysis.

[0095] 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.

[0096] 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.

[0097] [3. Composition containing (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A'') and epoxy compound (C)] One aspect of the present invention is a composition comprising a (meth)acrylic copolymer (A') and an epoxy compound (C). In one embodiment, the composition comprises a (meth)acrylic copolymer (A") and an epoxy compound (C). This composition makes it possible to reduce the storage viscosity (particularly the storage viscosity in a high-temperature environment) of the (meth)acrylic copolymer (A') and / or the (meth)acrylic copolymer (A").

[0098] The (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A'') have a high viscosity. Therefore, when the copolymer is transported from a polymerization vessel after production to a storage tank or a tank truck, the copolymer may be heated to reduce its viscosity. Furthermore, when the (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A'') are exported to countries in the Southern Hemisphere, such as Australia or Brazil, the ship passes directly under the equator, and the storage environment for the copolymer may reach 50°C or higher. Therefore, it is preferable that the viscosity of the copolymer does not increase in a high-temperature environment. According to one embodiment of the present invention, the viscosity of the copolymer immediately after production and / or during storage can be reduced by combining the (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A'') with an epoxy compound (C).

[0099] In this specification, an accelerated test for storage stability in a high-temperature environment is conducted by heating and maintaining the (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A'') at 80°C for 4 weeks. As a result of this test, a copolymer that exhibits a low viscosity increase rate is preferred. The viscosity increase rate is calculated by the formula "{(viscosity after test - viscosity before test) / viscosity before test} x 100". The viscosity increase rate of the composition after the test is preferably 65% or less, more preferably 50% or less, and even more preferably 30% or less.

[0100] Here, "high-temperature environment" refers to an environment of 50°C or higher (preferably 80°C or higher). "Reducing the storage viscosity" means that the viscosity of the composition when stored for one week or more (preferably four weeks or more) is lower than the viscosity of the (meth)acrylic copolymer (A') and / or (A") alone when stored for the same period. "Reducing the storage viscosity in a high-temperature environment" also includes "reducing the storage viscosity in an intermittent high-temperature environment." For example, "reducing the storage viscosity in a high-temperature environment" also applies when the viscosity of the composition when stored in an environment of 50°C or higher (preferably 80°C or higher) for a cumulative period of one week or more (preferably four weeks or more) is lower than the viscosity of the (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A") alone when stored for the same period.

[0101] The (meth)acrylic copolymer (A') and the (meth)acrylic copolymer (A'') contained in the composition according to one embodiment of the present invention are as described in Sections [1] and [2].

[0102] In one embodiment, the composition can be produced by mixing the (meth)acrylic copolymer (A') produced by the method described in Section [2] with an epoxy compound (C). That is, when the (meth)acrylic copolymer (A') has an XY diblock structure, it can be produced by the following step 3a or step 3b. When the (meth)acrylic copolymer (A') has an XYX triblock structure, it can be produced by the following step 3a. Even when the (meth)acrylic copolymer (A') has four or more blocks, a composition can be obtained by mixing it with an epoxy compound (C) in the same manner. Step 3a: a step of mixing the (meth)acrylic copolymer (A') obtained through Step 1a, Step 2a and the optionally included additional polymerization step (a) with an epoxy compound (C). Step 3b: a step of mixing the (meth)acrylic copolymer (A') obtained through Step 1b, Step 2b and the optionally included additional polymerization step (b) with an epoxy compound (C).

[0103] In the composition according to one embodiment of the present invention, the mechanism by which the storage viscosity of the (meth)acrylic copolymer (A') and / or the (meth)acrylic copolymer (A'') decreases is presumed to be as follows (however, this mechanism is intended to aid in understanding the present invention and is not intended to limit the present invention). 1. The (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A'') produced by the production method described in Patent Document 1 has a halogen atom remaining at the extended end of the molecular chain. When this halogen atom is eliminated, hydrogen halide is generated. 2. Because hydrogen halide is an acid, it promotes the hydrolysis of the alkoxysilyl groups contained in the (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A''). Furthermore, siloxane bonds are formed between the hydrolyzed alkoxysilyl groups. In other words, crosslinking between the molecules of the (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A'') progresses, causing an increase in viscosity (and ultimately resulting in a gel-like state). 3. However, by adding the epoxy compound (C), it is possible to capture the hydrogen halide, thereby suppressing the progress of the reaction described in 2. and keeping the viscosity low.

[0104] Therefore, the composition according to one embodiment of the present invention preferably contains the epoxy compound (C) in an amount sufficient to capture hydrogen halide that may be generated. This amount is preferably 1 molar equivalent or more, more preferably 2 molar equivalents or more, relative to the halogen atoms contained in the (meth)acrylic copolymer (A') and / or (A").

[0105] Adding the epoxy compound (C) to the (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A") can suppress an increase in viscosity of the copolymer at high temperatures and improve storage stability. The concentration of the (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A") in the composition is preferably 50 to 99.9% by weight, more preferably 70 to 99.5% by weight. The concentration of the epoxy compound (C) in the composition is preferably 0.01 to 50% by weight, more preferably 0.5 to 30% by weight. The upper limit of the amount of the epoxy compound (C) added, relative to 100 parts by weight of the (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A"), can be 100 parts by weight or less, 50 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less. When the (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A'') is taken as 100 parts by weight, the lower limit of the amount of the epoxy compound (C) may be 0.001 parts by weight or more, 0.005 parts by weight or more, 0.01 parts by weight or more, 0.05 parts by weight or more, 0.1 parts by weight or more, 0.2 parts by weight or more, 0.3 parts by weight or more, 0.4 parts by weight or more, or 0.5 parts by weight or more.

[0106] If the amount of epoxy compound (C) added is large, the viscosity of the composition tends to decrease. However, if the amount of epoxy compound (C) added is large, the mechanical strength of the composition when processed into a cured product may decrease. Therefore, it is preferable to appropriately adjust the amount of epoxy compound (C) added depending on the mechanical strength required for the cured product.

[0107] [3.1. Epoxy Compounds (C)] The epoxy compound (C) is not particularly limited, and conventionally known compounds can be used. Examples of the epoxy compound (C) include the following. These epoxy compounds may be used alone or in combination of two or more. In one embodiment, the epoxy compound (C) is one or more selected from the group consisting of epoxidized unsaturated fats and oils, epoxy plasticizers, and monoepoxides.

