JP6601515B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition.

  Conventionally, a composition containing a polyoxyalkylene polymer having a reactive silicon group and a (meth) acrylic polymer having a reactive silicon group is known as a sealing material.

  For example, Patent Document 1 discloses a crosslinkable silyl group-containing organic polymer (A) for the purpose of providing a sealing material composition having paint adhesion and paint non-staining properties and excellent workability, and A curable sealing material containing a specific crosslinkable silyl group terminal-containing (meth) acrylic ester polymer (B) having a glass transition temperature of −100 ° C. to −10 ° C. is described.

Japanese Patent No. 5138186

Under these circumstances, the present inventors prepared a composition with reference to Patent Document 1 and evaluated it. As a result, it was found that such a composition sometimes has low weather resistance. Moreover, it became clear that the above compositions may have low water-resistant adhesiveness with respect to a base material or a primer (comparative examples 4 and 5).
Then, an object of this invention is to provide the curable resin composition excellent in a weather resistance and water-resistant adhesiveness.

As a result of diligent research to solve the above problems, the present inventors have a vinyl polymer (a) in which a molecular chain has a repeating unit of a polymerizable vinyl monomer and a specific group is bonded to a terminal, Has reactive silyl groups at the end and side chain of the molecular chain, the molecular chain has a repeating unit of a polymerizable vinyl monomer, the total number of reactive silyl groups, the number of reactive silyl groups at the terminal and side chains , A vinyl polymer (A) having a specific range of weight average molecular weight, number average molecular weight and glass transition temperature, a polyoxyalkylene polymer (B), and an epoxy compound (C). The inventors have found that an effect can be obtained and have reached the present invention.
The present invention is based on the above knowledge and the like, and specifically, solves the above problems by the following configuration.

[1] It has a reactive silyl group at the end and side chain of the molecular chain, and the molecular chain has a repeating unit of a polymerizable vinyl monomer,
On an average per molecule, the total number of reactive silyl groups exceeds 1, the number of reactive silyl groups at the terminal exceeds 0.5, and the number of reactive silyl groups in the side chain is 0. More than 5,
A vinyl polymer (A) having a weight average molecular weight of 30,000 to 110,000, a number average molecular weight of 9,000 to 40,000, and a glass transition temperature of −100 to −10 ° C .;
A polyoxyalkylene polymer (B) having a reactive silyl group and having a molecular chain substantially polyoxyalkylene;
Containing an epoxy compound (C) having an epoxy group,
The vinyl polymer (A) is a vinyl polymer (a) having a molecular chain having a repeating unit of a polymerizable vinyl monomer and having a group represented by the following formula (I) at the end of the molecular chain. A curable resin composition comprising.
* -SL ¹ -X ¹ (I)
In formula (I), S is a sulfur atom, L ¹ represents a divalent linking group, X ¹ represents a reactive silyl group, and * represents a bonding position.
[2] The curable resin composition according to [1], wherein a mass ratio (A: B) of the vinyl polymer (A) and the polyoxyalkylene polymer (B) is 10:90 to 90:10. object.
[3] Further contains a curing catalyst (D),
The curing catalyst (D) is at least one selected from the group consisting of a tin compound, a titanium compound, an acidic compound and an amine compound,
Content of the said curing catalyst (D) is 0.1-20 mass parts with respect to a total of 100 mass parts of the said vinyl polymer (A) and the said polyoxyalkylene polymer (B), [1] Alternatively, the curable resin composition according to [2].
[4] The curable resin composition according to any one of [1] to [3], further including a resin hollow body.
[5] The curable resin composition according to any one of [1] to [4], further comprising an antioxidant.
[6] Furthermore, it contains at least one plasticizer of an oxyalkylene polymer and a vinyl polymer having a number average molecular weight of 1,500 to 15,000,
The content of the plasticizer is 1 to 100 parts by mass with respect to 100 parts by mass in total of the vinyl polymer (A) and the polyoxyalkylene polymer (B). The curable resin composition according to any one of the above.
[7] The curable resin composition according to any one of [1] to [6], wherein the vinyl polymer (A) has a weight average molecular weight of 45,000 to 90,000.
[8] The curable resin composition according to any one of [1] to [7], wherein the vinyl polymer (A) has a number average molecular weight of more than 10,000 and less than 20,000.
[9] The curable resin composition according to any one of [1] to [8], wherein the vinyl polymer (A) further has a hydrocarbon group in a side chain. However, the hydrocarbon group does not have a reactive silyl group.
[10] The curable resin composition according to [9], wherein the hydrocarbon group has 1 to 12 carbon atoms.
[11] The curable resin composition according to any one of [1] to [10], wherein the vinyl polymer (A) has a linear molecular chain.
[12] The curable resin composition according to any one of [1] to [11], wherein in formula (I), the reactive silyl group as X ₁ is a dialkoxysilyl group.
[13] Any of [1] to [12], wherein the molecular chain of the vinyl polymer (A) has a repeating unit represented by the following formula (II) and a repeating unit represented by the formula (III): The curable resin composition described in 1.
In formula (II), R ^2-1 represents a hydrogen atom or a monovalent hydrocarbon group, L ² represents a divalent linking group, and R ^2-2 represents a monovalent hydrocarbon group.
In formula (III), R ^3-1 represents a hydrogen atom or a monovalent hydrocarbon group, L ³ represents a divalent linking group, and R ^3-2 and R ^3-3 each independently represent a monovalent group. Represents a hydrocarbon group, m3 is 1 to 3, n3 is 0 to 2, and m3 + n3 is 3.
[14] The curable resin composition according to [13], wherein m3 is 2 and n3 is 1 in formula (III).
[15] The curable resin composition according to any one of [1] to [14], wherein the group represented by the formula (I) is a group represented by the following formula (I-1).
In formula (I-1), R ^1-1 represents a divalent hydrocarbon group, R ^1-2 and R ^1-3 each independently represent a monovalent hydrocarbon group, and m1 is from 1 to 3 Yes, n1 is 0 to 2, m1 + n1 is 3, and * represents a bonding position.
[16] The curable resin composition according to [15], wherein m1 is 2 and n1 is 1 in formula (I-1).
[17] The curable resin composition according to any one of [1] to [16], wherein the vinyl polymer (a) has one terminal having a group represented by the formula (I).
[18] The curable resin composition according to any one of [1] to [17], wherein the vinyl polymer (a) further has a reactive silyl group in a side chain of the molecular chain.
[19] The vinyl polymer (A) according to any one of [1] to [18], wherein the reactive silyl group at the end of the molecular chain is a group represented by the following formula (V). Curable resin composition.
* -SL ¹ -X ¹ (V)
In formula (V), S is a sulfur atom, L ¹ represents a divalent linking group, X ¹ represents a reactive silyl group, and * represents a bonding position.
[20] The content of the epoxy compound (C) is 1 to 50 parts by mass with respect to a total of 100 parts by mass of the vinyl polymer (A) and the polyoxyalkylene polymer (B). ] The curable resin composition in any one of [19].
[21] Further, an epoxy curing agent is contained,
The epoxy curing agent is at least one selected from the group consisting of amine, thiol, acid anhydride, ketimine, enamine, oxazolidine and aldimine;
Content of the said epoxy hardening | curing agent is 0.1-30 mass parts with respect to a total of 100 mass parts of the said vinyl polymer (A) and the said polyoxyalkylene polymer (B), [1]-[ 20]. The curable resin composition according to any one of [20].

  The curable resin composition of the present invention is excellent in weather resistance and water adhesion.

The present invention will be described in detail below.
In the present specification, (meth) acrylate represents acrylate or methacrylate, (meth) acryloyl represents acryloyl or methacryloyl, and (meth) acryl represents acryl or methacryl. Poly (meth) acrylate represents polyacrylate, polymethacrylate, or a copolymer of acrylate and methacrylate.
In addition, a numerical range expressed using “to” in this specification means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the manufacturing method of each component is not particularly limited. For example, a conventionally well-known thing is mentioned.
In this specification, unless otherwise specified, each component can be used alone or in combination of two or more of the substances corresponding to the component. When a component contains two or more types of substances, the content of the component means the total content of the two or more types of substances.

[Curable resin composition]
The curable resin composition of the present invention (the composition of the present invention)
Having a reactive silyl group at the end and side chain of the molecular chain, the molecular chain having a repeating unit of a polymerizable vinyl monomer;
The total number of reactive silyl groups exceeds 1 per molecule, the number of reactive silyl groups at the terminal exceeds 0.5, and the number of reactive silyl groups in the side chain is 0.5. More than
A vinyl polymer (A) having a weight average molecular weight of 30,000 to 110,000, a number average molecular weight of 9,000 to 40,000, and a glass transition temperature of −100 to −10 ° C .;
A polyoxyalkylene polymer (B) having a reactive silyl group and having a molecular chain substantially polyoxyalkylene;
Containing an epoxy compound (C) having an epoxy group,
The vinyl polymer (A) is a vinyl polymer (a) having a molecular chain having a repeating unit of a polymerizable vinyl monomer and having a group represented by the following formula (I) at the end of the molecular chain. And a curable resin composition.
* -SL ¹ -X ¹ (I)
In formula (I), S is a sulfur atom, L ¹ represents a divalent linking group, X ¹ represents a reactive silyl group, and * represents a bonding position.

Since the composition of this invention takes such a structure, it is thought that a desired effect is acquired. The reason is not clear, but it is presumed that it is as follows.
In general, when a polyoxyalkylene polymer having a reactive silyl group is exposed to an outdoor environment, the bond between carbon and oxygen in the polyoxyalkylene molecular chain (main chain) is affected by the external environment. Easy to cut. For this reason, the sealing material containing the polyoxyalkylene polymer usually has low weather resistance.

On the other hand, the vinyl polymer (A) and the vinyl polymer (a) contained in the present invention are chemically stable as compared with polyoxyalkylene.
Further, since the vinyl polymer (A) has a large weight average molecular weight and / or number average molecular weight, even if the polyoxyalkylene polymer is cleaved in the molecular chain, it can be obtained by the presence of the vinyl polymer (A). The elongation of the sealing material can be maintained within an appropriate range.
For the above reasons, it is estimated that the sealing material obtained using the composition of the present invention is excellent in weather resistance.

In addition, the epoxy compound (C) contained in the present invention is ring-opened upon curing to form a hydroxy group, and the hydroxy group can at least interact with the base material and / or the primer. It is presumed to be excellent in performance.
Hereinafter, each component contained in the composition of this invention is explained in full detail.

