CN111655796B

CN111655796B - Curable resin composition

Info

Publication number: CN111655796B
Application number: CN201980010460.3A
Authority: CN
Inventors: 幸则孝; 鹤田护; 上野俊之; 松田俊太
Original assignee: Sika Hamatite Co Ltd
Current assignee: Sika Technology AG; Sika Japan Ltd
Priority date: 2018-02-09
Filing date: 2019-02-08
Publication date: 2022-06-14
Anticipated expiration: 2039-02-08
Also published as: JPWO2019156233A1; JP6950758B2; CN111655796A; WO2019156233A1

Abstract

The purpose of the present invention is to provide a curable resin composition having excellent weather resistance. The present invention is a curable resin composition containing: a vinyl polymer (A) having reactive silyl groups at the terminal and side chain of the molecular chain, the molecular chain having repeating units formed from a polymerizable vinyl monomer, the total number of the reactive silyl groups being more than 1 on the average per 1 molecule, the number of the reactive silyl groups at the terminal or side chain being more than 0.5, the weight average molecular weight being 30,000 to 110,000, the number average molecular weight being 9,000 to 40,000, and the glass transition temperature being-100 to-10 ℃; a polyoxyalkylene polymer (B) having a reactive silyl group, a polyoxyalkylene molecular chain, and a number average molecular weight of 10,000 to 50,000; and a curing catalyst (C).

Description

Curable resin composition

Technical Field

The present invention relates to a curable resin composition.

Background

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

For example, patent document 1 describes a curable sealant or the like comprising a crosslinkable silyl group-containing organic polymer (a) and a specific crosslinkable silyl group-terminated (meth) acrylate polymer (B) having a glass transition temperature of from-100 ℃ to-10 ℃ for the purpose of providing a sealant composition having paint adhesion and paint non-staining properties and excellent handling properties.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 5138186

Disclosure of Invention

Problems to be solved by the invention

Under such circumstances, the present inventors have made reference to patent document 1 to prepare a composition containing a vinyl polymer having a reactive silyl group and a polyoxyalkylene polymer having a reactive silyl group and evaluated the composition, and as a result, it was found that such a composition may have low weather resistance (comparative example 5).

The present inventors have also found that a composition containing a vinyl polymer having a small weight average molecular weight and/or a small number average molecular weight (comparative example 4) and a composition containing a vinyl polymer having a small number of reactive silyl groups in the side chains and/or the total number of reactive silyl groups in the vinyl polymer (comparative example 6) are inferior in weather resistance.

Accordingly, an object of the present invention is to provide a curable resin composition having excellent weather resistance.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a composition containing: a vinyl polymer (a) having a molecular chain comprising a repeating unit formed from a polymerizable vinyl monomer and a specific group bonded to the terminal thereof, wherein the molecular chain comprises a repeating unit formed from a polymerizable vinyl monomer, and has reactive silyl groups at the terminal and side chains of the molecular chain, and the molecular chain comprises a repeating unit formed from a polymerizable vinyl monomer, and the total number of the reactive silyl groups, the number of the reactive silyl groups at the terminal and side chains, the weight average molecular weight, the number average molecular weight, and the glass transition temperature are each in a specific range; and a polyoxyalkylene polymer (B) having a number average molecular weight within a specific range, can obtain a desired effect, and the present invention has been completed.

The present invention is based on the above findings and the like, and specifically solves the above problems with the following configurations.

[1] A curable resin composition comprising:

a vinyl polymer (A) having reactive silyl groups at the terminal and side chain of the molecular chain, wherein the molecular chain has repeating units formed by a polymerizable vinyl monomer, the total number of the reactive silyl groups is more than 1, the number of the reactive silyl groups at the terminal is more than 0.5, the number of the reactive silyl groups at the side chain is more than 0.5, the weight average molecular weight is 30,000 to 110,000, the number average molecular weight is 9,000 to 40,000, and the glass transition temperature is-100 to-10 ℃;

a polyoxyalkylene polymer (B) having a reactive silyl group, a molecular chain substantially containing a polyoxyalkylene group, and a number average molecular weight of 10,000 to 50,000; and

a curing catalyst (C) for curing,

the vinyl polymer (a) contains a vinyl polymer (a) having a molecular chain having a repeating unit formed from a polymerizable vinyl monomer and having a group represented by the following formula (I) at the terminal of the molecular chain.

*-S-L¹-X¹ (I)

In the formula (I), S is a sulfur atom, L¹Represents a 2-valent linking group, X¹Denotes a reactive silyl group, and denotes a bonding site.

[2] The curable resin composition according to [1], wherein the mass ratio (A: B) of the vinyl polymer (A) to the polyoxyalkylene polymer (B) is 10: 90-90: 10.

[3] the curable resin composition according to [1] or [2], wherein the curing catalyst (C) is at least 1 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 relative to 100 parts by mass of the total of the vinyl polymer (A) and the polyoxyalkylene polymer (B).

[4] The curable resin composition according to any one of [1] to [3], further comprising a resin hollow body.

[5] The curable resin composition according to any one of [1] to [4], which further comprises an antioxidant.

[6] The curable resin composition according to any one of [1] to [5], further comprising a plasticizer having a number average molecular weight of 1,500 to 15,000 and being at least one of an oxyalkylene polymer and a vinyl polymer,

the content of the plasticizer is 1 to 100 parts by mass relative to 100 parts by mass of the total of the vinyl polymer (A) and the polyoxyalkylene polymer (B).

[7] The curable resin composition according to any one of [1] to [6], wherein the weight average molecular weight of the vinyl polymer (A) is 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 molecular chain of the vinyl polymer (A) is linear.

[12]According to [1]～[11]The curable resin composition of any one of the above formulas (I), wherein X is₁The reactive silyl group of (a) is a dialkoxysilyl group.

[13] The curable resin composition according to any one 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 following formula (III).

In the formula (II), R^2-1Represents a hydrogen atom or a 1-valent hydrocarbon group, L²Represents a 2-valent linking group, R^2-2Represents a 1-valent hydrocarbon group.

In the formula (III), R^3-1Represents a hydrogen atom or a 1-valent hydrocarbon group, L³Represents a 2-valent linking group, R^3-2And R^3-3Each independently represents a 1-valent 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 the 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 the formula (I-1), R^1-1Represents a 2-valent hydrocarbon group, R^1-2And R^1-3Each independently represents a 1-valent hydrocarbon group, m1 is 1 to 3, n1 is 0 to 2, m1+ n1 is3, and x represents a bonding site.

[16] The curable resin composition according to [15], wherein m1 is 2 and n1 is 1 in the formula (I-1).

[17] The curable resin composition according to any one of [1] to [16], wherein the vinyl polymer (a) has 1 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 curable resin composition according to any one of [1] to [18], wherein the reactive silyl group at the end of the molecular chain in the vinyl polymer (A) is a group represented by the following formula (V).

*-S-L¹-X¹ (V)

In the formula (V), S is a sulfur atom, L¹Represents a 2-valent linking group, X¹Denotes a reactive silyl group, and denotes a bonding site.

[20] The curable resin composition according to any one of [1] to [19], wherein the total number of the reactive silyl groups in the vinyl polymer (A) is more than 1 and less than 1.80 on an average of 1 molecule.

[21] The curable resin composition according to any one of [1] to [20], wherein in the vinyl polymer (A), at least one of the reactive silyl group at the terminal and the reactive silyl group at the side chain is a dialkoxysilyl group.

ADVANTAGEOUS EFFECTS OF INVENTION

The curable resin composition of the present invention has excellent weather resistance.

Detailed Description

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) acrylic acid represents acrylic acid or methacrylic acid. Poly (meth) acrylate means polyacrylate, polymethacrylate, or copolymers of acrylate and methacrylate.

In the present specification, the numerical range expressed by the term "to" means a range including the numerical values described before and after the term "to" as the lower limit value and the upper limit value.

In the present specification, the method for producing each component is not particularly limited. Examples thereof include conventionally known production methods.

In the present specification, unless otherwise specified, each component may be used alone or in combination of 2 or more kinds thereof. When the component contains 2 or more substances, the content of the component means the total content of the 2 or more substances.

In this specification, the more excellent weather resistance is sometimes referred to as the more excellent effect of the present invention.

[ curable resin composition ]

The curable resin composition of the present invention (the composition of the present invention) is a curable resin composition containing:

a curing catalyst (C) for curing,

*-S-L¹-X¹ (I)

It is considered that the composition of the present invention has such a constitution and thus can obtain a desired effect. The reason for this is not clear, but is presumed to be as follows.