[0108] (monoepoxide) Monoepoxides are compounds that contain one epoxy group per molecule. Specific examples of monoepoxides include: Hydrocarbon oxides with 2 to 24 carbon atoms: ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, α-olefin oxides with 5 to 24 carbon atoms, styrene oxide Substituted or unsubstituted glycidyl ethers of hydrocarbons having 2 to 19 carbon atoms: 2-phenoxyisopropyl glycidyl ether, n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether Glycidyl esters of monocarboxylic acids having 3 to 30 carbon atoms: glycidyl acrylate, glycidyl methacrylate Epihalohydrins: epichlorohydrin, epibromohydrin Hydroxyl-containing oxide: glycidol Epoxysilane compounds: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-oxiranylbutyltrimethoxysilane, 8-oxiranyloctyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane Monofunctional alicyclic epoxy compounds: 4-vinylepoxycyclohexane, dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, vinylcyclohexene monoepoxide.

[0109] (Polyepoxide) Polyepoxides are compounds that contain two or more epoxy groups in the molecule. Examples of polyepoxides include: Glycidyl ether type: (a) Diglycidyl ethers of dihydric phenols: For example, diglycidyl ethers of dihydric phenols having 6 to 30 carbon atoms. Specific examples include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether, and 9,9'-bis(4-hydroxyphenyl)fluorodiglycidyl ether. Another example is the diglycidyl ether obtained by reacting 2 moles of bisphenol A with 3 moles of epichlorohydrin.

[0110] (b) Polyglycidyl ethers of trihydric to hexahydric or higher polyhydric phenols; polyglycidyl ethers of trihydric to hexahydric or higher polyhydric phenols having 6 to 50 or more carbon atoms and a molecular weight of 250 to 5,000.

[0111] (c) Diglycidyl ethers of aliphatic dihydric alcohols: for example, diglycidyl ethers of diols having 2 to 100 carbon atoms and a molecular weight of 150 to 5000. Specific examples include 1,3-bis[3-(glycidyloxy)propyl]-1,1,3,3-tetramethylpropanedisiloxane.

[0112] (d) Polyglycidyl ethers of trihydric to hexahydric or higher aliphatic alcohols: for example, glycidyl ethers of trihydric to hexahydric or higher polyhydric alcohols having 3 to 50 or more carbon atoms and a molecular weight of 92 to 10,000. Glycidyl ester type: For example, a glycidyl ester of an aromatic polycarboxylic acid having 6 to 20 or more carbon atoms and having a valence of 2 to 6 or more. Another example is a glycidyl ester of an aliphatic or alicyclic polycarboxylic acid having 6 to 20 or more carbon atoms and having a valence of 2 to 6 or more. Glycidylamine type: For example, glycidylamines of aromatic amines having 6 to 20 or more carbon atoms and 2 to 10 or more active hydrogen atoms. Other examples include glycidylamines of aliphatic, alicyclic, or heterocyclic amines. · Linear aliphatic epoxides: For example, linear aliphatic epoxides having 6 to 50 or more carbon atoms and having a valence of 2 to 6 or more. Alicyclic epoxides: For example, alicyclic epoxides having 6 to 50 or more carbon atoms, a molecular weight of 90 to 2500, and 2 to 4 or more epoxy groups. Specific examples include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis(2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ether, 3,4-epoxy-6-methylcyclohexylmethyl 3',4'-epoxy-6'-methylcyclohexanecarboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, and bis(3,4-epoxy-6-methylcyclohexylmethyl)butylamine. Hydrogenated products of the above-mentioned phenolic epoxy compounds are also included in alicyclic epoxides.

[0113] (Further Examples of Epoxy Compounds) Bisphenol-type epoxy resins: bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AD-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, hydrogenated bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, glycidyl ester-type epoxy resin, glycidyl amine-type epoxy resin, novolac-type epoxy resin, glycidyl ether-type epoxy resin of bisphenol A propylene oxide adduct, hydrogenated bisphenol A-type epoxy resin, fluorinated epoxy resin, rubber-modified epoxy resin containing polybutadiene or NBR, flame-retardant epoxy Resins (such as glycidyl ether of tetrabromobisphenol A), p-oxybenzoic acid glycidyl ether ester type epoxy resins, m-aminophenol type epoxy resins, diaminodiphenylmethane type epoxy resins, urethane-modified epoxy resins with urethane bonds, alicyclic epoxy resins, N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ether of polyhydric alcohols such as glycerin, hydantoin type epoxy resins, epoxidized products of unsaturated polymers (such as petroleum resins), etc. "Hydrogenated" here refers to those in which hydrogen is added to the benzene ring moiety to change it to a cyclohexyl ring. Alicyclic epoxy resins: For example, compounds having a cyclohexene oxide group, a tricyclodecene oxide group, a cyclopentene oxide group, etc. Specific examples include vinylcyclohexene diepoxide, vinylcyclohexene monoepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl 5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl)adipate, and bis(3,4-epoxycyclohexylmethylene)adipate.

[0114] The epoxy compound (C) also includes the following examples: epoxidized unsaturated fats and oils (epoxidized soybean oil, epoxidized linseed oil, etc.), epoxidized unsaturated fatty acid esters (epoxyoctyl stearate, epoxybutyl stearate), alicyclic epoxy compounds (di-(2-ethylhexyl)4,5-epoxycyclohexane-1,2-dicarboxylate, etc.), epichlorohydrin derivatives, and mixtures thereof.

[0115] The epoxy compound (C) may be an epoxy plasticizer, specific examples of which 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.

[0116] Furthermore, the epoxy compound (C) may be a commercially available compound. Examples of such commercially available products include Sanso Cizer 2000H (epoxidized soybean oil; New Japan Chemical Co., Ltd.), Sanso Cizer 9000H (epoxidized linseed oil; New Japan Chemical Co., Ltd.), Sanso Cizer E-PS (di-(2-ethylhexyl) 4,5-epoxycyclohexane-1,2-dicarboxylate; New Japan Chemical Co., Ltd.), and Epolite M1230 (C12,13 mixed higher alcohol glycidyl ether; Kyoeisha Chemical Co., Ltd.).

[0117] [4. Curable composition] A curable composition according to one embodiment of the present invention contains the composition described in section [3] and a polyoxyalkylene polymer (B) having an alkoxysilyl group.

[0118] [4.1. Polyoxyalkylene polymer (B) having an alkoxysilyl group] (Main Chain of Polyoxyalkylene Polymer (B) Having Alkoxysilyl Group) 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.

[0119] An example of the main chain of the polyoxyalkylene polymer (B) is substantially a group represented by the general formula (3): -R 6 -O-" (wherein R 6 is a divalent alkylene group.) Here, the term "substantially" means that the repeating unit represented by general formula (3) accounts for 50% by weight or more (preferably 80% by weight or more) of the total weight of the polyoxyalkylene polymer (B).