<< Vinyl polymer (A) >>
The vinyl polymer (A) contained in the composition of the present invention has a reactive silyl group at the end and side chain of the molecular chain, and the molecular chain has a repeating unit of a polymerizable vinyl monomer,
On an average per molecule, the total number of reactive silyl groups exceeds 1, the number of reactive silyl groups at the terminal exceeds 0.5, and the number of reactive silyl groups in the side chain is 0. More than 5,
A polymer having a weight average molecular weight of 30,000 to 110,000, a number average molecular weight of 9,000 to 40,000, and a glass transition temperature of −100 to −10 ° C.
The composition of this invention is excellent in a weather resistance by containing the said vinyl polymer (A).

<Molecular chain>
In the present invention, the vinyl polymer (A) has a molecular chain, and the molecular chain has a repeating unit of a polymerizable vinyl monomer.
Since the molecular chain has a repeating unit of a polymerizable vinyl monomer, the molecular chain (main chain or skeleton) can be substantially a hydrocarbon.
In the present invention, the term “substantially” means that the molecular chain of the vinyl polymer (A) may further contain a repeating unit other than — [C—C] —. ]-Means that the content of the vinyl polymer (A) is 50% by mass or more based on the total of repeating units. The content of-[C-C]-is preferably 80% by mass or more based on the total.

  Examples of the molecular chain of the vinyl polymer (A) include a poly (meth) acrylate polymer. The same applies to the molecular chain of the vinyl polymer (a).

  The repeating unit of the polymerizable vinyl monomer constituting the molecular chain (or its skeleton) is not particularly limited as long as it is a repeating unit of a compound having a carbon-carbon double bond. For example, an olefin monomer such as ethylene; a (meth) acrylic monomer such as (meth) acrylate, (meth) acrylamide, (meth) acrylic acid; and an aromatic vinyl monomer such as styrene. Units are listed.

  In addition, at least one part of the repeating unit which comprises the molecular chain of the said vinyl polymer (A) can have a reactive silyl group. When the repeating unit has a reactive silyl group, the vinyl polymer (A) can have the reactive silyl group in a side chain, for example. As a repeating unit which has a reactive silyl group, the repeating unit by the (meth) acrylate which has a reactive silyl group is mentioned, for example.

(Repeating unit with (meth) acrylate monomer)
Especially, the repeating unit which comprises the molecular chain (skeleton) of the said vinyl polymer (A) is a repeating unit by a (meth) acrylate monomer from a viewpoint that it is excellent by a weather resistance and / or water-resistant adhesiveness. It is preferable. The (meth) acrylate monomer (repeating unit) may have a reactive silyl group. In addition, the repeating unit (or (meth) acrylate monomer) by the (meth) acrylate monomer mentioned later shall have a reactive silyl group.

The (meth) acrylate monomer is not particularly limited as long as it is a (meth) acrylic acid ester. Examples of the hydrocarbon group constituting the ester portion of the (meth) acrylic acid ester include an aliphatic hydrocarbon group (linear, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof. It is done.
When the (meth) acrylate monomer has a reactive silyl group, the reactive silyl group can be bonded to, for example, an ester residue in the (meth) acrylate monomer.

  The ester residue (hydrocarbon group constituting the ester) in the (meth) acrylate monomer is excellent in weather resistance and / or water-resistant adhesion, and is excellent in elongation of the cured product, and has 1 to 12 carbon atoms. It preferably has a hydrocarbon group. However, the carbon number of the ester residue in the (meth) acrylate monomer is such that when the (meth) acrylate monomer has a reactive silyl group in the ester residue, the reactive silyl group is converted from the ester residue. The number of carbon atoms in the ester residue after removal.

  Examples of the hydrocarbon group having 1 to 12 carbon atoms include aliphatic hydrocarbon groups such as propyl group, butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, isononyl group, and lauryl group; And a divalent or higher valent aliphatic hydrocarbon group obtained by further removing a hydrogen atom.

(The molecular chain is linear)
The shape of the molecular chain of the vinyl polymer (A) is not particularly limited. The shape of the molecular chain is one of the preferred embodiments from the viewpoint that the cured product obtained is excellent in elongation and the viscosity of the composition falls within an appropriate range.

<Reactive silyl group>
The reactive silyl group of the vinyl polymer (A) is not particularly limited as long as it has a silicon atom and is reactive. For example, the silyl group which 1-3 hydrolyzable groups couple | bonded with one silicon atom is mentioned.
The reactive silyl group possessed by the vinyl polymer (A) is excellent in weather resistance and / or water adhesion, excellent in elongation of the resulting cured product, and from the viewpoint that the viscosity of the composition falls within an appropriate range. A silyl group in which two hydrolyzable groups are bonded to one silicon atom is preferable. The same applies to the reactive silyl group at the side chain or terminal. The same applies to the reactive silyl group of the vinyl polymer (a).
Examples of the hydrolyzable group include a hydrogen atom, a halogen atom, an alkoxy group, an acyl oxide group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyl oxide group. Of these, an alkoxy group is preferable.

  The above-mentioned reactive silyl group is preferably a dialkoxysilyl group from the viewpoint that it is excellent in weather resistance and / or water adhesion, is excellent in elongation of the resulting cured product, and the viscosity of the composition is in an appropriate range. An alkoxysilyl group and a dimethoxysilyl group are more preferable.

  When one or two hydrolyzable groups are bonded to one silicon atom, groups other than the hydrolyzable group that can be bonded to the silicon atom are not particularly limited. For example, an aliphatic hydrocarbon group (straight, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof can be used. Of these, an aliphatic hydrocarbon group having 1 to 6 carbon atoms is preferable. Specific examples include a methyl group and an ethyl group.

(Reactive silyl group and molecular chain)
In this invention, the said vinyl polymer (A) has the said reactive silyl group in the terminal and side chain of a molecular chain.
The reactive silyl group can be bonded to the end of the molecular chain directly or via an organic group. The organic group is not particularly limited.
The reactive silyl group can be bonded to the side chain of the molecular chain directly or via an organic group. The organic group is not particularly limited.

  The vinyl polymer (A) is, for example, a mixture of vinyl polymers having the reactive silyl group at the end or side chain of the molecular chain; a vinyl polymer having the reactive silyl group at the end and side chain of the molecular chain. A vinyl polymer having the reactive silyl group at the end or side chain of the molecular chain, and a mixture of vinyl polymers having the reactive silyl group at the end and side chain of the molecular chain. In each of the above embodiments, the vinyl polymer (A) may further include a vinyl polymer having no reactive silyl group.

<Total number of reactive silyl groups>
In the present invention, the total number of the reactive silyl groups that the vinyl polymer (A) has on average per molecule exceeds one.
The total number of reactive silyl groups is the number of the reactive silyl groups that the vinyl polymer (A) has on average per molecule in the entire vinyl polymer (A).

The total number is preferably more than 1 and 3 or less, more preferably more than 1 and 2 or less on average from the viewpoint that it is more excellent in weather resistance and / or water adhesion.
The total number of reactive silyl groups can be the total number of reactive silyl groups at the ends and the number of reactive silyl groups in the side chain, which will be described later.

  In the present invention, the number (total number) of reactive silyl groups is theoretically determined from the composition ratio and number average molecular weight (Mn) of the monomer and chain transfer agent used in the production of the vinyl polymer (A). The number of reactive silyl groups per molecule of the polymer and the group represented by formula (I) can be calculated. About the said vinyl polymer (A) mentioned later, the number of the said reactive silyl groups which it has in a terminal or a side chain, the number of groups represented by the formula (V) which it has in a terminal; vinyl polymer (a) mentioned later has The same applies to the number of reactive silyl groups possessed and the number of groups represented by formula (I) at the terminal.

<Reactive silyl group at terminal>
The vinyl polymer (A) has a reactive silyl group at the terminal from the viewpoint of excellent weather resistance, excellent elongation of the cured product, and a viscosity of the composition within an appropriate range.

  When the reactive silyl group is bonded to the end of the molecular chain of the vinyl polymer (A) via an organic group, the group having the reactive silyl group is represented, for example, by the following formula (V): Groups.

* -SL ¹ -X ¹ (V)
In formula (V), S is a sulfur atom, L ¹ represents a divalent linking group, X ¹ represents a reactive silyl group, and * represents a bonding position.

  The formula (V) is the same as the group represented by the formula (I) that the vinyl polymer (a) described later has at the end of the molecular chain.

<Number of reactive silyl groups at the end>
In the present invention, the number of the reactive silyl groups that the vinyl polymer (A) has on average per molecule per terminal exceeds 0.5.
In addition, the number of the said reactive silyl groups is the number of the said reactive silyl groups which a vinyl polymer (A) has in the terminal per average per molecule in the said whole vinyl polymer (A).
The above number is preferably more than 0.5 and 2 or less on average, more preferably 1 or 2 from the viewpoint that it is more excellent in weather resistance and / or water adhesion.

<Reactive silyl group in side chain>
The vinyl polymer (A) has a reactive silyl group in the side chain from the viewpoint of excellent weather resistance and / or water adhesion, excellent elongation of the cured product, and the viscosity of the composition is in an appropriate range. .

  When the reactive silyl group is bonded to the side chain of the molecular chain of the vinyl polymer (A) through an organic group, the group having the reactive silyl group is represented by the following formula (IV), for example. Group.

* -L ⁴ -X ⁴ (IV)
In formula (IV), L ⁴ represents a divalent linking group, X ⁴ represents a reactive silyl group, and * represents a bonding position.
L ^{4 in} formula (IV) is the same as L ³ in formula (III) described later.
X ^{4 in the} formula (IV) is the same as X ^{1 in the} formula (I) representing a group that the vinyl polymer (a) described later has at the end of the molecular chain.

<Number of reactive silyl groups in side chain>
In the present invention, the number of the reactive silyl groups that the vinyl polymer (A) has in the side chain on an average per molecule exceeds 0.5.
In addition, the number of the said reactive silyl groups is the number of the said reactive silyl groups which a vinyl polymer (A) has in an average side chain per molecule in the whole said vinyl polymer (A).
The above number is preferably more than 0.5 and 2 or less on average, more preferably 1 or 2 from the viewpoint that it is more excellent in weather resistance and / or water adhesion.

(Another side chain)
The vinyl polymer (A) is excellent in weather resistance and / or water adhesion, is excellent in elongation of the cured product, and has a composition having an appropriate range of viscosity, and further has a hydrocarbon group in the side chain. It is preferable to have. In addition, the said hydrocarbon group does not have a reactive silyl group.
Examples of the hydrocarbon group include an aliphatic hydrocarbon group (linear, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof. Specifically, a C1-C12 hydrocarbon group is mentioned, for example, A C1-C8 aliphatic hydrocarbon group is preferable.

The hydrocarbon group can be bonded to the molecular chain directly or through an organic group.
The organic group is not particularly limited. For example, an ester bond, an amide bond, an ether bond, and a carbonyl group can be mentioned.