Generally, when a polyoxyalkylene polymer having a reactive silyl group is exposed to an outdoor environment, the bond between carbon and oxygen in the polyoxyalkylene as a molecular chain (main chain) is easily broken by the influence of the external environment. Therefore, the sealing material containing the polyoxyalkylene polymer is generally low in 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 high weight average molecular weight and/or a high number average molecular weight, even if the polyoxyalkylene polymer is cut in the molecular chain, the presence of the vinyl polymer (a) can maintain the elongation of the obtained sealing material in an appropriate range.

From the above reasons, it is estimated that the sealing material obtained by using the composition of the present invention has excellent weather resistance.

The components contained in the composition of the present invention will be described in detail below.

< vinyl Polymer (A) >)

The vinyl polymer (a) contained in the composition of the present invention is the following polymer: having reactive silyl groups at the ends and side chains of a molecular chain having a repeating unit formed from a polymerizable vinyl monomer,

the total number of the reactive silyl groups is more than 1, the number of the reactive silyl groups at the terminal is more than 0.5, and the number of the reactive silyl groups at the side chain is more than 0.5 on an average of 1 molecule,

the weight average molecular weight is 30,000-110,000, the number average molecular weight is 9,000-40,000, and the glass transition temperature is-100 to-10 ℃.

The composition of the present invention contains the vinyl polymer (a), and thus has excellent weather resistance.

< molecular chain >

In the present invention, the vinyl polymer (a) has a molecular chain having a repeating unit formed of a polymerizable vinyl monomer.

Since the molecular chain has a repeating unit formed of a polymerizable vinyl monomer, the molecular chain (main chain or skeleton) may be substantially 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 ] -, but the content of the- [ C-C ] -, is 50% by mass or more relative to the total of the repeating units of the vinyl polymer (A). The content of the above- [ C-C ] -is preferably 80% by mass or more based on the total amount.

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

The repeating unit of the polymerizable vinyl monomer constituting (the skeleton of) the molecular chain is not particularly limited as long as it is a repeating unit of a compound having a carbon-carbon double bond. Examples thereof include olefin monomers such as ethylene; (meth) acrylic monomers such as (meth) acrylic acid esters, (meth) acrylamides, and (meth) acrylic acids; a repeating unit of an aromatic vinyl monomer such as styrene.

At least a part of the repeating units constituting the molecular chain of the vinyl polymer (a) may have reactive silyl groups. In the case where the repeating unit has a reactive silyl group, the vinyl polymer (a) may have the reactive silyl group in a side chain, for example. Examples of the repeating unit having a reactive silyl group include a repeating unit formed from a (meth) acrylate having a reactive silyl group.

(repeating units formed from (meth) acrylate ester monomers)

Among these, from the viewpoint of more excellent weather resistance, the repeating unit constituting (the skeleton of) the molecular chain of the vinyl polymer (a) is preferably a repeating unit formed from a (meth) acrylate monomer. The above (meth) acrylate monomer (repeating unit formed) may have a reactive silyl group. The repeating unit formed from the (meth) acrylate monomer described later (or the (meth) acrylate monomer) may have a reactive silyl group.

The (meth) acrylate monomer is not particularly limited as long as it is a (meth) acrylate. Examples of the hydrocarbon group constituting the ester moiety of the (meth) acrylic ester include an aliphatic hydrocarbon group (linear, branched or cyclic), an aromatic hydrocarbon group, and a combination thereof.

When the (meth) acrylate monomer has a reactive silyl group, the reactive silyl group may 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 further excellent weather resistance and excellent elongation of the cured product. However, in the case where the (meth) acrylate monomer has a reactive silyl group in the ester residue, the number of carbon atoms in the ester residue in the (meth) acrylate monomer is the number of carbon atoms in the ester residue after the reactive silyl group has been removed from the ester residue.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include aliphatic hydrocarbon groups such as propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, isononyl and lauryl; aliphatic hydrocarbon groups having a valence of 2 or more from which hydrogen atoms are further removed.

(molecular chain is linear)

The molecular chain shape of the vinyl polymer (a) is not particularly limited. From the viewpoint of excellent elongation of the resulting cured product and an appropriate range of viscosity of the composition, one of preferable embodiments is that the molecular chain is linear.

< reactive silyl >)

The reactive silyl group of the vinyl polymer (a) is not particularly limited as long as it has a silicon atom and is a reactive group. Examples thereof include silyl groups in which 1 to 3 hydrolyzable groups are bonded to 1 silicon atom.

From the viewpoint of further excellent weather resistance, excellent elongation of the resulting cured product, and an appropriate range of viscosity of the composition, the reactive silyl group of the vinyl polymer (a) is preferably a silyl group in which 2 hydrolyzable groups are bonded to 1 silicon atom. The same applies to the reactive silyl group in the side chain or the 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 acyloxy group, a ketoxime ester (ケトキシメート) group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among them, preferred is an alkoxy group.

From the viewpoint of more excellent weather resistance, excellent elongation of the resulting cured product, and an appropriate range of viscosity of the composition, the reactive silyl group is preferably a dialkoxysilyl group, and more preferably an alkyldialkoxysilyl group or a dimethoxysilyl group.

When 1 or 2 hydrolyzable groups are bonded to 1 silicon atom, the group other than the hydrolyzable group which can be bonded to the silicon atom is not particularly limited. Examples thereof include an aliphatic hydrocarbon group (linear, branched or cyclic), an aromatic hydrocarbon group, and a combination thereof. Among them, an aliphatic hydrocarbon group having 1 to 6 carbon atoms is preferable. Specific examples thereof include methyl and ethyl.

(reactive silyl group and molecular chain)

In the present invention, the vinyl polymer (a) has the reactive silyl group at the terminal and side chain of the molecular chain.

The reactive silyl group may be bonded to the terminal of the molecular chain directly or via an organic group. The organic group is not particularly limited.

The reactive silyl group may be bonded to a side chain of the molecular chain directly or via an organic group. The organic group is not particularly limited.

In the vinyl polymer (a), from the viewpoint of more excellent weather resistance, excellent elongation of the obtained cured product, and an appropriate range of viscosity of the composition, at least one of the reactive silyl group at the terminal and the reactive silyl group at the side chain is preferably a dialkoxysilyl group, and more preferably a dimethoxysilyl group.

In the dialkoxysilyl group (or the dimethoxysilyl group), another hydrocarbon group capable of bonding to a silicon atom is not particularly limited. Examples thereof include alkyl groups. When the dialkoxysilyl group (or the dimethoxysilyl group) has an alkyl group as another hydrocarbon group capable of bonding to the silicon atom, the dialkoxysilyl group (or the alkyldimethoxysilyl group) is an alkyldialkoxysilyl group.

In the vinyl polymer (a), from the viewpoint of further excellent weather resistance, excellent elongation of the obtained cured product, and an appropriate range of viscosity of the composition, it is preferable that all of the reactive silyl groups at the terminal and the reactive silyl groups at the side chain are dialkoxysilyl groups.

The vinyl polymer (a) may be, for example, a mixture of vinyl polymers having the reactive silyl group at the terminal of the molecular chain or in the side chain; a vinyl polymer having the reactive silyl group at the terminal and side chain of the molecular chain; a mixture of a vinyl polymer having the reactive silyl group at the terminal or side chain of the molecular chain and a vinyl polymer having the reactive silyl group at the terminal or 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 of the vinyl polymer (a) is more than 1 on average per 1 molecule.

The total number of the reactive silyl groups is the number of the reactive silyl groups that the vinyl polymer (a) has on average per 1 molecule in the entire vinyl polymer (a).

From the viewpoint of more excellent weather resistance, the total number is preferably more than 1 and 3 or less, more preferably more than 1 and 2 or less, and further preferably more than 1 and less than 1.80 on average.

The total number of the reactive silyl groups may be the total number of the reactive silyl groups at the terminal and the reactive silyl groups at the side chain, which will be described later.

In the present invention, the number (total number) of the reactive silyl groups can be calculated from the number of the reactive silyl groups and the groups represented by the formula (I) per 1 molecule of the polymer theoretically calculated from the composition ratio of the monomer and the chain transfer agent used in the production of the vinyl polymer (a) and the number average molecular weight (Mn). The number of the reactive silyl groups at the terminal or side chain of the vinyl polymer (A), and the number of the groups represented by the formula (V) at the terminal, which will be described later; the same applies to the number of reactive silyl groups possessed by the vinyl polymer (a) described later and the number of groups represented by the formula (I) possessed at the terminal.