[0120] R in general formula (3) 6 is not particularly limited as long as it is a divalent alkylene group. 6 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.

[0121] The repeating unit represented by general formula (3) 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-.

[0122] The polyoxyalkylene polymer (B) may contain a urethane bond or a urea bond in the main chain structure.

[0123] The number average molecular weight of the polyoxyalkylene polymer (B) is not particularly limited. The number average molecular weight is preferably 5,000 or more, more preferably 5,000 to 50,000, and even more preferably 5,000 to 25,000. The number average molecular weight can be measured, for example, by gel permeation chromatography.

[0124] (Method for producing polyoxyalkylene polymer (B) having alkoxysilyl groups) 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.).

[0125] By employing a method using a catalyst comprising a porphyrin / aluminum complex catalyst, a composite metal cyanide complex catalyst, or a polyphosphazene salt, a polyoxyalkylene polymer having a molecular weight distribution (Mw / Mn) of 1.6 or less (preferably 1.5 or less) can be obtained. 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.

[0126] (alkoxysilyl group) The alkoxysilyl group contained in the polyoxyalkylene polymer (B) is not particularly limited. For example, it may be an alkoxysilyl group represented by general formula (1) described in Section [1]. The alkoxysilyl group contained in the polyoxyalkylene polymer (B) may have the same structure as or a different structure from the alkoxysilyl group contained in the (meth)acrylic copolymer (A') and / or the (meth)acrylic copolymer (A'').

[0127] The number of alkoxysilyl groups contained in the polyoxyalkylene polymer (B) per molecule is preferably more than 0.5, more preferably 1.2 to 6.0, and even more preferably 1.5 to 2.5. When the number of alkoxysilyl groups is within the above range, good curability can be imparted to the curable composition.

[0128] 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.

[0129] (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.

[0130] 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 epoxy compound having an unsaturated group 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.

[0131] 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 ...

[0132] (Amount of polyoxyalkylene polymer (B) having alkoxysilyl group) The amount of polyoxyalkylene polymer (B) blended in the curable composition according to one embodiment of the present invention can be adjusted as appropriate. The blending ratio of the (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A'') to the polyoxyalkylene polymer (B) is preferably from (95 / 5) to (5 / 95) by weight, more preferably from (90 / 10) to (10 / 90), and even more preferably from (80 / 20) to (20 / 80). When the blending ratio is within the above range, the weather resistance of the cured product can be sufficiently exhibited.

[0133] [4.2. Other additives] The curable composition according to one embodiment of the present invention may contain various additives in addition to the (meth)acrylic copolymer (A') (and / or the (meth)acrylic copolymer (A'')) and the polyoxyalkylene polymer (B). By adding these additives, various physical properties of the curable composition and the cured product can be adjusted. Examples of the additives include the following. These additives may be used alone or in combination of two or more.

[0134] (tin-based curing catalyst) The curable composition of the present invention can be crosslinked and cured by forming siloxane bonds using a known condensation catalyst, such as a tin-based curing catalyst. 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.).

[0135] 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.

[0136] The amount of the tin-based curing catalyst 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 (A') (and / or the (meth)acrylic copolymer (A'')) and the polyoxyalkylene polymer (B).

[0137] (adhesion imparting agent) An adhesion promoter may be added to the curable composition according to one embodiment of the present invention. Addition of an adhesion promoter can reduce the risk of the sealant peeling off from an 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.

[0138] 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.

[0139] 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 (A') (and / or the (meth)acrylic copolymer (A'')) and the polyoxyalkylene polymer (B).

[0140] (plasticizer) The 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.

[0141] 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 Examples of suitable plasticizers include ene-acrylonitrile, polychloroprene, chlorinated paraffins, hydrocarbon oils (such as alkyldiphenyls and partially hydrogenated terphenyls), process oils, polyethers (such as polyether polyols (such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol) and derivatives in which the hydroxyl groups of polyether polyols have been converted to ester groups, ether groups, etc.), polyester plasticizers obtained from dibasic acids and dihydric alcohols (such as polyesters obtained from sebacic acid, adipic acid, azelaic acid, phthalic acid, etc., and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol), and vinyl polymers (obtained by polymerizing vinyl monomers such as acrylic plasticizers using various methods).

[0142] 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.

[0143] 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, relative to 100 parts by weight of the total amount of the (meth)acrylic copolymer (A') (and / or (meth)acrylic copolymer (A'')) and the polyoxyalkylene polymer (B).

[0144] (filling material) The curable composition according to one embodiment of the present invention may contain a filler. 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 acid 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 balloon, etc.), and fibrous fillers (asbestos, glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber, etc.).

[0145] The amount of the filler to be blended 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 (A') (and / or (meth)acrylic copolymer (A'')) and the polyoxyalkylene polymer (B).

[0146] (Physical property adjuster) The 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. By using the physical property modifier, it is possible to increase the hardness of the cured product, or conversely, to decrease the hardness of the cured product to increase elongation.

[0147] 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.

[0148] The amount of the physical property adjuster to be blended 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 (A') (and / or the (meth)acrylic copolymer (A'')) and the polyoxyalkylene polymer (B).

[0149] (thixotropy imparting agent (anti-sagging agent)) The curable composition according to one embodiment of the present invention may contain a thixotropy-imparting agent (anti-sagging agent) in order to prevent sagging and improve workability.

[0150] Examples of the thixotropy-imparting agent include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps (calcium stearate, aluminum stearate, barium stearate, etc.).

[0151] 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 (A') (and / or the (meth)acrylic copolymer (A'')) and the polyoxyalkylene polymer (B).

[0152] (light curing substance) The 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 due to the action of light, resulting in a change in physical properties (such as curing). The inclusion of a photocurable substance can reduce the stickiness (residual tack) of the surface of the cured product. A typical photocurable substance can be cured by leaving it at room temperature for one day in a sunny location indoors (such as near a window). 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.

[0153] 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.

[0154] 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 (A') (and / or the (meth)acrylic copolymer (A'')) and the polyoxyalkylene polymer (B).

[0155] (Air oxidation curing substance) The 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 tackiness (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.

[0156] 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.

[0157] 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 (A') (and / or the (meth)acrylic copolymer (A'')) and the polyoxyalkylene polymer (B).

