Curable composition and cured product

Abstract

Provided is a curable composition the viscosity of which is lowered. A curable composition according to one mode of the present invention contains a (meth)acrylic copolymer (A) having an alkoxysilyl group and a polyoxyalkylene polymer (B) having an alkoxysilyl group. The (meth)acrylic copolymer (A) randomly includes a repeating unit derived from a (meth)acrylic acid ester monomer (α). The (meth)acrylic acid ester monomer (α) has an alkyl group forming an ester bond with a (meth)acrylic acid. Said alkyl group has an alkoxy group having 1-5 carbon atoms. The repeating unit derived from the (meth)acrylic acid ester monomer (α) accounts for 5-20 wt% with respect to the weight of all repeating units included in the (meth)acrylic copolymer (A).

Description

[Technical Field]

[0001] The present invention relates to a curable composition and a cured product. [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] An example of such a polymer is a polyoxyalkylene polymer having an alkoxysilyl group. A curable composition containing a polyoxyalkylene polymer having an alkoxysilyl group has good workability and an excellent balance of mechanical properties such as elongation at break and strength at break. However, unless an antioxidant is used, the hydrogen atoms bonded to the tertiary carbon of the polyoxyalkylene polymer are easily oxidized. This poses a problem of poor weather resistance of the curable composition.

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

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

[0006] The compositions disclosed in Patent Documents 1 to 4 have room for improvement in terms of viscosity. That is, there is still room for improving the workability of these compositions by further reducing their viscosity.

[0007] One aspect of the present invention is to provide a curable composition having reduced viscosity. [Means for solving the problem]

[0008] In order to solve the above problems, a curable composition according to one aspect of the present invention comprises: A curable composition comprising (A) a (meth)acrylic copolymer having an alkoxysilyl group and (B) a polyoxyalkylene polymer having an alkoxysilyl group, The (meth)acrylic copolymer (A) randomly contains 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). [Effects of the Invention]

[0009] According to one aspect of the present invention, a curable composition having a reduced viscosity can be provided. DETAILED DESCRIPTION OF THE INVENTION

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

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

[0012] [1. (Meth)acrylic copolymer (A) having alkoxysilyl groups] A curable composition according to one embodiment of the present invention comprises a (meth)acrylic copolymer (A) having an alkoxysilyl group. 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% by weight based on the weight of all repeating units contained in the (meth)acrylic copolymer (A) (this value is critical). Here, the (meth)acrylic acid ester monomer (α) refers to a monomer having an alkyl group ester-bonded to (meth)acrylic acid, the alkyl group having an alkoxy group having 1 to 5 carbon atoms. Preferably, the alkyl group ester-bonded to acrylic acid has 1 to 5 carbon atoms.

[0013] The lower limit of the content of the repeating units derived from the (meth)acrylic acid ester monomer (α) is more preferably 6% by weight or more, 7% by weight or more, 8% by weight or more, 9% by weight or more, or 10% by weight or more, based on the weight of all repeating units contained in the (meth)acrylic copolymer (A).The upper limit of the content of the repeating units derived from the (meth)acrylic acid ester monomer (α) is more preferably 19% by weight or less, or 18% by weight or less, based on the weight of all repeating units contained in the (meth)acrylic copolymer (A).

[0014] When repeating units derived from the (meth)acrylic acid ester monomer (α) are randomly included and their content is within the above-mentioned range, the viscosity of the (meth)acrylic copolymer (A) itself and the viscosity of a curable composition containing the (meth)acrylic copolymer (A) can be reduced. The viscosity of the (meth)acrylic copolymer (A) itself measured at 23°C is preferably 200 Pa·s or less, more preferably 150 Pa·s or less, and more preferably 130 Pa·s or less. The viscosity can be measured using an appropriate viscometer. Furthermore, the viscosity of the curable composition measured at 23°C is preferably 55 Pa·s or less, more preferably 53 Pa·s or less.

[0015] 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 copolymer (A) and the polyoxyalkylene polymer (B) having an alkoxysilyl group is enhanced, thereby enabling the production of a curable composition and a cured product with excellent properties.

[0016] If the repeating units derived from the (meth)acrylic acid ester monomer (α) are not randomly contained, this may adversely affect the viscosity of the (meth)acrylic copolymer (A) itself and its compatibility with the polyoxyalkylene polymer (B). This adverse effect is thought to be caused by the difference in polarity between the (meth)acrylic acid ester monomer (α) and other monomers. Examples of polymers that do not randomly contain repeating units derived from the (meth)acrylic acid ester monomer (α) include polymers whose main chain is mainly composed of repeating units derived from the (meth)acrylic acid ester monomer (α), and polymers that have repeating units derived from the (meth)acrylic acid ester monomer (α) in blocks.

[0017] In one embodiment, the number average molecular weight of the (meth)acrylic copolymer (A) is preferably 4,000 to 80,000, 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).

[0018] In one embodiment, 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 curable composition increases, and workability tends to decrease.

[0019] 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.

[0020] The (meth)acrylic copolymer (A) having such a narrow molecular weight distribution can be suitably produced, for example, by living radical polymerization.

[0021] In one embodiment, the (meth)acrylic copolymer (A) has alkoxysilyl groups distributed only at one end of the molecular chain. Therefore, the entire molecule has one or two alkoxysilyl groups. Such a copolymer can be produced, for example, by the production method described in Section [3.1.].

[0022] In one embodiment, the (meth)acrylic copolymer (A) has alkoxysilyl groups distributed near at least one end of the molecular chain. Therefore, the molecule as a whole has one or more alkoxysilyl groups, and may have more than two alkoxysilyl groups. Such a copolymer can be produced, for example, by the production method described in Section [3.2.] (This production method produces the (meth)acrylic copolymer (A1) described below).

[0023] The number of alkoxysilyl groups introduced into the (meth)acrylic copolymer (A) is, on average, 1.0 or more, or more than 1.0, across the entire molecule. In one embodiment, the number of alkoxysilyl groups is preferably 1.1 or more, more preferably 1.2 or more. In another embodiment, the number of alkoxysilyl groups is preferably 2.2 or more, 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 excellent. Furthermore, the (meth)acrylic copolymer (A) preferably has an alkoxysilyl group at at least one end (or terminal region) of the molecular chain, and preferably has alkoxysilyl groups at both ends (or terminal regions).

[0024] [1.1. (Meth)acrylic acid ester monomers] The (meth)acrylic copolymer (A) according to one embodiment of the present invention contains, in its main chain, a structural unit derived from a (meth)acrylic acid ester monomer. The (meth)acrylic acid ester monomer constituting the main chain is not particularly limited as long as it satisfies 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.