< reactive silyl group in terminal >

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

When the reactive silyl group is bonded to the terminal of the molecular chain of the vinyl polymer (a) through an organic group, examples of the group having the reactive silyl group include a group represented by the following formula (V).

*-S-L¹-X¹ (V)

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

< number of reactive silyl groups at terminal >

In the present invention, the number of the reactive silyl groups at the terminal of the vinyl polymer (a) is more than 0.5 on an average of 1 molecule.

The number of the reactive silyl groups is the number of the reactive silyl groups at the terminal of the vinyl polymer (a) on an average of 1 molecule in the entire vinyl polymer (a).

From the viewpoint of more excellent weather resistance, the number is preferably more than 0.5 and 2 or less, more preferably 0.6 to 1.0, and further preferably 0.6 or more and less than 0.9 on average.

< reactive silyl group in side chain >

The vinyl polymer (a) has a reactive silyl group in a side chain, from the viewpoints of excellent weather resistance, excellent elongation of a cured product, and an appropriate range of viscosity of the composition.

When the reactive silyl group is bonded to a side chain of the molecular chain of the vinyl polymer (a) through an organic group, examples of the group having the reactive silyl group include a group represented by the following formula (IV).

*-L⁴-X⁴ (IV)

In the formula (IV), L⁴Represents a 2-valent linking group, X⁴Denotes a reactive silyl group, and denotes a bonding site.

L of the formula (IV)⁴And L of the formula (III)³The same applies.

X of the formula (IV)⁴And X of the formula (I) representing a group of the vinyl polymer (a) having at the terminal of the molecular chain¹The same is true.

< number of reactive silyl groups in side chains >

In the present invention, the number of the reactive silyl groups in the side chain of the vinyl polymer (a) is more than 0.5 on an average per 1 molecule.

The number of the reactive silyl groups is the number of the reactive silyl groups in the side chain of the vinyl polymer (a) on an average of 1 molecule in the entire vinyl polymer (a).

From the viewpoint of further excellent weather resistance, the number is preferably more than 0.5 and 2 or less, more preferably 0.6 to 1.0, and further preferably 0.6 or more and less than 0.9 on average.

(other side chains)

From the viewpoint of further excellent weather resistance, excellent elongation of the cured product, and an appropriate range of viscosity of the composition, the vinyl polymer (a) preferably further has a hydrocarbon group in the side chain. The 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, and a combination thereof. Specifically, for example, a hydrocarbon group having 1 to 12 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms.

The hydrocarbon group may be bonded to the molecular chain directly or via an organic group.

The organic group is not particularly limited. Examples thereof include an ester bond, an amide bond, an ether bond and a carbonyl group.

(repeating units constituting the vinyl polymer (A))

A repeating unit of the formula (III)

From the viewpoint of more excellent weather resistance, excellent elongation of the cured product, and an appropriate range of viscosity of the composition, the molecular chain of the vinyl polymer (a) preferably has a repeating unit represented by formula (III).

·R^3-1

In the formula (III), R^3-1Represents a hydrogen atom or a 1-valent hydrocarbon group.

Examples of the 1-valent hydrocarbon group include aliphatic hydrocarbon groups such as methyl groups.

·L³

In the formula (III), L³Represents a 2-valent linking group.

As L³Examples of the 2-valent linking group include a 2-valent hydrocarbon group L^3-1(ii) a Substituent L such as ester bond, amide bond, ether bond, carbonyl group^3-2。

As 2-valent hydrocarbon radicals L^3-1Examples thereof include an aliphatic hydrocarbon group (linear, branched or cyclic), an aromatic hydrocarbon group, and a combination thereof. Specifically, for example, an aliphatic hydrocarbon group having 1 to 8 carbon atoms is mentioned.

As L³Examples thereof include a 2-valent hydrocarbon group L^3-1With a substituent L^3-2Combinations of (a) and (b).

Among them, a combination of an aliphatic hydrocarbon group having 1 to 8 carbon atoms and an ester bond is preferable.

·R^3-2、R^3-3

In the formula (III), R^3-2And R^3-3Each independently represents a 1-valent hydrocarbon group.

Examples of the 1-valent hydrocarbon group include an aliphatic hydrocarbon group (linear, branched, or cyclic), an aromatic hydrocarbon group, and a combination thereof.

Among them, aliphatic hydrocarbon groups such as methyl and ethyl groups are preferable.

·m3

In the formula (III), m3 is 1-3.

M3 is preferably 2 from the viewpoint that the weather resistance is further excellent, the elongation of the resulting cured product is excellent, the viscosity of the composition is within an appropriate range, and the service life can be ensured at an appropriate length.

·n3

In formula (III), n3 is 0 to 2.

From the viewpoint that the weather resistance is further excellent, the elongation of the obtained cured product is excellent, the viscosity of the composition is in an appropriate range, and the service life can be ensured at an appropriate length, n3 is preferably 1.

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

In the formula (III-1), R^3-1Represents a hydrogen atom or a 1-valent hydrocarbon group, R^3-2And R^3-3Each independently represents a 1-valent hydrocarbon group, R³ ^-4Represents a 2-valent hydrocarbon group, m3 is 1 to 3, n3 is 0 to 2, and m3+ n3 is 3.

R of the formula (III-1)^3-1、R^3-2、R^3-3M3 and n3 are the same as those of the formula (III).

R of the formula (III-1)^3-4With the above-mentioned 2-valent hydrocarbon group L^3-1The same is true. Among them, propylene is preferable.

A repeating unit of the formula (II)

The molecular chain of the vinyl polymer (a) may further have, for example, a repeating unit represented by the following formula (II) as the repeating unit formed from the (meth) acrylate monomer.

·R^2-1

In the formula (II), R^2-1Represents a hydrogen atom or a 1-valent hydrocarbon group.

·L²

In the formula (II), L²Represents a 2-valent linking group.

Examples of the 2-valent linking group include an ester bond, an amide bond, an ether bond, and a carbonyl group.

Among them, ester bonds are preferable.

·R^2-2

In the formula (II), R^2-2Represents a 1-valent hydrocarbon group.

R is more excellent in weather resistance and the elongation of the resulting cured product is excellent^2-2Preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 4 to 8 carbon atoms.

As R^2-2Specific examples thereof include aliphatic hydrocarbon groups such as butyl, pentyl, hexyl, octyl, 2-ethylhexyl, isononyl and lauryl. Among them, butyl, pentyl, hexyl, octyl, and 2-ethylhexyl are preferable.

< weight average molecular weight >

In the present invention, the weight average molecular weight of the vinyl polymer (A) is 30,000 to 110,000.

The weight average molecular weight is in the above range, and the composition of the present invention is excellent in weather resistance.

The weight average molecular weight of the vinyl polymer (a) is preferably 45,000 to 100,000, more preferably 50,000 to 90,000, from the viewpoint that the weather resistance is more excellent, the elongation of the obtained cured product is excellent, the initial elongation of the cured product can be maintained for a long period of time, and the viscosity of the composition is within an appropriate range.

In addition, the weight average molecular weight of the vinyl polymer (a) is preferably 45,000 to 100,000, more preferably 60,000 to 90,000, from the viewpoint that the weather resistance is further excellent and the viscosity of the composition is within an appropriate range.

< 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 preferably more than 10,000 and less than 20,000, more preferably 16,000 or more and less than 20,000, from the viewpoint that the weather resistance (particularly, the weather resistance over a longer period) is more excellent, the elongation of the obtained cured product is excellent, the initial elongation of the cured product can be maintained for a longer period, and the viscosity of the composition is within an appropriate range.

In the present invention, the vinyl polymer (a) was analyzed by a Gel Permeation Chromatography (GPC) method, and the weight average molecular weight or the number average molecular weight of the vinyl polymer (a) was calculated in terms of polystyrene under the following conditions.

An apparatus: GPC-8220 (manufactured by DONG ソー Co., Ltd.)

Column: 1G 7000HXL/7.8mmID, 2 GMHXL/7.8mmID and 1G 2500HXL/7.8mmID were used.

The medium: tetrahydrofuran (THF)

Flow rate: 1.0mL/min

Concentration: 1.5mg/ml

Sample size: 300 mu L

Column temperature: 40 deg.C

In the present invention, the glass transition temperature (Tg) of the vinyl polymer (A) is from-100 to-10 ℃.

When the glass transition temperature is in the above range, the composition of the present invention has excellent weather resistance.

The glass transition temperature is preferably from-60 to-10 ℃ from the viewpoints of further excellent weather resistance, excellent elongation of the resulting cured product, and an appropriate range of viscosity of the composition.