[0158] (antioxidants and light stabilizers) The curable composition according to one embodiment of the present invention may contain an antioxidant and / or a light stabilizer. Various antioxidants and light stabilizers are known. Examples include substances described in Kenichi Saruwatari et al., "Antioxidant Handbook," Taiseisha, 1976, and Zenjiro Osawa, editor, "Degradation and Stabilization of Polymer Materials," CMC, 1990, pp. 235-242.

[0159] 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.

[0160] 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.

[0161] 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).

[0162] 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.

[0163] 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.

[0164] 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.).

[0165] 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.

[0166] 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 (A') (and / or the (meth)acrylic copolymer (A'')) and the polyoxyalkylene polymer (B).

[0167] [4.3. Form of curable composition] The curable composition according to one embodiment of the present invention may be a one-component or two-component type. A one-component curable composition is one in which all components are blended in advance and then sealed and stored. A one-component curable composition cures after use due to moisture in the air. On the other hand, a two-component curable composition requires a separately prepared curing agent containing components such as a curing catalyst, a filler, a plasticizer, and water. A two-component curable composition is used by mixing a curing agent with a base agent containing a (meth)acrylic copolymer (A') and / or a (meth)acrylic copolymer (A''). The two-component curable composition may contain other agents (such as a colorant) in addition to the base agent and the curing agent.

[0168] When a two-component curable composition is prepared, a colorant can be added when the two components are mixed. This makes it possible, for example, to provide sealants with a wide range of colors to match the color of siding boards, even with a limited number of curable compositions. Therefore, two-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 prepared by mixing, for example, a pigment, a plasticizer, and, if necessary, a filler, is preferred for its ease of use.

[0169] Furthermore, a retarder can be added to a two-component curable composition when mixing the two components, allowing for fine adjustment of the curing speed at the work site.

[0170] [5. Cured product] A cured product according to one embodiment of the present invention is obtained by curing a composition containing a (meth)acrylic copolymer (A') and / or a (meth)acrylic copolymer (A"), and an epoxy compound (C). A cured product according to another embodiment of the present invention is obtained by curing a curable composition containing a (meth)acrylic copolymer (A') and / or a (meth)acrylic copolymer (A"), a polyoxyalkylene polymer (B), and an epoxy compound (C). That is, in the cured product, the polyoxyalkylene polymer (B) is an optional component and does not necessarily have to be contained.

[0171] The uses of the composition, 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.

[0172] Among the above, the composition, curable composition, and cured product according to one embodiment of the present invention are particularly useful as sealants and adhesives. They are particularly useful in applications requiring weather resistance or durability, or in applications requiring transparency. Furthermore, the curable composition and cured product according to one embodiment of the present invention have excellent weather resistance and adhesion, and can therefore be used in exterior wall tile adhesion methods that do not require joint filling. Furthermore, they are useful as elastic adhesives for bonding materials with different linear expansion coefficients or for bonding components that are repeatedly displaced by heat cycles. Furthermore, by taking advantage of their transparency, they are also useful as coating agents for applications in which the substrate is visible, and as adhesives for bonding transparent materials (glass, polycarbonate, methacrylic resin, etc.).

[0173] 〔summary〕 The present invention includes the following aspects. <1> A composition comprising a (meth)acrylic copolymer (A') and an epoxy compound (C), The (meth)acrylic copolymer (A') has an X block and a Y block, The molecule of the (meth)acrylic copolymer (A') contains an XY diblock structure or an XYX triblock structure in the molecule, 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 (A') has a molecular weight distribution (Mw / Mn) of 1.8 or less. composition. <2> The (meth)acrylic copolymer (A') is a (meth)acrylic copolymer (A'') that satisfies the following conditions: <1> The 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 (A″). <3> The (meth)acrylic acid ester monomer (α) is at least one selected from the group consisting of 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and isopropoxyethyl (meth)acrylate. <2> The composition described in <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 composition according to any one of the preceding claims. <5> The (meth)acrylic copolymer (A') contains, based on the weight of all repeating units, A total of 45 to 96% by weight of repeating units derived from a (meth)acrylic acid ester monomer (β) and a (meth)acrylic acid 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 composition according to any one of the preceding claims. <6> The (meth)acrylic acid ester monomer (δ) is at least one selected from the group consisting of pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, eicosyl (meth)acrylate, and docosyl (meth)acrylate. <5> The composition described in <7> the content of the (meth)acrylic copolymer (A') and / or the (meth)acrylic copolymer (A'') is 50 to 99.9% by weight, The content of the epoxy compound (C) is 0.1 to 50% by weight. <1> ~ <6> The composition according to any one of the preceding claims. <8> The epoxy compound (C) is one or more selected from the group consisting of epoxidized unsaturated fats and oils, epoxy plasticizers, and monoepoxides. <1> ~ <7> The composition according to any one of the preceding claims. <9> <1> ~ <8> a composition according to any one of the preceding claims, a polyoxyalkylene polymer (B) having an alkoxysilyl group; A curable composition comprising: <10> <1> ~ <8> or a composition according to any one of <9> A cured product obtained by curing the curable composition described in 1. <11> <1> ~ <8> The composition according to any one of the preceding claims. <9> or the curable composition according to <10> A sealant or adhesive containing the cured product described in 1. <12> <1> ~ <8> A method for storing a (meth)acrylic copolymer (A') and / or a (meth)acrylic copolymer (A''), comprising a step of preparing the composition according to any one of the following: In the above composition, the content of the (meth)acrylic copolymer (A') and / or the (meth)acrylic copolymer (A'') is 50 to 99.9% by weight, The content of the epoxy compound (C) is 0.1 to 50% by weight. Storage method. <13> After storage at 80°C for 4 weeks, the viscosity increase rate of the composition is 65% or less. <12> The method described below. <14> <1> A method for producing the composition according to claim 1, comprising the following steps 1a to 3a or steps 1b to 3b: (Step 1a) a step of polymerizing a (meth)acrylic acid ester monomer mixture containing more than 3% by weight of the (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 wt % of the (meth)acrylic acid ester monomer having an alkoxysilyl group to the reaction system after Step 1a, and polymerizing the mixture; (Step 3a) a step of mixing the (meth)acrylic copolymer (A') obtained through Step 2a and any optional additional polymerization steps with the epoxy compound (C); (Step 1b) a step of polymerizing a (meth)acrylic acid ester monomer mixture containing 0 to 3 wt % of the (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 wt % of the (meth)acrylic acid ester monomer having an alkoxysilyl group to the reaction system after Step 1b and polymerizing the mixture; (Step 3b) A step of mixing the (meth)acrylic copolymer (A') obtained through Step 2b and any additional polymerization steps that may be included, with the epoxy compound (C). <15> The living polymerization initiator is a living radical polymerization initiator. <14> A method for producing the composition described above.

