WO2021157584A1

WO2021157584A1 - Curable composition and cured product

Info

Publication number: WO2021157584A1
Application number: PCT/JP2021/003810
Authority: WO
Inventors: 平林　和彦; 岡井　次郎; 太亮佐々木; 健一吉橋
Original assignee: 株式会社カネカ
Priority date: 2020-02-04
Filing date: 2021-02-03
Publication date: 2021-08-12
Also published as: JPWO2021157584A1

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

Curable composition and cured product

The present invention relates to a curable composition and a cured product.

A polymer molecule having an alkoxysilyl group forms a siloxane bond with another polymer molecule by hydrolyzing the alkoxysilyl group. It is known that a rubber-like cured product can be obtained by this cross-linking reaction. Taking advantage of this feature, polymers having an alkoxysilyl group are used in a wide range of applications such as sealants, adhesives and paints.

An example of such a polymer is a polyoxyalkylene polymer having an alkoxysilyl group. The 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, in the polyoxyalkylene polymer, the hydrogen atom bonded to the tertiary carbon is easily oxidized unless an antioxidant is used. Therefore, there is a problem that the weather resistance of the curable composition is deteriorated.

In order to solve this problem, a curable composition in which a polyoxyalkylene-based polymer having an alkoxysilyl group is mixed with a (meth) acrylic copolymer having an alkoxysilyl group has been proposed. For example, Patent Document 1 describes a vinyl polymer (A) having an alkoxysilyl group, a polyoxyalkylene compound (B) having an alkoxysilyl group at the terminal, and a polypropylene glycol (C1) having a specific molecular weight or an alkoxysilyl group. A sealant composition containing a vinyl polymer (C2) that does not have it is disclosed. Patent Document 2 discloses a sealing material composition containing (A) an oxyalkylene polymer having an alkoxysilyl group and (B) a specific vinyl polymer having a crosslinkable functional group. Patent Document 3 includes 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. A curable resin composition comprising the above is disclosed. Patent Document 4 describes 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 end of the polymer. The thing is disclosed.

Japanese Patent Publication "Japanese Patent Laid-Open No. 2004-018748" International Publication No. 2008/059872 Pamphlet Japanese Patent Publication "Japanese Patent Laid-Open No. 2014-118502" International Publication No. 2005/095492 Pamphlet

The compositions disclosed in Patent Documents 1 to 4 had room for improvement in terms of viscosity. That is, there is room for improving workability by further reducing the viscosity of these compositions.

One aspect of the present invention is to provide a curable composition having a reduced viscosity.

In order to solve the above problems, the curable composition according to one aspect of the present invention may be used.
A curable composition comprising a (meth) acrylic copolymer (A) having an alkoxysilyl group and a polyoxyalkylene-based polymer (B) having an alkoxysilyl group.
The (meth) acrylic copolymer (A) randomly contains a repeating unit derived from the (meth) acrylic acid ester monomer (α).
The (meth) acrylic acid ester monomer (α) has an alkyl group ester-bonded to (meth) acrylic acid, and the alkyl group has an alkoxy group having 1 to 5 carbon atoms. And
The repeating unit derived from the (meth) acrylic acid ester monomer (α) is contained in an amount of 5 to 20% by weight based on the weight of all the repeating units contained in the (meth) acrylic copolymer (A). It has been.

According to one aspect of the present invention, it is possible to provide a curable composition having a reduced viscosity.

Hereinafter, an example of the embodiment of the present invention will be described in detail, but the present invention is not limited thereto.

Unless otherwise specified in the present specification, "AB" representing a numerical range means "A or more, B or less". As used herein, the term "(meth) acrylic" means "acrylic" and / or "methacryl".

[1. (Meta) acrylic copolymer having an alkoxysilyl group (A)]
The curable composition according to one aspect of the present invention contains a (meth) acrylic copolymer (A) having an alkoxysilyl group. This (meth) acrylic copolymer (A) randomly contains a repeating unit derived from the (meth) acrylic acid ester monomer (α). The repeating unit derived from the (meth) acrylic acid ester monomer (α) is contained in an amount of 5 to 20% by weight based on the weight of all the repeating units contained in the (meth) acrylic copolymer (A). (This value has a critical significance). Here, the (meth) acrylic acid ester monomer (α) has an alkyl group ester-bonded to (meth) acrylic acid, and the alkyl group is an alkoxy group having 1 to 5 carbon atoms. It is a monomer having. Preferably, the alkyl group ester-bonded with acrylic acid has 1 to 5 carbon atoms.

The lower limit of the content of the repeating unit derived from the (meth) acrylic acid ester monomer (α) is 6 weights based on the weight of all the repeating units contained in the (meth) acrylic copolymer (A). % Or more, 7% by weight or more, 8% by weight or more, 9% by weight or more, or 10% by weight or more is more preferable. The upper limit of the content of the repeating unit derived from the (meth) acrylic acid ester monomer (α) is 19 weight based on the weight of all the repeating units contained in the (meth) acrylic copolymer (A). More preferably, it is less than or equal to% or 18% by weight or less.

If the repeating unit derived from the (meth) acrylic acid ester monomer (α) is randomly contained and the content is within the above range, the viscosity of the (meth) acrylic copolymer (A) itself and ( The viscosity of the curable composition containing the meta) 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, preferably 150 Pa · s or less, and more preferably 130 Pa · s or less. Viscosity can be measured with a suitable viscometer. The viscosity of the curable composition measured at 23 ° C. is preferably 55 Pa · s or less, more preferably 53 Pa · s or less.

If the content of the repeating unit derived from the (meth) acrylic acid ester monomer (α) is within the above range, the (meth) acrylic copolymer (A) and the polyoxyalkylene-based polymer having an alkoxysilyl group (meth) The compatibility with B) is high. Therefore, a curable composition and a cured product having good properties can be obtained.

When the repeating unit derived from the (meth) acrylic acid ester monomer (α) is not randomly contained, the viscosity of the (meth) acrylic copolymer (A) itself or the polyoxyalkylene polymer (B) The compatibility with and may be adversely affected. It is considered that this adverse effect is caused by the difference in polarity between the (meth) acrylic acid ester monomer (α) and other monomers. As an example of a polymer that does not randomly contain a repeating unit derived from the (meth) acrylic acid ester monomer (α), the repeating unit derived from the (meth) acrylic acid ester monomer (α) is the main component of the main chain. Examples thereof include a polymer and a polymer having a repeating unit derived from a (meth) acrylic acid ester monomer (α) in a block.

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. When the number average molecular weight is 4,000 or more, the characteristics of the (meth) acrylic copolymer (A) can be fully exhibited. When 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).

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, still more preferably 1.5 or less, and particularly preferably 1. It is 4 or less, and most preferably 1.3 or less. If the molecular weight distribution is too large, the viscosity of the curable composition tends to increase, and workability tends to decrease.

The weight average molecular weight and the number average molecular weight can be measured by, for example, gel permeation chromatography (GPC). Chloroform can be used as the mobile phase and polystyrene gel column can be used as the stationary phase for GPC measurement. Moreover, these molecular weights can be calculated in terms of polystyrene.

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

In one embodiment, in the (meth) acrylic copolymer (A), an alkoxysilyl group is distributed only at at least one end of the molecular chain. Therefore, the molecule as a whole has one or two alkoxysilyl groups. Such a copolymer is, for example, [3.1. ] It can be manufactured by the manufacturing method described in the section.

In one embodiment, the (meth) acrylic copolymer (A) has an alkoxysilyl group distributed in the vicinity of at least one end of the molecular chain. Therefore, the molecule as a whole may have one or more alkoxysilyl groups and may have more than two alkoxysilyl groups. Such a copolymer is, for example, [3.2. ] Can be produced by the production method described in the section (according to this production method, the (meth) acrylic copolymer (A1) described later can be obtained).

The number of alkoxysilyl groups introduced into the (meth) acrylic copolymer (A) is 1.0 or more or more than 1.0 on average as a whole 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, and even more preferably 6.0 or less. 4.0 or less is particularly preferable. When the number of alkoxysilyl groups is in the above range, the physical properties of the curable composition and the cured product using the (meth) acrylic copolymer (A) are good. Further, the (meth) acrylic copolymer (A) preferably has an alkoxysilyl group at at least one end (or end region) of the molecular chain, and alkoxy is provided at both ends (or end regions). It preferably has a silyl group.

[1.1. (Meta) acrylic acid ester monomer]
The (meth) acrylic copolymer (A) according to the embodiment of the present invention contains a structural unit derived from the (meth) acrylic acid ester monomer in the main chain. The (meth) acrylic acid ester monomer constituting the main chain is not particularly limited as long as the above requirements are satisfied. 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.

Examples of the type of such (meth) acrylic acid ester monomer include the following.
(Meta) Acrylic Acid Ester Monomer (α): Has an alkyl group ester-bonded to (meth) acrylic acid, and the alkyl group has an alkoxy group having 1 to 5 carbon atoms. Monomer. The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 2. The number of carbon atoms of the alkoxy group is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.
(Meta) Acrylic Acid Ester Monomer (β): A monomer having 1 to 5 carbon atoms in an alkyl group ester-bonded to (meth) acrylic acid.
(Meta) Acrylic Acid Ester Monomer (γ): A monomer having 6 to 15 carbon atoms in an alkyl group ester-bonded to (meth) acrylic acid.
(Meta) Acrylic Acid Ester Monomer (δ): A monomer having 16 to 25 carbon atoms in an alkyl group ester-bonded to (meth) acrylic acid.

As described above, the content of the repeating unit derived from the (meth) acrylic acid ester monomer (α) is 5 based on the weight of all the repeating units contained in the (meth) acrylic copolymer (A). It is about 20% by weight, preferably 10 to 20% by weight. The content of the repeating unit derived from the (meth) acrylic acid ester monomer (β) is 45 to 70% by weight based on the weight of all the repeating units contained in the (meth) acrylic copolymer (A). Is preferable, and 50 to 70% by weight is more preferable. The content of the repeating unit derived from the (meth) acrylic acid ester monomer (γ) is 0 to 25% by weight based on the weight of all the repeating units contained in the (meth) acrylic copolymer (A). Is preferable, and 10 to 25% by weight is more preferable. The content of the repeating unit derived from the (meth) acrylic acid ester monomer (δ) is 15 to 25% by weight based on the weight of all the repeating units contained in the (meth) acrylic copolymer (A). Is preferable, and 15 to 20% by weight is more preferable. By containing each (meth) acrylic acid ester monomer with such a composition, the (meth) acrylic copolymer (A) can obtain good workability, mechanical properties and weather resistance.

If 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-based polymer (B) is high. It can be secured sufficiently. When the content of the repeating unit derived from the (meth) acrylic acid ester monomer (γ) is 10% by weight or more, it is possible to prevent an increase in viscosity at a low temperature and prevent a decrease in workability. Further, if the content of the repeating unit derived from the (meth) acrylic acid ester monomer (γ) is 25% by weight or less, the (meth) acrylic copolymer (A) and the polyoxyalkylene-based polymer (B) are combined. Sufficient compatibility can be ensured. If 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-based polymer (B) Can be sufficiently secured. Further, when the content of the repeating unit derived from the (meth) acrylic acid ester monomer (δ) is 25% by weight or less, it is possible to prevent an increase in viscosity at a low temperature and prevent a decrease in workability.

