JP6566058B2 - 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, in Patent Document 1, an organic polymer (A) having a hydroxyl group in a molecule and a compound (B) having an isocyanate group in the molecule are reacted using a zirconium compound (C) as a catalyst. Cured silylated urethane resin in which a crosslinkable silane compound (D) having an active hydrogen group capable of reacting with an isocyanate group in the molecule is reacted with a urethane resin having an isocyanate group in the molecule synthesized by 100 parts by mass, 0.1-30 parts by mass of an aminosilane compound (E) having a primary amino group and a crosslinkable silyl group in the molecule, and an adhesive silylated urethane-based resin composition Is described.

JP 2011-162666 A

Under these circumstances, the present inventors prepared a composition with reference to Patent Document 1 and evaluated it. As a result, such a composition was found to have weather resistance, physical properties after curing (hereinafter referred to as “cured physical properties”). It has become clear that it may be low (Comparative Example 1). Examples of the cured physical properties include tensile strength and elongation at break.
Then, an object of this invention is to provide the curable resin composition excellent in a weather resistance and hardened | cured material property.

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 predetermined organic polymer (B), and a curing catalyst (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 .;
An organic polymer (B) having a reactive silyl group, a urethane bond and / or a urea bond, and having at least one selected from the group consisting of polyoxyalkylene, polyester, polycarbonate and polyvinyl as a molecular chain;
A curing catalyst (C),
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 organic polymer (B) is 10:90 to 90:10.
[3] The curing catalyst (C) is at least one selected from the group consisting of a tin compound, a titanium compound, an acidic compound and an amine compound,
[1] or [1], wherein the content of the curing catalyst (C) is 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the vinyl polymer (A) and the organic polymer (B). 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,
Any one of [1] to [5], wherein 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 organic polymer (B). The curable resin composition described in 1.
[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 according to any one of [1] to [17], further comprising a polyoxyalkylene polymer (D) having a reactive silyl group and a molecular chain of polyoxyalkylene. Composition.
[19] The curable resin composition according to any one of [1] to [18], wherein the vinyl polymer (a) further has a reactive silyl group in a side chain of the molecular chain.
[20] The vinyl polymer (A) according to any one of [1] to [19], 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.

  The curable resin composition of the present invention is excellent in weather resistance and cured physical properties.

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 .;
An organic polymer (B) having a reactive silyl group, a urethane bond and / or a urea bond, and having at least one selected from the group consisting of polyoxyalkylene, polyester, polycarbonate and polyvinyl as a molecular chain;
A curing catalyst (C),
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 which is a molecular chain (molecular 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.

Moreover, this invention is excellent in hardened | cured material property by containing a predetermined | prescribed organic polymer (B). This is because when the organic polymer (B) has a urethane bond and / or a urea bond, a urethane bond and / or a urea bond having an ideal crosslinked form is introduced into the resulting cured product, The present inventors speculate that this is because flexibility is imparted.
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).

  In the present invention, the vinyl polymer (A) does not have a urethane bond or a urea bond.

<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 hardened | cured material property. Is preferred. 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 preferably has a hydrocarbon group having 1 to 12 carbon atoms from the viewpoint of superior weather resistance and / or cured properties. . 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 it is more excellent in weather resistance and / or cured properties 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 cured product properties, 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 the silicon atom is preferred. 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 reactive silyl group is preferably a dialkoxysilyl group, more preferably an alkyl dialkoxysilyl group or a dimethoxysilyl group from the viewpoint that the weatherability and / or cured product properties are excellent and the viscosity of the composition falls within an appropriate range. .

  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 except that it does not have a urethane bond or urea bond.
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 except that it does not have a urethane bond or urea bond.

  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).

From the viewpoint that the total number is more excellent in weather resistance and / or cured product properties, it is preferably more than 1 and 3 or less, more preferably more than 1 and 2 or less on average.
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; 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) is excellent in weather resistance and cured product properties, and has a reactive silyl group at the end from the viewpoint that the viscosity of the composition falls 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 above 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, more preferably 1 or 2 on average, from the viewpoint of superior weather resistance and / or cured properties.