(Repeating unit constituting vinyl polymer (A))
The repeating unit represented by the formula (III) The molecular chain of the vinyl polymer (A) is superior in weather resistance and / or water-resistant adhesion, excellent in elongation of the cured product, and the viscosity of the composition is in an appropriate range. From the viewpoint of becoming, it is preferable to have a repeating unit represented by the formula (III).

In formula (III), R ^3-1 represents a hydrogen atom or a monovalent hydrocarbon group, L ³ represents a divalent linking group, and R ^3-2 and R ^3-3 each independently represent a monovalent group. Represents a hydrocarbon group, m3 is 1 to 3, n3 is 0 to 2, and m3 + n3 is 3.

・ R ^3-1
In the formula (III), R ^3-1 represents a hydrogen atom or a monovalent hydrocarbon group.
Examples of the monovalent hydrocarbon group include an aliphatic hydrocarbon group such as a methyl group.

・ L ³
In the formula (III), L ³ represents a divalent linking group.
Examples of the divalent linking group as L ³ include a divalent hydrocarbon group L ^3-1 ; a substituent L ^3-2 such as an ester bond, an amide bond, an ether bond, and a carbonyl group.
Examples of the divalent hydrocarbon group L ^3-1 include an aliphatic hydrocarbon group (linear, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof. Specific examples include an aliphatic hydrocarbon group having 1 to 8 carbon atoms.

Examples of L ³ include a combination of a divalent hydrocarbon group L ^3-1 and a substituent L ^3-2 .
Of these, a combination of a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms and an ester bond is preferable.

・ R ^3-2 , R ^3-3
In formula (III), R ^3-2 and R ^3-3 each independently represent a monovalent hydrocarbon group.
Examples of the monovalent hydrocarbon group include an aliphatic hydrocarbon group (linear, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof.
Of these, an aliphatic hydrocarbon group such as a methyl group or an ethyl group is preferable.

・ M3
In formula (III), m3 is 1-3.
m3 is excellent in weather resistance and / or water-resistant adhesion, is excellent in elongation of the resulting cured product, has a viscosity of the composition in an appropriate range, and can ensure a pot life of an appropriate length, 2 is 2 preferable.

・ N3
In formula (III), n3 is 0-2.
n3 is excellent in weather resistance and / or water adhesion, is excellent in elongation of the resulting cured product, has a viscosity of the composition in an appropriate range, and can ensure a pot life of an appropriate length, 1 is 1 preferable.

Examples of the group represented by the formula (III) include a group represented by the following formula (III-1).

In formula (III-1), R ^3-1 represents a hydrogen atom or a monovalent hydrocarbon group, R ^3-2 and R ^3-3 each independently represent a monovalent hydrocarbon group, R ^{3- 4} represents a divalent hydrocarbon group, m3 is 1 to 3, n3 is 0 to 2, and m3 + n3 is 3.
R ^3-1 , R ^3-2 , R ^3-3 , m3, and n3 in formula (III-1) are the same as in formula (III).
R ^{3-4 in the} formula (III-1) is the same as the above divalent hydrocarbon group L ^3-1 . Of these, a propylene group is preferred.

-Repeating unit represented by formula (II) The molecular chain of the vinyl polymer (A) is further a repeating unit represented by the following formula (II), for example, as a repeating unit of the (meth) acrylate monomer. Can have units.

In formula (II), R ^2-1 represents a hydrogen atom or a monovalent hydrocarbon group, L ² represents a divalent linking group, and R ^2-2 represents a monovalent hydrocarbon group.

・ R ^2-1
In the formula (II), R ^2-1 represents a hydrogen atom or a monovalent hydrocarbon group.
Examples of the monovalent hydrocarbon group include an aliphatic hydrocarbon group such as a methyl group.

・ L ²
In formula (II), L ² represents a divalent linking group.
Examples of the divalent linking group include an ester bond, an amide bond, an ether bond, and a carbonyl group.
Of these, an ester bond is preferable.

・ R ^2-2
In the formula (II), R ^2-2 represents a monovalent hydrocarbon group.
Examples of the monovalent hydrocarbon group include an aliphatic hydrocarbon group (linear, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof.
R ^2-2 is preferably a hydrocarbon group having 1 to 12 carbon atoms and a hydrocarbon group having 3 to 8 carbon atoms from the viewpoint of being excellent in weather resistance and / or water adhesion, and excellent in elongation of the resulting cured product. Is more preferable, and a hydrocarbon group having 4 to 8 carbon atoms is still more preferable.
Specific examples of R ^2-2 include aliphatic hydrocarbon groups such as a butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, isononyl group, and lauryl group. Of these, a butyl group, a pentyl group, a hexyl group, an octyl group, and a 2-ethylhexyl group are preferable.

<Weight average molecular weight>
In the present invention, the vinyl polymer (A) has a weight average molecular weight of 30,000 to 110,000.
When the weight average molecular weight is in the above range, the composition of the present invention is excellent in weather resistance and / or water adhesion resistance.

  The weight average molecular weight of the vinyl polymer (A) is superior in weather resistance and / or water adhesion, excellent in elongation of the obtained cured product, can maintain the initial elongation of the cured product for a long period of time, and has a viscosity of the composition. Is preferably 45,000 to 100,000, more preferably 45,000 to 90,000, still more preferably 45,000 to 85,000, and 45,000 to 60,000. Particularly preferred.

<Number average molecular weight>
In the present invention, the vinyl polymer (A) has a number average molecular weight of 9,000 to 40,000.

  The number average molecular weight of the vinyl polymer (A) is excellent in weather resistance (particularly longer-term weather resistance) and / or water adhesion, excellent in elongation of the resulting cured product, and initial elongation of the cured product is long-term. From the viewpoint that the viscosity of the composition falls within an appropriate range, it is preferably more than 10,000 and less than 20,000.

  In the present invention, the vinyl polymer (A) was analyzed by gel permeation chromatography (GPC), and the weight average molecular weight or number average molecular weight of the vinyl polymer (A) was calculated in terms of polystyrene under the following conditions.

・ Device: GPC-8220 (manufactured by Tosoh Corporation)
Column: One G7000HXL / 7.8 mmID, two GMHXL / 7.8 mmIDs, and one G2500HXL / 7.8 mmID were used.
Medium: Tetrahydrofuran Flow rate: 1.0 mL / min
・ Concentration: 1.5mg / ml
・ Injection volume: 300 μL
-Column temperature: 40 ° C

In the present invention, the glass transition temperature (Tg) of the vinyl polymer (A) is −100 to −10 ° C.
When the glass transition temperature is in the above range, the composition of the present invention is excellent in weather resistance.

  The glass transition temperature is preferably −60 to −10 ° C. from the viewpoints of excellent weather resistance and / or water adhesion, excellent elongation of the obtained cured product, and a suitable viscosity of the composition.

  In the present invention, for the glass transition temperature (Tg) of the vinyl polymer (A), a differential thermal analysis (DTA) or a differential scanning calorimeter (DSC) is used, and the sample (vinyl polymer (A)) is kept at a constant speed. The Tg of the sample can be derived by measuring the intersection of the tangent of the base line in the DTA curve or DSC curve and the tangent of the steep descending position of the endothermic region due to the glass transition.

<< Vinyl polymer (a) >>
In the present invention, the vinyl polymer (A) includes a vinyl polymer (a).
In the present invention, the vinyl polymer (a) is a polymer having a molecular chain having a repeating unit of a polymerizable vinyl monomer and a group represented by the following formula (I) at the end of the molecular chain. .
* -SL ¹ -X ¹ (I)
In formula (I), S is a sulfur atom, L ¹ represents a divalent linking group, X ¹ represents a reactive silyl group, and * represents a bonding position.

<Molecular chain>
In the present invention, the molecular chain of the vinyl polymer (a) has a repeating unit of a polymerizable vinyl monomer.
The molecular chain of the vinyl polymer (a) can be the same as the molecular chain of the vinyl polymer (A).
The repeating unit by the polymerizable vinyl monomer that the molecular chain of the vinyl polymer (a) has can be the same as the repeating unit by the polymerizable vinyl monomer that the molecular chain of the vinyl polymer (A) has. .

-Side chain The vinyl polymer (a) is excellent in weather resistance and / or water adhesion, is excellent in elongation of the cured product, and has a reactive silyl group in the side chain from the viewpoint that the viscosity of the composition falls within an appropriate range. It preferably has a group.

-Number of reactive silyl groups in side chain The number of reactive silyl groups in the side chain of the vinyl polymer (a) can be 0 to 2 per molecule of the vinyl polymer (a).
From the viewpoint that the number of reactive silyl groups in the side chain of the vinyl polymer (a) is excellent in weather resistance and / or water-resistant adhesion, excellent in elongation of the cured product, and the viscosity of the composition is in an appropriate range. 1 to 2 is preferable per molecule of the vinyl polymer (a).

  The reactive silyl group that the vinyl polymer (a) can have in the side chain can be the same as the reactive silyl group that the vinyl polymer (A) has in the side chain.

<Terminal>
In the present invention, the vinyl polymer (a) has a group represented by the following formula (I) at the end of the molecular chain.
* -SL ¹ -X ¹ (I)
In formula (I), S is a sulfur atom, L ¹ represents a divalent linking group, X ¹ represents a reactive silyl group, and * represents a bonding position.

・ L ¹
In the formula (I), L ¹ represents a divalent linking group.
Examples of the divalent linking group include those similar to the above divalent hydrocarbon group ^L3-1 .
Of these, a propylene group is preferred.

・ X ¹
In the formula (I), X ¹ represents a reactive silyl group.
The reactive silyl group is not particularly limited. For example, the thing similar to the above is mentioned.

The reactive silyl group as X ¹ is preferably a dialkoxysilyl group from the viewpoints of excellent weather resistance and / or water adhesion, excellent elongation of a cured product to be obtained, and a viscosity of the composition within an appropriate range. An alkyl dialkoxysilyl group is more preferred, and a methyldimethoxysilyl group is still more preferred.

*
In the formula (I), * represents a bonding position.
In the present invention, the vinyl polymer (a) has a group represented by the formula (I) at the end of the molecular chain. The group represented by the formula (I) can be bonded to the end of the molecular chain of the vinyl polymer (a) in the above *.

  The group represented by the formula (I) can be bonded to the end of the molecular chain of the vinyl polymer (a) directly or via an organic group. The organic group is not particularly limited.

The vinyl polymer (a) preferably has one or more reactive silyl groups per molecule (on average). The reactive silyl group is the same as described above.
The number of reactive silyl groups that the vinyl polymer (a) has per molecule (on average) is 1 to 2 from the viewpoint of being excellent in weather resistance and / or water-resistant adhesion and excellent in elongation of the resulting cured product. It is preferable that it is a piece.