[0025] 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. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 2. The number of carbon atoms in the alkoxy group is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1. (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.

[0026] As described above, the content of repeating units derived from the (meth)acrylic acid ester monomer (α) is 5 to 20 wt%, preferably 10 to 20 wt%, 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 wt%, more preferably 50 to 70 wt%, 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 wt%, more preferably 10 to 25 wt%, 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 15 to 25 wt%, more preferably 15 to 20 wt%, 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 have good workability, mechanical properties and weather resistance.

[0027] When the content of the repeating unit derived from the (meth)acrylic acid ester monomer (β) is within the above range, the compatibility between the (meth)acrylic copolymer (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 10% by weight or more, 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 25% by weight or less, the compatibility between the (meth)acrylic copolymer (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 15% by weight or more, the compatibility between the (meth)acrylic copolymer (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 25% by weight or less, an increase in viscosity at low temperatures can be prevented, and a decrease in workability can be prevented.

[0028] 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.

[0029] Among the above-mentioned monomers, 2-methoxyethyl acrylate is preferred as the (meth)acrylic acid ester monomer (α). Butyl acrylate is preferred as the (meth)acrylic acid ester monomer (β). 2-ethylhexyl acrylate and dodecyl acrylate are preferred as the (meth)acrylic acid ester monomer (γ). Octadecyl acrylate is preferred as the (meth)acrylic acid ester monomer (δ). By selecting these monomers, the (meth)acrylic copolymer (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.

[0030] In one embodiment, the (meth)acrylic acid ester monomer (α) is (a) and / or (b) below:

[0031] (a) A monomer in which the number of carbon atoms in the alkyl group ester-bonded to (meth)acrylic acid is 1 to 5. However, the "number of carbon atoms in the alkyl group" does not include the carbon atoms contained in the alkoxy group of the alkyl group.

[0032] (b) one or more monomers selected from the group consisting of 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and isopropoxyethyl (meth)acrylate.

[0033] 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 polymer (A). When 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 good weather resistance, mechanical properties, and durability can be obtained.

[0034] [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).

[0035] In the formula, R 1 and R 2are independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a methoxymethyl group, or a triorganosiloxy group represented by (R')3SiO- (wherein R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's may be the same or different). 1 or R 2 When there are two or more R 1 or R 2 may be the same or different. Y is an alkoxy group having 1 to 20 carbon atoms (when there are two or more Y's, they may be the same or different). a is 0, 1, 2 or 3. b is 0, 1 or 2. m is an integer of 0 to 19. In addition, the relationship a+mb≧1 is satisfied.

[0036] 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).

[0037] 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).

[0038] 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 5are independently selected. m is an integer from 0 to 10. n is an integer from 0 to 2.

[0039] 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.

[0040] [2. (Meth)acrylic copolymer (A1)] In one embodiment, 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. Such a (meth)acrylic copolymer is referred to herein as a (meth)acrylic copolymer (A1). 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.

[0041] 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 XY diblock structure and the XYX triblock structure is preferably from (5 / 95) to (60 / 40), more preferably from (15 / 85) to (40 / 60).

[0042] In one embodiment, the molecule of the (meth)acrylic copolymer (A1) has an XY diblock structure. In a molecule of the XY diblock structure, the X block can be a region of 40% or less, 30% or less, or 25% or less from one end of the molecule (all units contained in the molecule are taken as 100%). Here, the X block is the block on the side where alkoxysilyl groups are distributed in a relatively large amount.

[0043] In one embodiment, the molecule of the (meth)acrylic copolymer (A1) has an XYX triblock structure. In the molecule of the XYX triblock structure, the X blocks may be 40% or less, 30% or less, or 25% or less of the region from the terminal of the molecule (all units contained in the molecule are taken as 100%). Here, the X blocks are blocks located at both terminals of the molecule.

[0044] The (meth)acrylic copolymer (A1) randomly contains 5 to 20% by weight of repeating units derived from the (meth)acrylic acid ester monomer (α) based on the weight of all repeating units contained in the (meth)acrylic copolymer (A1). Here, the repeating units derived from the (meth)acrylic acid ester monomer (α) may be different between the X block and the Y block. In other words, if, as a whole molecule, (i) the repeating units derived from the (meth)acrylic acid ester monomer (α) are randomly distributed, and (ii) the content of these repeating units is 5 to 20% by weight (preferably 10 to 20% by weight), then the copolymer falls within the category of the (meth)acrylic copolymer (A1).

[0045] In one embodiment, the (meth)acrylic copolymer (A1) contains a repeating unit derived from a (meth)acrylic ester monomer having an alkoxysilyl group. The repeating unit derived from a (meth)acrylic ester monomer having an alkoxysilyl group is contained in a relatively large amount in the X block. Specifically, the repeating unit derived from a (meth)acrylic ester monomer having an alkoxysilyl group contained in the X block is 1.0 or more on average. On the other hand, the repeating unit derived from a (meth)acrylic 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. Therefore, the repeating unit derived from a (meth)acrylic ester monomer having an alkoxysilyl group is localized at a terminal (one end or both ends) in the (meth)acrylic copolymer (A1).

[0046] 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.

[0047] In one embodiment, the number of alkoxysilyl groups introduced into the (meth)acrylic copolymer (A1) differs between the X block and the Y block, as specifically described above. When the (meth)acrylic copolymer (A1) has an XY diblock structure, the average number of alkoxysilyl groups introduced into the entire molecule is 1 or more, preferably 1.1 or more, and more preferably 1.2 or more. When the (meth)acrylic copolymer (A1) has an XYX triblock structure or an XYXY tetrablock structure, the average number of alkoxysilyl groups introduced into the entire molecule is 2 or more, preferably 2.2 or more, and more preferably 2.4 or more. The upper limit of the number of alkoxysilyl groups introduced into the (meth)acrylic copolymer (A1) is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 6.0 or less, and particularly preferably 4.0 or less. When the number of alkoxysilyl groups is within the above range, the physical properties of a curable composition and a cured product using the (meth)acrylic copolymer (A1) are good.