[0174] The present invention also includes the following aspects. <1a> In the composition, the total weight of repeating units derived from (meth)acrylic acid ester monomers contained in the (meth)acrylic copolymer (A') and / or the (meth)acrylic copolymer (A'') may be 70% by weight or more, or 90% by weight or more, based on the weight of all repeating units contained in the (meth)acrylic copolymer (A') and / or the (meth)acrylic copolymer (A''). <2a> In the composition, the (meth)acrylic acid ester monomer (β) may be butyl acrylate. <3a> In the composition, the (meth)acrylic acid ester monomer (γ) may be one or more selected from the group consisting of 2-ethylhexyl acrylate and dodecyl acrylate. <4a> In the composition, the (meth)acrylic acid ester monomer (δ) may be octadecyl acrylate. <5a> In the composition, the (meth)acrylic copolymer (A') and / or the (meth)acrylic copolymer (A'') may have a number average molecular weight of 4,000 or more, or 30,000 or more, as measured by gel permeation chromatography. The number average molecular weight may be 80,000 or less. <6a> In the composition, the (meth)acrylic copolymer (A') and / or the (meth)acrylic copolymer (A'') may contain 10.0 or less alkoxysilyl groups on average per molecule. <7a> In the curable composition, the blending ratio of the (meth)acrylic copolymer (A') and / or the (meth)acrylic copolymer (A'') to the polyoxyalkylene polymer (B) having an alkoxysilyl group may be (95 / 5) to (5 / 95). <8a> In the curable composition, one or more selected from the group consisting of the (meth)acrylic copolymer (A'), the (meth)acrylic copolymer (A''), and the polyoxyalkylene polymer (B) having an alkoxysilyl group may have an alkoxysilyl group represented by the following general formula (1): -[Si(R 1 ) 2-b (Y) b O] m -Si(R 2 ) 3-a (Y) a (1) (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')SiO-; R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different; R 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 two or more Y's are present, the Y's may be the same or different, a is 0, 1, 2 or 3; b is 0, 1 or 2; m is an integer from 0 to 19, a+mb≧1).

[0175] Furthermore, the present invention also includes the following aspects. <1b> A method for storing a (meth)acrylic copolymer (A') at 50°C or higher for 168 hours or longer, comprising: The (meth)acrylic copolymer (A') is stored in the form of a composition containing an epoxy compound (C), The (meth)acrylic copolymer (A') has an X block and a Y block, The (meth)acrylic copolymer (A') has 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 (A') has a molecular weight distribution (Mw / Mn) of 1.8 or less. method. <2b> The (meth)acrylic copolymer (A') randomly contains repeating units derived from the (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 (A'); The method described in <1b>.

[0176] The contents described in each of the above sections can be appropriately incorporated into other sections. The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Therefore, embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0177] All scientific and patent literature mentioned herein is hereby incorporated by reference.

[0178] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. [Example]

[0179] [Production Example 1: Production of (meth)acrylic copolymer (A″)-1] (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."

[0180] 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.

[0181] In addition, another stirring vessel was prepared. 30.8 mL of methanol, 1.0 g of ascorbic acid, and 1.58 mL of triethylamine were charged into the vessel, and the mixture was stirred for 30 minutes under a nitrogen stream to obtain a homogeneous solution. This homogeneous solution is referred to as the "ascorbic acid solution."

[0182] (1st step) 5.84 g of ethyl α-bromobutyrate (initiator; 0.030 mol), 200 g of a (meth)acrylic acid ester monomer mixture (20 wt % of the total), 13.93 g of 3-(trimethoxysilyl)propyl methacrylate (0.060 mol; 1.93 molar equivalents relative to the initiator), 151.76 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.

[0183] 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 ascorbic acid solution was added dropwise at a rate of 144 mg of ascorbic acid per hour.

[0184] 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.

[0185] (2nd process) Next, the remainder of the (meth)acrylic acid ester monomer mixture not added in the first step (80 wt % of the total amount) was continuously added dropwise to the polymerization system over a period of 150 minutes. The ascorbic acid solution was added dropwise at a rate of 48 mg of ascorbic acid per hour. After the (meth)acrylic acid ester monomer mixture was added dropwise, the ascorbic acid solution was added dropwise at a rate of 60 mg of ascorbic acid per hour. Sampling was also performed sequentially and analyzed by gas chromatography. The polymerization was continued until 94 wt % of the total amount of the (meth)acrylic acid ester monomer mixture added to the polymerization system was consumed.

[0186] (3rd step) Next, 15.32 g (0.066 mol) of 3-(trimethoxysilyl)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.

[0187] 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.

[0188] (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.).

[0189] 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) dissolved in approximately 20 g of butyl acetate was added to this solution and mixed until homogeneous. The solvent was then volatilized from the solution to obtain (meth)acrylic copolymer (A'')-1. A diaphragm pump was used first for volatilization, followed by a vacuum pump.

[0190] [Production Example 2: Production of (meth)acrylic copolymer (A')-1] A polymer was produced in the same manner as in Production Example 1, except that the composition of the raw material monomers was changed to those shown in Table 1. As the (meth)acrylic acid ester monomer mixture, 687 g of n-butyl acrylate, 104 g of ethyl acrylate, and 18.1 g of octadecyl acrylate (total: 997.2 g) were used. 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 (A') but not to the (meth)acrylic copolymer (A'').

[0191] [Production Example 3: Production of (meth)acrylic copolymer (A″)-2] A polymer was produced in the same manner as in Production Example 1, except that the composition of the raw material monomers was changed to that shown in Table 1. The same (meth)acrylic acid ester monomer mixture was used as in Production Example 1. 3-(dimethoxymethylsilyl)propyl methacrylate was used as the (meth)acrylic acid ester monomer having an alkoxysilyl group.

[0192] [Production Example 4: Production of (meth)acrylic copolymer (A')-2] A polymer was produced in the same manner as in Production Example 1, except that the composition of the raw material monomers was changed to those shown in Table 1. The same (meth)acrylic acid ester monomer mixture as in Production Example 2 was used. 3-(dimethoxymethylsilyl)propyl methacrylate was used as the (meth)acrylic acid ester monomer having an alkoxysilyl group. The polymer produced in Production Example 4 does not contain the (meth)acrylic acid ester monomer (α) as a raw material, and therefore corresponds to the (meth)acrylic copolymer (A') but not to the (meth)acrylic copolymer (A'').