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) acrylic acid, 2-ethoxyethyl (meth) acrylic acid, 2-butoxyethyl (meth) acrylic acid, and (meth) acrylic acid. Isopropoxyethyl can be mentioned. Examples of (meth) acrylic acid ester monomer (β) are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic. Examples thereof include isobutyl acid and tert-butyl (meth) acrylate. Examples of (meth) acrylic acid ester monomer (γ) are n-hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, (meth). Nonyl acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate can be mentioned. Examples of the (meth) acrylic acid ester monomer (δ) include pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, and icosyl (meth) acrylate. (Meta) Docosyl acrylate can be mentioned.

Among the above-mentioned monomers, 2-methoxyethyl acrylate is preferable as the (meth) acrylic acid ester monomer (α). As the (meth) acrylate monomer (β), butyl acrylate is preferable. As the (meth) acrylic acid ester monomer (γ), 2-ethylhexyl acrylate and dodecyl acrylate are preferable. As the (meth) acrylic acid ester monomer (δ), octadecyl acrylate is preferable. The (meth) acrylic copolymer (A) produced by selecting these monomers has viscosity, compatibility with the polyoxyalkylene polymer (B), weather resistance, mechanical properties, and durability. It can be achieved at a high level and in a well-balanced manner.

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

(A) A monomer having 1 to 5 carbon atoms in an alkyl group ester-bonded with (meth) acrylic acid. However, the "carbon number of the alkyl group" does not include the carbon contained in the alkoxy group of the alkyl group.

(B) One or more selected from the group consisting of 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and isopropoxyethyl (meth) acrylate. Monomer.

The repeating unit derived from the (meth) acrylic acid ester monomer contained in the (meth) acrylic copolymer (A) is 70% by weight based on all the repeating units contained in the polymer (A). The above is preferable, and 90% or more by weight is more preferable. When the content of the repeating unit derived from the (meth) acrylic acid ester monomer is 70% or more, the produced (meth) acrylic copolymer (A) is in phase with the polyoxyalkylene-based polymer (B). Sufficient solubility can be ensured, and good weather resistance, mechanical properties and durability can be obtained.

[1.2. (Meta) acrylic acid ester monomer 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).

In the formula, R ¹ and R ² are independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a methoxymethyl group, or (R') ₃ It is a triorganosyloxy group represented by SiO− (at this time, R'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R'existing may be the same or different. May be good). When two or more R ¹ or R ² are present, the 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 Ys are present, the Ys 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. Moreover, the relationship of a + mb ≧ 1 is satisfied.

In general, the alkoxy group has higher reactivity when it has a smaller number of carbon atoms. That is, the reactivity decreases in the order of methoxy group, ethoxy group, propoxy group, and so on. Therefore, an alkoxy group can be appropriately selected depending on the production method and application of the (meth) acrylic copolymer (A).

The specific structure of the (meth) acrylic acid ester monomer having an alkoxysilyl group is not particularly limited. As an example, a monomer represented by the following general formula (2) can be mentioned.
H ₂ C = CR ³ C (= O) O- (CH ₂ ) _m- SiR ⁴ _n (OR ⁵ ) _3-n (2).

In the formula, R ³ is a hydrogen or methyl group. R ⁴ and R ⁵ are one or more selected from the group consisting of hydrogen, methyl group and ethyl group. When there are a plurality of ^{R 4} and / or R ⁵ ^{, the R 4} and / or R ⁵ are independently selected. m is an integer from 0 to 10. n is an integer of 0 to 2.

Specific examples of the (meth) acrylic acid ester monomer having an alkoxysilyl group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxy. Examples thereof include propyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane.

[2. (Meta) 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 as a (meth) acrylic copolymer (A1) in the present specification. The structure of the entire molecule 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 tetrapod structure. ..

Here, the "XYX triblock structure" means the "ABA triblock structure" generally referred to by those skilled in the art. The ratio of XY in the XY diblock structure and the XYX triblock structure is preferably (5/95) to (60/40), more preferably (15/85) to (40/60).

In one embodiment, the molecule of the (meth) acrylic copolymer (A1) has an XY diblock structure. In a molecule having an 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 100%). Here, the X block is a block on the side where a relatively large number of alkoxysilyl groups are distributed.

In one embodiment, the molecule of the (meth) acrylic copolymer (A1) has an XYX triblock structure. In a molecule having an XYX triblock structure, the X block can be a region of 40% or less, 30% or less, or 25% or less from the end of the molecule (all units contained in the molecule are 100%). Here, the X block is a block located at both ends of the molecule.

The (meth) acrylic copolymer (A1) is a repeating unit derived from the (meth) acrylic acid ester monomer (α), and all the repeating units contained in the (meth) acrylic copolymer (A1). It is randomly included in an amount of 5 to 20% by weight based on the weight. Here, the repeating unit derived from the (meth) acrylic acid ester monomer (α) may be different between the X block and the Y block. That is, (i) (meth) acrylic acid ester monomer (α) -derived repeating units are randomly distributed throughout the molecule, and (ii) the content of the repeating units is 5 to 20% by weight (preferably 10). If it is ~ 20% by weight), it is included in the category of the (meth) acrylic copolymer (A1).

In one embodiment, the (meth) acrylic copolymer (A1) has a repeating unit derived from a (meth) acrylic acid ester monomer having an alkoxysilyl group. The repeating unit derived from the (meth) acrylic acid ester monomer having an alkoxysilyl group is relatively abundantly contained in the X block. Specifically, the number of repeating units derived from the (meth) acrylic acid 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 the (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 the repeating units contained in the Y block. be. Therefore, the repeating unit derived from the (meth) acrylic acid ester monomer having an alkoxysilyl group is localized at the end (one end or both ends) in the (meth) acrylic copolymer (A1).

The number of repeating units derived from the (meth) acrylic acid ester monomer having an alkoxysilyl group contained in the X block is preferably 1.5 or more on average, and more preferably 1.7 or more. Similarly, the repeating unit derived from the (meth) acrylic acid ester monomer having an alkoxysilyl group contained in the X block is preferably more than 3% by weight based on the weight of all the repeating units contained in the X block. , 4.5% by weight or more is more preferable, and 5% by weight or more is further preferable. The upper limit of the repeating unit derived from the (meth) acrylic acid ester monomer having an alkoxysilyl group contained in the Y block is 2% by weight or less based on the weight of all the repeating units contained in the Y block. Preferably, it is 1% by weight or less, more preferably. The lower limit of the repeating unit derived from the (meth) acrylic acid ester monomer having an alkoxysilyl group contained in the Y block is more than 0% by weight based on the weight of all the repeating units contained in the Y block. It is preferable, and 0% by weight or more is more preferable.

In one embodiment, the number of alkoxysilyl groups introduced into the (meth) acrylic copolymer (A1) differs between the X block and the Y block, and is specifically as described above. When the (meth) acrylic copolymer (A1) has an XY diblock structure, the number of molecules as a whole is 1 or more on average, preferably 1.1 or more, and more preferably 1.2 or more. The alkoxysilyl group of is introduced. When the (meth) acrylic copolymer (A1) has an XYX triblock structure or an XYXY tetrapod structure, the number of molecules as a whole is 2 or more, preferably 2.2 or more, more preferably 2. Four or more alkoxysilyl groups have been introduced. 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, and even more preferably 6.0 or less. 4.0 or less is particularly preferable. When the number of alkoxysilyl groups is in the above range, the physical properties of the curable composition and the cured product using the (meth) acrylic copolymer (A1) are good.

[3. Method for Producing (Meta) Acrylic Copolymer (A) and (Meta) Acrylic Copolymer (A1)]
The polymerization method of the (meth) acrylic copolymer (A) is not particularly limited, and a known polymerization method can be used (radical polymerization method, cationic polymerization method, anion polymerization method, etc.). Above all, the living polymerization method is preferable because a functional group can be introduced into the terminal of the polymer molecule and an XY block polymer or an XYX block polymer can be synthesized. Examples of the living radical polymerization method include a living radical polymerization method, a living cationic polymerization method, and a living anion polymerization method. Among them, the living radical polymerization method is suitable for polymerizing an acrylic acid ester monomer. Examples of the living radical polymerization method 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; see JPSChem 2007, 45, 1607))
-Reversible Chain Transfer Catalyzed Polymerization; RTCP ("Living Radical Polymerization Controlled by Organocatalysis", "Polymer Papers" 68, 223-231 (2011);
(Refer to Japanese Patent Application Laid-Open No. 2014-111798))
-Reversible addition-Cleavage chain transfer polymerization (RAFT polymerization)
・ Nitroxy radical method (NMP method)
-Polymerization method using organic tellurium compounds (TERP) -Polymerization method using organic antimony compounds (SBRP method)
-Polymerization method using organic bismuth compounds (BIRP)
-Iodine transfer polymerization method.

[3.1. First form of manufacturing method]
In one example, the (meth) acrylic copolymer (A) is produced by the method described in JP-A-2007-302479. Among them, a method of adding a hydrosilane compound having an alkoxysilyl group to a (meth) acrylic polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst is preferable in that control is easier.

In this method, the alkoxysilyl group is introduced into the (meth) acrylic polymer as follows.
1. 1. The (meth) acrylic acid ester-based monomer is subjected to living radical polymerization to obtain a (meth) acrylic acid-based polymer.
The (meth) acrylic polymer obtained in 2.1 is reacted with a compound having at least two alkenyl groups having low polymerizable properties (diene compound) to obtain a vinyl polymer having at least one alkenyl group.
A hydrosilane compound having an alkoxysilyl group is added to the vinyl polymer obtained in 3.2 in the presence of a hydrosilylation catalyst.

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

The hydrosilane compound having an alkoxysilyl group is not particularly limited. As a typical example, the compound represented by the general formula (3) is exemplified.
H- [Si (R ⁶ ) _2-b (Y) _b O] _m ^{-Si (R 7} ) _3-a (Y) _a (3).

In the general formula (3), R ⁶ and R ⁷ are independently alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, methoxymethyl groups, or groups. ^(R ₈₎ in selected from triorganosiloxy group represented by 3 SiO- (wherein, ^{R 8} ^{R 8} is present .3 or a monovalent hydrocarbon group having 1 to 20 carbon atoms, with the same May be present or different). When two or more R ⁶ or R ⁷ are present, they may be the same or different. Y represents an alkoxy group having 1 to 20 carbon atoms. When there are two or more Ys, the Ys may be the same or different. a represents 0, 1, 2 or 3. b represents 0, 1, or 2. m is an integer from 0 to 19. However, it is satisfied that a + mb ≧ 1.

Among these hydrosilane compounds, the compound represented by the following general formula (4) is preferable from the viewpoint of easy availability.
H-Si (R ⁶ ) _3-a (Y) _a (4).

In the general formula (4), ^{R 6} and Y are as described above. a is an integer of 1 to 3.

When adding a hydrosilane compound having an alkoxysilyl group to an alkenyl group, a transition metal catalyst is usually used. Examples of transition metal catalysts include platinum-based catalysts. Platinum alone; Platinum solid dispersed in a carrier (alumina, silica, carbon black, etc.); Platinum chloride acid; Complex of platinum chloride acid with alcohol, aldehyde, ketone, etc .; Platinum-olefin complex; Platinum (0)- Examples thereof include a divinyltetramethyldisiloxane complex. Examples of catalysts other than platinum-based catalysts include RhCl (PPh ₃ ) ₃ , RhCl ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ · H ₂ O, NiCl ₂ , and TiCl ₄ .