[0048] 3. Method for producing (meth)acrylic copolymer (A) and (meth)acrylic copolymer (A1) The polymerization method for the (meth)acrylic copolymer (A) is not particularly limited, and known polymerization methods can be used (radical polymerization, cationic polymerization, anionic polymerization, etc.). Among these, living polymerization is preferred because it allows functional groups to be introduced into the terminals of polymer molecules and enables the synthesis of XY block polymers and XYX block polymers. Examples of living polymerization methods include living radical polymerization, living cationic polymerization, and living anionic polymerization, and among these, living radical polymerization is suitable for polymerizing acrylic acid ester monomers. Examples of living radical polymerization methods include the following. Atom Transfer Radical Polymerization (ATRP) (see J. Am. Chem. Soc. 1995, 117, 5614; Macromolecules. 1995, 28, 1721) ·Sigle Electron Transfer Polymerization; SET-LRP (J. Am. Chem. Soc. 2006, 128, 14156; JPSChem 2007, 45, 1607) Reversible Chain Transfer Catalyzed Polymerization (RTCP) ("Living Radical Polymerization Controlled by Organic Catalysts," Polymer Review, 68, 223-231 (2011); See JP 2014-111798 Reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) Nitroxy radical method (NMP method) Organotellurium Polymerization (TERP) method Polymerization method using organoantimony compounds (SBRP method) Organobismuth polymerization method (BIRP) -Iodine transfer polymerization method.

[0049] [3.1. First embodiment of manufacturing method] In one example, the (meth)acrylic copolymer (A) is produced by the method described in JP 2007-302749 A. Among these, a method in which a hydrosilane compound having an alkoxysilyl group is added to a (meth)acrylic polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst is preferred because it is easier to control.

[0050] In this method, an alkoxysilyl group is introduced into a (meth)acrylic polymer as follows. 1. (Meth)acrylic polymers are obtained by living radical polymerization of (meth)acrylic acid ester monomers. 2. The (meth)acrylic polymer obtained in 1 is reacted with a compound (diene compound) having at least two alkenyl groups with low polymerizability to obtain a vinyl polymer having at least one alkenyl group. 3. An alkoxysilyl group-containing hydrosilane compound is added to the vinyl polymer obtained in 2 in the presence of a hydrosilylation catalyst.

[0051] More specifically, the above method is carried out by reacting a diene compound (1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, etc.) at the end of the polymerization reaction or after the completion of the reaction of a predetermined monomer in the production of a (meth)acrylic polymer by living radical polymerization.

[0052] The hydrosilane compound having an alkoxysilyl group is not particularly limited, and a typical example is a compound represented by general formula (3). H-[Si(R 6 ) 2-b (Y) b O] m -Si(R 7 ) 3-a (Y) a (3).

[0053] In general formula (3), R 6 and R 7are each 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 (R 8 )3SiO— (wherein R 8 is a monovalent hydrocarbon group having 1 to 20 carbon atoms. 8 may be the same or different). 6 or R 7 When two or more Y's are present, they may be the same or different. Y represents an alkoxy group having 1 to 20 carbon atoms. When two or more Y's are present, they may be the same or different. a represents 0, 1, 2 or 3. b represents 0, 1 or 2. m is an integer of 0 to 19, provided that a+mb≧1 is satisfied.

[0054] Among these hydrosilane compounds, the compound represented by the following general formula (4) is preferred from the viewpoint of easy availability. H-Si(R 6 ) 3-a (Y) a (4).

[0055] In general formula (4), R 6 and Y are as defined above. a is an integer of 1 to 3.

[0056] A transition metal catalyst is typically used to add a hydrosilane compound bearing an alkoxysilyl group to an alkenyl group. Examples of transition metal catalysts include platinum catalysts. These include platinum alone; solid platinum dispersed on a support (alumina, silica, carbon black, etc.); chloroplatinic acid; complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc.; platinum-olefin complexes; and platinum(0)-divinyltetramethyldisiloxane complexes. Examples of catalysts other than platinum catalysts include RhCl(PPh3)3, RhCl3, RuCl3, IrCl3, FeCl3, AlCl3, PdCl2·H2O, NiCl2, and TiCl4.

[0057] [3.2. Second embodiment of the manufacturing method] 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. Since this production method produces a block copolymer, the resulting (meth)acrylic copolymer (A) is the (meth)acrylic copolymer (A1). The (meth)acrylic copolymer (A1) produced by this production method is preferable in that the viscosity of the polymer is reduced.

[0058] 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."

[0059] (Step 1a) A step of polymerizing a (meth)acrylic acid ester monomer mixture containing (preferably more than 3% by weight) a (meth)acrylic acid ester monomer having an alkoxysilyl group using a living polymerization initiator.

[0060] (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.

[0061] (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.

[0062] (Step 2b) A step of adding a (meth)acrylic acid ester monomer mixture containing a (meth)acrylic acid ester monomer having an alkoxysilyl group (preferably more than 3% by weight) to the reaction system after Step 1b and polymerizing the mixture.

[0063] Hereinafter, each step will be described in more detail for each structure of the (meth)acrylic copolymer (A1).

[0064] (When the copolymer has an XY diblock structure) The (meth)acrylic acid copolymer (A1), which is a molecule having an XY diblock structure, can be produced by the above-mentioned steps 1a and 2a or steps 1b and 2b. In this case, steps 1a and 2b form an X block containing a relatively large amount of alkoxysilyl groups. On the other hand, steps 2a and 1b form a Y block containing a relatively small amount of alkoxysilyl groups.

[0065] 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. Preferably, 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.

[0066] 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.

[0067] 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.

[0068] 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. Preferably, 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.

[0069] In the above process, examples of the "(meth)acrylic acid ester monomer not having an alkoxysilyl group" include the (meth)acrylic acid ester monomers (α), (β), (γ), and (δ) described in Section [1.1.]. This also applies to the following description.

[0070] (When the copolymer has an XYX triblock structure) The (meth)acrylic acid copolymer (A1), which is a molecule having an XYX triblock structure, can be produced by carrying out the above-mentioned steps 1a and 2a followed by an additional polymerization step (a). At this time, the step 1a and the additional polymerization step (a) form an X block containing a relatively large amount of alkoxysilyl groups. For details of this production method, please refer to the description in JP 2018-162394 A.

[0071] 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. Preferably, 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 wt% of the monomer mixture added to the reaction system in that step.

[0072] The (meth)acrylic acid copolymer (A1), 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.

[0073] 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.

[0074] (When the copolymer has four or more blocks) By appropriately combining the above-mentioned steps 1a, 2a, 1b, 2b, and the additional polymerization step, it is possible to produce a (meth)acrylic copolymer (A1) having four or more blocks, such as a (meth)acrylic copolymer (A1) having an XYXY tetrablock structure.

[0075] In the above-described production method, the (meth)acrylic acid ester monomer having no alkoxysilyl group added as the (meth)acrylic acid ester monomer having no alkoxysilyl group contains 5 to 20% by weight of the (meth)acrylic acid ester monomer (α) based on the weight of all monomers.