[0193] [Table 1] [Evaluation of physical properties of copolymers (Production Examples 1 and 2)] The physical properties of the (meth)acrylic copolymer (A'')-1 and the (meth)acrylic copolymer (A')-1 obtained in Production Examples 1 and 2 were evaluated. In addition, the physical properties of a curable composition containing the copolymer and the polyoxyalkylene polymer (B) and a cured product obtained by curing the curable composition were also evaluated. In Table 2, the measurement methods for each evaluation item are as follows.

[0194] [Monomer distribution] (Distribution of repeating units derived from (meth)acrylic acid ester monomers having an alkoxysilyl group) Assuming that all (meth)acrylic acid ester monomers are incorporated into the polymer block at the same reaction rate, the distribution of repeating units derived from (meth)acrylic acid ester monomers having alkoxysilyl groups (repeating units derived from 3-(trimethoxysilyl)propyl methacrylate) in (meth)acrylic copolymer (A'') and (meth)acrylic copolymer (A') was derived. Specifically, the following three parameters were calculated for repeating units derived from 3-(trimethoxysilyl)propyl methacrylate. The results are shown in Table 2.

[0195] (a) Average number of the above repeating units contained in the X block.

[0196] (b) The weight ratio (wt %) of the repeating units contained in the X block to the entire polymer molecule.

[0197] (c) The weight ratio (wt %) of the repeating units contained in the Y block to the entire polymer molecule.

[0198] (Distribution of repeating units derived from (meth)acrylic acid ester monomer (α)) Regarding the (meth)acrylic copolymer (A″), the weight ratio (wt %) of the repeating units derived from the (meth)acrylic acid ester monomer (α) (repeating units derived from 2-methoxyethyl acrylate) to the entire polymer molecules was calculated from the weight of the charged monomer and the consumption rate of the monomer (the results are shown in Table 2). Furthermore, according to the production method of Production Example 1 described above, the repeating units derived from 2-methoxyethyl acrylate are randomly distributed in the (meth)acrylic copolymer (A″).

[0199] [Evaluation of copolymers] (Molecular weight and molecular weight distribution) The number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the copolymer were calculated using gel permeation chromatography (GPC) in terms of standard polystyrene. A column packed with crosslinked polystyrene gel (Shodex GPC K-804; Showa Denko K.K.) was used for the GPC. Chloroform was used as the solvent. The results are shown in Table 2.

[0200] (viscosity) The viscosity of the copolymer was measured at 23°C using a viscometer (Toki Sangyo VISCOMETER TV-25, 3° x R14 cone rotor, 1 rpm). The measurement was performed in accordance with JIS K 7117-2. The amount of sample used for the measurement was 0.4 mL. The results are shown in Table 2.

[0201] [Evaluation of Curable Composition] The copolymer and the polyoxyalkylene polymer (B) were mixed to prepare a curable composition. SAX220 (manufactured by Kaneka Corporation) was used as the polyoxyalkylene polymer (B). The mixing ratio of the two was 50:50 by weight.

[0202] (Evaluation of compatibility) The copolymer and polyoxyalkylene polymer (B) were stirred and mixed. The curable composition was then mixed and degassed using a planetary stirring and mixing device (Thinky's Awatori Rentaro). The operating parameters of the device during mixing were revolution: 1600 rpm, rotation: 640 rpm, and mixing time: 1.3 minutes. The operating parameters of the device during degassing were revolution: 2200 rpm, rotation: 60 rpm, and mixing time: 3 minutes. The resulting mixture was placed in a sample bottle and left in an oven at 60°C for 2 hours, after which the compatibility was confirmed. The mixture was then left at room temperature for another week, after which the compatibility was confirmed. The results are shown in Table 2. In Table 2, "○" indicates compatibility under all conditions, and "×" indicates incompatibility under at least one of the conditions.

[0203] (Viscosity evaluation) The viscosity of the curable composition was measured at 23°C using a viscometer (Toki Sangyo VISCOMETER TV-25, 3° x R14 cone rotor, 1 rpm). The measurement was performed in accordance with JIS K 7117-2. The amount of sample used for the measurement was 0.4 mL. The results are shown in Table 2.

[0204] [Evaluation of the cured product] A reaction product of 2 parts by weight of tin octoate and 0.5 parts by weight of laurylamine was added to 100 parts by weight of the curable composition and mixed thoroughly. The resulting mixture was poured into a mold and degassed under reduced pressure. It was then heated and cured at 50°C for 20 hours to obtain a sheet-like cured product with rubber elasticity.

[0205] (Evaluation of mechanical properties) From the resulting sheet-like cured product, No. 3 dumbbell-shaped test pieces as specified in JIS K 7113 were punched out. These test pieces were subjected to a tensile test to measure their mechanical properties. Specifically, the stress at 50% elongation, the stress at break, and the elongation at break (elongation relative to the distance between chucks) were measured. The results are shown in Table 2. An autograph (Shimadzu) was used for the measurement, and the measurement temperature was 23°C and the tensile speed was 200 mm / min.

[0206] [Table 2] [result] Table 2 shows that the (meth)acrylic copolymers (A'')-1 and (A')-1 exhibit properties roughly equivalent to those of conventional copolymers in terms of compatibility with the polyoxyalkylene polymer (B), viscosity when formed into a curable composition, and mechanical properties of the cured product. Meanwhile, the viscosity (initial viscosity) of the copolymer immediately after production was significantly lower for (meth)acrylic copolymer (A'')-1 than for (meth)acrylic copolymer (A')-1. In other words, among the (meth)acrylic copolymers (A'), the (meth)acrylic copolymer (A'') containing a predetermined amount of repeating units derived from the (meth)acrylic acid ester monomer (α) had the advantage of a low initial viscosity.

[0207] [Evaluation of Copolymer Properties (Production Examples 3 and 4)] The physical properties of the (meth)acrylic copolymer (A'')-2 and the (meth)acrylic copolymer (A')-2 obtained in Production Examples 3 and 4 were evaluated. The physical properties of the cured products obtained by curing the copolymers were also evaluated. The methods for evaluating the physical properties were as described above. However, when preparing the cured products, only the (meth)acrylic copolymer (A'')-2 or the (meth)acrylic copolymer (A')-2 was cured without blending the polyoxyalkylene polymer (B).

[0208] [Table 3] [result] Table 3 shows that (meth)acrylic copolymer (A'')-2 and (meth)acrylic copolymer (A')-2 exhibit properties roughly equivalent to those of conventional copolymers in terms of compatibility with polyoxyalkylene polymer (B) and mechanical properties of the cured products. On the other hand, the viscosity (initial viscosity) of the copolymer immediately after production was significantly lower for (meth)acrylic copolymer (A'')-2 than for (meth)acrylic copolymer (A')-2. In other words, among the (meth)acrylic copolymers (A'), the (meth)acrylic copolymer (A'') containing a predetermined amount of repeating units derived from the (meth)acrylic acid ester monomer (α) had the advantage of a low initial viscosity.