<Reactive silyl group in side chain>
The vinyl polymer (A) is excellent in weather resistance and / or cured properties, and has a reactive silyl group in the side chain from the viewpoint that the viscosity of the composition falls within 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, more preferably 1 or 2 on average, from the viewpoint of superior weather resistance and / or cured properties.

(Another side chain)
The vinyl polymer (A) is more excellent in weather resistance and / or cured product properties, is excellent in elongation of the cured product, and has a hydrocarbon group in the side chain from the viewpoint that the viscosity of the composition falls within an appropriate range. It is preferable. 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 excellent in weather resistance and / or cured properties, and the viscosity of the composition falls within an appropriate range, so that the formula (III It is preferable to have a repeating unit represented by

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 preferably 2 from the viewpoint that it is excellent in weather resistance and / or cured product properties, the viscosity of the composition is in an appropriate range, and the pot life can be secured in an appropriate length.

・ N3
In formula (III), n3 is 0-2.
n3 is preferably 1 from the viewpoint that it is excellent in weather resistance and / or cured product properties, the viscosity of the composition is in an appropriate range, and the pot life can be secured in an appropriate length.

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, more preferably a hydrocarbon group having 3 to 8 carbon atoms, from the viewpoint of being excellent in weather resistance and / or cured product properties and excellent in elongation of the resulting cured product. More preferred is a hydrocarbon group having 4 to 8 carbon atoms.
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 cured properties.

  From the viewpoint that the weight average molecular weight of the vinyl polymer (A) is excellent in weather resistance and / or cured product properties, can maintain the initial elongation of the cured product over a long period of time, and the viscosity of the composition falls within an appropriate range. 45,000-100,000 are preferable, 45,000-90,000 are more preferable, 45,000-85,000 are still more preferable, and 45,000-60,000 are especially preferable.

<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 cured product properties, excellent in elongation of the resulting cured product, and long-term in the initial elongation of the cured product. 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 viewpoint that the weather resistance and / or cured product properties are excellent and the viscosity of the composition falls within an appropriate range.

  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 It is preferable that the said vinyl polymer (a) has a reactive silyl group in a side chain from a viewpoint that it is excellent in a weather resistance and / or hardened | cured material property, and the viscosity of a composition becomes an appropriate range.

-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 superior in weather resistance and / or cured product properties, excellent in elongation of the cured product, and the viscosity of the composition is in an appropriate range. One to two 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, more preferably an alkyl dialkoxysilyl group, from the viewpoint that the weather resistance and / or cured product properties are excellent and the viscosity of the composition falls within an appropriate range. A methyldimethoxysilyl group is 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 except that it does not have a urethane bond or a urea bond.

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 preferably 1 or 2 from the viewpoint of being superior in weather resistance and / or cured properties.

The vinyl polymer (a) preferably has one terminal having a group represented by the formula (I) from the viewpoint of superior weather resistance and / or cured properties.
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 preferably a group represented by the following formula (I-1) from the viewpoint that the weather resistance and / or cured product properties are excellent and the viscosity of the composition falls within an appropriate range.
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 preferably 2 from the viewpoints that it is excellent in weather resistance and / or cured product properties, the viscosity of the composition is in an appropriate range, and the pot life can be secured in an appropriate length.

・ N1
In formula (I-1), n1 is 0-2.
n1 is preferably 1 from the viewpoint that it is excellent in weather resistance and / or cured product properties, the viscosity of the composition is in an appropriate range, and the pot life can be secured in an appropriate length.

*
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, The use amount of the compound represented by the formula (III ′) is excellent in weather resistance and / or cured product properties, 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 is preferably 0.1 to 100 parts by weight, more preferably 0.4 to 2.0 parts by weight, and 0.5 to 1 part per 100 parts by weight of the compound represented by the formula (II ′). More preferably, it is 5 parts by mass.

  When the molecular 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 (A) is produced. The molar ratio of the compound represented by the above formula (II ′) and the compound represented by the above formula (III ′) used in the process of constituting the molecular chain of the vinyl polymer (A), This can be reflected in the number of repeating units of the repeating unit represented by the formula (II) and the repeating unit represented by the formula (III).

-Use amount of chain transfer agent The use amount of the chain transfer agent is superior from the viewpoint of weather resistance and / or cured product properties, excellent elongation of the resulting cured product, and the viscosity of the composition is in 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.