In the present invention, the glass transition temperature (Tg) of the vinyl polymer (a) can be derived by raising the temperature of the sample (vinyl polymer (a)) at a constant rate using Differential Thermal Analysis (DTA) or Differential Scanning Calorimeter (DSC), and measuring the intersection of the tangent to the base line in the DTA curve or DSC curve and the tangent to the sharp drop position of the endothermic region caused by 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 formed of a polymerizable vinyl monomer and having a group represented by the following formula (I) at an end of the molecular chain.

*-S-L¹-X¹ (I)

< molecular chain >

In the present invention, the molecular chain of the vinyl polymer (a) has a repeating unit formed of a polymerizable vinyl monomer.

The molecular chain of the vinyl polymer (a) may be the same as the molecular chain of the vinyl polymer (a).

The repeating units of the polymerizable vinyl monomer in the molecular chain of the vinyl polymer (a) may be the same as the repeating units of the polymerizable vinyl monomer in the molecular chain of the vinyl polymer (a).

Side chain

The vinyl polymer (a) preferably has a reactive silyl group in a side chain, from the viewpoints of more excellent weather resistance, excellent elongation of a cured product, and an appropriate range of viscosity of the composition.

Number of reactive silyl groups in the side chain

The number of the reactive silyl groups in the side chain of the vinyl polymer (a) may be 0 to 2 per 1 molecule of the vinyl polymer (a).

From the viewpoint of more excellent weather resistance, excellent elongation of the cured product, and an appropriate range of viscosity of the composition, the number of reactive silyl groups in the side chain of the vinyl polymer (a) is preferably 1 to 2 per 1 molecule of the vinyl polymer (a).

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

< end >)

In the present invention, the vinyl polymer (a) has a group represented by the following formula (I) at the terminal of the molecular chain.

*-S-L¹-X¹ (I)

·L¹

In the formula (I), L¹Represents a 2-valent linking group.

Examples of the 2-valent linking group include those linked to the above-mentioned 2-valent hydrocarbon group L^3-1The same 2-valent linking group.

Among them, propylene is preferable.

·X¹

In the formula (I), X¹Represents a reactive silyl group.

The reactive silyl group is not particularly limited. Examples thereof include the same reactive silyl groups as those described above.

X is a number in the range of more excellent weather resistance, excellent elongation of the resulting cured product, and appropriate viscosity of the composition¹The reactive silyl group of (3) is preferably a dialkoxysilyl group, more preferably an alkyldialkoxysilyl group, and still more preferably a methyldimethoxysilyl group.

·*

In formula (I), a represents a binding site.

In the present invention, the vinyl polymer (a) has a group represented by the formula (I) at the terminal of the molecular chain. The group represented by the formula (I) may be bonded to the terminal of the molecular chain of the vinyl polymer (a).

The group represented by the formula (I) may be bonded to the terminal 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 1 or more reactive silyl groups per 1 molecule (on average). The reactive silyl group is the same as described above.

The vinyl polymer (a) preferably has 1 to 6 reactive silyl groups per 1 molecule (on average) from the viewpoint of further excellent weather resistance and excellent elongation of the resulting cured product.

From the viewpoint of more excellent weather resistance and excellent elongation of the resulting cured product, the vinyl polymer (a) preferably has 1 terminal having a group represented by the formula (I).

The other terminal of the vinyl polymer (a) may be bonded with a residue derived from, for example, a polymerization initiator used in the production of the vinyl polymer (A).

In the vinyl polymer (a), a residue derived from, for example, a polymerization initiator used in the production of the vinyl polymer (a) may be bonded to the terminal.

Formula (I-1)

The group represented by the formula (I) is preferably a group represented by the following formula (I-1) from the viewpoints of further excellent weather resistance, excellent elongation of the resulting cured product, and an appropriate range of viscosity of the composition.

·R^1-1

In the formula (I-1), R^1-1Represents a 2-valent hydrocarbon group.

Examples of the 2-valent hydrocarbon group include an aliphatic hydrocarbon group (linear, branched, or cyclic), an aromatic hydrocarbon group, and a combination thereof. Among them, an aliphatic hydrocarbon group having 1 to 6 carbon atoms is preferable, and a propylene group is more preferable.

·R^1-2、R^1-3

In the formula (I-1), R^1-2And R^1-3Each independently represents a 1-valent hydrocarbon group.

·m1

In the formula (I-1), m1 is 1-3.

M1 is preferably 2 from the viewpoint that the weather resistance is further excellent, the elongation of the resulting cured product is excellent, the viscosity of the composition is within an appropriate range, and the service life can be ensured at an appropriate length.

·n1

In the formula (I-1), n1 is 0 to 2.

From the viewpoint that the weather resistance is further excellent, the elongation of the obtained cured product is excellent, the viscosity of the composition is in an appropriate range, and the service life can be ensured at an appropriate length, n1 is preferably 1.

·*

In formula (I-1), a represents a binding site. The same as in formula (I), is used for formula (I-1).

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

In the present invention, all or a part of the vinyl polymer (a) may be the vinyl polymer (a).

In the case where a part of the vinyl polymer (a) is the vinyl polymer (a), the vinyl polymer (a) may further contain, in addition to the vinyl polymer (a), a vinyl polymer (a') having a repeating unit of a polymerizable vinyl monomer in a molecular chain and having a reactive silyl group at a terminal and/or a side chain (except for the vinyl polymer (a)).

Further, the vinyl polymer (a) may further contain a vinyl polymer (a ") having a molecular chain having a repeating unit formed of a polymerizable vinyl monomer and having no reactive silyl group.

The vinyl polymer (a') or (a ") may be a by-product in the production of the vinyl polymer (A).

Content of vinyl Polymer (a)

The content of the vinyl polymer (a) may be 0.1 to 100% by mass based on the whole vinyl polymer (A).

(Process 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

The polymerizable vinyl monomer is not particularly limited as long as it is a compound having a carbon-carbon double bond.

Examples of the polymerizable vinyl monomer include compounds represented by the following formula (III'). As the polymerizable vinyl monomer, for example, a compound represented by the following formula (II') can be further used. As the polymerizable vinyl monomer, a combination of a compound represented by the following formula (III ') and a compound represented by the following formula (II') is preferably used.

The repeating unit represented by the above formula (II) can be formed by the compound represented by the above formula (II').

The repeating unit represented by the above formula (III) can be formed by the compound represented by the above formula (III').

Chain transfer agent

Examples of the chain transfer agent include those of the formula (I'): HS-L¹-X¹The compounds shown.

The compound represented by the above formula (I') can form a group represented by the above formula (I) at the terminal of the vinyl polymer (a). The same applies to the vinyl polymer (A).

The amount of the compound represented by the formula (III') used

In the case where 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 amount of the compound represented by the formula (III ') is preferably 0.1 to 100 parts by mass, more preferably 0.4 to 2.0 parts by mass, and even more preferably 0.5 to 1.5 parts by mass, based on 100 parts by mass of the compound represented by the formula (II'), from the viewpoints of further excellent weather resistance, excellent elongation of the resulting cured product, and an appropriate range of viscosity of the composition.

In the case where the molecular chain (main chain) of the vinyl polymer (a) has the repeating unit represented by the formula (II) and the repeating unit represented by the formula (III), the molar ratio of the compound represented by the formula (II ') to the compound represented by the formula (III') used in the production of the vinyl polymer (a) may be reflected on the number of repeating units of the repeating unit represented by the formula (II) and the repeating unit represented by the formula (III) constituting the molecular chain (main chain) of the vinyl polymer (a).

Amount of chain transfer agent used

The amount of the chain transfer agent used is preferably 0.2 to 5 parts by mass, more preferably 0.8 to 3.6 parts by mass, based on 100 parts by mass of the total amount of the polymerizable vinyl monomers, from the viewpoints of more excellent weather resistance, excellent elongation of the resulting cured product, and an appropriate range of viscosity of the composition.

When the amount of the chain transfer agent used is small, the weight average molecular weight and/or the number average molecular weight of the vinyl polymer (A) can be made large.

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 mass, more preferably 0.1 to 3.0 parts by mass, per 100 parts by mass of the total amount of the polymerizable vinyl monomers.

In the above production method, a solvent may be used as necessary.

One of preferable embodiments is that the 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 is a polymer having a reactive silyl group, a molecular chain (main chain) substantially consisting of a polyoxyalkylene group, and a number average molecular weight of 10,000 to 50,000.

The composition of the present invention contains the polyoxyalkylene polymer (B) and thus has favorable handling properties as a sealing material.