[0209] Example 1-1 It was confirmed that the addition of an epoxy compound (C) to the (meth)acrylic copolymer (A″)-1 produced in Production Example 1 could suppress an increase in viscosity during storage at high temperatures. Specifically, in the purification step of Production Example 1, the epoxy compound (C) and 1.5 g (0.15 parts by weight) of an antioxidant (Sumilizer GS) were added to a clear polymer solution obtained by filtration through a filter equipped with a bag filter cloth. In this case, the epoxy compound (C) and the antioxidant were added in a state of being dissolved in approximately 20 g of butyl acetate. The solution was then mixed until homogeneous, and the solvent was removed to obtain a composition containing the (meth)acrylic copolymer (A″)-1 and the epoxy compound (C).

[0210] The mixing ratio of the (meth)acrylic copolymer (A″)-1 to the epoxy compound (C) is as shown in Table 4.

[0211] 10 mL of the obtained composition was placed in a vial and placed in a thermostatic bath at 80°C. The viscosity was measured at 23°C using a viscometer (Toki Sangyo VISCOMETER TV-25, 3° x R14 cone rotor, 1 rpm). The measurement was performed in accordance with JIS K 7117-2. The amount of sample used for the measurement was 0.4 mL. The results are shown in Table 4.

[0212] Examples 1-2 to 1-4 It was confirmed that the addition of an epoxy compound (C) to the (meth)acrylic copolymer (A')-1 produced in Production Example 2 could suppress the increase in viscosity during storage at high temperatures. Specifically, a composition containing the (meth)acrylic copolymer (A')-1 and the epoxy compound (C) was prepared using the same procedure as in Example 1-1 (the type and mixing ratio of the epoxy compound (C) used are as shown in Table 4). The increase in viscosity of this composition under high-temperature conditions was then monitored. The results are shown in Table 4.

[0213] Comparative Example 1-1 The (meth)acrylic copolymer (A')-1 was stored under the same conditions as in Examples 1-2 to 1-4, except that the epoxy compound (C) was not added, and the increase in viscosity under high temperature conditions was monitored. The results are shown in Table 4.

[0214] [Table 4] [result] As can be seen from Example 1-1, the addition of the epoxy compound (C) to the (meth)acrylic copolymer (A")-1 improved the stability during storage at high temperatures. Furthermore, as can be seen from Examples 1-2 to 1-4, the addition of the epoxy compound (C) also improved the stability of the (meth)acrylic copolymer (A')-1 during storage at high temperatures. On the other hand, as can be seen from Comparative Example 1, when the epoxy compound (C) was not added, the (meth)acrylic copolymer (A')-1 gelled within one week of storage. These results suggest that the addition of the epoxy compound (C) generally suppresses an increase in the storage viscosity of the (meth)acrylic copolymer (A") and the (meth)acrylic copolymer (A').

[0215] Examples 2-1 to 2-5 It was confirmed that the addition of an epoxy compound (C) to the (meth)acrylic copolymer (A″)-2 produced in Production Example 3 could suppress an increase in viscosity during storage at high temperatures. Specifically, in the purification step of Production Example 3, the epoxy compound (C) and 1.5 g of an antioxidant (Sumilizer GS) were added to a clear polymer solution obtained by filtration through a filter equipped with a bag filter cloth. In this case, the epoxy compound (C) and the antioxidant were added in a state of being dissolved in approximately 20 g of butyl acetate. The solution was then mixed until homogeneous, and the solvent was removed to obtain a composition containing the (meth)acrylic copolymer (A″)-2 and the epoxy compound (C).

[0216] The mixing ratio of the (meth)acrylic copolymer (A″)-2 to the epoxy compound (C) is as shown in Table 5.

[0217] 10 mL of the obtained composition was placed in a vial and placed in a thermostatic bath at 80°C. Viscosity was measured at 23°C using a viscometer (Toki Sangyo VISCOMETER TV-25, 3° x R14 cone rotor, 1 rpm) in accordance with JIS K 7117-2. The amount of sample used for measurement was 0.4 mL. The results are shown in Table 5.

[0218] The gel fraction of the composition was measured immediately after it was obtained. Specifically, the composition was immersed in toluene and kept at 23°C for 24 hours. The gel fraction was then calculated as follows. Gel fraction (%)=(weight of remaining undissolved solid component / weight of composition before immersion in toluene)×100.

[0219] Furthermore, a reaction product of 2 parts by weight of tin octylate and 0.5 parts by weight of laurylamine was added to 100 parts by weight of the composition and mixed thoroughly (note that this composition does not contain polyoxyalkylene resin (B)). 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. From the resulting sheet-like cured product, a No. 3 dumbbell test piece as specified in JIS K 7113 was punched out. This test piece was subjected to a tensile test to measure its mechanical properties. Specifically, the stress at 50% elongation, the stress at 100% elongation, the stress at break, and the elongation at break (elongation relative to the distance between chucks) were measured. The results are shown in Table 5. An autograph (Shimadzu Corporation) was used for the measurement, with a measurement temperature of 23°C and a tensile speed of 200 mm / min.

[0220] Comparative Example 2-1 The (meth)acrylic copolymer (A'')-2 produced in Production Example 3 was stored under the same conditions as in Examples 2-1 to 2-5, except that the epoxy compound (C) and the antioxidant were not added, and the increase in viscosity under high temperature conditions was monitored. Furthermore, the gel fraction of the composition and the mechanical properties of the cured product were measured in the same manner as in Examples 2-1 to 2-5. The results are shown in Table 5.

[0221] Comparative Example 2-2 The (meth)acrylic copolymer (A'')-2 produced in Production Example 3 was stored under the same conditions as in Examples 2-1 to 2-5, except that no epoxy compound (C) was added, and the increase in viscosity under high temperature conditions was monitored. Furthermore, the gel fraction of the composition and the mechanical properties of the cured product were measured in the same manner as in Examples 2-1 to 2-5. The results are shown in Table 5.