The vinyl polymer (a) may have one terminal having a group represented by the formula (I) from the viewpoint of being excellent in weather resistance and / or water-resistant adhesion and excellent in elongation of a cured product obtained. preferable.
The other end of the vinyl polymer (a) may be bonded with, for example, a residue from a polymerization initiator used in producing the vinyl polymer (A).
In addition, the residue by the polymerization initiator used when manufacturing a vinyl polymer (A) may be couple | bonded with the terminal in a vinyl polymer (A).

Formula (I-1)
The group represented by the formula (I) is excellent in weather resistance and / or water-resistant adhesion, excellent in elongation of the resulting cured product, and from the viewpoint that the viscosity of the composition falls within an appropriate range, the following formula (I- The group represented by 1) is preferred.
In formula (I-1), R ^1-1 represents a divalent hydrocarbon group, R ^1-2 and R ^1-3 each independently represent a monovalent hydrocarbon group, and m1 is from 1 to 3 Yes, n1 is 0 to 2, m1 + n1 is 3, and * represents a bonding position.

・ R ^1-1
In formula (I-1), R ^1-1 represents a divalent hydrocarbon group.
Examples of the divalent hydrocarbon group include an aliphatic hydrocarbon group (linear, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof. Especially, a C2-C6 aliphatic hydrocarbon group is preferable and a propylene group is more preferable.

・ R ^1-2 , R ^1-3
In formula (I-1), R ^1-2 and R ^1-3 each independently represent a monovalent hydrocarbon group.
Examples of the monovalent hydrocarbon group include an aliphatic hydrocarbon group (linear, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof.
Of these, an aliphatic hydrocarbon group such as a methyl group or an ethyl group is preferable.

・ M1
In formula (I-1), m1 is 1-3.
m1 is excellent in weather resistance and / or water-resistant adhesion, is excellent in elongation of the obtained cured product, has a viscosity of the composition in an appropriate range, and can ensure a pot life of an appropriate length, 2 is 2 preferable.

・ N1
In formula (I-1), n1 is 0-2.
n1 is excellent in weather resistance and / or water-resistant adhesion, is excellent in elongation of the obtained cured product, has a viscosity of the composition in an appropriate range, and can ensure a pot life of an appropriate length, 1 is 1 preferable.

*
In formula (I-1), * represents a bonding position. * In the formula (I-1) is the same as * in the formula (I).

  The weight average molecular weight, number average molecular weight or glass transition temperature of the vinyl polymer (a) can be the same as that of the vinyl polymer (A).

In the present invention, all or part of the vinyl polymer (A) may be the vinyl polymer (a).
When a part of the vinyl polymer (A) is the vinyl polymer (a), the vinyl polymer (A) has a molecular chain having a polymerizable vinyl monomer in addition to the vinyl polymer (a). And a vinyl polymer (a ′) having a repeating silyl group at the terminal and / or side chain (excluding the vinyl polymer (a)).
The vinyl polymer (A) may further include a vinyl polymer (a ″) having a repeating unit of a polymerizable vinyl monomer but having no reactive silyl group.
The vinyl polymer (a ′) or the vinyl polymer (a ″) may be a by-product in producing the vinyl polymer (A).

-Content of vinyl polymer (a) Content of the said vinyl polymer (a) can be 0.1-100 mass% with respect to the said whole vinyl polymer (A).

(Method for producing vinyl polymer (A))
The method for producing the vinyl polymer (A) is not particularly limited. For example, the vinyl polymer (A) can be produced by polymerizing the polymerizable vinyl monomer in the presence of a polymerization initiator and a chain transfer agent.

-Polymerizable vinyl monomer A polymerizable vinyl monomer will not be restrict | limited especially if it is a compound which has a carbon-carbon double bond.
Examples of the polymerizable vinyl monomer include a compound represented by the following formula (III ′). As the polymerizable vinyl monomer, for example, a compound represented by the following formula (II ′) can be used. One preferred embodiment of the polymerizable vinyl monomer is to use a compound represented by the following formula (III ′) and a compound represented by the following formula (II ′) together.

The compound represented by the above formula (II ′) can form a repeating unit represented by the above formula (II).
The compound represented by the above formula (III ′) can form a repeating unit represented by the above formula (III).

Chain transfer agent Examples of the chain transfer agent include compounds represented by the formula (I '): HS-L ¹ -X ¹ .
By the compound represented by the formula (I ′), a group represented by the formula (I) can be formed at the terminal of the vinyl polymer (a). The same applies to the vinyl polymer (A).

-Use amount of the compound represented by the formula (III ') When the compound represented by the formula (II') and the compound represented by the formula (III ') are used in combination as the polymerizable vinyl monomer, From the viewpoint that the amount of the compound represented by the above formula (III ′) is excellent in weather resistance and / or water adhesion, excellent in elongation of the resulting cured product, and the viscosity of the composition is in an appropriate range, It is preferably 0.1 to 100 parts by weight, preferably 0.4 to 2.0 parts by weight, based on 100 parts by weight of the compound represented by the above formula (II ′), 0.5 to More preferably, it is 1.5 parts by mass.

  When the molecular chain (main chain) of the vinyl polymer (A) has a repeating unit represented by the above formula (II) and a repeating unit represented by the formula (III), the vinyl polymer ( The molar ratio of the compound represented by the above formula (II ′) and the compound represented by the above formula (III ′) used in the production of A) is defined as the molecular chain of the vinyl polymer (A). It can be reflected in the number of repeating units of the repeating unit represented by the above formula (II) and the repeating unit represented by the formula (III) constituting the (main chain).

-Amount of chain transfer agent used The amount of the chain transfer agent used is superior in terms of weather resistance and / or water adhesion, excellent in elongation of the resulting cured product, and from the viewpoint that the viscosity of the composition falls within an appropriate range, The amount of the polymerizable vinyl monomer is preferably 0.2 to 5 parts by mass and more preferably 0.8 to 3.6 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable vinyl monomer.
When the amount of chain transfer agent used is reduced, the weight average molecular weight and / or number average molecular weight of the vinyl polymer (A) can be increased.

-Polymerization initiator The polymerization initiator is not particularly limited. Examples thereof include azo compounds such as azobisisobutyronitrile, organic peroxides, and metallocene catalysts.
The amount of the polymerization initiator used is not particularly limited.
The amount of the polymerization initiator used is preferably 0.05 to 5.0 parts by weight, and 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable vinyl monomer. It is more preferable.

  In the said manufacturing method, a solvent can be used as needed.

  In addition, it is mentioned as one of the preferable aspects that the said vinyl polymer (A) does not have a urethane bond or a urea bond. The same applies to the vinyl polymer (a).

<< Polyoxyalkylene Polymer (B) >>
The polyoxyalkylene polymer (B) contained in the composition of the present invention has a reactive silyl group, and the molecular chain (main chain) is substantially polyoxyalkylene.
The composition of this invention has the preferable workability | operativity (handling property) as a sealing material by containing the said polyoxyalkylene polymer (B).

<Reactive silyl group>
The reactive silyl group that the polyoxyalkylene polymer (B) has is not particularly limited. The reactive silyl group is preferably a silyl group having a hydrolyzable group. The silyl group having hydrolyzability is the same as described above.
The reactive silyl group possessed by the polyoxyalkylene polymer (B) is superior in weather resistance and / or water adhesion, excellent in the elongation of the resulting cured product, the viscosity of the composition is in an appropriate range, and the pot life Is preferably a silyl group in which two hydrolyzable groups are bonded to one silicon atom.
The above-mentioned reactive silyl group is excellent in weather resistance and / or water adhesion, is excellent in elongation of a cured product to be obtained, has a composition having an appropriate range of viscosity, and can secure a pot life in an appropriate length. Therefore, a dialkoxysilyl group is preferable, and an alkyl dialkoxysilyl group and a dimethoxysilyl group are more preferable.

  From the viewpoint that the polyoxyalkylene polymer (B) is superior in weather resistance, excellent in cured properties, has a composition having an appropriate range of viscosity, and can secure a pot life in an appropriate length. It is preferable to have one or more groups on average per molecule, and more preferably 1-2 groups.

The average number of reactive silyl groups possessed by the polyoxyalkylene polymer (B) is the average number determined by a method of quantifying protons on carbon to which the reactive silyl groups are directly bonded by high resolution ¹ H-NMR measurement. Can be defined. In the calculation of the average number of reactive silyl groups possessed by the polyoxyalkylene polymer (B), reactive silyl groups were introduced into the polyoxyalkylene polymer precursor prior to introduction of the reactive silyl groups. The same main chain is used for the polyoxyalkylene polymer precursor in which no reactive silyl group is introduced and the modified polyoxyalkylene polymer precursor in which no by-product reactive silyl group is introduced. As part of the component of the polyoxyalkylene polymer (B) having a structure, the calculation is performed by including the average number of reactive silyl groups in one molecule in the parameter (number of molecules). Can do.

<Molecular chain>
The molecular chain of the polyoxyalkylene polymer (B) is substantially polyoxyalkylene.
In the present invention, the “substantially” means that the molecular chain of the polyoxyalkylene polymer (B) may further contain a repeating unit other than an oxyalkylene group, but the content of the oxyalkylene group is It means that it is 50% by mass or more based on the total of repeating units of the polyoxyalkylene polymer (B). The content of the oxyalkylene group is preferably 80% by mass or more based on the total.

  Examples of the polyoxyalkylene include polyoxyethylene, polyoxypropylene, polyoxytrimethylene, polyoxytetramethylene, copolymers thereof, derivatives thereof having a substituent, and the like.

The reactive silyl group can be bonded to the molecular chain directly or via an organic group. The organic group is not particularly limited.
The polyoxyalkylene polymer (B) can have the reactive silyl group at the terminal and / or side chain of the molecular chain.
The polyoxyalkylene polymer (B) preferably has the reactive silyl group at the end of the molecular chain.

  When the polyoxyalkylene polymer (B) has the reactive silyl group at the end of the molecular chain, it is superior in weather resistance, excellent in the elongation of the resulting cured product, and the viscosity of the composition is in an appropriate range. From the viewpoint that the time can be secured with an appropriate length, it is preferable to have a reactive silyl group at 50% or more of all terminals of the molecular chain, more preferably 60% or more, and still more preferably 60 to 85%.

(Number average molecular weight)
The number average molecular weight of the polyoxyalkylene polymer (B) is superior in weather resistance (particularly longer-term weather resistance) and / or water-resistant adhesion, excellent in elongation of the resulting cured product, and appropriate in viscosity of the composition. From the viewpoint that it is within such a range, it is preferably 3,000 to 50,000, more preferably 10,000 to 40,000, and still more preferably 15,000 to 35,000.

  In the present invention, the number average molecular weight of the polyoxyalkylene polymer (B) is a standard polystyrene equivalent value based on a measured value by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

  In addition, it is mentioned as one of the aspects with preferable that the said polyoxyalkylene polymer (B) does not have a urethane bond or a urea bond.