[3.2. Second form of 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 a block copolymer is produced by this production method, the obtained (meth) acrylic copolymer (A) is a (meth) acrylic copolymer (A1). The (meth) acrylic copolymer (A1) obtained by this production method is preferable in that the viscosity of the polymer is lowered.

In the following description, "containing 0% by weight of the (meth) acrylic acid ester monomer having an alkoxysilyl group" means "not containing the (meth) acrylic acid ester monomer having an alkoxysilyl group". ..

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

(Step 2a) A step of adding a (meth) acrylic acid ester monomer mixture containing 0 to 3% by weight of a (meth) acrylic acid ester monomer having an alkoxysilyl group to the reaction system after the first step and polymerizing.

(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 by a living polymerization initiator.

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

Hereinafter, each step will be described more specifically for each structure of the (meth) acrylic copolymer (A1).

(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 by the steps 1b and 2b. At this time, the first step 1a and the second step 2b form an X block containing a relatively large amount of alkoxysilyl groups. On the other hand, the steps 2a and 1b form a Y block containing a relatively small amount of alkoxysilyl groups.

In the first step, a (meth) acrylic acid ester monomer having an alkoxysilyl group is polymerized by a living polymerization initiator. As the living polymerization initiator, for example, an initiator having one halogen group in the molecule can be used. The amount of the (meth) acrylic acid ester monomer having an alkoxysilyl group can be 1-10 molar equivalents relative to 1 molar equivalent of the initiator. Further, if necessary, 1 to 100 molar equivalents of (meth) acrylic acid ester monomer having no alkoxysilyl group may 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.

In the second step, a (meth) acrylic acid ester monomer having no alkoxysilyl group is added to the reaction system after the first step and polymerized. The input amount of the (meth) acrylic acid ester monomer having no alkoxysilyl group can be 2 to 600 molar equivalents with respect to 1 molar equivalent of the polymer obtained in the first step a. 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 the second a step accounts for 0 to 3% by weight of the monomer mixture added to the reaction system in the second a step.

In the first step, the (meth) acrylic acid ester monomer having no alkoxysilyl group is polymerized by the living polymerization initiator. As the living polymerization initiator, the same one as in the first step can be used. The amount of the (meth) acrylic acid ester monomer having no alkoxysilyl group can be 2 to 600 molar equivalents relative to 1 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 the first b step accounts for 0 to 3% by weight of the monomer mixture added to the reaction system in the first b step.

In the second b step, a (meth) acrylic acid ester monomer having an alkoxysilyl group is added to the reaction system after the first b step and polymerized. The amount of the (meth) acrylic acid ester monomer having an alkoxysilyl group can be 1 to 10 molar equivalents with respect to 1 molar equivalent of the polymer obtained in the first b step. Further, if necessary, 1 to 100 molar equivalents of (meth) acrylic acid ester monomer having no alkoxysilyl group may 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% by weight of the monomer mixture added to the reaction system in step 2b.

In the above step, as an example of "(meth) acrylic acid ester monomer having no alkoxysilyl group", [1.1. ] The (meth) acrylic acid ester monomer (α), (β), (γ), and (δ) described in the section can be mentioned. This also applies to the following description.

(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 undergoing an additional polymerization step (a) after the above-mentioned first step 1a and second a step. At this time, the first step a and the additional polymerization step (a) form an X block containing a relatively large amount of alkoxysilyl groups. Regarding this production method, the description of JP-A-2018-162394 can be referred to.

In the additional polymerization step (a), a (meth) acrylic acid ester monomer having an alkoxysilyl group is added to the reaction system after the second a step to polymerize. The input amount of the (meth) acrylic acid ester monomer having an alkoxysilyl group can be 1 to 10 molar equivalents with respect to 1 molar equivalent of the polymer obtained in the second a step. Further, if necessary, 1 to 100 molar equivalents of (meth) acrylic acid ester monomer having no alkoxysilyl group may 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% by weight of the monomer mixture added to the reaction system in the step. ing.

The (meth) acrylic acid copolymer (A1), which is a molecule having a YXY triblock structure, can be produced by undergoing an additional polymerization step (b) after the above-mentioned first step and second b step. At this time, the second b step forms an X block containing a relatively large amount of alkoxysilyl groups.

In the additional polymerization step (b), a (meth) acrylic acid ester monomer having no alkoxysilyl group is added to the reaction system after the second b step to polymerize. The input amount of the (meth) acrylic acid ester monomer having no alkoxysilyl group can be 2 to 600 molar equivalents with respect to 1 molar equivalent of the polymer obtained in the second b step. 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% by weight of the monomer mixture added to the reaction system in the step. ..

(When the copolymer has 4 or more blocks)
By appropriately combining the above-mentioned first step, second a step, first b step, second b step and additional polymerization step, the (meth) acrylic copolymer (A1) having four or more blocks can be produced. For example, a (meth) acrylic copolymer (A1) having an XYXY tetrapod structure can be produced.

In the above-mentioned production method, the (meth) acrylic acid ester monomer having no alkoxysilyl group added as the (meth) acrylic acid ester monomer having no alkoxysilyl group is (based on the weight of all the monomers). Meta) Acrylic ester monomer (α) is contained in an amount of 5 to 20% by weight.

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

[3.3. General matters concerning the production of (meth) acrylic polymers by living radical polymerization]
Any of the production methods exemplified above can be suitably carried out by adopting the living radical polymerization method. Among them, atom transfer radical polymerization, one-electron transfer polymerization, and reversible transfer catalyst polymerization are preferable.

As a more preferable production method, there is a living radical polymerization method of a vinyl-based monomer using ATRP or SET-LRP and using a transition metal or a transition metal complex (composed of a transition metal compound and a ligand) as a catalyst. be able to. Further, RTCP which does not use transition metals as a catalyst can be mentioned.

At present, there are two interpretations of the mechanism of living radical polymerization catalyzed by a transition metal complex: ATRP and SET-LRP. Interpreted based on ATRP, living radical polymerization consists of the equilibrium of the following two reactions (as an example, the case of using a copper complex will be described).

(A) The monovalent copper complex abstracts the halogen at the end of the polymer to generate radicals, and becomes a divalent copper complex.

(B) The divalent copper complex becomes a monovalent copper complex by adding a halogen to the radical at the polymerization terminal.

On the other hand, when interpreted based on SET LRP, living radical polymerization consists of the equilibrium of the following three reactions (as an example, the case of using a copper complex will be described).

(A) The zero-valent metallic copper or copper complex abstracts the halogen at the end of the polymer to generate radicals, and becomes a divalent copper complex.

(B) The divalent copper complex becomes a zero-valent copper complex by adding a halogen to the radical at the polymerization terminal.

(C) The monovalent copper complex is disproportionated into 0-valent and divalent copper complexes.

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 a transition metal compound and a ligand as a catalyst is included in the scope of the present invention.

In addition, Activators Regenerated by Electron Transfer: ARGET, which is an improved synthesis method of ATRP, has also been reported (Macromolecules. 2006, 39, 39). In this method, the high oxidation transition metal complex that causes the delay or termination of polymerization is reduced by using a reducing agent, so that the polymerization reaction can be rapidly advanced to a high reaction rate even under low catalytic conditions with few transition metal complexes. Can be made to. This ARGET can also be adopted in the present invention.

(Specification of the structure of the (meth) acrylic copolymer (A) by the manufacturing method)
In one embodiment, the (meth) acrylic copolymer (A) is defined as the copolymer obtained by the above-mentioned production method. That is, the (meth) acrylic copolymer (A) can be a copolymer obtained by a production method including steps 1a and 2a, or steps 1b and 2b.

In the above-mentioned production method, a (meth) acrylic acid ester monomer having an alkoxysilyl group is introduced by copolymerization. Therefore, it is not practical to specifically specify the position of the alkoxysilyl group in the obtained copolymer molecule.

Further, in the above-mentioned production method, when a (meth) acrylic acid ester monomer having no alkoxysilyl group of the same type is added to the reaction system in the first step and the second step (or the first step and the second b step). The main chain structure of the obtained copolymer is the same for both the X block and the Y block. In such a copolymer, it is practically impractical to specifically specify the boundary between the X block and the Y block.

Due to such circumstances, the (meth) acrylic copolymer (A) must be defined not as a specific structure of the copolymer molecule but as a copolymer obtained by the above-mentioned production method. May not be obtained.

Hereinafter, various agents that can be used in the production method according to the embodiment of the present invention will be individually described. Any of these agents may be used alone or in combination of two or more. Further, these agents themselves may be put into the polymerization system, or these agents may be produced in the polymerization system.

(A. Initiator)
As the initiator, a radical initiator having one halogen group in the molecule can be used. Examples of such initiators are ethyl 2-bromoisobutyrate, ethyl 2-bromobutyrate (also referred to as ethyl α-bromobutyrate), ethyl bromoacetate, methyl bromoacetate, (1-bromoethyl) benzene, allyl bromide, 2 -Methyl bromopropionate, methyl chloroacetate, methyl 2-chloropropionate, (1-chloroethyl) benzene can be mentioned.

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

Further, as the initiator, an initiator having an alkoxysilyl group may be used. Alternatively, an alkoxysilyl group may be introduced into the initiator before or after the polymerization reaction. Also by such a method, the (meth) acrylic copolymer (A) having an alkoxysilyl group at least at the terminal portion can be produced.

(B. Polymerization catalyst)
Regardless of whether a reducing agent is used or not, in the ATRP system, a metal complex having a group 7, group 8, group 9, group 10 or group 11 element in the periodic table as a central metal can be used. .. Among them, a metal complex having monovalent copper, divalent ruthenium, and divalent iron as the central metal is particularly preferable.

Specific examples include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous acetate, and cuprous perchlorate. When a copper compound is used as a polymerization catalyst, it is preferable to add an amine ligand to the polymerization system in order to enhance the catalytic activity. A triphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When this catalyst is used, it is preferable to add an aluminum compound (trialkoxyaluminum or the like) to the polymerization system in order to enhance the catalytic activity. Further, a triphenylphosphine complex of divalent iron chloride (FeCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst.

Among the above, the copper catalyst is preferable because it is inexpensive. It is more preferable to use a polydentate amine and a copper catalyst in combination in order to increase the catalytic activity and increase the productivity.

(C. Polydentate amine)
Examples of polydentate amines that can be used as ligands include:
Bidentate polydentate amines: 2,2-bipyridine, 4,4'-di- (5-nonyl) -2,2'-bipyridine, N- (n-propyl) pyridylmethaneimine, N- ( n-octyl) pyridylmethaneimine tridentate polydentate amines: N, N, N', N'', N''-pentamethyldiethylenetriamine, N-propyl-N, N-di (2-pyridylmethyl) ) Amine / tetradentate polydentate amines: hexamethyltris (2-aminoethyl) amine (Me ₆ TREN), 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 ((pyridine-2-yl) methyl) ethane-1,2-diamine, tris [ (2-Pyridyl) Methyl] Amine, 2,5,8,12-Tetramethyl-2,5,8,12-Tetraazatetradecane / pentadentate polydentate amine: N, N, N', N'',N''',N'''',N''''-Heptamethyltetraethylenetetramine / hexadentate polydentate amine: N, N, N', N'-tetrakis (2-pyridylmethyl) ) Ethylenediamine / polyamine: Polyethyleneimine.