Further, when the number average molecular weight of the polyoxyalkylene polymer (B) is within the above-specified range, the composition of the present invention is excellent in weather resistance.

< reactive silyl >)

The reactive silyl group of the polyoxyalkylene polymer (B) is not particularly limited. The reactive silyl group is preferably a silyl group having a hydrolyzable group. The hydrolyzable silyl group is the same as described above.

From the viewpoint that the weather resistance is further excellent, the elongation of the resulting cured product is excellent, the viscosity of the composition is in an appropriate range, and the service life can be ensured in an appropriate length, the reactive silyl group of the polyoxyalkylene polymer (B) is preferably a silyl group in which 2 hydrolyzable groups are bonded to 1 silicon atom.

The reactive silyl group is preferably a dialkoxysilyl group, and more preferably an alkyldialkoxysilyl group or a dimethoxysilyl group, from the viewpoints that the weather resistance is more excellent, the elongation of the resulting cured product is excellent, the viscosity of the composition is in an appropriate range, and the service life can be ensured in an appropriate length.

From the viewpoint of further excellent weather resistance, excellent curing properties, and the viscosity of the composition being within an appropriate range, and ensuring a useful life with an appropriate length, the polyoxyalkylene polymer (B) preferably has 1 or more reactive silyl groups on average in 1 molecule, and more preferably has 1 to 2 reactive silyl groups.

The average number of the reactive silyl groups of the polyoxyalkylene polymer (B) can be defined as a number of reactive silyl groups directly bonded to carbon atomsSub-pass high resolution¹The average number of the samples was determined by a quantitative method in H-NMR measurement. In the calculation of the average number of reactive silyl groups in the polyoxyalkylene polymer (B), when a reactive silyl group is introduced into the polyoxyalkylene polymer precursor before the reactive silyl group is introduced, the modified product of the polyoxyalkylene polymer precursor to which no reactive silyl group is introduced and the polyoxyalkylene polymer precursor to which no reactive silyl group is introduced, which is produced as a by-product, may be calculated as the number of bases (number of molecules) included in the calculation of the average number of reactive silyl groups in one molecule, as part of the components of the polyoxyalkylene polymer (B) having the same main chain structure.

< molecular chain >

The polyoxyalkylene polymer (B) has a molecular chain which is substantially polyoxyalkylene.

In the present invention, the term "substantially" means that the molecular chain of the polyoxyalkylene polymer (B) may further contain repeating units other than oxyalkylene groups, but the content of the oxyalkylene groups is 50% by mass or more with respect to the total of the repeating units of the polyoxyalkylene polymer (B). The content of the oxyalkylene group is preferably 80% by mass or more based on the total amount.

Examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, a polyoxytrimethylene group, a polyoxytetramethylene group, a copolymer thereof, and a derivative thereof having a substituent.

The reactive silyl group may be bonded to the molecular chain directly or via an organic group. The organic group is not particularly limited.

The polyoxyalkylene polymer (B) may have the reactive silyl group at the molecular chain, the terminal and/or the side 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, the reactive silyl group is preferably present at 50% or more, more preferably 60% or more, and even more preferably 60 to 85% of the entire end of the molecular chain, from the viewpoints that the weather resistance is further excellent, the elongation of the resulting cured product is excellent, the viscosity of the composition is within an appropriate range, and the service life can be ensured at an appropriate length.

< number average molecular weight >

In the present invention, the number average molecular weight of the polyoxyalkylene polymer (B) is 10,000 to 50,000.

The number average molecular weight of the polyoxyalkylene polymer (B) is preferably 15,000 to 35,000 from the viewpoints of more excellent weather resistance (particularly, weather resistance over a longer period), excellent elongation of the resulting cured product, and an appropriate range of viscosity of the composition.

In the present invention, the number average molecular weight of the polyoxyalkylene polymer (B) is a standard polystyrene equivalent value based on a measurement value obtained by Gel Permeation Chromatography (GPC) using Tetrahydrofuran (THF) as a solvent.

One of preferable embodiments is that the polyoxyalkylene polymer (B) does not have a urethane bond or a urea bond.

(method for producing polyoxyalkylene polymer (B))

The method for producing the polyoxyalkylene polymer (B) is not particularly limited. For example, a method in which a polyoxyalkylene polymer precursor having an unsaturated group represented by the formula (VI) at the end of the molecule 1 and a reactive silyl group-containing compound represented by the formula (VII) are reacted in the presence of a group VIII transition metal catalyst is mentioned.

Formula (VI): CH (CH)₂＝C(R³)-R²-O-

(in the formula (VI), R²Represents a 2-valent organic group having 1 to 20 carbon atoms, R₃Represents a hydrogen atom or a 1-valent hydrocarbon group. )

Formula (VII): H-X

(in the formula (VII), X represents a reactive silyl group.)

In the formula (VI), as the 2-valent organic group having 1 to 20 carbon atoms,examples thereof include CH₂＝CH-CH₂-、CH₂＝CH-C₂H₄-、CH₂＝C(CH₃)-CH₂-. The organic group is preferably CH from the viewpoint of reactivity₂＝CH-CH₂- (allyl), CH₂＝C(CH₃)-CH₂- (methallyl).

In the formula (VI), the 1-valent hydrocarbon group includes an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as a methyl group.

The polyoxyalkylene polymer precursor may be produced by a known method, for example.

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

As the group VIII transition metal catalyst, for example, H₂PtCl₆·6H₂O, platinum-vinylsiloxane complex, platinum-olefin complex, Pt metal, RhCl (PPh)₃)₃、RhCl₃、Rh/Al₂O₃、RuCl₃、IrCl₃、FeCl₃、PdCl₂·2H₂O、NiCl₂. The above group VIII transition metal catalyst is preferably H from the viewpoint of reactivity of hydrosilylation₂PtCl₆·6H₂O, a platinum- (di) vinylsiloxane complex compound, and a platinum-olefin complex compound.

Commercially available products of the polyoxyalkylene polymer (B) include, for example, MS ポリマー (product of カネカ Co., Ltd.), サイリルポリマー (product of カネカ Co., Ltd.), エクセスター (product of Asahi glass Co., Ltd.), and the like.

(ratio by mass of vinyl polymer (A) to polyoxyalkylene polymer (B))

From the viewpoint that the composition has excellent weather resistance (particularly, weather resistance over a longer period of time), can maintain the initial elongation of the cured product over a long period of time, and has an appropriate viscosity range, the mass ratio (a: B) of the vinyl polymer (a) to the polyoxyalkylene polymer (B) is preferably 10: 90-90: 10, more preferably 50: 50-90: 10, more preferably 60: 40-90: 10.

< curing catalyst (C) >)

The curing catalyst (C) contained in the composition of the present invention is not particularly limited as long as it can act on the reactive silyl group or the group represented by the formula (I).

As the curing catalyst (C), for example, a catalyst for hydrolyzing and/or condensing a hydrolyzable silyl group, or a conventionally known curing catalyst generally used as a silanol condensation catalyst can be used. Examples thereof include tin compounds, titanium compounds, acidic compounds and amine compounds.

Among these, tin compounds are preferable from the viewpoint of excellent curing speed and/or storage stability.

Examples of the tin compound include 4-valent dialkyltin compounds (e.g., dimethyltin compound, dibutyltin compound, dioctyltin compound),

A reactant of dibutyltin oxide and phthalic acid ester,

Dialkyl stannoxane dicarboxylates,

Dialkyl tin alkoxide such as dibutyl tin dimethoxide,

(dialkylstannoxane) disilicate compounds,

4-valent dialkyltin compounds such as dialkyltin chelate compounds such as dibutyltin diacetylacetonate;

4-valent monoalkyltin compounds such as monobutyltin trioctoate, monobutyltin triisopropoxide, and monooctyltin compounds;

and 2-valent tin compounds such as tin octylate, tin naphthenate, and tin stearate.

Content of curing catalyst (C)

The content of the curing catalyst (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 5.0 parts by mass, based on 100 parts by mass of the total of the vinyl polymer (a) and the polyoxyalkylene polymer (B), from the viewpoints of further excellent weather resistance, excellent elongation of the resulting cured product, and an appropriate range of viscosity of the composition.

(hollow resin)

From the viewpoint of excellent handling properties, the composition of the present invention preferably further contains resin hollow bodies (resin spheres).

The outer shell of the resin hollow body is made of resin, and the interior thereof is hollow.

The resin hollow body may function as a filler.