[0076] When the second production method is employed, halogen atoms may remain at one or both ends of the (meth)acrylic copolymer (A1) molecule (the elongated ends of the molecular chain during polymerization). In one embodiment, the (meth)acrylic copolymer (A1) has, on average, one or more halogen atoms per elongated end of the molecular chain during polymerization.

[0077] [3.3. General matters regarding the production of (meth)acrylic polymers by living radical polymerization] All of the above-mentioned production methods can be suitably carried out by adopting living radical polymerization, among which atom transfer radical polymerization, single electron transfer polymerization, and reversible transfer catalytic polymerization are preferred.

[0078] 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.

[0079] 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):

[0080] (a) The monovalent copper complex abstracts the halogen at the end of the polymer to generate a radical, which then becomes a divalent copper complex.

[0081] (b) The divalent copper complex adds a halogen to the radical at the polymer end to form a monovalent copper complex.

[0082] On the other hand, when interpreted based on SET LRP, living radical polymerization consists of the equilibrium of the following three reactions (explained using a copper complex as an example):

[0083] (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.

[0084] (b) The divalent copper complex adds a halogen to the radical at the polymer end to become a zero-valent copper complex.

[0085] (c) The monovalent copper complex disproportionates to give zero- and divalent copper complexes.

[0086] 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.

[0087] 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.

[0088] (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, i.e., the (meth)acrylic copolymer (A) may be a copolymer obtained by a production method including steps 1a and 2a, or steps 1b and 2b.

[0089] 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.

[0090] 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.

[0091] Due to these circumstances, there are cases where it is necessary to define the (meth)acrylic copolymer (A) not as a specific structure of the copolymer molecule, but as a copolymer obtained by the above-mentioned production method.

[0092] 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.

[0093] (a. 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.

[0094] 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.

[0095] 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.

[0096] (b. 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.

[0097] 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.

[0098] 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.

[0099] (c. 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.

[0100] (d. base) 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.

[0101] (e. reducing agent) 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:

[0102] (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.

[0103] (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.

[0104] Alternatively, the reducing agent may be generated in the polymerization system by electrolytic reduction. In electrolytic reduction, electrons generated at the cathode directly (or after solvation) exhibit a reducing effect. In other words, the reducing agent may be generated by electrolysis.

[0105] (f. Solvent) 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.

[0106] 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.

[0107] [4. Polyoxyalkylene polymer (B) having an alkoxysilyl group] The curable composition according to one embodiment of the present invention contains a polyoxyalkylene polymer (B) having an alkoxysilyl group.

[0108] [4.1. Main chain of polyoxyalkylene polymer (B)] The main chain structure of the polyoxyalkylene polymer (B) may be linear or branched. It may also be a mixture of molecules having these structures. Among these, a main chain derived from one or more selected from the group consisting of polyoxypropylene diols and polyoxypropylene triols is particularly preferred.

[0109] An example of the main chain of the polyoxyalkylene polymer (B) is substantially a group represented by the general formula (5): -R 7 -O-" (wherein R 7 is a divalent alkylene group.) Here, the term "substantially" means that the repeating unit represented by general formula (5) accounts for 50% by weight or more (preferably 80% by weight or more) of the total weight of the polyoxyalkylene polymer (B).

[0110] R in general formula (5) 7 is not particularly limited as long as it is a divalent alkylene group. 7 is preferably an alkylene group having 1 to 14 carbon atoms, and more preferably a linear or branched alkylene group having 2 to 4 carbon atoms.

[0111] The repeating unit represented by general formula (5) 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-.

[0112] The polyoxyalkylene polymer (B) may contain a urethane bond or a urea bond in the main chain structure.

[0113] 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.

[0114] [4.2. Production method of polyoxyalkylene polymer (B)] The molecular structure of the polyoxyalkylene polymer (B) varies depending on the intended use and desired properties. For example, the compounds described in JP-A-63-112642 can be used as the polyoxyalkylene polymer (B). Such polyoxyalkylene polymer (B) can be synthesized by a conventional polymerization method (anionic polymerization using caustic alkali). Furthermore, it can also be synthesized by a method using a cesium metal catalyst, a porphyrin / aluminum complex catalyst (see JP-A-61-197631, JP-A-61-215622, JP-A-61-215623, and JP-A-61-218632, etc.), a composite metal cyanide complex catalyst (see JP-B-46-27250, JP-B-59-15336, etc.), or a catalyst made of a polyphosphazene salt (see JP-A-10-273512, etc.).

[0115] 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, particularly preferably 1.2 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.

[0116] (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 the alkoxysilyl group contained in the (meth)acrylic copolymer (A), or may have a different structure.

[0117] 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.

[0118] 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.

[0119] (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.

[0120] 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.

[0121] 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 ...

[0122] [5. Curable composition] A curable composition according to one aspect of the present invention includes a (meth)acrylic copolymer (A) having an alkoxysilyl group and a polyoxyalkylene polymer (B) having an alkoxysilyl group. The curable composition may also include other additives. The composition can be produced by mixing the (meth)acrylic copolymer (A) and the polyoxyalkylene polymer (B).

[0123] [5.1. Blending ratio of (meth)acrylic copolymer (A) and polyoxyalkylene polymer (B)] In the curable composition according to one embodiment of the present invention, the blending ratio of the (meth)acrylic copolymer (A) to the polyoxyalkylene polymer (B) can be adjusted as appropriate. The blending ratio of the (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.

[0124] 5.2 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 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.

[0125] (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.).

[0126] 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.

[0127] 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 the polyoxyalkylene polymer (B).

[0128] (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.

[0129] Examples of adhesion promoters include silane coupling agents.Specific examples of the silane coupling agent 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-aminopropyltriethoxy ... Methoxysilane, 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, N-vinylbenzyl-γ-aminopropyltriethoxysilane, etc.; mercapto group-containing silanes (γ-mercaptopropyltrimethoxysilane, γ- Mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc.; epoxy group-containing silanes (γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, etc.); carboxysilanes (β-carboxyethyltriethoxysilane, ... 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.

[0130] 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 the polyoxyalkylene polymer (B).

[0131] (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.