<< Organic polymer (B) >>
The organic polymer (B) contained in the composition of the present invention has a reactive silyl group, a urethane bond and / or a urea bond, and a polyoxyalkylene, polyester, polycarbonate, and molecular chain (main chain). A polymer having at least one selected from the group consisting of polyvinyl.

<Reactive silyl group>
The reactive silyl group that the organic 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 above-mentioned reactive silyl group is preferably a dialkoxysilyl group from the viewpoint that it is excellent in weather resistance and / or cured product properties, the viscosity of the composition is in an appropriate range, and the pot life can be secured with an appropriate length. A dialkoxysilyl group and a dimethoxysilyl group are more preferable.

  From the viewpoint that the organic polymer (B) is excellent in weather resistance and / or cured properties, the viscosity of the composition is in an appropriate range, and the pot life can be ensured with an appropriate length, the reactive silyl group is added. It is preferable to have one or more on average in one molecule, and more preferable to have one or two.

<Urethane bond and / or urea bond>
The organic polymer (B) has a urethane bond and / or a urea bond.
-Urethane bond A urea bond is a group represented by -NR-CO-O-. R represents a hydrogen atom or an organic group. The organic group is not particularly limited.

-Urea bond A urea bond is a group represented by -NR-CO-NR-. Said R represents a hydrogen atom or an organic group each independently. The organic group is not particularly limited.

  The organic polymer (B) can have one or more urethane bonds and / or urea bonds in one molecule. The organic polymer (B) preferably has 1 or 2 urethane bonds and / or urea bonds in one molecule from the viewpoint of better weather resistance and / or cured properties.

<Molecular chain>
In the present invention, the molecular chain of the organic polymer (B) has at least one selected from the group consisting of polyoxyalkylene, polyester, polycarbonate and polyvinyl.

The molecular chain of the organic polymer (B) is preferably at least one selected from the group consisting of polyoxyalkylene, polyester, polycarbonate, and polyvinyl.
A urethane bond and / or a urea bond may be introduced into the main chain portion of the molecular chain.
In the present invention, the term “substantially” means that the molecular chain of the organic polymer (B) may further contain a repeating unit other than an oxyalkylene group, etc. It means that the amount is 50% by mass or more based on the total number of repeating units of the organic polymer (B). The content of the oxyalkylene group or the like is preferably 80% by mass or more with respect to the total.

  The above molecular chain is a polyoxyalkylene (polyether) from the viewpoint that it is excellent in weather resistance and / or cured product properties, the viscosity of the composition is in an appropriate range, and the pot life can be secured in an appropriate length. Is preferred.

  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.
In the case where the reactive silyl group is bonded to the molecular chain via an organic group, it is preferable that the organic group includes the urethane bond and / or urea bond. When the organic group includes the urethane bond and / or urea bond, the organic group may further have a hydrocarbon group in addition to the urethane bond and / or urea bond. One preferred embodiment of the hydrocarbon group is divalent. The hydrocarbon group may be an aliphatic hydrocarbon group (straight chain, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof, and is preferably an aliphatic hydrocarbon group.
In the organic polymer (B), the reactive silyl group can be bonded to a terminal and / or as a side chain. The organic polymer (B) preferably has the reactive silyl group at its ends, and more preferably has both ends.

The organic polymer (B) includes an alkyl dialkoxysilylalkylene urethane group or an alkyl dialkoxysilylalkylene urea group at the side chain and / or terminal of the molecular chain as one of preferable embodiments.
The organic polymer (B) is preferably a compound having a molecular chain of polyoxyalkylene (polyether) and having an alkyl dialkoxysilylalkylene urethane group at the side chain and / or terminal of the molecular chain.
Examples of the organic polymer (B) include polyethers having methyldimethoxysilylmethyl carbamate (urethane bond) at both ends.

  The weight average molecular weight of the organic polymer (B) is preferably 3,000 to 20,000 from the viewpoint that the weather resistance and / or cured properties are excellent and the viscosity of the composition falls within an appropriate range. It is more preferably 5,000 to 15,000.

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

-Mass ratio of vinyl polymer (A) and organic polymer (B) The mass ratio (A: B) of vinyl polymer (A) and organic polymer (B) depends on the weather resistance and / or cured properties. From the viewpoint that it is excellent and the viscosity of the composition falls within an appropriate range, it is preferably 10:90 to 90:10, more preferably 50:50 to 90:10, and 50:50 to 65:35. More preferably.