(D. Base)
Bases may be added to the polymerization system to neutralize the acids present or generated in the polymerization system and prevent acid accumulation. Examples of bases include:
-Monoamine: A monoamine refers to a compound having one site per molecule that acts as a base. Examples of monoamines include primary amines (methylamine, aniline, lysine, etc.), secondary amines (dimethylamine, piperidine, etc.), tertiary amines (trimethylamine, triethylamine, etc.), aromatic amines (pyridine, pyrrol, etc.), Ammonia can be mentioned.
-Polyamines: Examples of polyamines include diamines (ethylenediamine, tetramethylethylenediamine, etc.), triamines (diethylenetriamine, pentamethyldiethylenetriamine, etc.), tetramines (triethylenetetramine, hexamethyltriethylenetetramine, hexamethylenetetramine, etc.), polyethyleneimine, etc. Can be mentioned.
-Inorganic base: An inorganic base refers to a simple substance or a compound of an element belonging to Group 1 and Group 2 of the periodic table. Examples of elemental elements belonging to Group 1 and Group 2 of the periodic table include lithium, sodium, and calcium. Examples of compounds of elements belonging to Group 1 and Group 2 of the Periodic Table are sodium methoxydo, potassium ethoxydo, methyllithium, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydrogencarbonate, ammonium hydrogencarbonate, phosphoric acid. Examples include trisodium, disodium hydrogen phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, sodium acetate, potassium acetate, sodium oxalate, potassium oxalate, phenoxysodium, phenoxypotassium, sodium ascorbate, and potassium ascorbate. ..

(E. Reducing agent)
In living radical polymerization using a copper complex as a catalyst, it is known that the polymerization activity is improved by using a reducing agent in combination (ARGET ATRP). In ARGET ATRP, it is considered that the polymerization activity is improved by reducing and reducing the highly oxidized transition metal complex (generated by coupling of radicals or the like) that causes the delay or termination of the polymerization reaction. This makes it possible to reduce the transition metal catalyst, which normally requires hundreds to thousands of ppm, to tens to hundreds of ppm. In the production method according to the embodiment of the present invention, a reducing agent can be used to have a reaction mechanism similar to that of ARGET ATRP. Examples of reducing agents include:

(Reducing agent that does not generate acid when reducing copper complex)
-Metal: Examples of metals include alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (berylium, magnesium, calcium, barium, etc.), typical metals (aluminum, zinc, etc.), transition metals (copper, nickel, etc.). , Luthenium, iron, etc.). These metals can also be used in the form of alloys with mercury (amalgam).
-Metal compounds: Examples of metal compounds include metal salts and metal complexes. Examples of ligands coordinated to metal complexes include carbon monoxide, olefins, nitrogen-containing compounds, oxygen-containing compounds, phosphorus-containing compounds, and sulfur-containing compounds. More specific examples include metal and ammonia / amine compounds, titanium trichloride, titanium alkoxide, chromium chloride, chromium sulfate, chromium acetate, iron chloride, copper chloride, copper bromide, tin chloride, zinc acetate, water. Zinc oxide, carbonyl complex (Ni (CO) ₄ , Co ₂ CO _8, etc.), olefin complex ([Ni (cod) ₂ ], [RuCl ₂ (cod)], [PtCl ₂ (cod)], etc .; cod is cyclo (Representing octadiene), phosphine complex ([RhCl (P (C ₆ H ₅ ) ₃ ) ₃ ], [RuCl ₂ (P (C ₆ H ₅ ) ₃ ) ₂ ], [PtCl ₂ (P (C ₆ H _{5) 5)} ) ₃ ) ₂ ] etc.).
-Organotin compounds: Specific examples thereof include tin octylate, tin 2-ethylhexylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimalate, and dioctyltinthiocarboxylate.
-Phosphorus or phosphorus compound: Specific examples include phosphorus, trimethylphosphine, triethylphosphine, triphenylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine, hexamethylphosphorustriamide, and hexaethylphosphorustriamide. Can be mentioned.
-Sulfur or sulfur compounds: Specific examples include sulfur, longalits, hydrosulfites, and thiourea dioxide. Longarit refers to a formaldehyde derivative of sulfoxyphosphate and is _{represented by the general formula: MSO 2} · CH ₂ O (in the formula, M is Na or Zn). Specific examples of Longarit include sodium formaldehyde sulfoxylate and zinc formaldehyde sulfoxylate. Hydrosulfite refers to sodium hyposulfite and formaldehyde derivatives of sodium hyposulfite.

(Reducing agent that generates acid when reducing copper complex (hydride reducing agent))
-Metal hydride: Specific examples include sodium hydride, germanium hydride, tungsten hydride, and aluminum hydride (diisobutyl aluminum hydride, lithium aluminum hydride, sodium aluminum hydrogen, triethoxyaluminum hydride, bis hydride. (2-methoxyethoxy) sodium aluminum, etc.), Organic tin hydrides (triphenyltin hydride, tri-n-butyltin hydride, diphenyltin hydride, di-n-butyltin hydride, triethyltin hydride, trimethyl hydride (Suzu, etc.).
-Silicon hydride: Specific examples thereof include trichlorosilane, trimethylsilane, triethylsilane, diphenylsilane, phenylsilane, and polymethylhydrosiloxane.
-Boron hydride. Specific examples include borane, diborane, sodium borohydride, sodium trimethoxyborate hydride, sodium borohydride, sodium borohydride cyanide, lithium borohydride cyanide, lithium borohydride, lithium triethylborohydride, and hydrogen. Examples thereof include tri-s-butylborone lithium borohydride, tri-t-butylborane borohydride lithium, calcium borohydride, potassium borohydride, zinc borohydride, and tetra-n-butylammonium borohydride.
-Nitrogen hydrogen compound: Specific examples include hydrazine and diimide.
-Phosphorus or phosphorus compound: Specific examples include phosphine and diazaphosphoren.
-Sulfur or sulfur compounds: Specific examples include hydrogen sulfide.
-Organic compounds exhibiting a reducing action: 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, ascorbic acid salt, and ascorbic acid ester.

Further, the reducing agent may be produced in the polymerization system by electrolytic reduction. In electrolytic reduction, the electrons generated at the cathode directly (or after solvation) exhibit a reducing action. That is, the reducing agent may be produced by electrolysis.

(F. Solvent)
Examples of the solvent include the following. However, ATRP can be carried out under the condition that no solvent is used.
-Highly polar aprotonic solvent: dimethylsulfoxide (DMSO), dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone-carbonate-based solvent: ethylene carbonate, propylene carbonate-alcohol-based solvent: methanol , Ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol / nitrile solvent: acetonitrile, propionitrile, benzonitrile / ketone solvent: acetone, methyl ethyl ketone, methyl isobutyl ketone / ether solvent: diethyl ether, tetrahydrofuran -Halogenized carbide solvent: methylene chloride, chloroform-ester solvent: ethyl acetate, butyl acetate-hydrocarbon solvent: pentane, hexane, heptane, cyclohexane, octane, decane, benzene, toluene, xylene-Other solvents: ions Solvents, waters, supercritical solvents.

In the ATRP (ARGET) system using a reducing agent, the reaction control and polymerization reaction are that the transition metal or transition metal compound, polydentate amine, base, reducing agent, monomer and initiator are uniform in the polymerization system. Preferred in terms of speed, ease of preparation and scale-up risk. Therefore, it is preferable to select a solvent that can dissolve these substances.

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

[4.1. Main chain of polyoxyalkylene polymer (B))]
The main chain structure of the polyoxyalkylene polymer (B) may be linear or branched. Further, it may 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 diol and polyoxypropylene triol is particularly preferable.

Examples of the main chain of the polyoxyalkylene polymer (B) ^{include those having a repeating unit represented by the general formula (5) "-R 7-} O-" (in the formula, R ⁷ is It is a divalent alkylene group). Here, "substantially" means that the repeating unit represented by the general formula (5) is 50% by weight or more (preferably 80% by weight) based on the total weight of the polyoxyalkylene polymer (B). (Above) It means that it is included.

^{R 7} in the general formula (5) is not particularly limited as long as it is a divalent alkylene group. R 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.

The repeating unit represented by the general formula (5) is not particularly limited. Specific _{_{_{_{examples, -CH 2 O -, - CH}}}} 2 CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3 ) ₂ O-, -CH ₂ CH ₂ CH ₂ CH ₂ O- can be mentioned. Among these, the main chain of the main chain of the polyoxyalkylene polymer (B) is preferably polypropylene oxide composed of _{—CH 2} CH (CH _{3) O—.}

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

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.

[4.2. Method for Producing Polyoxyalkylene Polymer (B)]
The molecular structure of the polyoxyalkylene polymer (B) differs depending on the intended use and the intended properties. For example, as the polyoxyalkylene polymer (B), the compound described in JP-A-63-112642 can be used. Such a polyoxyalkylene polymer (B) can be synthesized by a usual polymerization method (anionic polymerization method using caustic alkali). Further, refer to cesium metal catalyst, porphyrin / aluminum complex catalyst (Japanese Patent Laid-Open No. 61-197631, JP-A-61-215622, JP-A-61-215623, JP-A-61-218632, etc.). ), Composite metal cesium complex catalyst (see Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, etc.), catalyst composed of polyphosphazene salt (see Japanese Patent Application Laid-Open No. 10-273512, etc.) It can also be synthesized by the method used.

If a method using a porphyrin / aluminum complex catalyst, a composite metal cyanation complex catalyst, or a catalyst composed of a polyphosphazene salt is adopted, the molecular weight distribution (Mw / Mn) is 1.6 or less (preferably 1.5 or less, particularly preferable). 1.2 or less) can be obtained. It is preferable to use the polyoxyalkylene polymer (B) having a small molecular weight distribution because the viscosity of the curable composition can be reduced while maintaining low modulus and high elongation of the cured product.

(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 the 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. It may be.

The number of alkoxysilyl groups contained in the polyoxyalkylene polymer (B) is preferably more than 0.5, more preferably 1.2 to 6.0, and 1.5 to 2 per molecule. .5 is more preferable. When the number of alkoxysilyl groups is in the above range, good curability can be imparted to the curable composition.

The alkoxysilyl group contained in the polyoxyalkylene polymer (B) is preferably located at at least one end of the molecule, and more preferably located at both ends of the molecule. If the alkoxysilyl group is located at the end of the molecule, good rubber elasticity can be given to the cured product. Even if the polyoxyalkylene polymer (B) in which the alkoxysilyl group is located at one end of the molecule and the polyoxyalkylene polymer (B) in which the alkoxysilyl group is located at both ends of the molecule are used in combination. good.

(Introduction method of alkoxysilyl group)
As a method for introducing an alkoxysilyl group into a polyoxyalkylene polymer, a conventionally known method can be used. For example, for the introduction of the alkoxysilyl group into the oxyalkylene polymer obtained by using the composite metal cyanide complex catalyst, Japanese Patent Application Laid-Open No. 3-72527 can be referred to. Further, for the introduction of the alkoxysilyl group into the oxyalkylene polymer obtained by using the polyphosphazene salt and active hydrogen as a catalyst, Japanese Patent Application Laid-Open No. 11-60723 can be referred to.