(Production method of polyoxyalkylene polymer (B))
The method for producing the polyoxyalkylene polymer (B) is not particularly limited. For example, the formula (VI) in one ^{_{molecule: CH 2 = C (R 3}} ) -R 2 -O-
(In the formula (VI), R ² represents a divalent organic group having 1 to 20 carbon atoms, and R ₃ represents a hydrogen atom or a monovalent hydrocarbon group.) An alkylene polymer precursor;
Formula (VII): H-X
(In formula (VII), X represents a reactive silyl group.) A method in which a reactive silyl group-containing compound represented by formula (VII) is reacted in the presence of a group VIII transition metal catalyst can be mentioned.

In the formula (VI), examples of the divalent organic group having 1 to 20 carbon atoms include CH ₂ ═CH—CH ₂ —, CH ₂ ═CH—C ₂ H ₄ —, and CH ₂ ═C (CH ₃ ). -CH ₂ -, and the like. The organic groups, from the viewpoint of _{reactivity, CH 2 = CH-CH 2} - ( allyl _{group), CH 2 = C (CH} 3) -CH 2 - ( methallyl group).
In the formula (VI), examples of the monovalent hydrocarbon group include an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as a methyl group.
In addition, as a manufacturing method of the said polyoxyalkylene type polymer precursor, a conventionally well-known thing is mentioned, for example.

  The reactive silyl group in formula (VII) is the same as described above.

Examples of the Group VIII transition metal catalyst include H ₂ PtCl ₆ .6H ₂ O, platinum-vinylsiloxane complex, platinum-olefin complex, Pt metal, RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O _3. , RuCl ₃ , IrCl ₃ , FeCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ . The group VIII transition metal catalyst is preferably any of H ₂ PtCl ₆ .6H ₂ O, a platinum- (di) vinylsiloxane complex, and a platinum-olefin complex from the viewpoint of hydrosilylation reactivity.

  Examples of commercially available products of the polyoxyalkylene polymer (B) include MS polymer (manufactured by Kaneka), silyl polymer (manufactured by Kaneka), Exester (manufactured by Asahi Glass).

(Mass ratio of vinyl polymer (A) and polyoxyalkylene polymer (B))
The mass ratio (A: B) of the vinyl polymer (A) and the polyoxyalkylene polymer (B) is superior in weather resistance (particularly longer-term weather resistance) and / or water-resistant adhesion, From the viewpoint that the initial elongation can be maintained over a long period of time and the viscosity of the composition falls within an appropriate range, it is preferably 10:90 to 90:10, and 50:50 to 90:10. Is more preferable, and it is still more preferable that it is 50: 50-65: 35.

<< Epoxy Compound (C) >>
The epoxy compound (C) contained in the composition of the present invention is a compound having an epoxy group.
The composition of this invention is excellent in water-resistant adhesiveness by containing the said epoxy compound (C).

-Number of epoxy groups The number of epoxy groups which the said epoxy compound (C) has should just be 1 or more in 1 molecule. The number can be 4 or less per molecule. The number is preferably 2 to 4 from the viewpoint of better weather resistance and / or water adhesion.

  Examples of the compound having a plurality of epoxy groups in one molecule include epoxy resins. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, glycerin glycidyl ether type epoxy resin, polyalkylene oxide glycidyl ether type epoxy resin, phenol Examples include novolak glycidyl ether type epoxy resins and dimer acid glycidyl ester type epoxy resins.

  Of these, bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferred, and bisphenol A type epoxy resins are more preferred from the viewpoint of superior weather resistance and / or water adhesion.

-Epoxy equivalent of the epoxy compound (C) The epoxy equivalent of the epoxy compound (C) is superior in weather resistance and / or water-resistant adhesion, the viscosity of the composition is in an appropriate range, and excellent in water-resistant adhesion, It is preferable that it is 150-250 g / eq, and it is more preferable that it is 170-200 g / eq.

-Viscosity of the epoxy compound (C) The viscosity of the epoxy compound (C) is 5,000 to 25,000 mPa · s from the viewpoint that the viscosity of the composition is in an appropriate range and the workability (handling property) is excellent. It is preferable that it is 8,000 to 15,000 mPa · s.

-Content of epoxy compound (C) From the viewpoint that the content of the epoxy compound (C) is more excellent in weather resistance and / or water-resistant adhesion, the vinyl polymer (A) and the polyoxyalkylene polymer (B ) Is preferably 1 to 50 parts by mass, and more preferably 10 to 30 parts by mass.

(Epoxy curing agent)
The composition of the present invention preferably further contains an epoxy curing agent from the viewpoint of superior weather resistance and / or water adhesion.

The epoxy curing agent is not particularly limited as long as it is a compound having a functional group having reactivity with an epoxy group. Examples of the functional group include an amino group (for example, —NH ₂ and / or —NH—), a mercapto group, a carboxy group, an acid anhydride group, C═N, C═CN, a tetrahydrooxazole skeleton, H— C = N.

Examples of the epoxy curing agent include at least one selected from the group consisting of amine, thiol (mercapto), acid anhydride, ketimine, enamine, oxazolidine, and aldimine.
Of these, amines and ketimines are preferred and amines are more preferred from the viewpoint of superior weather resistance and / or water adhesion.

Amine amine as the epoxy cured product is not particularly limited as long as it is a compound having a primary amino group (-NH ₂₎ or secondary amino group (-NH-).

  The number of the amino groups that the amine has in one molecule can be one or more. The number of the amino groups is preferably 1 to 2 in one amine molecule from the viewpoint of being excellent in weather resistance and / or water-resistant adhesion and excellent in elongation of the obtained cured product.

  In the amine, the amino group can be bonded to a hydrocarbon group. The hydrocarbon group is not particularly limited. For example, an aliphatic hydrocarbon group (straight, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof can be used.

The number of carbon atoms of the hydrocarbon group is preferably 2 to 18 from the viewpoint of excellent weather resistance and / or water-resistant adhesion and excellent elongation of the resulting cured product.
The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a linear or cyclic aliphatic hydrocarbon group, from the viewpoints of excellent weather resistance and / or water adhesion, and excellent elongation of the resulting cured product. A linear aliphatic hydrocarbon group is preferable.
As the aliphatic hydrocarbon group, for example, a group obtained by removing hydrogen atoms corresponding to the number of the above-mentioned amino groups of an amine from ethane, propane, hexane, heptane, octane, nonane or decane can be mentioned.
Further, among the carbon atoms constituting the hydrocarbon group of the amine, carbon atoms other than the terminal in the hydrocarbon group may be optionally replaced with, for example, a nitrogen atom. In this case, the nitrogen atom can constitute a secondary amine or a tertiary amine.

The amine may further have an alkoxysilyl group. Further, an amine having an alkoxysilyl group may be hereinafter referred to as “aminosilane”.
The alkoxysilyl group of the aminosilane is not particularly limited. For example, an alkyl dialkoxysilyl group and a trialkoxysilyl group can be mentioned.
In the aminosilane, the amino group and the alkoxysilyl group can be bonded via a hydrocarbon group.
The hydrocarbon group is the same as the hydrocarbon group that the amine can have.
Further, among the carbon atoms constituting the hydrocarbon group of the aminosilane, carbon atoms other than the terminal in the hydrocarbon group may be optionally replaced with, for example, a nitrogen atom. In this case, the nitrogen atom can constitute a secondary amine or a tertiary amine.

Examples of the amine include monoamines (excluding aminosilane) such as hexylamine, heptylamine, octylamine, nonylamine, and decylamine;
Diamines (excluding aminosilanes) such as hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, decylenediamine, bis (aminomethyl) cyclohexane;
Examples thereof include aminosilanes such as N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and 3-aminopropyltrimethoxysilane.
In addition, the said monoamine originates in the hydrocarbon group in the said monoamine, and the compound of linear, branched, cyclic, or these combination is contained. The same applies to the diamine.

  Of these amines, monoamines and aminosilanes are preferred, and linear monoamines and aminosilanes are more preferred from the viewpoints of superior weather resistance and / or water adhesion and excellent elongation of the resulting cured product.

  Examples of the linear monoamine include n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine.

-Ketimine Ketimine will not be restrict | limited especially if it is a compound which has C = N formed from a ketone and an amine compound. The ketimine can be decomposed by water to produce an amine having an amino group.

  The ketone that can form the ketimine is not particularly limited. For example, methyl isobutyl ketone (MIBK), methyl-t-butyl ketone (MTBK), methyl isopropyl ketone (MIPK), methyl cyclohexanone, ethyl cyclohexanone, methyl cyclohexyl ketone, diisobutyl ketone, acetophenone, propiophenone and the like can be mentioned. Of these, MTBK and MIPK are preferred.

  The amine compound that can form the ketimine is not particularly limited. For example, the thing similar to the said amine is mentioned.

-Content of epoxy curing agent The content of the epoxy curing agent is superior in weather resistance and / or water adhesion, and is excellent in elongation of the resulting cured product. The vinyl polymer (A) and the polyoxy The amount is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the alkylene polymer (B).

<< Curing Catalyst (D) >>
The composition of the present invention preferably further contains a curing catalyst (D) from the viewpoint of excellent curability. The curing catalyst (D) is not particularly limited as long as it is a catalyst that can act on the reactive silyl group or the group represented by the formula (I).

  As said hardening catalyst (D), the conventionally well-known thing generally used as a catalyst which hydrolyzes and / or condenses a hydrolysable silyl group, or a silanol condensation catalyst can be used, for example. For example, a tin compound, a titanium compound, an acidic compound, and an amine compound are mentioned.

Of these, tin compounds are preferred from the viewpoint of excellent curing speed and / or storage stability.
Examples of the tin compound include tetravalent dialkyltin compounds (for example, dimethyltin compounds, dibutyltin compounds, dioctyltin compounds),
Reaction product of dibutyltin oxide and phthalate,
Dialkylstannoxane dicarboxylate,
Dialkyltin alcoholates, such as dibutyltin dimethoxide,
(Dialkylstannoxane) disilicate compound,
Tetravalent dialkyltin compounds such as dialkyltin chelates such as dibutyltin diacetylacetonate;
Tetravalent monoalkyltin compounds such as monobutyltin trisoctoate, monobutyltin triisopropoxide, monooctyltin compounds and the like;
Bivalent tin compounds such as tin octylate, tin naphthenate, tin stearate and the like can be mentioned.

-Content of curing catalyst (D) The content of the curing catalyst (D) is superior in weather resistance and / or water-resistant adhesion, excellent in elongation of the resulting cured product, and the viscosity of the composition is in an appropriate range. In view of the above, it is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the vinyl polymer (A) and the polyoxyalkylene polymer (B), and 0.1 to 5.0 parts by mass. More preferably, it is part by mass.