[0132] Examples of plasticizers include phthalate esters (dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, etc.); non-aromatic dibasic acid esters (dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, etc.); aliphatic esters (butyl oleate, methyl acetylricinoleate, etc.); esters of polyalkylene glycols (diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol ester, etc.); phosphate esters (tricresyl phosphate, tributyl phosphate, etc.); trimellitic acid esters, polystyrenes (polystyrene, poly-α-methylstyrene, etc.); polybutadiene; polybutene; polyisobutylene; butadiene-acrylonitrile; polychloroprene; chlorinated paraffins; hydrocarbon oils ( alkyldiphenyls, partially hydrogenated terphenyls, etc.); process oils; polyethers (polyether polyols (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.), and derivatives of polyether polyols in which the hydroxyl groups have been converted to ester groups, ether groups, etc.); epoxy plasticizers (epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof, etc.); polyester plasticizers obtained from dibasic acids and dihydric alcohols (polyesters obtained from sebacic acid, adipic acid, azelaic acid, phthalic acid, etc., and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc.); and vinyl polymers (obtained by polymerizing vinyl monomers such as acrylic plasticizers by various methods).

[0133] Specific examples of epoxy plasticizers include epoxidized soybean oil, epoxidized linseed oil, di-(2-ethylhexyl) 4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, and epoxy butyl stearate. Among the above-mentioned epoxy plasticizers, E-PS is preferred. Using a compound having an epoxy group as a plasticizer can improve the recovery of the cured product.

[0134] 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.

[0135] The amount of the plasticizer to be added is preferably 5 to 800 parts by weight, more preferably 10 to 600 parts by weight, and even more preferably 10 to 500 parts by weight, per 100 parts by weight of the total amount of the (meth)acrylic copolymer (A) and the polyoxyalkylene polymer (B).

[0136] (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.).

[0137] The amount of the filler to be added is preferably 5 to 5,000 parts by weight, more preferably 10 to 2,500 parts by weight, and particularly preferably 15 to 1,500 parts by weight, per 100 parts by weight of the total amount of the (meth)acrylic copolymer (A) and the polyoxyalkylene polymer (B).

[0138] (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.

[0139] Examples of the physical property adjuster include alkylalkoxysilanes (methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, etc.); alkylisopropenoxysilanes (dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, etc.); alkoxysilanes having functional groups (γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.); silicone varnishes; and polysiloxanes.

[0140] The amount of the physical property adjuster to be added is preferably 0.1 to 80 parts by weight, more preferably 0.1 to 50 parts by weight, per 100 parts by weight of the total amount of the (meth)acrylic copolymer (A) and the polyoxyalkylene polymer (B).

[0141] (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.

[0142] Examples of the thixotropy-imparting agent include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps (calcium stearate, aluminum stearate, barium stearate, etc.).

[0143] 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 the polyoxyalkylene polymer (B).

[0144] (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.

[0145] 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.

[0146] 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 the polyoxyalkylene polymer (B).

[0147] (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.

[0148] Examples of air-oxidatively curable substances include drying oils (such as tung oil and linseed oil); various alkyd resins obtained by modifying drying oils; substances obtained by modifying acrylic polymers, epoxy resins, 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 (such as maleated modified products and boiled oil modified products). Of the above, tung oil, liquid diene polymers, and modified products thereof are preferred.

[0149] 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 the polyoxyalkylene polymer (B).

[0150] (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.

[0151] 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.

[0152] 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.

[0153] 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).

[0154] 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.

[0155] 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.

[0156] 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.).

[0157] 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.

[0158] 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 the polyoxyalkylene polymer (B).

[0159] [5.3. Form of curable composition] The curable composition according to one embodiment of the present invention may be either a one-component type or a two-component type. A one-component type curable composition is one in which all components are blended in advance and then sealed and stored. A one-component type curable composition cures after use due to moisture in the air. On the other hand, a two-component type curable composition requires a separately prepared curing agent containing components such as a curing catalyst, a filler, a plasticizer, and water. A two-component type 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 (A1). The two-component type curable composition may contain other agents (such as a colorant) in addition to the base agent and the curing agent.

[0160] 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.

[0161] 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.

[0162] [5.4. Uses of the curable composition] The uses of the 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 coating materials 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 the like, potting agents for electrical and electronic applications, 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.

[0163] Among the above, the 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, because the curable composition and cured product according to one embodiment of the present invention have excellent weather resistance and adhesion, they can 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.).

[0164] 〔summary〕 The present invention includes the following aspects. <1> A curable composition comprising (A) a (meth)acrylic copolymer having an alkoxysilyl group and (B) a polyoxyalkylene polymer having an alkoxysilyl group, The (meth)acrylic copolymer (A) randomly contains 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); Curable composition. <2> The (meth)acrylic copolymer (A) has, based on the weight of all repeating units, 45 to 70% by weight of repeating units derived from a (meth)acrylic acid ester monomer (β), 0 to 25% by weight of a repeating unit derived from a (meth)acrylic acid ester monomer (γ), 15 to 25% 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> The curable composition according to claim 1. <3> The (meth)acrylic copolymer (A) has a molecular weight distribution (Mw / Mn) of 1.8 or less. <1> or <2> The curable composition according to claim 1. <4> The molecule of the (meth)acrylic copolymer (A) is a (meth)acrylic copolymer (A1) containing an XY diblock structure having an X block and a Y block 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 repeating unit derived from a (meth)acrylic acid ester monomer having an alkoxysilyl group contained in the Y block is 0 to 3% by weight based on the weight of all repeating units contained in the Y block; <1> ~ <3> The curable composition according to any one of the preceding claims. <5> 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; <4> The curable composition according to claim 1. <6> The (meth)acrylic acid ester monomer (α) is the following (a) and / or (b): <1> ~ <5> The curable composition according to any one of the preceding claims: (a) a monomer in which the alkyl group ester-bonded to (meth)acrylic acid has 1 to 5 carbon atoms (excluding carbon atoms contained in the alkoxy group); (b) one or more monomers selected from the group consisting of 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and isopropoxyethyl (meth)acrylate. <7> 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, icosyl (meth)acrylate, and docosyl (meth)acrylate. <2> The curable composition according to claim 1. <8> The number of alkoxysilyl groups contained in the (meth)acrylic copolymer (A) is 1.0 to 10.0 on average in the entire molecule. <1> ~ <7> The curable composition according to any one of the preceding claims. <9> The number average molecular weight of the polyoxyalkylene polymer (B) is 5,000 to 50,000. <1> ~ <8> The curable composition according to any one of the preceding claims. <10> the blending ratio of the (meth)acrylic copolymer (A) to the polyoxyalkylene polymer (B) is (95 / 5) to (5 / 95) by weight; <1> ~ <9> The curable composition according to any one of the preceding claims. <11> The following conditions (a) and / or (b) are met: <1> ~ <10> The curable composition according to any one of the preceding claims: Condition (a): the viscosity of the (meth)acrylic copolymer (A) measured at 23°C is 200 Pa·s or less; Condition (b): The viscosity of the curable composition measured at 23° C. is 55 Pa·s or less. <12> <1> ~ <11> A cured product obtained by curing the curable composition according to any one of the above items. <13> <1> ~ <11> The curable composition according to any one of the above items, or <12> A sealant or adhesive containing the cured product described in 1. <14> <1> A method for producing the curable composition according to claim 1, a step of polymerizing the (meth)acrylic copolymer (A) by a living polymerization method; a step of mixing the (meth)acrylic copolymer (A) and the polyoxyalkylene polymer (B); A manufacturing method comprising: <15> the step of polymerizing the (meth)acrylic copolymer (A) by a living polymerization method includes a step of polymerizing the (meth)acrylic copolymer (A) by a living radical polymerization method; <14> A method for producing the curable composition according to claim 1.