In addition, the following introduction methods can be mentioned.
Method 1: An unsaturated group-containing oxyalkylene by reacting an oxyalkylene polymer having a functional group such as a hydroxyl group at the terminal with an organic compound having an active group and an unsaturated group exhibiting reactivity with this functional group. Obtain a polymer. Alternatively, an unsaturated group-containing oxyalkylene polymer is obtained by copolymerizing an oxyalkylene polymer having a functional group such as a hydroxyl group at the terminal with an unsaturated group-containing epoxy compound. Then, a hydrosilane having an alkoxysilyl group is allowed to act on the obtained reaction product to hydrosilylate it.
Method 2: The 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: A compound having a Y'functional group and an alkoxysilyl group is reacted with an oxyalkylene polymer having a functional group of a Y functional group at the terminal. Here, the Y functional group is a hydroxyl group, an epoxy group, an isocyanate group, or the like. The Y'functional group is a functional group that exhibits reactivity with the Y functional group.

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-methylpropyl Trimethoxysilane, 4-amino-3-methylpropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane; further, a partial Michael addition reaction product of an amino group-containing silane and a maleic acid ester or acrylate compound, etc. ), Mercapto group-containing silanes (γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.), epoxysilanes (γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl)) Ethyltrimethoxysilane, etc.), Vinyl-type unsaturated group-containing silanes (vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, etc.), Chlorine atom-containing silanes (γ-chloro) (Propyltrimethoxysilane, etc.), isocyanate-containing silanes (γ-isocyanoxidetriethoxysilane, γ-isocyanabomethyldimethoxysilane, γ-isocyanoxidetrimethoxysilane, etc.), hydrosilanes (methyldimethoxysilane, trimethoxysilane, etc.) Methyldiethoxysilane, triethoxysilane, etc.).

[5. Curable composition]
The curable composition according to one aspect of the present invention contains a (meth) acrylic copolymer (A) having an alkoxysilyl group and a polyoxyalkylene-based polymer (B) having an alkoxysilyl group. There is. In addition, the curable composition may contain other additives. The above composition can be produced by mixing the (meth) acrylic copolymer (A) and the polyoxyalkylene polymer (B).

[5.1. Mixing ratio of (meth) acrylic copolymer (A) and polyoxyalkylene polymer (B)]
The blending ratio of the (meth) acrylic copolymer (A) and the polyoxyalkylene-based polymer (B) in the curable composition according to the embodiment of the present invention can be appropriately adjusted. The blending ratio of the (meth) acrylic copolymer (A) and the polyoxyalkylene-based polymer (B) is preferably (95/5) to (5/95) in terms of weight ratio, and is preferably (90/10). )-(10/90) is more preferable, and (80/20)-(20/80) is even more preferable. When the compounding ratio is in the above range, the weather resistance of the cured product can be sufficiently exhibited.

[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-based polymer (B). .. By containing these additives, the physical properties of the curable composition and the cured product can be adjusted. Examples of additives include: Only one kind of these additives may be used, or two or more kinds of these additives may be used in combination.

(Tin-based curing catalyst)
The curable composition in the present invention can be crosslinked and cured by forming a siloxane bond using a known condensation catalyst. An example of such a condensation catalyst is a tin-based curing catalyst. Specific examples of tin-based curing catalysts include dialkyltin carboxylates (dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, and dibutyltin dibutyl. Malate, dibutyltin diisooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin Diisooctylmalate, etc.); Dialkyltin oxides (dibutyltin oxide, dioctyltin oxide, mixture of dibutyltin oxide and phthalate ester, etc.); With tetravalent tin compounds (dialkyltin oxide, dialkyltin diacetate, etc.) Reactants with low molecular weight silicon compounds having an alkoxysilyl group (tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, etc.); divalent tin compounds (tin octylate, tin naphthenate, stear) Tin acid (such as tin acid); monoalkyl tins (monobutyltin compounds (monobutyltin trisoctate, monobutyltin triisopropoxide, etc.), monooctyltin compounds, etc.); reactants or mixtures of amine compounds and organotin compounds ( Reactants or mixtures of laurylamine and tin octylate, etc.); Chelate compounds (dibutyltin bisacetylacetonate, dioctyltin bisacetylsettnate, dibutyltin bisethylacetonate, dioctyltin bisethylacetonate, etc.); tin alcoholates (Dibutyltin dimethylate, dibutyltin diethylate, dioctyltin dimethylate, dioctyltin diethylate, etc.) can be mentioned.

Among these, chelate compounds (dibutyltin bisacetylacetonate, etc.) and tin alcoholates are preferably highly active as silanol condensation catalysts. Further, it is preferable that dibutyltin dilaurate is less colored even when added to a curable composition, is inexpensive, and is easily available.

The blending amount of the tin-based curing catalyst is preferably 0.1 to 20 parts by weight, preferably 0, based on 100 parts by weight of the total amount of the (meth) acrylic copolymer (A) and the polyoxyalkylene-based polymer (B). .5 to 10 parts by weight is more preferable.

(Adhesive imparting agent)
An adhesiveness-imparting agent may be added to the curable composition according to the embodiment of the present invention. By adding the adhesive, the risk of the sealing material peeling from the adherend such as a siding board can be reduced (this peeling occurs when the joint width or the like fluctuates due to an external force). It may also eliminate the need to use primers to improve adhesion. In this case, simplification of construction work is expected.

An example of an adhesive-imparting agent is a silane coupling agent. Specific examples of the silane coupling agent include isocyanate group-containing silanes (γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, etc.). Amino group-containing isocyanates (γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ -Aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl)- γ-Aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyl Triethoxysilane, etc.); Mercapto group-containing isocyanates (γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc.); Silanes (γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc.); Carboxylsilanes (β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N- (β-carboxymethyl) amino Ethyl-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, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives obtained by modifying silane coupling agents, are also silane coupling agents. Can be used as.

The blending amount of the adhesiveness-imparting agent is preferably 0.1 to 20 parts by weight, preferably 0, based on 100 parts by weight of the total amount of the (meth) acrylic copolymer (A) and the polyoxyalkylene polymer (B). .5 to 10 parts by weight is more preferable.

(Plasticizer)
The curable composition according to one embodiment of the present invention may contain a plasticizer. When the plasticizer and the filler (described later) are used in combination, the elongation of the cured product is increased and a large amount of the filler can be mixed.

Examples of plasticizers include phthalates (dibutylphthalate, diheptylphthalate, di (2-ethylhexyl) phthalate, diisodecylphthalate, butylbenzylphthalate, etc.); non-aromatic dibasic acid esters (dioctyl adipate, dioctyl ceva). Kate, dibutyl sebacate, isodecyl succinate, etc.); aliphatic esters (butyl oleate, methyl acetyllithinolate, etc.); polyalkylene glycol esters (diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol ester, etc.) Phthalates (tricresyl phosphate, tributyl phosphate, etc.); Trimellitic acid esters, polystyrene (polystyrene, poly-α-methylstyrene, etc.); Polybutadiene; Polybutene; Polyisobutylene; butadiene-acrylonitrile; Polychloroprene; Chlorinated paraffins; hydrocarbon oils (alkyldiphenyl, partially hydrogenated phthallate, etc.); process oils; polyethers (polyether polyols (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.), and polyethers Derivatives in which the hydroxyl groups of polyols are converted to ester groups, ether groups, etc.); Epoxide 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 acid and dihydric alcohol (sevacinic acid, adipic acid, azelaic acid, phthalate, etc., and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc.) , Etc.); Vinyl-based polymers (obtained by polymerizing vinyl-based monomers such as acrylic plasticizers by various methods) can be mentioned.

Specific examples of epoxy plasticizers include epoxidized soybean oil, epoxidized linseed oil, di- (2-ethylhexyl) 4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), and epoxy. Examples include octyl stearate and epoxy butyl steerate. Among the above-mentioned epoxy plasticizers, E-PS is preferable. When a compound having an epoxy group is used as a plasticizer, the resilience of the cured product can be enhanced.

The acrylic plasticizer can be produced by a high-temperature continuous polymerization method without using a solvent and a chain transfer agent (US Pat. No. 4,414,370, JP-A-59-6207, JP-A-5-58805). , Japanese Patent Application Laid-Open No. 1-313522, US Pat. No. 5,010166). Specific examples of acrylic plasticizers include ARUFON UP-1000, UP-1020, UP-1110 (above, manufactured by Toagosei Co., Ltd.), JDX-P1000, JDX-P1010, JDX-P1020 (above, Johnson Polymer (above, Johnson Polymer)). Made by Co., Ltd.). Further, an acrylic reactive plasticizer having an alkoxysilyl group may be used. A specific example of such a plasticizer is ARFUON US-6100.

The amount of the plasticizer to be blended is preferably 5 to 800 parts by weight, preferably 10 to 600 parts by weight, based on 100 parts by weight of the total amount of the (meth) acrylic copolymer (A) and the polyoxyalkylene polymer (B). Is more preferable, and 10 to 500 parts by weight is further preferable.

(Filler)
The curable composition according to one embodiment of the present invention may contain a filler. Examples of fillers are wood flour; reinforcing fillers (pulp, cotton chips, asbestos, mica, walnut shell powder, fir shell powder, graphite, white clay, silica (hummed silica, precipitated silica, crystalline silica, molten). Silica, dolomite, silicon dioxide, hydrous silicic acid, etc.), carbon black, etc.); Fillers (heavy calcium carbonate, collagen carbonate, magnesium carbonate, zelkova soil, calcined clay, clay, talc, titanium oxide, bentonite, organic Bentnite, ferric oxide, Bengara, fine aluminum powder, flint powder, zinc oxide, active zinc white, zinc powder, zinc carbonate, silas balloon, etc.; Fibrous fillers (asbestos, glass fibers and glass filaments, carbon fibers, etc.) Kevlar fiber, polyethylene fiber, etc.).

The blending amount of the filler is preferably 5 to 5000 parts by weight, preferably 10 to 2500 parts by weight, based on 100 parts by weight of the total amount of the (meth) acrylic copolymer (A) and the polyoxyalkylene polymer (B). More preferably, 15 to 1500 parts by weight is particularly preferable.

(Physical characteristic adjuster)
The curable composition according to one embodiment of the present invention may contain a physical property adjusting agent for adjusting the tensile properties of the cured product. By using the physical property adjusting agent, the hardness of the cured product can be increased, or conversely, the hardness of the cured product can be decreased to increase the elongation.

Examples of physical property adjusting agents include alkylalkoxysilanes (methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, etc.); alkylisopropenoxysilane (dimethyldiisopropenoxysilane, methyltri). Isopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, etc.); alkoxysilanes having a functional group (γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltri) Methoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.); Silicone varnish Kind: Polysiloxanes can be mentioned.

The blending amount of the physical property adjusting agent is preferably 0.1 to 80 parts by weight, preferably 0.1 to 80 parts by weight, based on 100 parts by weight of the total amount of the (meth) acrylic copolymer (A) and the polyoxyalkylene polymer (B). More preferably, 1 to 50 parts by weight.

(Tixogenic agent (anti-dripping agent))
The curable composition according to one embodiment of the present invention may contain a thixophilic imparting agent (anti-dripping agent) in order to prevent dripping and improve workability.

Examples of the thixophilic imparting agent include polyamide waxes; hydrogenated castor oil derivatives; metal soaps (calcium stearate, aluminum stearate, barium stearate, etc.).

The blending amount of the thixophilicity-imparting agent is preferably 0.1 to 50 parts by weight, preferably 0, based on 100 parts by weight of the total amount of the (meth) acrylic copolymer (A) and the polyoxyalkylene-based polymer (B). .2 to 25 parts by weight is more preferable.