(Resin hollow body)
It is preferable that the composition of this invention contains a resin hollow body (resin balloon) further from a viewpoint that it is excellent in workability | operativity.

The hollow resin body has an outer shell made of resin and a hollow inside.
The resin hollow body can function as a filler.
Examples of the material of the outer shell of the resin-based hollow body include, for example, phenol resin; urea resin; polystyrene resin; polyvinylidene chloride; acrylonitrile copolymer (for example, a copolymer of acrylonitrile and methacrylonitrile, acrylonitrile and acrylonitrile, Copolymerizable butadiene, copolymers with vinyl monomers such as styrene, etc.), and thermoplastic resins such as vinylidene chloride polymers.
The average particle diameter of the resin hollow body can be 20 μm or more, and is preferably 20 to 70 μm.
The true specific gravity of the resin-based hollow body is preferably 0.05 to 0.35 from the viewpoint of excellent workability.

  The resin hollow body may expand by heating. The temperature at which the resin hollow body can start expansion (heat resistance temperature) can be set to 100 to 190 ° C., for example.

  The resin hollow body may be coated with a filler such as calcium carbonate, talc, or titanium oxide.

The manufacturing method of the resin-based hollow body is not particularly limited, and can be manufactured by a conventionally known method.
As a commercial item of the said resin hollow body, Matsumoto Yushi Seiyaku Co., Ltd. MFL-60CAS etc. are mentioned, for example.

  The content of the resin hollow body is 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the vinyl polymer (A) and the polyoxyalkylene polymer (B) from the viewpoint of excellent workability. It is preferable that it is 0.1-5 mass parts.

(Anti-aging agent)
The composition of the present invention preferably further contains an anti-aging agent from the viewpoint of excellent weather resistance and / or water adhesion, and excellent elongation of the resulting cured product.

  Examples of the antioxidant include butylhydroxytoluene (BHT), butylhydroxytolueneanisole (BHA), benzotriazole, 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6 Examples thereof include tert-butylphenol.

  The content of the anti-aging agent is 0.1 with respect to a total of 100 parts by mass of the vinyl polymer (A) and the polyoxyalkylene polymer (B) from the viewpoint of excellent crack prevention on the surface of the sealing material. It is preferable that it is 10 mass parts, and it is more preferable that it is 0.1-5 mass parts.

-Plasticizer The composition of this invention can contain a plasticizer from a viewpoint that it is more excellent in a weather resistance and / or water-resistant adhesiveness, and is excellent in the elongation of the hardened | cured material obtained.
The plasticizer is not particularly limited. Examples thereof include oxyalkylene polymers and vinyl polymers. The vinyl polymer (A) or the polyoxyalkylene polymer (B) does not correspond to the plasticizer.

  Examples of the oxyalkylene polymer include polyoxyalkylene polyols such as polyethylene glycol and polypropylene glycol.

  Examples of the vinyl polymer include (meth) acrylic oligomers.

The number average molecular weight of the oxyalkylene polymer or vinyl polymer is preferably 1,500 to 15,000 from the viewpoint that it is excellent in weather resistance and / or water-resistant adhesion and excellent in elongation of the resulting cured product.
The weight-average molecular weight of the oxyalkylene polymer or vinyl polymer is preferably 1,500 to 15,000 from the viewpoint of being excellent in weather resistance and / or water-resistant adhesion and excellent in elongation of the resulting cured product.
The number average molecular weight or the weight average molecular weight is a standard polystyrene conversion value based on a value measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

..Plasticizer content From the viewpoint that the plasticizer content is superior in weather resistance and / or water adhesion, and is excellent in elongation of the resulting cured product, the vinyl polymer (A) and the polyoxyalkylene It is preferable that it is 1-100 mass parts with respect to a total of 100 mass parts of a polymer (B), and it is more preferable that it is 40-70 mass parts.

-Additive The composition of this invention can contain an additive further. Examples of the additive include fillers such as calcium carbonate, titanium oxide, silane coupling agents, adhesion-imparting agents, anti-sagging agents, ultraviolet absorbers, antioxidants, and pigments.

-Silane coupling agent It is preferable that the composition of this invention contains a silane coupling agent further from a viewpoint that it is excellent in sclerosis | hardenability, adhesiveness, or storage stability.
Examples of the silane coupling agent include a vinyl group-containing silane coupling agent, an amino group and / or imino group-containing silane coupling agent (excluding the aminosilane), and a (meth) acryloyl group-containing silane coupling agent. , Mercapto group-containing silane coupling agents, and isocyanate group-containing silane coupling agents.

  The content of the silane coupling agent is based on a total of 100 parts by mass of the vinyl polymer (A) and the polyoxyalkylene polymer (B) from the viewpoint of excellent curability, adhesion, and storage stability. 0.1 to 5 parts by mass is preferable, and 0.1 to 3 parts by mass is more preferable.

(Production method)
The method for producing the composition of the present invention is not particularly limited. For example, the composition of this invention can be manufactured by mixing the said essential component and the arbitrary component which can be further used as needed.

(Applicable substrate)
The substrate to which the composition of the present invention can be applied is not particularly limited. For example, metals, plastics, rubber, glass, concrete, tiles, stones and the like can be mentioned.
The method for applying the composition of the present invention to the substrate is not particularly limited.

(Primer)
A primer may be added to the substrate.
The primer is not particularly limited as long as it can be applied to the substrate. For example, a conventionally well-known thing is mentioned.
Examples of the primer include those containing an isocyanate compound and / or a silane coupling agent.
A preferred embodiment of the isocyanate compound is a compound having a plurality of isocyanate groups in one molecule.
The said primer contains an isocyanate compound and a silane coupling agent as a preferable aspect.
The primer may further contain, for example, a solvent, a catalyst, and the like.
The component that the primer can contain is not particularly limited.

  When the said primer is provided to the said base material, for example, after apply | coating the said primer to the said base material and drying the said primer, the composition of this invention can be applied on the said primer.

(Curing)
The composition of the present invention can be cured when used in the presence of moisture. The moisture is not particularly limited. For example, moisture in the air can be mentioned.
The temperature conditions for using or curing the composition of the present invention can be, for example, room temperature conditions.

(Use)
As a use of the composition of this invention, a sealing material (for example, for construction), an adhesive agent, and a coating agent are mentioned, for example.

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these.
In the present specification, Example 6 is read as Reference Example 6.
<Preparation of ketimine 1>
710 g of 1,3BAC (1,3-bis (aminomethyl) cyclohexane, manufactured by Mitsubishi Chemical Corporation), 860 g of methyl isopropyl ketone (reagent, manufactured by Wako Pure Chemical Industries), 710 g of toluene (reagent, manufactured by Wako Pure Chemical Industries), Then, 1.65 g of acetic acid (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was placed in the flask, and the reaction was continued at 120 ° C. for 15 hours while removing generated water by azeotropic distillation. Next, distillation under reduced pressure at 150 ° C. and 5 mmHg was carried out to remove toluene, residual ketone and the like, and ketimine 1 was prepared by combining 1,3BAC and methylisopropylketone.

<Production of vinyl polymer (A)>
Each vinyl polymer (A) was manufactured as follows. In addition, the unit “part” of the amount of the component used in the following production means “part by mass”.

・ Vinyl polymer (A-1)
The reaction vessel was charged with 50 parts of methyl ethyl ketone and heated to 60 ° C. with stirring. Thereto, 100 parts of n-butyl acrylate and 1.86 parts of γ-methacryloxypropylmethyldimethoxysilane (trade name KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd., the same applies below) are added dropwise, and the inside of the reaction vessel is stirred. Replaced with nitrogen. Next, 1.40 parts of γ-mercaptopropylmethyldimethoxysilane (trade name KBM-802, manufactured by Shin-Etsu Chemical Co., Ltd., the same applies hereinafter) was added, and after stirring for 30 minutes, 2,2′-azobisisobutyronitrile ( 0.05 part of Tokyo Chemical Industry Co., Ltd. (same below) was added. Thereafter, 0.5 part of 2,2′-azobisisobutyronitrile was added 4 times in 30 minute portions. Furthermore, it was made to react for 4 hours, maintaining the temperature in reaction container, and the vinyl polymer solution was obtained. The solvent was removed from the vinyl polymer solution with an evaporator to obtain a vinyl polymer (A-1).

・ Vinyl polymer (A-2)
The reaction vessel was charged with 50 parts of methyl ethyl ketone and heated to 60 ° C. with stirring. Thereto, 100 parts of n-butyl acrylate and 1.24 parts of γ-methacryloxypropylmethyldimethoxysilane were added dropwise, and the inside of the reaction vessel was purged with nitrogen while stirring. Next, 0.90 part of γ-mercaptopropylmethyldimethoxysilane was added, and after stirring for 30 minutes, 0.05 part of 2,2′-azobisisobutyronitrile was added. Thereafter, 0.5 part of 2,2′-azobisisobutyronitrile was added 4 times in 30 minute portions. Furthermore, it was made to react for 4 hours, maintaining the temperature in reaction container, and the vinyl polymer solution was obtained. From the vinyl polymer solution, the solvent was removed with an evaporator to obtain a vinyl polymer (A-2).

・ Vinyl polymer (A-3)
The reaction vessel was charged with 50 parts of methyl ethyl ketone and heated to 60 ° C. with stirring. Thereto, 100 parts of n-butyl acrylate and 0.74 part of γ-methacryloxypropylmethyldimethoxysilane were added dropwise, and the inside of the reaction vessel was purged with nitrogen while stirring. Next, 0.80 part of γ-mercaptopropylmethyldimethoxysilane was added, and after stirring for 30 minutes, 0.05 part of 2,2′-azobisisobutyronitrile was added. Thereafter, 0.5 part of 2,2′-azobisisobutyronitrile was added 4 times in 30 minute portions. Furthermore, it was made to react for 4 hours, maintaining the temperature in reaction container, and the vinyl polymer solution was obtained. The solvent was removed from the vinyl polymer solution with an evaporator to obtain a vinyl polymer (A-3).

・ (Comparison) Vinyl polymer (A-4)
The reaction vessel was charged with 50 parts of methyl ethyl ketone and heated to 80 ° C. with stirring. Thereto, 100 parts of n-butyl acrylate and 2.40 parts of γ-methacryloxypropylmethyldimethoxysilane were added dropwise and refluxed in the reaction vessel while stirring. Next, 0.05 part of 2,2′-azobisisobutyronitrile was added. Thereafter, 0.5 part of 2,2′-azobisisobutyronitrile was added 4 times in 30 minute portions. Furthermore, it was made to react for 4 hours, maintaining the temperature in reaction container, and the vinyl polymer solution was obtained. The solvent was removed from the vinyl polymer solution with an evaporator to obtain a (comparative) vinyl polymer (A-4).