[0165] The present invention also includes the following aspects. <1a> In the curable composition, the total weight of repeating units derived from (meth)acrylic acid ester monomers contained in the (meth)acrylic copolymer (A) may be 90% by weight or more based on the weight of all repeating units contained in the (meth)acrylic copolymer (A). <2a> In the curable composition, the (meth)acrylic acid ester monomer (β) may be butyl acrylate. <3a> In the curable 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 curable composition, the (meth)acrylic acid ester monomer (δ) may be octadecyl acrylate. <5a> In the curable composition, the (meth)acrylic copolymer (A) may have a number average molecular weight of 30,000 or more as measured by gel permeation chromatography. <6a> In the curable composition, the blending ratio of the (meth)acrylic copolymer (A) to the polyoxyalkylene polymer (B) may be (95 / 5) to (5 / 95). <7a> In the curable composition, one or more selected from the group consisting of the (meth)acrylic copolymer (A) and the polyoxyalkylene polymer (B) 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, R1 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).

[0166] Furthermore, the present invention also includes the following aspects. <1b> A method for producing a (meth)acrylic copolymer (A) by atom transfer radical polymerization, comprising the following steps: (i) a first step of polymerizing 1 to 10 molar equivalents of a (meth)acrylic acid ester monomer having an alkoxysilyl group and 1 to 100 molar equivalents of a (meth)acrylic acid ester monomer not having an alkoxysilyl group with respect to 1 molar equivalent of an initiator having one halogen group in the molecule; (ii) a second step of adding 2 to 600 molar equivalents of a (meth)acrylic acid ester monomer having no alkoxysilyl group to a reaction system relative to 1 molar equivalent of the polymer obtained in the first step, and polymerizing the resulting mixture; (iii) a third step of adding 1 to 10 molar equivalents of a (meth)acrylic acid ester monomer having an alkoxysilyl group to a reaction system relative to 1 molar equivalent of the polymer obtained in the second step, and polymerizing the resulting mixture; wherein the (meth)acrylic acid ester monomer having no alkoxysilyl group added to the reaction system in the first step and the third 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 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. Manufacturing method.

[0167] 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.

[0168] All scientific and patent literature mentioned herein is hereby incorporated by reference.

[0169] 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]

[0170] [Production Example 1] (preparation) The (meth)acrylic acid ester monomers (α), (β), (γ), and (δ) were mixed in the amounts shown in Table 1 to obtain 1000 g of a mixture. This mixture is referred to as "(meth)acrylic acid ester monomer mixture A."

[0171] (polymerization) The inside of a stainless steel reaction vessel equipped with a stirrer was deoxygenated. 7.41 g of cuprous bromide and 200 g of (meth)acrylic acid ester monomer mixture A were charged into the reaction vessel and heated with stirring. Next, 88.73 g of acetonitrile and 10.79 g of initiator (diethyl 2,5-dibromoadipate) were added and mixed. The temperature of the mixture was adjusted to approximately 65°C, and 0.15 g of pentamethyldiethylenetriamine was added to initiate the polymerization reaction. The remaining 800 g of (meth)acrylic acid ester monomer mixture A was then gradually added, and the polymerization reaction was allowed to proceed. During the polymerization reaction, pentamethyldiethylenetriamine was appropriately added to adjust the polymerization rate. The total amount of pentamethyldiethylenetriamine used throughout the polymerization reaction was 1.49 g. As the polymerization progressed, the temperature of the reaction system tended to rise due to the heat of reaction, but the temperature of the reaction system was controlled to approximately 80°C to 90°C. When the monomer conversion rate (polymerization reaction rate) reached 95%, the volatile matter was removed by devolatilization under reduced pressure to obtain a polymer concentrate. The time required to reach this stage was 5 hours.

[0172] To the obtained polymer concentrate were added 189.85 g of 1,7-octadiene, 354.94 g of acetonitrile, and 2.99 g of pentamethyldiethylenetriamine. Next, the reaction system was heated and stirred for 4 hours while adjusting the temperature to about 80°C to about 90°C, thereby reacting 1,7-octadiene with the terminals of the polymer.

[0173] (purification) At the end of the reaction, an oxygen-nitrogen mixed gas was introduced into the gas phase of the reaction vessel. Next, the reaction solution was heated and stirred for 4 hours while maintaining the temperature of the reaction system at approximately 80°C to approximately 90°C, thereby bringing the polymerization catalyst contained in the reaction solution into contact with oxygen. Next, acetonitrile and unreacted 1,7-octadiene were removed by devolatilization under reduced pressure, yielding a polymer concentrate. The process up to this point took 6 hours.

[0174] The polymer concentrate was diluted with 1000 g of butyl acetate, and then a filter aid was added and stirred, followed by filtering off the insoluble catalyst components.

[0175] The filtrate was placed in a stainless steel reactor equipped with a stirrer, and adsorbents (Kyoward 700SEN-S and Kyoward 500SH) were added. Next, an oxygen-nitrogen mixed gas was introduced into the gas phase of the reactor, and the mixture was heated and stirred at approximately 100°C for 1 hour. Next, insoluble components (such as the adsorbent) were removed by filtration, yielding a clear filtrate. This procedure was repeated twice, and the filtrate was then concentrated to yield a crude polymer.

[0176] A thermal stabilizer (Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd.) and adsorbents (Kyoward 700SEN-S, Kyoward 500SH) were added to the crude polymer. The system was heated and stirred at a high temperature of approximately 170°C to approximately 200°C for approximately 2 hours, followed by degassing under reduced pressure, to purify the crude polymer by adsorption. Next, the polymer was diluted with 10 times the amount of butyl acetate, and adsorbents (Kyoward 700SEN and Kyoward 500SH) were added. Next, the gas phase in the reaction vessel was filled with an oxygen-nitrogen mixed gas atmosphere, and the mixture was heated and stirred at a high temperature of approximately 170°C to approximately 200°C for approximately 4 hours to continue the adsorption purification. Next, the polymer was diluted with 90 times the amount of butyl acetate and then filtered to remove the adsorbent. The filtrate was concentrated to obtain a polymer having alkenyl groups at both ends.