<< Curing catalyst (C) >>
The composition of the present invention contains a curing catalyst (C) from the viewpoint of excellent curability. The curing catalyst (C) 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 the curing catalyst (C), for example, a conventionally known catalyst generally used as a catalyst for hydrolyzing and / or condensing a hydrolyzable silyl group or a silanol condensation catalyst can be used. 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 (C) The content of the curing catalyst (C) is more excellent in weather resistance and / or cured properties, and from the viewpoint that the viscosity of the composition falls within an appropriate range, the vinyl polymer (A ) And the organic polymer (B) in a total of 100 parts by mass (or when the composition of the present invention further contains a polyoxyalkylene polymer (D) described later, the vinyl polymer (A) and the organic polymer (B). It is preferably 0.1 to 20 parts by weight, and preferably 0.1 to 5.0 parts by weight with respect to the combined body (B) and the polyoxyalkylene polymer (D) described later in total 100 parts by weight. Is more preferable.

(Polyoxyalkylene polymer (D))
The composition of the present invention has a reactive silyl group and a molecular chain (main chain) from the viewpoint of being excellent in workability (handling property) as a sealing material and / or capable of imparting appropriate waterproof functionality. It is mentioned as one of the preferable aspects that further contains the polyoxyalkylene polymer (D) which is substantially polyoxyalkylene.

  One preferred embodiment of the polyoxyalkylene polymer (D) is that it has no urethane bond or urea bond.

<Reactive silyl group>
The reactive silyl group that the polyoxyalkylene polymer (D) 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 (D) is superior in weather resistance and / or cured properties, has a composition viscosity in an appropriate range, and can ensure a pot life of an appropriate length. Therefore, a silyl group in which two hydrolyzable groups are bonded to one silicon atom 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 cured product properties, the viscosity of the composition is in an appropriate range, and the pot life can be secured with an appropriate length. A dialkoxysilyl group and a dimethoxysilyl group are more preferable.

  The above-mentioned polyoxyalkylene polymer (D) is superior in weather resistance and / or cured product properties, the viscosity of the composition is in an appropriate range, and the reactive silylation can be ensured 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 (D) is the average number determined by a method of quantifying protons on carbon directly bonded with reactive silyl groups by a high resolution ¹ H-NMR measurement method. Can be defined. In the calculation of the average number of reactive silyl groups possessed by the polyoxyalkylene polymer (D), reactive silyl groups were introduced into the polyoxyalkylene polymer precursor before introducing the reactive silyl groups. In this case, 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 are the same molecular chain. As part of the component of the polyoxyalkylene polymer (D) having a structure, the calculation is performed by including it in the parameter (number of molecules) when calculating the average number of reactive silyl groups in one molecule. Can do.

<Molecular chain>
The molecular chain of the polyoxyalkylene polymer (D) is substantially polyoxyalkylene.
In the present invention, the “substantially” means that the molecular chain of the polyoxyalkylene polymer (D) may further contain a repeating unit other than an oxyalkylene group, but the content of the oxyalkylene group is It means that the content is 50% by mass or more based on the total number of repeating units of the polyoxyalkylene polymer (D). 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 except that it does not have a urethane bond or a urea bond.
The polyoxyalkylene polymer (D) can have the reactive silyl group at the terminal and / or side chain of the molecular chain.
The polyoxyalkylene polymer (D) preferably has the reactive silyl group at the end of the molecular chain.

  When the polyoxyalkylene polymer (D) has the reactive silyl group at the end of the molecular chain, it is superior in weather resistance and / or cured properties, the composition has an appropriate viscosity, and has an appropriate pot life. From the viewpoint of ensuring the length, it is preferable to have a reactive silyl group at 50% or more of all ends of the molecular chain, more preferably 60% or more, and still more preferably 60 to 85%.

(Number average molecular weight)
From the viewpoint that the number average molecular weight of the polyoxyalkylene polymer (D) is more excellent in weather resistance (particularly longer-term weather resistance) and / or cured properties, and the viscosity of the composition falls within an appropriate range. It is preferable that it is 000-35,000, and it is more preferable that it is 20,000-30,000.