[0222] Examples 2-6 to 2-8 It was confirmed that the addition of an epoxy compound (C) to the (meth)acrylic copolymer (A')-2 produced in Production Example 4 could suppress an increase in viscosity during storage at high temperatures. Specifically, a composition containing the (meth)acrylic copolymer (A')-2 and the epoxy compound (C) was prepared in the same manner as in Examples 2-1 to 2-5 (the type and mixing ratio of the epoxy compound (C) used are as shown in Table 5). The increase in viscosity of this composition under high-temperature conditions was then monitored. Furthermore, the gel fraction of the curable composition and the mechanical properties of the cured product were measured in the same manner as in Examples 2-1 to 2-5. The results are shown in Table 5.

[0223] Comparative Example 2-3 The (meth)acrylic copolymer (A')-2 produced in Production Example 4 was stored under the same conditions as in Examples 2-6 to 2-8, except that the epoxy compound (C) was not added, and the increase in viscosity under high temperature conditions was monitored. Furthermore, the gel fraction of the curable composition and the mechanical properties of the cured product were measured in the same manner as in Examples 2-1 to 2-5. The results are shown in Table 5.

[0224] [Table 5] TIFF0007725377000006.tif218110[Result] As can be seen from Examples 2-1 to 2-5, the addition of the epoxy compound (C) to the (meth)acrylic copolymer (A")-2 improved the stability during storage at high temperatures. Furthermore, as can be seen from Examples 2-6 to 2-8, the addition of the epoxy compound (C) also improved the stability of the (meth)acrylic copolymer (A')-2 during storage at high temperatures. In particular, Example 2-8 demonstrates that even a small amount of the epoxy compound (C), such as 0.06 parts by weight, can reduce the viscosity. On the other hand, as can be seen from Comparative Examples 2-1 to 2-3, when the epoxy compound (C) was not added, the (meth)acrylic copolymer (A")-2 or the (meth)acrylic copolymer (A')-2 gelled within 1 to 2 weeks of storage. These results suggest that the addition of the epoxy compound (C) generally suppresses the increase in the storage viscosity of the (meth)acrylic copolymer (A") and the (meth)acrylic copolymer (A').

[0225] Furthermore, when Examples 2-2 and 2-3, and Examples 2-4 and 2-5 are compared, it is clear that the mechanical properties of the cured product tend to improve when the amount of epoxy compound (C) added is smaller. On the other hand, when Examples 2-6 to 2-8 are compared, the mechanical properties of the curable composition do not improve even when the amount of epoxy compound (C) added is reduced. This suggests that, from the viewpoint of mechanical strength, the amount of epoxy compound (C) added is preferably about 0.5 parts by weight (e.g., 0.3 to 1 part by weight) per 100 parts by weight of (meth)acrylic copolymer (A') and / or (meth)acrylic copolymer (A''). [Industrial Applicability]

[0226] The present invention can be used for sealing materials, adhesives, etc.

Claims

1. A composition comprising a (meth)acrylic copolymer (A') and an epoxy compound (C), the epoxy compound (C) is one or more selected from the group consisting of epoxidized unsaturated fats and oils, epoxy plasticizers, and monoepoxides; The (meth)acrylic copolymer (A′) has an X block and a Y block, The molecule of the (meth)acrylic copolymer (A') 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 (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 (A') has a molecular weight distribution (Mw / Mn) of 1.8 or less. composition.

2. The composition according to claim 1, wherein the (meth)acrylic copolymer (A') is a (meth)acrylic copolymer (A'') 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) are contained in an amount of 5 to 20% by weight based on the weight of all repeating units contained in the (meth)acrylic copolymer (A″).

3. The composition according to claim 2, wherein the (meth)acrylic acid ester monomer (α) is one or more selected from the group consisting of 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and isopropoxyethyl (meth)acrylate.

4. The composition according to any one of claims 1 to 3, wherein the repeating units derived from a (meth)acrylic acid ester monomer having an alkoxysilyl group contained in the X block are in an amount of more than 3 wt% based on the weight of all repeating units contained in the X block.

5. The (meth)acrylic copolymer (A′) contains, based on the weight of all repeating units, a total of 45 to 96% by weight of repeating units derived from a (meth)acrylic acid ester monomer (β) and a (meth)acrylic acid monomer (γ); 4 to 35% by weight of repeating units 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 an alkyl group ester-bonded to (meth)acrylic acid having 16 to 25 carbon atoms. The composition according to any one of claims 1 to 4.

6. The (meth)acrylic acid ester monomer (δ) is one or more selected from the group consisting of pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, eicosyl (meth)acrylate, and docosyl (meth)acrylate. The composition according to claim 5.

7. the content of the (meth)acrylic copolymer (A') and / or the (meth)acrylic copolymer (A'') is 50 to 99.9% by weight, The content of the epoxy compound (C) is 0.1 to 50% by weight. The composition according to any one of claims 1 to 6.

8. The composition according to any one of claims 1 to 7, a polyoxyalkylene polymer (B) having an alkoxysilyl group; A curable composition comprising:

9. A cured product obtained by curing the composition according to any one of claims 1 to 7 or the curable composition according to claim 8.

10. A sealant or adhesive comprising the composition according to any one of claims 1 to 7, the curable composition according to claim 8, or the cured product according to claim 9.

11. A method for storing the (meth)acrylic copolymer (A') and / or the (meth)acrylic copolymer (A''), comprising a step of preparing the composition according to any one of claims 1 to 7, In the above composition, the content of the (meth)acrylic copolymer (A') and / or the (meth)acrylic copolymer (A'') is 50 to 99.9% by weight, The content of the epoxy compound (C) is 0.1 to 50% by weight. Storage method.

12. 12. The method of claim 11, wherein the composition thickens by no more than 65% after storage at 80°C for 4 weeks.

13. A method for producing the composition according to claim 1, comprising the following steps 1a to 3a or steps 1b to 3b: (Step 1a) a step of polymerizing the (meth)acrylic acid ester monomer mixture containing more than 3% by weight of the (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 wt % of the (meth)acrylic acid ester monomer having an alkoxysilyl group to the reaction system after Step 1a, and polymerizing the mixture; (Step 3a) A step of mixing the (meth)acrylic copolymer (A') obtained through Step 2a and any additional polymerization step that is optionally included, with the epoxy compound (C). (Step 1b) a step of polymerizing a (meth)acrylic acid ester monomer mixture containing 0 to 3% by weight of the (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 wt % of the (meth)acrylic acid ester monomer having an alkoxysilyl group to the reaction system after Step 1b, and polymerizing the mixture; (Step 3b) A step of mixing the (meth)acrylic copolymer (A') obtained through Step 2b and any additional polymerization step that is optionally included, with the epoxy compound (C).

14. The method for producing a composition according to claim 13, wherein the living polymerization initiator is a living radical polymerization initiator.

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