(Photocurable 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 time by the action of light to cause a physical change (curing or the like). By containing a photocurable substance, the adhesiveness (residual tack) on the surface of the cured product can be reduced. A typical photocurable substance can be cured by allowing it to stand at room temperature for one day, for example, in a sunny position in a room (near a window or the like). Many known photocurable substances include organic monomers, oligomers, resins, and compositions containing these, and the types thereof are not particularly limited. Examples of photocurable substances include unsaturated acrylic compounds, vinyl chlorides, and azide resins.

Specific examples of unsaturated acrylic compounds include (meth) acrylic acid esters of low molecular weight alcohols (ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, neopentyl alcohol, etc.); acids (bisphenol A, isocyanuric acid). Alternatively, (meth) acrylic acid esters of alcohols obtained by modifying low molecular weight alcohols with ethylene oxide, propylene oxide, etc .; (meth) acrylic acid esters (polymers having a main chain of polyether and a hydroxyl group at the end). Polypoly, polymer polyol obtained by radical polymerization of vinyl-based monomer in polyol whose main chain is polyether, polyester polyol whose main chain is polyester and has a hydroxyl group at the end, main chain is vinyl-based or (meth) acrylic-based Polycarbonate which is a copolymer and has a hydroxyl group in the main chain); Epoxyacrylate-based oligomers obtained by reacting an epoxy resin (bisphenol A type, novolak type, etc.) with (meth) acrylic acid; polyol, polyisocyanate , A urethane acrylate-based oligomer having a urethane bond and a (meth) acrylic group in the molecular chain obtained by reacting with a hydroxyl group-containing (meth) acrylate or the like.

The blending amount of the photocurable substance is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylic copolymer (A) and the polyoxyalkylene polymer (B).

(Air oxidative curable substance)
The curable composition according to one embodiment of the present invention may contain an air oxidative curable substance. The air oxidatively curable substance refers to a compound having an unsaturated group that can be crosslinked and cured by oxygen in the air. By containing an air oxidatively curable substance, the adhesiveness (residual tack) on the surface of the cured product can be reduced. A typical air oxidatively curable substance can be cured by allowing it to stand indoors for one day, for example, in the air.

Examples of air oxidatively curable substances include drying oil (tung oil, flaxseed oil, etc.); various alkyd resins obtained by modifying the drying oil; acrylic polymers, epoxy resins, silicone resins, etc. are modified with the drying oil. Substances; 1,2-polybutadiene; 1,4-polybutadiene; polymers or copolymers of C5-C8 diene; polymers of C5-C8 diene or various modified products of copolymers (maleinized modified products, boiling oil) Modified products, etc.). Among the above, tung oil, a liquid diene polymer and a modified product thereof are preferable.

The blending amount of the air oxidatively curable substance is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylic copolymer (A) and the polyoxyalkylene polymer (B).

(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 kinds of antioxidants and light stabilizers are known. For example, [Kenichi Saruwatari et al., "Handbook of Antioxidants" Taiseisha, 1976] [Supervised by Zenjiro Osawa, "Deterioration and Stabilization of Polymer Materials", CMC, 1990, pp. 235-242] Can be mentioned.

Examples of antioxidants are thioether-based antioxidants such as Adecastab PEP-36 and Adecastab AO-23 (all manufactured by Asahi Denka Kogyo); Irgafos38, Irgafos168, IrgafosP-EPQ (all Ciba Specialty Chemicals). ), Etc. Phosphorus-based antioxidants; hindered phenol-based antioxidants; Among the above, hindered phenolic antioxidants are preferred.

Specific examples of hindered phenolic 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 (4methyl-6-t-butylphenol), 4,4'-butylidenebis (3-) Methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, tri Ethyleneglycol-bis- [3- (3-t-butyl-5-methyl-4hydroxyphenyl) 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-diethylenebis [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-hydroxybenzylphosphonate) 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-hydroxypheni) Le) 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-5- (2H-benzotriazole-2-yl) -4-hydroxyphenyl] Propionate-polyethylene glycol (molecular weight about 300) condensate, hydroxyphenylbenzotriazole derivative, 2- (3,5-) Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalate bis (1,2,2,6,6-pentamethyl-4-piperidyl), 2,4-di-t-butylphenyl-3 , 5-Di-t-Butyl-4-hydroxybenzoate.

Examples of commercially available antioxidants are Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7. , Nocrack DAH (all manufactured by Ouchi Shinko Kagaku Kogyo); Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-616, Adekastab AO-635, Adekastab AO-658, Adekastab AO-80, Adekastab AO-15, Adekastab AO-18, Adekastab 328, Adekastab 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 Ciba Specialty Chemicals); , All made by Sumitomo Chemical).

Examples of light stabilizers include benzotriazole compounds such as UV absorbers (Tinubin P, Tinubin 234, Tinubin 320, Tinubin 326, Tinubin 327, Tinubin 329, Tinubin 213 (all manufactured by Ciba Specialty Chemicals); Examples thereof include triazine-based photostabilizers such as tinuvin 1577; benzophenone-based compounds such as CHIMASSORB81; benzoate-based compounds such as tinubin 120 (manufactured by Ciba Specialty Chemicals); hindered amine-based compounds). Among the above, hindered amine compounds are preferable.

Specific examples of the hindered amine compound include dimethyl-1- (2-hydroxyethyl) succinate-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 (3 aminopropyl) 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, bis succinate (2,2,6,6-tetramethyl-4-piperidinyl) ester can be mentioned.

Examples of commercially available light stabilizers include Cibabin 622LD, Chinubin 144, CHIMASSORB944LD, CHIMASORB119FL; (all manufactured by Ciba Specialty Chemicals), Adecastab LA-52, Adecastab LA-57, Adecastab LA-62, Adecastab. LA-67, Adecastab LA-63, Adecastab LA-68, Adecastab LA-82, Adecastab LA-87 (all manufactured by Asahi Denka Kogyo); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS -2626, Sanol LS-1114, Sanol LS-744, Sanol LS-440 (all manufactured by Sankyo).

Antioxidants and light stabilizers may be used in combination. By using these in combination, the respective effects may be further improved, and the heat resistance, weather resistance, etc. of the cured product may be improved. For example, an ultraviolet absorber and a hindered amine compound (HALS) can be combined to improve weather resistance. This combination is preferable because the effect of each drug can be further improved.

The blending amount of the antioxidant and / or the light stabilizer is 0.1 to 100 parts by weight, respectively, with respect to 100 parts by weight of the total amount of the (meth) acrylic copolymer (A) and the polyoxyalkylene polymer (B). 20 parts by weight is preferable.

[5.3. Morphology of curable composition]
The curable composition according to one embodiment of the present invention may be a one-component type or a two-component type. The one-component curable composition is a composition in which all the ingredients are mixed in advance and then sealed and stored. The one-component curable composition is cured by moisture in the air after use. On the other hand, in the two-component curable composition, a curing agent containing components such as a curing catalyst, a filler, a plasticizer, and water is separately prepared. The two-component curable composition is used by mixing a curing agent and a main agent containing a (meth) acrylic copolymer (A) and / or a (meth) acrylic copolymer (A1). The two-component curable composition may contain an agent (coloring agent, etc.) other than the main agent and the curing agent.

When the curable composition is prepared as a two-component type, a colorant can be further added when the two components are mixed. This makes it possible to provide a sealant having a wide variety of colors to match the color of the siding board, for example, from a limited variety of curable compositions. Therefore, the two-component curable composition can easily meet the market demand for multicoloring, and is suitable for low-rise building applications and the like. As the colorant, for example, a pigment, a plasticizer, and a filler mixed with a filler as needed to form a paste are preferable because of their high workability.

Further, in the two-component curable composition, a retarder can be added when the two components are mixed. As a result, the curing speed can be finely adjusted at the work site.

[5.4. Uses of curable composition]
The use of the curable composition and the cured product according to the embodiment of the present invention is not particularly limited. As an example, building and industrial sealing materials (high durability building elastic sealing materials used for working joints, siding board sealing materials, multi-layer glass sealing materials, vehicle sealing materials, etc.), electricity・ Electronic component materials (solar cell backside sealants, etc.), electrical insulation materials (electric wire / cable insulation coating materials, etc.), adhesives, adhesives, elastic adhesives, contact adhesives, tile adhesives, reactive hots Melt adhesives, paints, powder paints, coating materials, foams, sealing materials for can lids, electrical and electronic potting agents, films, gaskets, casting materials, various molding materials, artificial marble, meshed glass and laminated glass Anti-rust / waterproof sealing material, anti-vibration / anti-vibration / soundproof / seismic isolation material (used for automobiles, ships, home appliances, etc.), liquid sealant (automobile parts, electrical parts, various mechanical parts) (Used for etc.), waterproofing agents can be mentioned.

Among the above, the curable composition and the cured product according to the embodiment of the present invention are particularly useful as a sealing material and an adhesive. In particular, it is useful for applications that require weather resistance or durability, or applications that require transparency. Further, since the curable composition and the cured product according to the embodiment of the present invention are excellent in weather resistance and adhesiveness, they can be used in an outer wall tile bonding method without joint filling. Further, it is useful for bonding materials having different coefficients of linear expansion and for bonding elastic adhesives used for bonding members that are repeatedly displaced by a heat cycle. Further, it is also useful as a coating agent for applications where the base can be seen by utilizing transparency, and as an adhesive used for bonding transparent materials (glass, polycarbonate, methacrylic resin, etc.).

〔summary〕
The present invention includes the following aspects.
<1>
A curable composition comprising a (meth) acrylic copolymer (A) having an alkoxysilyl group and a polyoxyalkylene-based polymer (B) having an alkoxysilyl group.
The (meth) acrylic copolymer (A) randomly contains a repeating unit derived from the (meth) acrylic acid ester monomer (α).
The (meth) acrylic acid ester monomer (α) has an alkyl group ester-bonded to (meth) acrylic acid, and the alkyl group has an alkoxy group having 1 to 5 carbon atoms. And
The repeating unit derived from the (meth) acrylic acid ester monomer (α) is contained in an amount of 5 to 20% by weight based on the weight of all the repeating units contained in the (meth) acrylic copolymer (A). Is
Curable composition.
<2>
The (meth) acrylic copolymer (A) is based on the weight of all repeating units.
Repeating unit derived from (meth) acrylic acid ester monomer (β), 45-70% by weight,
Repeating unit derived from (meth) acrylic acid ester monomer (γ), 0 to 25% by weight,
Repeating unit derived from (meth) acrylic acid ester monomer (δ), 15 to 25% by weight,
Includes
The (meth) acrylic acid ester monomer (β) has 1 to 5 carbon atoms in the alkyl group ester-bonded to the (meth) acrylic acid.
The (meth) acrylic acid ester monomer (γ) has an alkyl group ester-bonded to (meth) acrylic acid having 6 to 15 carbon atoms.
The (meth) acrylic acid ester monomer (δ) has 16 to 25 carbon atoms of the alkyl ester-bonded to the (meth) acrylic acid.
The curable composition according to <1>.
<3>
The curable composition according to <1> or <2>, wherein the molecular weight distribution (Mw / Mn) of the (meth) acrylic copolymer (A) is 1.8 or less.
<4>
The molecule of the (meth) acrylic copolymer (A) is a (meth) acrylic copolymer (A1) containing an XY diblock structure or an XYX triblock structure having an X block and a Y block in the molecule. ,
The number of repeating units derived from the (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 the (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 the repeating units contained in the Y block. be,
The curable composition according to any one of <1> to <3>.
<5>
The repeating unit derived from the (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 the repeating units contained in the X block. , <4>.
<6>
The curable composition according to any one of <1> to <5>, wherein the (meth) acrylic acid ester monomer (α) is the following (a) and / or (b):
(A) Monomer having 1 to 5 carbon atoms in the alkyl group ester-bonded with (meth) acrylic acid (however, carbon contained in the alkoxy group is not included);
(B) One or more selected from the group consisting of 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and isopropoxyethyl (meth) acrylate. Monomer.
<7>
The (meth) acrylic acid ester monomer (δ) includes pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, icosyl (meth) acrylate and (meth). ) The curable composition according to <2>, which is one or more selected from the group consisting of docosil acrylate.
<8>
The number of alkoxysilyl groups contained in the (meth) acrylic copolymer (A) is 1.0 to 10.0 on average as a whole molecule, of <1> to <7>. The curable composition according to any one.
<9>
The curable composition according to any one of <1> to <8>, wherein the polyoxyalkylene polymer (B) has a number average molecular weight of 5,000 to 50,000.
<10>
The compounding ratio of the (meth) acrylic copolymer (A) and the polyoxyalkylene-based polymer (B) is (95/5) to (5/95) by weight, <1> to The curable composition according to any one of <9>.
<11>
The curable composition according to any one of <1> to <10>, 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.
<12>
A cured product obtained by curing the curable composition according to any one of <1> to <11>.
<13>
A sealant or adhesive containing the curable composition according to any one of <1> to <11> or the cured product according to <12>.
<14>
The method for producing a curable composition according to <1>.
A step of polymerizing the above (meth) acrylic copolymer (A) by a living polymerization method, and
A step of mixing the (meth) acrylic copolymer (A) and the polyoxyalkylene-based polymer (B),
Manufacturing method, including.
<15>
The step of polymerizing the (meth) acrylic copolymer (A) by the living radical polymerization method includes a step of polymerizing the (meth) acrylic copolymer (A) by the living radical polymerization method, according to <14>. The method for producing a curable composition according to the above.