  In the present invention, the number average molecular weight of the polyoxyalkylene polymer (D) 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 (D) does not have a urethane bond or a urea bond.

(Production method of polyoxyalkylene polymer (D))
The production method of the polyoxyalkylene polymer (D) 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.

  As a commercial item of the said polyoxyalkylene polymer (D), MS polymer (made by Kaneka), a silyl polymer (made by Kaneka), Exester (made by Asahi Glass) etc. are mentioned, for example.

-Content of polyoxyalkylene polymer (D) The content of the polyoxyalkylene polymer (D) is superior in weather resistance and / or cured properties, the viscosity of the composition is in an appropriate range, and the pot life is reduced. From the viewpoint of ensuring an appropriate length, it is 1 to 50% by mass with respect to the total amount of the vinyl polymer (A), the organic polymer (B), and the polyoxyalkylene polymer (D). It is preferably 10 to 30% 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.

  From the viewpoint of excellent workability, the content of the resin hollow body is 100 parts by mass in total of the vinyl polymer (A) and the organic polymer (B) (or the composition of the present invention further comprises the polyoxy When the alkylene polymer (D) is contained, it is 0.1 to 0.1 parts by mass with respect to the vinyl polymer (A), the organic polymer (B) and the polyoxyalkylene polymer (D). The amount is preferably 10 parts by mass, and more preferably 0.1 to 5 parts by mass.

(Anti-aging agent)
The composition of the present invention preferably further contains an antiaging agent from the viewpoint that it is more excellent in weather resistance and / or cured product properties.

  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 100 parts by mass (or the composition of the present invention) of the vinyl polymer (A) and the organic polymer (B) from the viewpoint of excellent crack prevention on the surface of the sealing material. Furthermore, when the polyoxyalkylene polymer (D) is contained, the vinyl polymer (A), the organic polymer (B), and the polyoxyalkylene polymer (D) in total 100 parts by mass) It is preferable that it is 0.1-10 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 further excellent by a weather resistance and / or hardened | cured material property.
The plasticizer is not particularly limited. Examples thereof include oxyalkylene polymers and vinyl polymers. The vinyl polymer (A), the organic polymer (B), or the polyoxyalkylene polymer (D) 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 of being excellent in weather resistance and / or cured properties.
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 cured product properties 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.

.. Content of plasticizer The content of the plasticizer is 100 parts by mass (or a total of the vinyl polymer (A) and the organic polymer (B) from the viewpoint of being superior in weather resistance and / or cured properties. When the composition of the present invention further contains the polyoxyalkylene polymer (D), a total of 100 of the vinyl polymer (A), the organic polymer (B), and the polyoxyalkylene polymer (D). 1 to 100 parts by mass, and more preferably 40 to 70 parts by mass with respect to (parts by mass).

-Additive The composition of this invention can contain an additive further. Examples of the additive include a vinyl polymer having a reactive silyl group other than the vinyl polymer (A), a filler such as calcium carbonate, titanium oxide, a silane coupling agent, an adhesion-imparting agent, and an anti-sagging agent. , 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, a (meth) acryloyl group-containing silane coupling agent, and a mercapto group-containing silane coupling agent. And isocyanate group-containing silane coupling agents.

  The content of the silane coupling agent is 100 parts by mass (or the present invention) of the vinyl polymer (A) and the organic polymer (B) from the viewpoint of excellent curability, adhesiveness or storage stability. When the composition further contains the polyoxyalkylene polymer (D), the vinyl polymer (A), the organic polymer (B), and the polyoxyalkylene polymer (D) in total 100 parts by mass) It is preferable that it is 0.1-5 mass parts with respect to it, and it is more preferable that it is 0.1-3 mass parts.

(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.

(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.

<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).

・ (Comparison) 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 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-6).

Details of the vinyl polymers (A-1) to (A-6) are summarized in Table 1.
With reference to the column “Number of Reactive Silyl Groups at the Terminal of Vinyl Polymer (A)” in Table 1, the above numbers of vinyl polymers (A-1) to (A-3) and (A-6) Is greater than zero. For this reason, in the vinyl polymers (A-1) to (A-3) and (A-6), the molecular chain has a repeating unit of a polymerizable vinyl monomer, and the molecular chain ends (one end). It is considered that at least the vinyl polymer (a) having a group represented by the above formula (I) is included.