・ (Comparison) Vinyl polymer (A-5)
The reaction vessel was charged with 50 parts of methyl ethyl ketone and heated to 80 ° C. with stirring. Thereto, 100 parts of n-butyl acrylate and 3.60 parts of γ-methacryloxypropylmethyldimethoxysilane were added dropwise and refluxed in the reaction vessel while stirring. Next, 0.10 parts of 2,2′-azobisisobutyronitrile was added. Thereafter, 0.1 part of 2,2′-azobisisobutyronitrile was added four times in 30 minute portions. Furthermore, it was made to react for 4 hours, maintaining the temperature in reaction container, and the vinyl polymer solution was obtained. The solvent was removed from the vinyl polymer solution with an evaporator to obtain a (comparative) vinyl polymer (A-5).

・ Vinyl polymer (A-6)
The reaction vessel was charged with 50 parts of methyl ethyl ketone and heated to 60 ° C. with stirring. Thereto, 100 parts of n-butyl acrylate and 0.9 part of γ-methacryloxypropylmethyldimethoxysilane were added dropwise, and the inside of the reaction vessel was purged with nitrogen while stirring. Next, 1.2 parts of γ-mercaptopropyltrimethoxysilane was added, and after stirring for 30 minutes, 0.05 part of 2,2′-azobisisobutyronitrile was added. Thereafter, 0.5 part of 2,2′-azobisisobutyronitrile was added 4 times in 30 minute portions. Furthermore, it was made to react for 4 hours, maintaining the temperature in reaction container, and the vinyl polymer solution was obtained. The solvent was removed from the vinyl polymer solution with an evaporator to obtain a vinyl polymer (A-6).

・ Vinyl polymer (A-7)
The reaction vessel was charged with 50 parts of methyl ethyl ketone and heated to 60 ° C. with stirring. Thereto, 100 parts of n-butyl acrylate and 0.8 part of γ-methacryloxypropyltrimethoxysilane were added dropwise, and the inside of the reaction vessel was purged with nitrogen while stirring. Next, 1.24 parts of γ-mercaptopropylmethyldimethoxysilane was added, and after stirring for 30 minutes, 0.05 parts of 2,2′-azobisisobutyronitrile was added. Thereafter, 0.5 part of 2,2′-azobisisobutyronitrile was added 4 times in 30 minute portions. Furthermore, it was made to react for 4 hours, maintaining the temperature in reaction container, and the vinyl polymer solution was obtained. The solvent was removed from the vinyl polymer solution with an evaporator to obtain a vinyl polymer (A-7).

・ (Comparison) Vinyl polymer (A-8)
The reaction vessel was charged with 50 parts of methyl ethyl ketone and heated to 60 ° C. with stirring. Thereto, 100 parts of n-butyl acrylate and 5 parts of γ-methacryloxypropylmethyldimethoxysilane were dropped, and the inside of the reaction vessel was purged with nitrogen while stirring. Next, 4 parts of γ-mercaptopropylmethyldimethoxysilane was added, and after stirring for 30 minutes, 0.05 part of 2,2′-azobisisobutyronitrile was added. Thereafter, 0.5 part of 2,2′-azobisisobutyronitrile was added every 30 minutes for 4 times. Furthermore, it was made to react for 4 hours, maintaining the temperature in reaction container, and the vinyl polymer solution was obtained. The solvent was removed from the vinyl polymer solution with an evaporator to obtain a (comparative) vinyl polymer (A-8).

・ (Comparison) Vinyl polymer (A-9)
The reaction vessel was charged with 50 parts of methyl ethyl ketone and heated to 60 ° C. with stirring. Thereto, 100 parts of n-butyl acrylate and 0.15 part of γ-methacryloxypropylmethyldimethoxysilane were added dropwise, and the inside of the reaction vessel was purged with nitrogen while stirring. Next, 0.89 part of γ-mercaptopropylmethyldimethoxysilane was added, and after stirring for 30 minutes, 0.05 part of 2,2′-azobisisobutyronitrile was added. Thereafter, 0.5 part of 2,2′-azobisisobutyronitrile was added 4 times in 30 minute portions. Furthermore, it was made to react for 4 hours, maintaining the temperature in reaction container, and the vinyl polymer solution was obtained. The solvent was removed from the vinyl polymer solution with an evaporator to obtain a (comparative) vinyl polymer (A-9).

Details of vinyl polymers (A-1) to (A-9) are summarized in Table 1.
Referring to the column “Number of Reactive Silyl Groups at Terminals of Vinyl Polymer (A)” in Table 1, vinyl polymers (A-1) to (A-3), (A-6) to (A The number in 9) is greater than 0. For this reason, in the vinyl polymers (A-1) to (A-3) and (A-6) to (A-9), the molecular chain has a repeating unit of a polymerizable vinyl monomer, It is considered that at least the vinyl polymer (a) having a group represented by the above formula (I) at the terminal (one terminal) is included.

<Production of polyoxyalkylene polymer (B)>
・ Polyoxyalkylene polymer (B-1)
Polyoxypropylene diol having a number average molecular weight of about 2,000 was used as an initiator, and propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a polyoxypropylene diol having a number average molecular weight of 29,000. A 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the resulting polyoxypropylene diol to distill off the methanol, and 1.6-fold equivalent 3-chloro-2-methyl-1-propene was further removed. Was added to convert the terminal hydroxyl group into a methallyl group. Next, the inside of the container was substituted with 6% O ₂ / N ₂ , and 100 ppm of sulfur (0.25% by weight of hexane solution), platinum divinyl dichloride with respect to 100 parts by weight of the obtained methallyl group-terminated polyoxypropylene polymer. While adding 100 ppm of a siloxane complex (3% by weight isopropanol solution in terms of platinum) and stirring, 2.30 parts by weight of dimethoxymethylsilane was slowly added dropwise. By reacting the mixed solution at 100 ° C. for 5 hours, a linear reaction in which the terminal is a dimethoxymethylsilyl group, the average number of silicon groups per molecule is 1.9, and the number average molecular weight is 29,000. A functional silicon group-containing polyoxypropylene polymer (polyoxyalkylene polymer (B-1)) was obtained.

・ Polyoxyalkylene polymer (B-2)
Polyoxypropylene diol having a number average molecular weight of about 2,000 was used as an initiator, and propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a polyoxypropylene diol having a number average molecular weight of 29,000. A methanol solution of NaOMe equivalent to 1.2 times equivalent to the hydroxyl group of the obtained polyoxypropylene diol was added to distill off the methanol, and further 3-chloro-1-propene was added to make the terminal hydroxyl group an allyl group. Converted to. Next, 36 ppm of platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) was added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene polymer, and TES (triethoxysilane) 1 was added while stirring. .48 parts by weight were slowly added dropwise and reacted at 90 ° C. for 2 hours. Further, by adding 20 parts by weight of methanol and 12 ppm of HCl to convert the terminal ethoxy group into a methoxy group, the terminal is a trimethoxysilyl group, the average number of silicon groups per molecule is 1.6, and the number average molecular weight is A linear reactive silicon group-containing polyoxypropylene polymer (polyoxyalkylene polymer (B-2)) of 29,000 was obtained.

<Production of composition>
Each component of the following Table 2 was used in the composition (parts by mass) shown in the same table, and these were mixed with a stirrer to produce a composition.

<Evaluation>
The following evaluation was performed using each composition manufactured as mentioned above. The results are shown in Table 2.
-Viscosity Using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., No. 7 rotor), the initial viscosity of each composition produced as described above was measured under the conditions of a rotational speed of 1 rpm and 23 ° C. (unit: Pa · s).
In the present invention, the viscosity of the composition is preferably 2,000 to 4,000 Pa · s from the viewpoint of workability.

・ Elongation at break (elongation at break)
-Sample preparation Each composition produced as described above was cured for 7 days under conditions of 23 ° C and 50% RH (relative humidity). Thereafter, a JIS No. 3 dumbbell-shaped sample (initial sample) having a thickness of 2 mm was punched from the obtained cured product.

.. Weather resistance test Using each initial sample prepared as described above, a metal halide weather meter (conditions: 63 ° C., 50% RH, light energy 75 mW / cm ² , shower with water every 120 hours for 120 seconds) A weather resistance test was performed for 500 hours or 750 hours, and a sample was prepared after the weather resistance test.

.. Tensile test Tensile speed of 500 mm according to JIS K6251: 2010 (vulcanized rubber and thermoplastic rubber-how to determine tensile properties) using each initial sample or each sample after weathering test prepared as described above / Min, at room temperature, a tensile test was performed, and the initial elongation at break or the elongation after breakage (unit%) was measured after each weather resistance test.

-Evaluation criteria of initial breaking elongation In this invention, when initial breaking elongation is 300% or more, it shall be excellent in breaking elongation.

-Evaluation criteria of retention rate of elongation at break The retention rate (%) of elongation at break was calculated by applying the elongation value of each initial sample and the sample after the weather resistance test corresponding thereto to the following formula.
Retention rate of elongation at break (%) = (B / A) × 100
A: Initial breaking elongation B: Breaking elongation after weathering test In the present invention, when the retention rate is 80% or more, the breaking elongation after the weathering test is excellent.

-Preparation of a sample for water-resistant adhesion--water-resistant adhesion evaluation A primer containing an isocyanate compound, a silane coupling agent and a solvent was applied to an aluminum plate, and the primer was dried.
Next, each composition prepared as described above is applied onto the primer, cured for 7 days at 20 ° C, and further cured for 7 days at 50 ° C. An initial sample (with an aluminum plate) having a layer (sealing material) of a cured product of the above composition was prepared.
A water resistance test was conducted in which the initial sample (with an aluminum plate) was immersed in warm water at 50 ° C. for 7 days. After the water resistance test, the sample was pulled up from the hot water and dried to obtain a sample for water resistance adhesion evaluation.

.. Peel test Grasp the end of the sealing material of each water-resistant adhesion evaluation sample obtained as described above by hand, and seal the sealing material from the water-resistant adhesion evaluation sample at an angle of 180 ° C. under the condition of 23 ° C. A peeling test for peeling was performed. The results of the peel test were evaluated according to the following evaluation criteria.

・ Evaluation criteria for water-resistant adhesion When the sample for water-resistant adhesion evaluation after the above peel test was complete cohesive failure (destruction of the sealing material itself), it was evaluated that it was very excellent in water-resistant adhesion. Is displayed.
If the result of the above peeling test is not complete cohesive failure, and the total ratio of cohesive failure and thin layer failure is 80% or more with respect to the total area of the sealing material, the water adhesion is somewhat excellent. This was evaluated and indicated as “B”.
As a result of the above peeling test, when the total ratio of cohesive failure and thin layer failure is 20% or more and less than 80% with respect to the total area of the sealing material, it is evaluated that the water-resistant adhesion is slightly poor. Is displayed as “C”.
In the result of the above peeling test, when the total ratio of cohesive failure and thin layer failure was less than 20% with respect to the total area of the sealing material, it was evaluated that the water-resistant adhesion was very bad. D ".