The present invention also includes the following aspects.
<1a>
In the curable composition, the total weight of the repeating units derived from the (meth) acrylic acid ester monomer contained in the (meth) acrylic copolymer (A) is the (meth) acrylic copolymer. It may be 90% by weight or more based on the weight of all the repeating units contained in (A).
<2a>
In the curable composition, the (meth) acrylate 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 number average molecular weight of the (meth) acrylic copolymer (A) measured by gel permeation chromatography may be 30,000 or more.
<6a>
In the curable composition, the compounding ratio of the (meth) acrylic copolymer (A) and the polyoxyalkylene-based polymer (B) is (95/5) to (5/95). You may.
<7a>
In the curable composition, one or more selected from the group consisting of the (meth) acrylic copolymer (A) and the polyoxyalkylene-based polymer (B) is the following general formula (1). It may have an alkoxysilyl group represented by:
-[Si (R ¹ ) _2-b (Y) _b O] _m ^{-Si (R 2} ) _3-a (Y) _a (1)
(During the ceremony,
R ¹ and R ² are independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a methoxymethyl group, or (R') ₃ SiO-. It is a triorganosyloxy group indicated by
R'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R'existing may be the same or different.
When R ¹ or ^{R 2} there are two or more, the ^{R 1} or ^{R 2} can be identical or different,
Y is an alkoxy group having 1 to 20 carbon atoms.
When there are two or more Ys, the Ys 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 and
a + mb ≧ 1).

Furthermore, the present invention also includes the following aspects.
<1b>
Method for producing (meth) acrylic copolymer (A) by atom transfer radical polymerization, which comprises the following steps:
(I) 1 to 10 molar equivalents of a (meth) acrylic acid ester monomer having an alkoxysilyl group and no alkoxysilyl group with respect to 1 molar equivalent of an initiator having one halogen group in the molecule. First step of polymerizing (meth) acrylic acid ester monomer in 1-100 molar equivalents;
(Ii) To 1 molar equivalent of the polymer obtained in the first step, 2 to 600 molar equivalents of the (meth) acrylic acid ester monomer having no alkoxysilyl group is added to the reaction system for polymerization. Process;
(Iii) In the third step, 1 to 10 molar equivalents of the (meth) acrylic acid ester monomer having an alkoxysilyl group are added to the reaction system for polymerization with respect to 1 molar equivalent of the polymer obtained in the second step;
Here, the (meth) acrylic acid ester monomer having no alkoxysilyl group added to the reaction system in the first step and the third step is a (meth) acrylic acid ester based on the weight of all the monomers. Contains 5 to 20% by weight of monomer (α)
The (meth) acrylic acid ester monomer (α) has an alkyl group ester-bonded to (meth) acrylic acid, and the alkyl group has an alkoxy group having 1 to 5 carbon atoms. ing,
Production method.

The contents described in each of the above items can be appropriately used in other items as well. The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims. Therefore, embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also included in the technical scope of the present invention.

All academic and patent documents described herein are incorporated herein by reference.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[Manufacturing 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".

(polymerization)
The inside of the stainless steel reaction vessel with a stirrer was deoxidized. 7.41 g of cuprous bromide and 200 g of (meth) acrylic acid ester monomer mixture A were charged into this reaction vessel, and the mixture was heated and stirred. Next, 88.73 g of acetonitrile and 10.79 g of the initiator (diethyl 2,5-dibromoadipate) were added and mixed. After adjusting the temperature of the mixture to about 65 ° C., 0.15 g of pentamethyldiethylenetriamine was added to initiate the polymerization reaction. Then, the remaining 800 g of the (meth) acrylic acid ester monomer mixture A was sequentially added to allow the polymerization reaction to proceed. During the polymerization reaction, pentamethyldiethylenetriamine was appropriately added to adjust the polymerization rate. The total amount of pentamethyldiethylenetriamine used in the whole 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 adjusted to about 80 ° C. to about 90 ° C. When the monomer conversion rate (polymerization reaction rate) reached 95%, the volatile matter was removed by devolatile under reduced pressure to obtain a polymer concentrate. The time required to reach this stage was 5 hours.

To the obtained polymer concentrate, 189.85 g of 1,7-octadiene, 354.94 g of acetonitrile, and 2.99 g of pentamethyldiethylenetriamine were added. Next, 1,7-octadiene was reacted at the end of the polymer by heating and stirring for 4 hours while adjusting the temperature of the reaction system to about 80 ° C. to about 90 ° C.

(purification)
At the end of the reaction, an oxygen-nitrogen mixed gas was introduced into the gas phase part in the reaction vessel. Next, while maintaining the temperature of the reaction system at about 80 ° C. to about 90 ° C., the reaction solution was heated and stirred for 4 hours to bring the polymerization catalyst contained in the reaction solution into contact with oxygen. Next, acetonitrile and unreacted 1,7-octadien were removed by volatilization under reduced pressure to obtain a polymer concentrate. The time required for the process up to this point was 6 hours.

After diluting the polymer concentrate by adding 1000 g of butyl acetate, a filtration aid was added and the mixture was stirred. Next, the insoluble catalyst component was removed by filtration.

The filtrate was placed in a stainless steel reaction vessel 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 portion in the reaction vessel, and the mixture was heated and stirred at about 100 ° C. for 1 hour. Next, insoluble components (adsorbents and the like) were removed by filtration to obtain a clear filtrate. After repeating this operation twice, the filtrate was concentrated to obtain a crude polymer product.

A heat stabilizer (Smilizer GS: manufactured by Sumitomo Chemical Co., Ltd.) and an adsorbent (Kyoward 700SEN-S, Kyoward 500SH) were added to the crude polymer product. The temperature of the system was raised, and the crude polymer product was adsorbed and purified by heating, stirring, and devolatile under reduced pressure at a high temperature of about 170 ° C. to about 200 ° C. for about 2 hours. Next, 10 times the amount of butyl acetate was added to the polymer for dilution, and adsorbents (Kyoward 700SEN and Kyoward 500SH) were added. Next, the gas phase portion in the reaction vessel was set to an oxygen-nitrogen mixed gas atmosphere, and the adsorption purification was continued by heating and stirring at a high temperature of about 170 ° C. to about 200 ° C. for about 4 hours. 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 give a polymer having alkenyl groups at both ends.

(Introduction of alkoxysilyl group)
19.1 g of methyldimethoxysilane (DMS), 5.4 g of methyl orthoate, and a platinum complex catalyst of bis (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) with respect to 1000 g of the obtained polymer. 0.388 mL of the isopropanol solution (1.32 × 10 ^-4 mmol / μL) of the above was mixed, and the mixture was heated and stirred at about 115 ° C. After about 1 hour, volatile components (unreacted DMS, etc.) were distilled off under reduced pressure to obtain a (meth) acrylic copolymer (A). This (meth) acrylic copolymer (A) is a polymer having dimethoxysilyl groups at both ends of the molecule.

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

Next, another stirring container was prepared. 52.7 mg of cupric bromide (CuBr ₂ ), 54.4 mg of hexamethyltris (2-aminoethyl) amine (Me ₆ TEN), and 1.82 g of methanol were charged therein and uniformly under a nitrogen stream. Stirring was performed until a solution was obtained. This uniform solution is referred to as a "copper solution". The amount of copper contained in the copper solution corresponds to 15 ppm with respect to the total amount of the (meth) acrylic acid ester monomer mixture B.

Furthermore, another stirring container was prepared. To this, 40.4 mL of methanol, 0.5 g of ascorbic acid, and 0.79 mL of triethylamine were charged, and the mixture was stirred under a nitrogen stream for 30 minutes to prepare a uniform solution. This uniform solution is referred to as an "ascorbic acid solution".

(First step)
In a stirrer, 5.24 g of ethyl α-bromobutyrate (initiator), 20% by weight 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.), the entire amount of the copper solution was added, and the mixture was stirred under a nitrogen stream for 30 minutes to obtain a uniform solution. The stirrer used at this time was a stirrer with a jacket temperature control.

Next, when the temperature in the polymerization system reached 50 ° C. or higher, the polymerization reaction was started by continuously dropping an ascorbic acid solution. The dropping rate of the ascorbic acid solution at this time was the rate at which 3 mg of ascorbic acid was added to the polymerization system per hour.

When the temperature inside the polymerization system was monitored, the temperature rose at the same time as the start of dropping ascorbic acid, and after reaching the maximum temperature, the temperature gradually decreased. When the temperature difference obtained by subtracting the jacket temperature from the temperature in the polymerization system became 2 ° C., a small amount of the reaction solution in the polymerization system was sampled and analyzed by a gas chromatograph. As a result, 81% by weight of the (meth) acrylic acid ester monomer mixture B initially charged was consumed.

(Second step)
Next, the rest (80% by weight of the total amount) of the (meth) acrylic acid ester monomer mixture B that was not charged in the first step was continuously added dropwise to the polymerization system over 90 minutes. In addition, sampling was performed sequentially and analyzed by gas chromatography. Then, the mixture was polymerized until 98% by weight of the total amount of the (meth) acrylic acid ester monomer mixture B charged into the polymerization system was consumed.

(Third step)
Next, 13.73 g of 3- (trimethoxysilyl) propyl methacrylate was added to this polymerization system. After continuous dropping of the ascorbic acid solution was continued for 1.5 hours, the dropping of the ascorbic acid solution was stopped to complete the polymerization.

After changing the jacket temperature to 80 ° C, the solvent was devolatile. For volatilization, a diaphragm pump was used first, and then a vacuum pump was used. After the volatilization was completed, the jacket was cooled to 60 ° C. or lower.