[0177] (Introduction of alkoxysilyl groups) To 1,000 g of the resulting polymer, 19.1 g of methyldimethoxysilane (DMS), 5.4 g of methyl orthoformate, and an isopropanol solution of bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst (1.32 × 10 -4 The mixture was mixed with 0.388 mL of dimethylaminobenzoate (DMSO) (0.388 mmol / μL) and stirred under heating at approximately 115°C. After about one hour, volatile components (unreacted DMS, etc.) were removed by distillation under reduced pressure to obtain (meth)acrylic copolymer (A). This (meth)acrylic copolymer (A) is a polymer having dimethoxysilyl groups at both ends of the molecule.

[0178] [Production Example 2] (preparation) A 2000 mL three-neck flask was prepared. The (meth)acrylic acid ester monomers (α), (β), (γ), and (δ) were added and mixed in the amounts shown in Table 1 (total 975 g). This mixture is referred to as "(meth)acrylic acid ester monomer mixture B."

[0179] 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 (meth)acrylic acid ester monomer mixture B.

[0180] In addition, another stirring vessel was prepared. 40.4 mL of methanol, 0.5 g of ascorbic acid, and 0.79 mL of triethylamine were charged into this vessel and stirred for 30 minutes under a nitrogen stream to obtain a homogeneous solution. This homogeneous solution is referred to as the "ascorbic acid solution."

[0181] (1st step) 5.24 g of ethyl α-bromobutyrate (initiator), 20 wt % of the (meth)acrylic acid ester monomer mixture B, 12.48 g of 3-(trimethoxysilyl)propyl methacrylate, 151.76 g of methanol (manufactured by Wako Pure Chemical Industries, Ltd.), and the entire amount of the 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.

[0182] Next, when the temperature in the polymerization system reached 50°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 3 mg of ascorbic acid per hour.

[0183] 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 2°C, a small amount of the reaction solution in the polymerization system was sampled and analyzed by gas chromatography. The results showed that 81% by weight of the (meth)acrylic acid ester monomer mixture B initially added had been consumed.

[0184] (2nd process) Next, the remainder of the (meth)acrylic acid ester monomer mixture B that was not added in the first step (80 wt % of the total amount) was continuously added dropwise to the polymerization system over a period of 90 minutes. Sampling was also carried out sequentially and analyzed by gas chromatography. The polymerization was continued until 98 wt % of the total amount of (meth)acrylic acid ester monomer mixture B added to the polymerization system was consumed.

[0185] (3rd step) Next, 13.73 g of 3-(trimethoxysilyl)propyl methacrylate was added to this polymerization system. After the continuous dropwise addition of the ascorbic acid solution was continued for 1.5 hours, the dropwise addition of the ascorbic acid solution was stopped to terminate the polymerization.

[0186] 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.

[0187] (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 20 g of Kyoward 500SH (Kyowa Chemical Industry Co., Ltd.) and 20 g of Kyoward 700SEN-S (Kyowa Chemical Industry Co., Ltd.).

[0188] After stirring, the resulting mixture was filtered through a filter equipped with a bag filter cloth. This yielded 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 the solution and mixed until homogeneous. The solvent was then volatilized from the solution to obtain a (meth)acrylic copolymer (A1). A diaphragm pump was used first for volatilization, followed by a vacuum pump. This (meth)acrylic copolymer (A1) is a polymer having an XYX triblock structure.

[0189] [Production Examples 3 and 4] The composition of the (meth)acrylic monomer mixture B was changed as shown in Table 1. Otherwise, the same procedure as in Production Example 2 was carried out to produce a (meth)acrylic copolymer (A1).

[0190] [Production Example 5] The composition of the (meth)acrylic monomer mixture A was changed as shown in Table 1. Otherwise, a (meth)acrylic copolymer was produced in the same manner as in Production Example 1. This copolymer does not contain units derived from the (meth)acrylic acid ester monomer (α).

[0191] [Production Example 6] The composition of the (meth)acrylic monomer mixture B was changed as shown in Table 1. Otherwise, a (meth)acrylic copolymer was produced in the same manner as in Production Example 2. This copolymer does not contain units derived from the (meth)acrylic acid ester monomer (α).

[0192] [Table 1] [Examples 1 to 4, Comparative Examples 1 and 2] The physical properties of the (meth)acrylic copolymers obtained in Production Examples 1 to 6 were evaluated. In addition, the physical properties of a curable composition containing the (meth)acrylic copolymer and the polyoxyalkylene polymer (B) and a cured product obtained by curing the curable composition were also evaluated. The (meth)acrylic copolymers (A) evaluated in Examples 1 to 4 were produced in Production Examples 1 to 4, respectively. The (meth)acrylic copolymers evaluated in Comparative Examples 1 and 2 were produced in Production Examples 5 and 6, respectively.

[0193] [Monomer distribution] (Distribution of repeating units derived from (meth)acrylic acid ester monomers having an alkoxysilyl group) Assuming that all (meth)acrylate monomers are incorporated into the polymer block at the same reaction rate, the distribution of repeating units derived from (meth)acrylate monomers having alkoxysilyl groups (repeating units derived from 3-(trimethoxysilyl)propyl methacrylate) was calculated. Specifically, the following three parameters were calculated for repeating units derived from 3-(trimethoxysilyl)propyl methacrylate. The results are shown in Table 2. (a) Average number of the above repeating units contained in the X block.

[0194] (b) The weight ratio (wt %) of the repeating units contained in the X block to the entire polymer molecule.

[0195] (c) The weight ratio (wt %) of the repeating units contained in the Y block to the entire polymer molecule.

[0196] (Distribution of repeating units derived from (meth)acrylic acid ester monomer (α)) 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 molecule 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 above-mentioned production example, the repeating units derived from 2-methoxyethyl acrylate are randomly distributed in the (meth)acrylic copolymer (A).

[0197] [Evaluation of (meth)acrylic 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 (meth)acrylic 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 for the GPC. The results are shown in Table 2.

[0198] (viscosity) The viscosity of the (meth)acrylic copolymer was measured at 23°C using a viscometer (Toki Sangyo VISCOMETER TV-25, 3° x R14 cone rotor, 1 rpm). The measurement was carried out in accordance with 7117-2. The amount of sample used for the measurement was 0.4 mL. The results are shown in Table 2.