As the material of the outer shell of the resin hollow body, for example, phenol resin; a urea resin; a polystyrene-based resin; polyvinylidene 1, 1-dichloroethylene; acrylonitrile copolymers (e.g., copolymers of acrylonitrile and methacrylonitrile, copolymers of acrylonitrile and vinyl monomers such as butadiene and styrene copolymerizable with acrylonitrile), thermoplastic resins such as 1, 1-dichloroethylene polymers, and the like.

From the viewpoint of more excellent weather resistance and excellent workability, the material of the outer shell of the resin hollow body is preferably an acrylonitrile copolymer.

The average particle diameter of the resin hollow body may be 20 μm or more, preferably 20 to 70 μm.

The average particle diameter of the resin hollow bodies can be measured by a laser diffraction method.

From the viewpoint of excellent workability, the true specific gravity of the resin hollow body is preferably 0.05 to 0.35.

The resin hollow body described above can be expanded by heating. The temperature at which the resin hollow body can start to expand (heat resistance temperature) may be, for example, 100 to 190 ℃.

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

From the viewpoint of more excellent weather resistance and excellent workability, the resin hollow body is preferably coated with the filler.

The method for producing the resin hollow body is not particularly limited, and the resin hollow body can be produced by a conventionally known method.

Examples of commercially available products of the resin hollow body include MFL-60CAS manufactured by Songbo oil and fat pharmaceuticals, Inc.

The content of the resin hollow body is preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, based on 100 parts by mass of the total of the vinyl polymer (a) and the polyoxyalkylene polymer (B), from the viewpoint of excellent handling properties.

(anti-aging agent)

The composition of the present invention preferably further contains an antioxidant from the viewpoint of further excellent weather resistance and excellent elongation of the resulting cured product.

Examples of the antioxidant include Butylated Hydroxytoluene (BHT), Butylated Hydroxytoluene Anisole (BHA), benzotriazole, and 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol.

The content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total of the vinyl polymer (a) and the polyoxyalkylene polymer (B), from the viewpoint of excellent prevention of cracks on the surface of a sealing material.

Plasticizers

The composition of the present invention may further contain a plasticizer from the viewpoint of further excellent weather resistance and excellent elongation of the resulting cured product.

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 oxyalkylene polymer or vinyl polymer preferably has a number average molecular weight of 1,500 to 15,000 from the viewpoint of further excellent weather resistance and excellent elongation of the resulting cured product.

The oxyalkylene polymer or vinyl polymer preferably has a weight average molecular weight of 1,500 to 15,000 from the viewpoint of further excellent weather resistance and excellent elongation of the resulting cured product.

The number average molecular weight or the weight average molecular weight is a standard polystyrene equivalent value based on a measurement value obtained by Gel Permeation Chromatography (GPC) using Tetrahydrofuran (THF) as a solvent.

Content of plasticizer

The content of the plasticizer is preferably 1 to 100 parts by mass, more preferably 30 to 60 parts by mass, based on 100 parts by mass of the total of the vinyl polymer (a) and the polyoxyalkylene polymer (B), from the viewpoint of further excellent weather resistance and excellent elongation of the resulting cured product.

Additives

The composition of the present invention may further contain an additive. Examples of the additive include fillers such as calcium carbonate (except for the hollow resin body), titanium oxide, silane coupling agents, tackifiers, anti-sagging agents, ultraviolet absorbers, antioxidants, and pigments.

The content of the filler (excluding the resin hollow body) is preferably 10 to 300 parts by mass with respect to 100 parts by mass of the total of the vinyl polymer (a) and the polyoxyalkylene polymer (B).

Silane coupling agent

The composition of the present invention preferably further contains a silane coupling agent from the viewpoint of excellent curability, adhesiveness, and 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, a mercapto group-containing silane coupling agent, and an isocyanate group-containing silane coupling agent.

The content of the silane coupling agent is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total of the vinyl polymer (a) and the polyoxyalkylene polymer (B), from the viewpoint of excellent curability, adhesiveness, and storage stability.

(production method)

The method for producing the composition of the present invention is not particularly limited. For example, the composition of the present invention can be produced by mixing the above-mentioned essential components with optional components which can be further used as needed.

(application base)

The substrate to which the composition of the present invention can be applied is not particularly limited. Examples thereof include metal, plastic, rubber, glass, concrete, tile, stone, and the like.

The method of applying the composition of the present invention to a substrate is not particularly limited.

(curing)

The compositions of the present invention can cure if used in the presence of moisture. The above-mentioned moisture is not particularly limited. For example, moisture in the air can be cited.

The temperature conditions under which the composition of the present invention is used or cured may be, for example, room temperature conditions.

(use)

Examples of the use of the composition of the present invention include a sealing material (for example, for construction), an adhesive, and a coating agent.

Examples

The present invention will be specifically described with reference to the following examples. However, the present invention is not limited thereto.

< production of vinyl Polymer (A) >

Each vinyl polymer (a) was produced as follows. The unit "part" of the amount of the component used in the following production is referred to as "part by mass".

Vinyl Polymer (A-1)

50 parts of methyl ethyl ketone was added to the reaction vessel, and the temperature was raised to 60 ℃ with stirring. To this solution, 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 shall apply hereinafter) were added dropwise, and the inside of the reaction vessel was replaced with nitrogen gas while stirring. Then, 1.40 parts of γ -mercaptopropylmethyldimethoxysilane (trade name KBM-802, the same shall apply hereinafter) was added, and after stirring for 30 minutes, 0.05 parts of 2, 2' -azobisisobutyronitrile (the same shall apply hereinafter, available from Tokyo chemical industry Co., Ltd.) was added. Then, 0.5 part of 2, 2' -azobisisobutyronitrile was added in 4 portions, 1 portion every 30 minutes. Further, the reaction was carried out for 4 hours while maintaining the temperature in the reaction vessel, thereby obtaining a vinyl polymer solution. The solvent was removed from the vinyl polymer solution by an evaporator to obtain a vinyl polymer (A-1).

Vinyl Polymer (A-2)

50 parts of methyl ethyl ketone was added to the reaction vessel, and the temperature was raised to 60 ℃ with stirring. 100 parts of n-butyl acrylate and 1.24 parts of γ -methacryloxypropylmethyldimethoxysilane were added dropwise thereto, and the inside of the reaction vessel was purged with nitrogen while stirring. Then, 0.90 part of γ -mercaptopropylmethyldimethoxysilane was added, and after stirring for 30 minutes, 0.05 part of 2, 2' -azobisisobutyronitrile was added. Then, 0.5 part of 2, 2' -azobisisobutyronitrile was added in 4 portions, 1 portion every 30 minutes. Further, the reaction was carried out for 4 hours while maintaining the temperature in the reaction vessel, thereby obtaining a vinyl polymer solution. The solvent was removed from the vinyl polymer solution by an evaporator to obtain a vinyl polymer (A-2).

Vinyl Polymer (A-3)

50 parts of methyl ethyl ketone was added to the reaction vessel, and the temperature was raised to 60 ℃ with stirring. To this, 100 parts of n-butyl acrylate and 0.74 part of γ -methacryloxypropylmethyldimethoxysilane were added dropwise, and the inside of the reaction vessel was replaced with nitrogen gas while stirring. Then, 0.80 part of γ -mercaptopropylmethyldimethoxysilane was added, and after stirring for 30 minutes, 0.05 part of 2, 2' -azobisisobutyronitrile was added. Then, 0.5 part of 2, 2' -azobisisobutyronitrile was added 4 times, 1 time every 30 minutes. Further, the reaction was carried out for 4 hours while maintaining the temperature in the reaction vessel, thereby obtaining a vinyl polymer solution. The solvent was removed from the vinyl polymer solution by an evaporator to obtain a vinyl polymer (A-3).

Comparative vinyl Polymer (A-4)

50 parts of methyl ethyl ketone was added to the reaction vessel, and the temperature was raised to 80 ℃ while stirring. 100 parts of n-butyl acrylate and 2.40 parts of γ -methacryloxypropylmethyldimethoxysilane were added dropwise thereto, and the reaction vessel was refluxed while stirring. Next, 0.05 part of 2, 2' -azobisisobutyronitrile was added. Then, 0.5 part of 2, 2' -azobisisobutyronitrile was added 4 times, 1 time every 30 minutes. Further, the reaction was carried out for 4 hours while maintaining the temperature in the reaction vessel, thereby obtaining a vinyl polymer solution. The solvent was removed from the vinyl polymer solution by an evaporator to obtain (comparative) vinyl polymer (A-4).