-Weather resistance-Sample preparation The composition produced as described above was cured for 7 days under conditions of 23 ° C and 50% RH (relative humidity). Thereafter, a sample having a thickness of 5 mm was prepared from the obtained cured product.

.. Weather resistance test Using each sample prepared as described above, according to a metal halide weather meter (conditions: 63 ° C., 50% RH, light energy 75 mW / cm ² , shower with water for 120 seconds every 2 hours). A weather resistance test was performed in which the treatment was performed for 500 hours or 750 hours.

-Evaluation criteria Each sample was visually observed after the weather resistance test to confirm the presence or absence of cracks.
When there was no crack in the sample, it was evaluated that the weather resistance was very excellent, and this was indicated as “A”.
When there was a crack that was barely visible in the sample, it was evaluated that the weather resistance was slightly superior, and this was indicated as “B”.
When there was a crack that was clearly visible in the sample, it was evaluated that the weather resistance was slightly poor, and this was indicated as “C”.
When the sample had a large crack (the width of the crack was 0.5 mm to 1.0 mm), it was evaluated that the weather resistance was very bad, and this was indicated as “D”.

The details of each component shown in Table 2 are as follows.
Vinyl polymers (A-1) to (A-9): Vinyl polymers (A-1) to (A-9) produced as described above

  Polyoxyalkylene polymers (B-1) to (B-2): Polyoxyalkylene polymers (B-1) to (B-2) produced as described above

Epoxy resin 1 (BPA type): Bisphenol A type epoxy resin. Product name YD-128, manufactured by Tohto Kasei Co., Ltd. Epoxy equivalent 184 to 194 g / eq, viscosity 11,000 to 15,000 mPa · s.
Epoxy resin 2 (BPF type): Bisphenol F type epoxy resin. Product name YDF-170, manufactured by Tohto Kasei Co., Ltd. Epoxy equivalent 160-180 g / eq, viscosity 2,000-5,000 mPa · s.

Colloidal calcium carbonate: Calfine 200M, manufactured by Maruo Calcium Co., Ltd. Heavy calcium carbonate: Ryton A-4, manufactured by Bihoku Flour Processing Co., Ltd. Titanium oxide: R820, manufactured by Ishihara Sangyo Co., Ltd.

-Plasticizer 1: Acrylic oligomer, UP1000, manufactured by Toagosei Co., Ltd. Number average molecular weight 2,500
Plasticizer 2: Polypropylene glycol, preminol 4002, manufactured by Asahi Glass Co., Ltd. Number average molecular weight 4,000

  ・ Vinyl group-containing silane coupling agent: vinyltrimethoxysilane, KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.

Epoxy curing agent 1 (aminosilane): N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd. Epoxy curing agent 2 (monoamine): n-octylamine. Manufactured by Tokyo Chemical Industry Co., Ltd. Epoxy curing agent 3 (diamine): 1,3-bis (aminomethyl) cyclohexane, 1,3-BAC, manufactured by Mitsubishi Gas Chemical Co., Ltd. Epoxy curing agent 4 (ketimine 1): prepared as described above. Ketimine 1 (1,3-BAC / MIPK)

  Curing catalyst (D): Dibutyltin diacetylacetonate (trade name: Neostan U-220, manufactured by Nitto Kasei Co., Ltd.)

  -Resin hollow body: A plastic microballoon having a shell composition of acrylonitrile copolymer and coated with calcium carbonate. Trade name MFL-60CAS, Matsumoto Yushi Seiyaku Co., Ltd. Average particle size 60 μm. Heat resistant temperature 140-150 ° C.

  Anti-aging agent: 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol, trade name Tinuvin 326, manufactured by BASF

As is apparent from the results shown in Table 2, Comparative Example 1 containing no predetermined vinyl polymer (A) and epoxy compound (C) had poor weather resistance and water-resistant adhesion.
Comparative Examples 2 and 3 that do not contain the predetermined vinyl polymer (A), but instead contain a vinyl polymer that does not have the group represented by the above formula (I) and do not contain the epoxy compound (C). The weather resistance and water adhesion were poor.
Comparative Example 4 which does not contain the predetermined vinyl polymer (A), contains a vinyl polymer whose weight average molecular weight and / or number average molecular weight is outside the predetermined range, and does not contain the epoxy compound (C) instead. The weather resistance and water adhesion were poor.
Comparative Example 5 which does not contain the predetermined vinyl polymer (A) and contains a vinyl polymer whose weight average molecular weight and / or number average molecular weight is outside the predetermined range instead has poor weather resistance and water adhesion resistance. It was.
Comparative Example 6 which does not contain the predetermined vinyl polymer (A) and contains a vinyl polymer in which the total number of reactive silyl groups and / or the number of reactive silyl groups in the side chain are out of the predetermined range instead. The weather resistance was poor.

  On the other hand, the composition of the present invention was excellent in weather resistance and water adhesion.

Claims (23)

Having a reactive silyl group at the end and side chain of the molecular chain, the molecular chain having a repeating unit of a polymerizable vinyl monomer;
On an average per molecule, the total number of reactive silyl groups exceeds 1, the number of reactive silyl groups at the terminal exceeds 0.5, and the number of reactive silyl groups in the side chain is 0. More than 5,
A vinyl polymer (A) having a weight average molecular weight of 30,000 to 110,000, a number average molecular weight of 9,000 to 40,000, and a glass transition temperature of −100 to −10 ° C .;
A polyoxyalkylene polymer (B) having a reactive silyl group and having a molecular chain substantially polyoxyalkylene;
An epoxy compound (C) having an epoxy group;
Furthermore, containing an epoxy curing agent,
The vinyl polymer (A) is a vinyl polymer (a) having a molecular chain having a repeating unit of a polymerizable vinyl monomer and having a group represented by the following formula (I) at the end of the molecular chain. Including
A curable resin composition, wherein the epoxy curing agent is an amine.
* -SL ¹ -X ¹ (I)
In formula (I), S is a sulfur atom, L ¹ represents a divalent linking group, X ¹ represents a reactive silyl group, and * represents a bonding position.   The curable resin composition of Claim 1 whose mass ratio (A: B) of the said vinyl polymer (A) and the said polyoxyalkylene polymer (B) is 10: 90-90: 10. Furthermore, it contains a curing catalyst (D),
The curing catalyst (D) is at least one selected from the group consisting of a tin compound, a titanium compound, an acidic compound and an amine compound;
The content of the curing catalyst (D) is 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the vinyl polymer (A) and the polyoxyalkylene polymer (B). Or the curable resin composition of 2.   Furthermore, the curable resin composition of any one of Claims 1-3 containing a resin hollow body.   Furthermore, the curable resin composition of any one of Claims 1-4 containing an anti-aging agent. Furthermore, it contains at least one plasticizer of oxyalkylene polymer and vinyl polymer having a number average molecular weight of 1,500 to 15,000,
The content of the plasticizer is 1 to 100 parts by mass with respect to 100 parts by mass in total of the vinyl polymer (A) and the polyoxyalkylene polymer (B). The curable resin composition according to Item 1.   The curable resin composition according to any one of claims 1 to 6, wherein the vinyl polymer (A) has a weight average molecular weight of 45,000 to 90,000.   The number average molecular weight of the said vinyl polymer (A) is more than 10,000 and less than 20,000, The curable resin composition of any one of Claims 1-7.   The curable resin composition according to any one of claims 1 to 8, wherein the vinyl polymer (A) further has a hydrocarbon group in a side chain. However, the hydrocarbon group does not have a reactive silyl group.   The curable resin composition according to claim 9, wherein the hydrocarbon group has 1 to 12 carbon atoms.   The curable resin composition according to any one of claims 1 to 10, wherein the molecular chain of the vinyl polymer (A) is linear. The molecular chain of the vinyl polymer (A) has a repeating unit represented by the following formula (II) and a repeating unit represented by the formula (III), according to any one of claims 1 to 11 . Curable resin composition.
In formula (II), R ^2-1 represents a hydrogen atom or a monovalent hydrocarbon group, L ² represents a divalent linking group, and R ^2-2 represents a monovalent hydrocarbon group.
In formula (III), R ^3-1 represents a hydrogen atom or a monovalent hydrocarbon group, L ³ represents a divalent linking group, and R ^3-2 and R ^3-3 each independently represent a monovalent group. Represents a hydrocarbon group, m3 is 1 to 3, n3 is 0 to 2, and m3 + n3 is 3. The curable resin composition according to claim 12 , wherein m3 is 2 and n3 is 1 in formula (III). The curable resin composition according to any one of claims 1 to 13 , wherein in formula (I), the reactive silyl group as X ¹ is a dialkoxysilyl group. The curable resin composition according to any one of claims 1 to 13 , wherein the group represented by the formula (I) is a group represented by the following formula (I-1).
In formula (I-1), R ^1-1 represents a divalent hydrocarbon group, R ^1-2 and R ^1-3 each independently represent a monovalent hydrocarbon group, and m1 is from 1 to 3 Yes, n1 is 0 to 2, m1 + n1 is 3, and * represents a bonding position.   The curable resin composition according to claim 15, wherein m1 is 2 and n1 is 1 in formula (I-1).   The curable resin composition according to any one of claims 1 to 16, wherein the vinyl polymer (a) has one terminal having a group represented by the formula (I).   The curable resin composition according to any one of claims 1 to 17, wherein the vinyl polymer (a) further has a reactive silyl group in a side chain of the molecular chain. The curable property according to any one of claims 1 to 18, wherein in the vinyl polymer (A), a reactive silyl group at the end of the molecular chain is a group represented by the following formula (V). Resin composition.
* -SL ¹ -X ¹ (V)
In formula (V), S is a sulfur atom, L ¹ represents a divalent linking group, X ¹ represents a reactive silyl group, and * represents a bonding position.   The content of the epoxy compound (C) is 1 to 50 parts by mass with respect to 100 parts by mass in total of the vinyl polymer (A) and the polyoxyalkylene polymer (B). The curable resin composition according to any one of the above.   The content of the epoxy curing agent is 0.1 to 30 parts by mass with respect to 100 parts by mass in total of the vinyl polymer (A) and the polyoxyalkylene polymer (B). The curable resin composition according to any one of the above. The curable resin composition according to claim 1, wherein the amine is a compound having a primary amino group (—NH ₂ ) and / or a secondary amino group (—NH—). object.   The curable resin composition according to any one of claims 1 to 22, wherein the amine further has an alkoxysilyl group.