(purification)
1000 g of butyl acetate was put into a stirrer with jacket temperature control, and the mixture was mixed and stirred with the devolatile polymer until a uniform solution was obtained. An adsorbent was added to this uniform solution, and the mixture was stirred for 1 hour. As the adsorbent, 20 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) and 20 g of Kyoward 700SEN-S (manufactured by Kyowa Chemical Industry Co., Ltd.) were used.

After the stirring was completed, the obtained mixture was filtered through a filter lined with a bag filter filter cloth. This gave a clear polymer solution. To this solution, 1.5 g of an antioxidant (Sumilizer GS; manufactured by Sumitomo Chemical Co., Ltd.) dissolved in about 20 g of butyl acetate was added, and the mixture was mixed until uniform. Then, the solvent was devolatile from the solution to obtain a (meth) acrylic copolymer (A1). For volatilization, a diaphragm pump was used first, and then a vacuum pump was used. This (meth) acrylic copolymer (A1) is a polymer having an XYX triblock structure.

[Manufacturing Examples 3 and 4]
The composition of the (meth) acrylic monomer mixture B was changed as shown in Table 1. A (meth) acrylic copolymer (A1) was produced in the same manner as in Production Example 2 except for the above.

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

[Manufacturing Example 6]
The composition of the (meth) acrylic monomer mixture B was changed as shown in Table 1. A (meth) acrylic copolymer was produced in the same manner as in Production Example 2 except for the above. This copolymer does not contain a unit derived from the (meth) acrylic acid ester monomer (α).

[Examples 1 to 4, Comparative Examples 1 and 2]
The physical characteristics of the (meth) acrylic copolymers obtained in Production Examples 1 to 6 were evaluated. In addition, the physical properties of a curable composition containing a (meth) acrylic copolymer and a polyoxyalkylene-based 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.

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

(B) The weight ratio (% by weight) of the repeating unit contained in the X block to the entire polymer molecule.

(C) The weight ratio (% by weight) of the repeating unit contained in the Y block to the entire polymer molecule.

(Distribution of repeating units derived from (meth) acrylic acid ester monomer (α))
The weight ratio (% by weight) of the repeating unit derived from the (meth) acrylic acid ester monomer (α) (repeating unit derived from 2-methoxyethyl acrylate) to the entire polymer molecule is the weight of the charged monomer and the monomer. (Results are shown in Table 2). Further, according to the above-mentioned production example, the repeating units derived from 2-methoxyethyl acrylate are randomly distributed in the (meth) acrylic copolymer (A).

[Evaluation of (meth) acrylic copolymer]
(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 by a standard polystyrene conversion method using gel permeation chromatography (GPC). .. As the GPC column, a column filled with polystyrene crosslinked gel (shodex GPC K-804; manufactured by Showa Denko KK) was used. Chloroform was used as the solvent for GPC. The results are shown in Table 2.

(viscosity)
The viscosity of the (meth) acrylic copolymer was measured at 23 ° C. using a viscometer (VISCOMETER TV-25 manufactured by Toki Sangyo Co., Ltd., 3 ° × R14 cone rotor, 1 rpm). The measurement is JIS K
This was done in accordance with 7117-2. The amount of sample used for the measurement was 0.4 mL. The results are shown in Table 2.

[Evaluation of curable composition]
A curable composition was prepared by mixing a (meth) acrylic copolymer and a polyoxyalkylene-based polymer (B). As the polyoxyalkylene polymer (B), SAX220 (manufactured by Kaneka Corporation) was used. The mixing ratio of the two was 50:50 by weight.

(Evaluation of compatibility)
The (meth) acrylic copolymer and the polyoxyalkylene-based polymer (B) were stirred and mixed. Then, the curable composition was mixed and defoamed using a planetary stirring and mixing device (Awatori Rentaro manufactured by Shinky). The operating parameters of the device at the time of mixing were revolution: 1600 rpm, rotation: 640 rpm, and stirring time: 1.3 minutes. The operating parameters of the device at the time of defoaming were revolution: 2200 rpm, rotation: 60 rpm, and stirring time: 3 minutes. The obtained mixture was placed in a sample bottle and left in an oven at 60 ° C. for 2 hours, and then the compatibility state was confirmed. Then, even after the mixture was left at room temperature for another week, the compatibility state was confirmed. The results are shown in Table 2. In Table 2, "○" indicates that they were compatible under all conditions, and "x" indicates that they were incompatible under at least one condition.

(Evaluation of viscosity)
The viscosity of the curable composition was measured at 23 ° C. using a viscometer (VISCOMETER TV-25 manufactured by Toki Sangyo Co., Ltd., 3 ° × 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.

[Evaluation of cured product]
To 100 parts by weight of the curable composition, a reaction product of 2 parts by weight of tin octylate and 0.5 part by weight of laurylamine was added and mixed well. The obtained mixture was poured into a mold and degassed under reduced pressure. Then, it was heat-cured at 50 ° C. for 20 hours to obtain a sheet-like cured product having rubber elasticity.

(Evaluation of mechanical properties)
From the obtained cured sheet, a No. 3 dumbbell type test piece specified in JIS K 7113 was punched out. This test piece was subjected to a tensile test to measure mechanical properties. Specifically, the stress at 50% elongation, the stress at fracture, and the elongation at fracture (elongation with respect 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.

[result]
The (meth) acrylic copolymer (A) according to Examples 1 to 4 has a significantly lower viscosity of the copolymer itself than the (meth) acrylic copolymer according to Comparative Examples 1 and 2. The viscosity of the curable composition was also reduced. This suggests that the viscosity of the copolymer itself and the viscosity of the curable composition can be reduced by randomly including a predetermined ratio of repeating units derived from the (meth) acrylic acid ester monomer (α). .. Further, the (meth) acrylic copolymer (A) according to Examples 1 to 4 had good compatibility with the polyoxyalkylene-based polymer (B) and good mechanical properties of the cured product.

[Manufacturing Examples 7 and 8]
A copolymer was produced by the same method 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 is a (meth) acrylic copolymer (A1) because it contains a unit derived from the (meth) acrylic acid ester monomer (α). The copolymer according to Production Example 8 does not contain a unit 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.

[Example 5, Comparative Example 3]
The physical characteristics of the (meth) acrylic copolymers obtained in Production Examples 7 and 8 were evaluated. In addition, the physical characteristics of the cured product obtained by curing the (meth) acrylic copolymer were also evaluated (note that this cured product does not contain the polyoxyalkylene copolymer (B)). The results are shown in Table 4. The (meth) acrylic copolymer (A) evaluated in Example 5 was produced in Production Example 7. The (meth) acrylic copolymer evaluated in Comparative Example 3 was produced in Production Example 8.

[result]
In the (meth) acrylic copolymer (A) according to Example 5, the viscosity of the copolymer itself was significantly reduced as compared with the (meth) acrylic copolymer according to Comparative Example 3. From this, even if the type of the monomer having an alkoxysilyl group is changed, the viscosity of the copolymer itself is obtained by randomly including a predetermined ratio of repeating units derived from the (meth) acrylic acid ester monomer (α). It is suggested that can be reduced. Further, the (meth) acrylic copolymer (A) according to Example 5 had good compatibility with the polyoxyalkylene-based polymer (B) and good mechanical properties of the cured product.

The present invention can be used as a sealing material, an adhesive, and the like.

Claims

A curable composition comprising a (meth) acrylic copolymer (A) having an alkoxysilyl group and a polyoxyalkylene-based polymer (B) having an alkoxysilyl group.
The (meth) acrylic copolymer (A) randomly contains a repeating unit derived from the (meth) acrylic acid ester monomer (α).
The (meth) acrylic acid ester monomer (α) has an alkyl group ester-bonded to (meth) acrylic acid, and the alkyl group has an alkoxy group having 1 to 5 carbon atoms. And
The repeating unit derived from the (meth) acrylic acid ester monomer (α) is contained in an amount of 5 to 20% by weight based on the weight of all the repeating units contained in the (meth) acrylic copolymer (A). Is
Curable composition.
The (meth) acrylic copolymer (A) is based on the weight of all repeating units.
Repeating unit derived from (meth) acrylic acid ester monomer (β), 45-70% by weight,
Repeating unit derived from (meth) acrylic acid ester monomer (γ), 0 to 25% by weight,
Repeating unit derived from (meth) acrylic acid ester monomer (δ), 15 to 25% by weight,
Includes
The (meth) acrylic acid ester monomer (β) has 1 to 5 carbon atoms in the alkyl group ester-bonded to the (meth) acrylic acid.
The (meth) acrylic acid ester monomer (γ) has an alkyl group ester-bonded to (meth) acrylic acid having 6 to 15 carbon atoms.
The (meth) acrylic acid ester monomer (δ) has 16 to 25 carbon atoms of the alkyl ester-bonded to the (meth) acrylic acid.
The curable composition according to claim 1.
The (meth) acrylic copolymer (A) is
The number average molecular weight is 4,000-80,000,
The molecular weight distribution (Mw / Mn) is 1.8 or less.
The curable composition according to claim 1 or 2.
The molecule of the (meth) acrylic copolymer (A) is a (meth) acrylic copolymer (A1) containing an XY diblock structure or an XYX triblock structure having an X block and a Y block in the molecule. ,
The number of repeating units derived from the (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 the (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 the repeating units contained in the Y block. be,
The curable composition according to any one of claims 1 to 3.
The repeating unit derived from the (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 the repeating units contained in the X block. , The curable composition according to claim 4.
The curable composition according to any one of claims 1 to 5, wherein the (meth) acrylic acid ester monomer (α) is the following (a) and / or (b).
(A) Monomer having 1 to 5 carbon atoms in the alkyl group ester-bonded with (meth) acrylic acid (however, carbon contained in the alkoxy group is not included);
(B) One or more selected from the group consisting of 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and isopropoxyethyl (meth) acrylate. Monomer.
The (meth) acrylic acid ester monomer (δ) includes pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, icosyl (meth) acrylate and (meth). ) The curable composition according to claim 2, which is one or more selected from the group consisting of docosil acrylate.
Any of claims 1 to 7, wherein the number of alkoxysilyl groups contained in the (meth) acrylic copolymer (A) is 1.0 to 10.0 on average as a whole molecule. The curable composition according to item 1.
The curable composition according to any one of claims 1 to 8, wherein the polyoxyalkylene polymer (B) has a number average molecular weight of 5,000 to 50,000.
The compounding ratio of the (meth) acrylic copolymer (A) and the polyoxyalkylene-based polymer (B) is (95/5) to (5/95) in terms of weight ratio, claim 1 to 1. 9. The curable composition according to any one of 9.
The curable composition according to any one of claims 1 to 10, 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.
A cured product obtained by curing the curable composition according to any one of claims 1 to 11.
A sealant or adhesive containing the curable composition according to any one of claims 1 to 11 or the cured product according to claim 12.
The method for producing a curable composition according to claim 1.
A step of polymerizing the above (meth) acrylic copolymer (A) by a living polymerization method, and
A step of mixing the (meth) acrylic copolymer (A) and the polyoxyalkylene-based polymer (B),
Manufacturing method, including.
14. The step of polymerizing the (meth) acrylic copolymer (A) by the living radical polymerization method includes a step of polymerizing the (meth) acrylic copolymer (A) by the living radical polymerization method, according to claim 14. The method for producing a curable composition according to the above.