Comparative vinyl Polymer (A-5)

50 parts of methyl ethyl ketone was added to the reaction vessel, and the temperature was raised to 80 ℃ with stirring. To this solution, 100 parts of n-butyl acrylate and 3.60 parts of γ -methacryloxypropylmethyldimethoxysilane were added dropwise, and the reaction vessel was refluxed while stirring. Next, 0.10 parts of 2, 2' -azobisisobutyronitrile was added. Then, 0.1 part of 2, 2' -azobisisobutyronitrile was added in 4 portions, 1 portion every 30 minutes. Further, the reaction was carried out for 4 hours while maintaining the temperature in the reaction vessel, thereby obtaining a vinyl polymer solution. The solvent was removed from the vinyl polymer solution by an evaporator to obtain (comparative) vinyl polymer (A-5).

Vinyl Polymer (A-6)

50 parts of methyl ethyl ketone was added to the reaction vessel, and the temperature was raised to 60 ℃ with stirring. 100 parts of n-butyl acrylate and 0.9 part of γ -methacryloxypropylmethyldimethoxysilane were added dropwise thereto, and the inside of the reaction vessel was replaced with nitrogen while stirring. Then, 1.2 parts of γ -mercaptopropyltrimethoxysilane was added, and after stirring for 30 minutes, 0.05 part of 2, 2' -azobisisobutyronitrile was added. Then, 0.5 part of 2, 2' -azobisisobutyronitrile was added in 4 portions, 1 portion every 30 minutes. Further, the reaction was carried out for 4 hours while maintaining the temperature in the reaction vessel, thereby obtaining a vinyl polymer solution. The solvent was removed from the vinyl polymer solution by an evaporator to obtain a vinyl polymer (A-6).

Vinyl Polymer (A-7)

50 parts of methyl ethyl ketone was added to the reaction vessel, and the temperature was raised to 60 ℃ with stirring. 100 parts of n-butyl acrylate and 0.8 part of gamma-methacryloxypropyltrimethoxysilane were added dropwise thereto, and the inside of the reaction vessel was purged with nitrogen while stirring. Then, 1.24 parts of γ -mercaptopropylmethyldimethoxysilane was added, and after stirring for 30 minutes, 0.05 part of 2, 2' -azobisisobutyronitrile was added. Then, 0.5 part of 2, 2' -azobisisobutyronitrile was added in 4 portions, 1 portion every 30 minutes. Further, the reaction was carried out for 4 hours while maintaining the temperature in the reaction vessel, thereby obtaining a vinyl polymer solution. The solvent was removed from the vinyl polymer solution by an evaporator to obtain a vinyl polymer (A-7).

Comparative vinyl Polymer (A-8)

50 parts of methyl ethyl ketone was added to the reaction vessel, and the temperature was raised to 60 ℃ with stirring. To this, 100 parts of n-butyl acrylate and 5 parts of γ -methacryloxypropylmethyldimethoxysilane were added dropwise, and the inside of the reaction vessel was purged with nitrogen while stirring. Subsequently, 4 parts of γ -mercaptopropylmethyldimethoxysilane was added, and after stirring for 30 minutes, 0.05 part of 2, 2' -azobisisobutyronitrile was added. Then, 0.5 part of 2, 2' -azobisisobutyronitrile was added in 4 portions, 1 portion every 30 minutes. Further, the reaction was carried out for 4 hours while maintaining the temperature in the reaction vessel, thereby obtaining a vinyl polymer solution. The solvent was removed from the vinyl polymer solution by an evaporator to obtain (comparative) vinyl polymer (A-8).

Comparative vinyl Polymer (A-9)

50 parts of methyl ethyl ketone was added to the reaction vessel, and the temperature was raised to 60 ℃ with stirring. To this solution, 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. Then, 0.89 part of γ -mercaptopropylmethyldimethoxysilane was added, and after stirring for 30 minutes, 0.05 part of 2, 2' -azobisisobutyronitrile was added. Then, 0.5 part of 2, 2' -azobisisobutyronitrile was added in 4 portions, 1 portion every 30 minutes. Further, the reaction was carried out for 4 hours while maintaining the temperature in the reaction vessel, thereby obtaining a vinyl polymer solution. The solvent was removed from the vinyl polymer solution by an evaporator to obtain (comparative) vinyl polymer (A-9).

The details of the vinyl polymers (A-1) to (A-9) are summarized in Table 1.

Referring to the column "number of reactive silyl groups at terminal of vinyl polymer (A)" in Table 1, the above-mentioned number of vinyl polymers (A-1) to (A-3) and (A-6) to (A-9) is more than 0. Therefore, it is considered that the vinyl polymers (A-1) to (A-3) and (A-6) to (A-9) include at least the vinyl polymer (a) having a repeating unit of a polymerizable vinyl monomer in the molecular chain and having a group represented by the above formula (I) at the terminal (single terminal) of the molecular chain.

[ Table 1]

< production of polyoxyalkylene Polymer (B) >

Polyoxyalkylene polymer (B-1)

Propylene oxide was polymerized using polypropylene oxide having a number average molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to obtain polypropylene oxide having a number average molecular weight of 29,000. A methanol solution of NaOMe was added in an amount of 1.2 times the equivalent of the hydroxyl group of the resulting polyoxypropylene glycol to distill off the methanol, and 1.6 times the equivalent of 3-chloro-2-methyl-1-propene was further added to convert the terminal hydroxyl group to a methallyl group. The vessel was then filled with 6% O₂/N₂Substitution, 100ppm of sulfur (0.25 wt% hexane solution) and 100ppm of platinum divinyl disiloxane complex (3 wt% isopropyl alcohol solution in terms of platinum) were added to 100 parts by weight of the obtained methallyl end-capped polyoxypropylene polymer, and dimethoxymethylsilane 2.3 was slowly added dropwise with stirring0 part by weight. This mixed solution was reacted at 100 ℃ for 5 hours to obtain a linear reactive silyl group-containing polyoxypropylene polymer (polyoxyalkylene polymer (B-1)) having dimethoxymethylsilyl groups at the ends, an average of 1.9 silyl groups per 1 molecule, and a number average molecular weight of 29,000.

Polyoxyalkylene polymer (B-2)

Propylene oxide was polymerized using polypropylene oxide having a number average molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to obtain polypropylene oxide having a number average molecular weight of 29,000. A1.2-fold equivalent of NaOMe in methanol to the hydroxyl group of the resulting polyoxypropylene glycol was added, the methanol was distilled off, and 3-chloro-1-propene was further added to convert the terminal hydroxyl group to an allyl group. Then, 36ppm of a platinum divinyl disiloxane complex (an isopropyl alcohol solution of 3 wt% in terms of platinum) was added to 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer, and 1.48 parts by weight of TES (triethoxysilane) was slowly added dropwise with stirring, and the mixture was reacted at 90 ℃ for 2 hours. Further, 20 parts by weight of methanol and 12ppm of HCl were added to convert the ethoxy group at the terminal into a methoxy group, thereby obtaining a linear reactive silyl group-containing polyoxypropylene polymer (polyoxyalkylene polymer (B-2)) having trimethoxysilyl groups at the terminal, an average of 1.6 silyl groups per 1 molecule, and a number average molecular weight of 29,000.

Comparative polyoxyalkylene Polymer (B-3)

Propylene oxide was polymerized using a zinc hexacyanocobaltate glyme complex catalyst using polypropylene oxide having a number average molecular weight of 2,000 as an initiator to obtain polypropylene oxide having a number average molecular weight of 8,400. Subsequently, 1.2 equivalents of NaOMe in methanol to the hydroxyl group of the hydroxyl-terminated polyoxypropylene glycol was added to the reaction mixture, and methanol was distilled off, and 1.6 equivalents of 3-chloro-1-propene was further added to the reaction mixture to convert the hydroxyl group at the terminal into an allyl group. Then, 36ppm of a platinum divinyl disiloxane complex (an isopropyl alcohol solution of 3 wt% in terms of platinum) was added to 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer, and dimethoxymethylsilane was added dropwise in an amount of 0.9 equivalent to the allyl group while stirring. After this mixed solution was reacted at 90 ℃ for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure, and a linear reactive silyl group-containing polyoxypropylene polymer having dimethoxymethylsilyl groups at the ends, an average of 1.5 silyl groups per 1 molecule, and a number average molecular weight of 8,900 was obtained ((comparative polyoxyalkylene polymer (B-3)).

< production of composition >

The components shown in table 2 below were used in the compositions (parts by mass) shown in the table, and the compositions were prepared by mixing them with a mixer.

< evaluation >

The following evaluations were made using the compositions produced as described above. The results are shown in table 2.

Viscosity of

The initial viscosity (unit: pas) of the composition produced as described above was measured at a rotational speed of 1rpm at 23 ℃ using a type B viscometer (manufactured by Toyobo industries, Ltd., spindle No. 7).