[0199] [Evaluation of Curable Composition] A curable composition was prepared by mixing the (meth)acrylic copolymer and the polyoxyalkylene polymer (B). SAX220 (manufactured by Kaneka Corporation) was used as the polyoxyalkylene polymer (B). The mixing ratio of the two was 50:50 by weight.

[0200] (Evaluation of compatibility) The (meth)acrylic 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 state of compatibility was confirmed. The mixture was then left at room temperature for another week, after which the state of compatibility was also 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.

[0201] (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.

[0202] [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.

[0203] (Evaluation of mechanical properties) From the resulting cured sheet, a No. 3 dumbbell-shaped test piece, as specified in JIS K 7113, was punched out. The test piece was subjected to a tensile test to measure its 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 (manufactured by Shimadzu Corporation) was used for the measurement, and the measurement temperature was 23°C and the tensile speed was 200 mm / min.

[0204] [Table 2] [result] The (meth)acrylic copolymers (A) according to Examples 1 to 4 had significantly lower viscosities of the copolymers themselves and of the curable compositions compared to the (meth)acrylic copolymers according to Comparative Examples 1 and 2. This suggests that the viscosity of the copolymers themselves and the viscosity of the curable compositions can be reduced by randomly incorporating a predetermined proportion of repeating units derived from the (meth)acrylic acid ester monomer (α). Furthermore, the (meth)acrylic copolymers (A) according to Examples 1 to 4 had good compatibility with the polyoxyalkylene polymer (B) and exhibited good mechanical properties in the cured products.

[0205] [Production Examples 7 and 8] Copolymers were produced in the same manner as in Production Example 2, except that 3-(dimethoxymethylsilyl)propyl methacrylate was used as the alkoxysilyl group-containing monomer. Of these, the copolymer according to Production Example 7 contains units derived from the (meth)acrylic acid ester monomer (α), and therefore corresponds to the (meth)acrylic copolymer (A1). The copolymer according to Production Example 8 does not contain units derived from the (meth)acrylic acid ester monomer (α). The specific composition of the (meth)acrylic monomer mixture B is as shown in Table 3.

[0206] [Table 3] [Example 5, Comparative Example 3] The physical properties of the (meth)acrylic copolymers obtained in Production Examples 7 and 8 were evaluated. In addition, the physical properties of the cured products obtained by curing the (meth)acrylic copolymers were also evaluated (it should be noted that the cured products did not contain the polyoxyalkylene copolymer (B)). The results are shown in Table 4. The (meth)acrylic copolymer (A) evaluated in Example 5 was the one produced in Production Example 7. The (meth)acrylic copolymer evaluated in Comparative Example 3 was the one produced in Production Example 8.

[0207] [Table 4] [result] The viscosity of the (meth)acrylic copolymer (A) according to Example 5 was significantly reduced compared to the (meth)acrylic copolymer according to Comparative Example 3. This suggests that even if the type of monomer having an alkoxysilyl group is changed, the viscosity of the copolymer itself can be reduced by randomly incorporating a predetermined proportion of repeating units derived from the (meth)acrylic acid ester monomer (α). Furthermore, the (meth)acrylic copolymer (A) according to Example 5 also had good compatibility with the polyoxyalkylene polymer (B) and the mechanical properties of the cured product were also good. [Industrial Applicability]

[0208] The present invention can be used for sealing materials, adhesives, etc.

Claims

1. A curable composition comprising (A) an alkoxysilyl group-containing (meth)acrylic copolymer and (B) an alkoxysilyl group-containing polyoxyalkylene polymer, The (meth)acrylic copolymer (A) randomly contains 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 (meth)acrylic acid ester monomer (α) has an alkyl group ester-bonded to (meth)acrylic acid and having 1 to 5 carbon atoms (excluding carbon atoms contained in the alkoxy group), 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 (meth)acrylic copolymer (A) has, based on the weight of all repeating units, 45 to 70% by weight of repeating units derived from (meth)acrylic acid ester monomer (β), 0 to 25% by weight of a repeating unit derived from a (meth)acrylic acid ester monomer (γ), 15 to 25% 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 (meth)acrylic copolymer (A) has a number average molecular weight of 4,000 to 80,000, The polyoxyalkylene polymer (B) is The main chain is polypropylene oxide, The number average molecular weight is 5,000 to 50,000, the blending ratio of the (meth)acrylic copolymer (A) to the polyoxyalkylene polymer (B) is (80 / 20) to (20 / 80) by weight; Curable composition.

2. The curable composition according to claim 1, wherein the (meth)acrylic copolymer (A) has a molecular weight distribution (Mw / Mn) of 1.8 or less.

3. The molecule of the (meth)acrylic copolymer (A) is a (meth)acrylic copolymer (A1) containing an XY diblock structure having an X block and a Y block 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 (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 curable composition according to claim 1 or 2.

4. 4. The curable composition according to claim 3, wherein the repeating units derived from the (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 curable composition according to any one of claims 1 to 4, wherein the (meth)acrylic acid ester monomer (α) is one or more monomers selected from the group consisting of 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and isopropoxyethyl (meth)acrylate.

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 curable composition according to any one of claims 1 to 5.

7. The curable composition according to any one of claims 1 to 6, wherein the number of alkoxysilyl groups contained in the (meth)acrylic copolymer (A) is 1.0 to 10.0 on average in the entire molecule.

8. The curable composition according to any one of claims 1 to 7, which satisfies the following conditions (a) and / or (b): Condition (a): the viscosity of the (meth)acrylic copolymer (A) measured at 23°C is 200 Pa s or less; Condition (b): The viscosity of the curable composition measured at 23° C. is 55 Pa·s or less.

9. In the (meth)acrylic copolymer (A), repeating units derived from a (meth)acrylic acid ester monomer having no silyl group are randomly distributed, Here, when there are two or more types of repeating units derived from a (meth)acrylic acid ester monomer having no alkoxysilyl group, the repeating units derived from any of the monomers are randomly distributed. The curable composition according to any one of claims 1 to 8.

10. A cured product obtained by curing the curable composition according to any one of claims 1 to 9.

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

12. An adhesive comprising the curable composition according to any one of claims 1 to 9 or the cured product according to claim 10.

13. A method for producing the curable composition according to any one of claims 1 to 9, comprising: a step of polymerizing the (meth)acrylic copolymer (A) by a living polymerization method; a step of mixing the (meth)acrylic copolymer (A) and the polyoxyalkylene polymer (B); A manufacturing method comprising:

14. The method for producing a curable composition according to claim 13, wherein the step of polymerizing the (meth)acrylic copolymer (A) by a living polymerization method includes a step of polymerizing the (meth)acrylic copolymer (A) by a living radical polymerization method.

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