<Production of polyoxyalkylene polymer (D)>
・ Polyoxyalkylene polymer (D-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 (D-1)) 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.

(Curing property)
-Preparation of initial sample 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.

.. Tensile test Using each initial sample prepared as described above, in accordance with JIS K6251: 2010 (vulcanized rubber and thermoplastic rubber-how to obtain tensile properties), at a tensile speed of 500 mm / min at room temperature A tensile test was conducted to measure initial tensile strength (N / m ² ) and initial breaking elongation (unit%).

.. Evaluation criteria for initial tensile strength In the present invention, when the initial tensile strength is 0.7 N / m ² or more, the initial tensile strength is excellent.

.. Evaluation criteria for initial breaking elongation In the present invention, when the initial breaking elongation is 300% or more, the initial breaking elongation is excellent.

-Weather resistance test Using each initial 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, and a sample was prepared after the weather resistance test.

.. Tensile test Using the samples after each weather resistance test prepared as described above, the same tensile test as described above was performed, and the elongation at break (unit%) after each weather resistance test was measured.

.. Evaluation Criteria of Retention Ratio of Breaking Elongation The breaking elongation retention ratio (%) was calculated by applying the value of the breaking elongation of each initial sample and the corresponding sample after the weather resistance test to the following equation.
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.

(Weatherability)
-Preparation of sample 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, treatment with a metal halide weather meter (conditions: 63 ° C, 50% RH, light energy 75 mW / cm ² , shower with water every 2 hours for 120 seconds). 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 by visual inspection, 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-6): Vinyl polymers (A-1) to (A-6) produced as described above.

  Organic polymer (B-1): An organic polymer having methyldimethoxysilylmethyl carbamate (urethane bond) at both ends and having a molecular chain of polyoxyalkylene (polyether). Product name STP-30, manufactured by Asahi Kasei Wacker Silicone.

  Polyoxyalkylene polymer (D-1): polyoxyalkylene polymer (D-1) produced as described above

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

Silane 1: Vinyltrimethoxysilane, KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd. Silane 2: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.

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

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

As is clear from the results shown in Table 2, Comparative Example 1 which does not contain the predetermined vinyl polymer (A) has poor weather resistance, and cured properties after the weather resistance test deteriorated.
Comparative Examples 2 and 3, which do not contain the predetermined vinyl polymer (A) and contain a vinyl polymer having no group represented by the above formula (I), have poor weather resistance and cured product properties. It was.
Comparative Example 4 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 cured properties. .

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

Claims (17)

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, and the reactive silyl group is a dialkoxysilyl group;
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 .;
An organic polymer (B) having a reactive silyl group, a urethane bond and / or a urea bond, and having at least one selected from the group consisting of polyoxyalkylene, polyester, polycarbonate and polyvinyl as a molecular chain;
A curing catalyst (C),
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 the reactive silyl group as X ¹ is a dialkoxysilyl group , * 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 organic polymer (B) is 10: 90-90: 10. The curing catalyst (C) 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 (C) is 0.1 to 20 parts by mass with respect to a total of 100 parts by mass of the vinyl polymer (A) and the organic polymer (B). The curable resin composition described in 1.   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 organic polymer (B). The curable resin composition described in 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 2 , n3 is 1 , and m3 + n3 is 3. The curable resin composition according to any one of claims 1 to 12 , 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, m1 is 2 , n1 is 1 , m1 + n1 is 3, and * represents a bonding position. The curable resin composition according to any one of claims 1 to 13 , 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 14 , further comprising a polyoxyalkylene polymer (D) having a reactive silyl group and having a molecular chain of polyoxyalkylene. The vinyl polymer (a) is further have a reactive silyl group in the side chain of the molecular chain, the reactive silyl groups of the vinyl polymer (a) further has a side chain of the molecular chain di alkoxy Ru silyl group der curable resin composition according to any one of claims 1 to 15. In the vinyl polymer (A), a reactive silyl group having a terminal end of the molecular chain, a group represented by the following formula (V), curability according to any one of claims 1-16 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 the reactive silyl group as X ¹ is a dialkoxysilyl group. , * Represents a bonding position.