In the present invention, when the viscosity of the composition is 2,000 to 4,000Pa · s, the viscosity of the composition can be said to be appropriate.

In the present invention, the viscosity of the composition is preferably 2,000 to 4,000 pas from the viewpoint of handling properties.

Initial elongation at Break

Preparation of sample

The composition thus prepared was cured at 23 ℃ and 50% RH (relative humidity) for 7 days. Then, a JIS3 dumbbell specimen (initial specimen) having a thickness of 2mm was punched out from the obtained cured product.

Tensile test

Each of the initial samples prepared as described above was used, and the reaction conditions were adjusted in accordance with JIS K6251: 2010 (method for determining tensile properties of vulcanized rubber and thermoplastic rubber), a tensile test was conducted at a tensile rate of 500 mm/min at room temperature, and the initial elongation at break (in%) was measured.

Evaluation criteria for initial elongation at Break

In the present invention, when the initial elongation at break is 300% or more, the elongation at break is excellent.

Weather resistance

Preparation of sample

The composition thus prepared was cured at 23 ℃ and 50% RH (relative humidity) for 7 days. Then, a sample having a thickness of 5mm was prepared from the obtained cured product.

Weather resistance test

Using the samples prepared as described above, the weather resistance of the sample was measured by passing through a metal halide weatherometer (conditions: 63 ℃, 50% RH, luminous energy 75 mW/cm)². Every 2 hours 120 seconds with water spray. ) Weather resistance tests were carried out for 500 hours or 750 hours of treatment.

Evaluation Standard

After the weather resistance test, the samples were visually observed to confirm the presence or absence of cracks.

In the case where the sample had no cracks at all, the weather resistance was evaluated to be very excellent, and it was denoted by "a".

When the sample had a crack barely visible in visual observation, the weather resistance was evaluated to be slightly excellent, and this was denoted as "B".

In the case where the sample had a clearly visible crack upon visual observation, the weather resistance was evaluated as slightly inferior, which was denoted as "C".

In the case where the sample had a large crack (the width of the crack was 0.5mm to 1.0mm), the weather resistance was evaluated as very poor, which was expressed as "D".

[ Table 2]

The details of each component shown in table 2 are as follows.

Vinyl polymers (A-1) to (A-9): the vinyl polymers (A-1) to (A-9) produced as described above

Polyoxyalkylene polymers (B-1) to (B-3): polyoxyalkylene polymers (B-1) to (B-3) produced as described above

Colloidal calcium carbonate: カルファイン 200M manufactured by pill Tail カルシウム Co., Ltd

Ground calcium carbonate: ライトン A-4, manufactured by Beibei powder processing Co., Ltd

Titanium oxide: r820, manufactured by stone industries Ltd

Plasticizer 1: acrylic oligomer, UP1000, manufactured by Toyo Synthesis Co. Number average molecular weight 2,500

Plasticizer 2: polypropylene glycol, プレミノール 4002, manufactured by Asahi glass company. Number average molecular weight 4,000

Silane 1: vinyltrimethoxysilane, KBM-1003, manufactured by shin-Etsu chemical industries Ltd

Silane 2: n-2- (aminoethyl) -3-aminopropyltrimethoxysilane, KBM-603, from shin-Etsu chemical Co., Ltd

Resin hollow body: the shell is composed of acrylonitrile copolymer and plastic microspheres coated by calcium carbonate. The trade name is MFL-60CAS, manufactured by Songban oil and fat pharmaceuticals. The average particle size was 60 μm. The heat resistance temperature is 140-150 ℃.

Curing catalyst (C): dibutyl tin diacetylacetonate (trade name: ネオスタン U-220, manufactured by Ridonghua Kaisha)

Anti-aging agent: 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol, trade name チヌビン 326, BASF

As is clear from the results shown in table 2, in comparative example 1 which does not contain the predetermined vinyl polymer (a), the weather resistance (particularly, the weather resistance after 500 hours) is very poor, and the weather resistance test is deteriorated immediately after the start.

In comparative examples 2 and 3, which contained no specific vinyl polymer (A) and contained no vinyl polymer (a), the weather resistance was poor.

Comparative example 4, which contained no specific vinyl polymer (a) and contained a vinyl polymer having a weight average molecular weight and/or a number average molecular weight outside the specific ranges, was inferior in weather resistance.

In comparative example 5, which contained no predetermined polyoxyalkylene polymer (B) and contained a polyoxyalkylene polymer having a number average molecular weight outside the predetermined range instead, the weather resistance was poor.

In comparative example 6, which contained no specific vinyl polymer (A) and contained no vinyl polymer having the total number of reactive silyl groups and/or the number of reactive silyl groups in the side chains out of the specific ranges, the weather resistance was poor.

In contrast, the composition of the present invention is excellent in weather resistance.

Claims

1. A curable resin composition comprising:

a vinyl polymer (A) having reactive silyl groups at the terminal and side chain of a molecular chain having repeating units formed from a polymerizable vinyl monomer, wherein the total number of the reactive silyl groups is more than 1 and less than 1.80, the number of the reactive silyl groups at the terminal is more than 0.5, the number of the reactive silyl groups at the side chain is more than 0.5, the weight average molecular weight is 30,000 to 110,000, the number average molecular weight is 9,000 to 40,000, and the glass transition temperature is-100 to-10 ℃;

a polyoxyalkylene polymer (B) having a reactive silyl group, a molecular chain substantially being a polyoxyalkylene group, and a number average molecular weight of 10,000 to 50,000; and

a curing catalyst (C) for curing,

the vinyl polymer (A) contains a vinyl polymer (a) having a molecular chain having a repeating unit formed from a polymerizable vinyl monomer and having a group represented by the following formula (I) at the terminal of the molecular chain,

*-S-L¹-X¹ (I)

2. The curable resin composition according to claim 1, wherein the mass ratio of the vinyl polymer (A) to the polyoxyalkylene polymer (B), A: b is 10: 90-90: 10.

3. the curable resin composition according to claim 1 or 2, wherein the curing catalyst (C) is at least 1 selected from the group consisting of a tin compound, a titanium compound, an acidic compound and an amine compound,

4. The curable resin composition according to claim 1 or 2, further comprising a resin hollow body.

5. The curable resin composition according to claim 1 or 2, further comprising an antioxidant.

6. The curable resin composition according to claim 1 or 2, further comprising a plasticizer having a number average molecular weight of 1,500 to 15,000 and being at least one of an oxyalkylene polymer and a vinyl polymer,

7. The curable resin composition according to claim 1 or 2, wherein the weight average molecular weight of the vinyl polymer (A) is from 45,000 to 90,000.

8. The curable resin composition according to claim 1 or 2, 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 claim 1 or 2, wherein the vinyl polymer (A) further has a hydrocarbon group in a side chain, but the hydrocarbon group does not have a reactive silyl group.

10. The curable resin composition according to claim 9, wherein the hydrocarbon group has 1 to 12 carbon atoms.

11. The curable resin composition according to claim 1 or 2, wherein the molecular chain of the vinyl polymer (A) is linear.

12. The curable resin composition according to claim 1 or 2, wherein X is X in the formula (I)₁The reactive silyl group of (a) is a dialkoxysilyl group.

13. The curable resin composition according to claim 1 or 2, 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 following formula (III),

in the formula (II), R^2-1Represents a hydrogen atom or a 1-valent hydrocarbon group, L²Represents a 2-valent linking group, R^2-2Represents a 1-valent hydrocarbon group;

14. The curable resin composition according to claim 13, wherein in formula (III), m3 is 2 and n3 is 1.

15. The curable resin composition according to claim 1 or 2, wherein the group represented by formula (I) is a group represented by the following formula (I-1),

16. The curable resin composition according to claim 15, wherein in formula (I-1), m1 is 2 and n1 is 1.

17. The curable resin composition according to claim 1 or 2, wherein the vinyl polymer (a) has 1 terminal having a group represented by formula (I).

18. The curable resin composition according to claim 1 or 2, wherein the vinyl polymer (a) further has a reactive silyl group in a side chain of the molecular chain.

19. The curable resin composition according to claim 1 or 2, wherein in the vinyl polymer (A), the reactive silyl group at the terminal of the molecular chain is a group represented by the following formula (V),

*-S-L¹-X¹ (V)

20. The curable resin composition according to claim 1 or 2, wherein in the vinyl polymer (A), at least one of the reactive silyl group at the terminal and the reactive silyl group at the side chain is a dialkoxysilyl group.