JP7500282B2 - Vinyl Polymers - Google Patents

Description

The present invention relates to vinyl polymers.

Vinyl polymers are used for a variety of purposes because they are weather resistant, heat resistant, oil resistant, transparent, etc.

For example, vinyl polymers having polymerizable functional groups at the molecular terminals (Patent Document 1) and vinyl polymers having crosslinkable functional groups in the side chains (Patent Document 2) are known as vinyl polymers.

JP 2000-072816 A JP 2002-060449 A

However, the above-mentioned conventional techniques leave room for further improvement in terms of (a) the types of functional groups that vinyl polymers have in their side chains, and (b) achieving compatibility between the diversity of polymerizable functional groups at the molecular ends and the diversity of functional groups in the side chains.

One embodiment of the present invention has been made in consideration of the above problems, and its purpose is to provide (a) multiple types of novel vinyl polymers having different types of functional groups in their side chains, and (b) multiple types of novel vinyl polymers having polymerizable functional groups at the molecular terminals and different types of functional groups in their side chains.

As a result of intensive research to solve the above problems, the inventors have completed the present invention.

That is, one embodiment of the present invention has the following configuration:

[1] (a) (a-1) a vinyl polymer having 0.5 or more radical polymerizable groups at the molecular end per molecule, and (a-2) a structure represented by the following general formula (1) and/or the following general formula (2) in the main chain, or (b) (b-1) a vinyl polymer having 0.5 or more halogen groups at the molecular end per molecule, and (b-2) a structure represented by the following general formula (1) in the main chain:

(In the general formula (1), A represents an organic group having one or more selected from the group consisting of an oxycarbonyl group, an alkoxy group, a hydroxyl group, and an amino group, or a halogen group, ^R1 represents hydrogen or an alkyl group having 1 to 20 carbon atoms, and p represents an integer of 0 or more); and

(In the general formula (2), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and p represents an integer of 0 or more).
[2] The vinyl polymer according to [1], wherein the radical polymerizable group is a group represented by the following general formula (3):

(In the general formula (3), ^R2 represents hydrogen or an alkyl group having 1 to 20 carbon atoms).
[3] The vinyl polymer according to [1] or [2], which has a number average molecular weight of 1,000 or more.
[4] The vinyl polymer according to any one of [1] to [3], which has a ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by size exclusion chromatography of less than 1.8.
[5] A curable resin composition comprising the vinyl polymer according to any one of [1] to [4].
[6] A method for producing a vinyl polymer, comprising: (a) a step of introducing a radically polymerizable group into a molecular terminal of a polymer X having a structure represented by the following general formula (2) in its main chain; and/or (b) a step of reacting the structure represented by the following general formula (2) with one or more compounds selected from the group consisting of a carboxylic acid compound, a hydroxy compound, an amine compound, and a hydrogen halide to form a structure represented by the following general formula (1):

(In the general formula (2), R ¹ represents hydrogen or an alkyl group having 1 to 20 carbon atoms, and p represents an integer of 0 or more); and

(In the general formula (1), A represents an organic group having one or more selected from the group consisting of an oxycarbonyl group, an alkoxy group, a hydroxyl group, and an amino group, or a halogen group; ^R1 represents hydrogen or an alkyl group having 1 to 20 carbon atoms; and p represents an integer of 0 or more.)
[7] The method for producing a vinyl polymer according to [6], further comprising a step of preparing the polymer X by living radical polymerization.
[8] The method for producing a vinyl polymer according to [7], wherein in the polymer X preparation step, one or more complexes selected from the group consisting of copper complexes, nickel complexes, ruthenium complexes and iron complexes are used as a catalyst.

According to one embodiment of the present invention, it is possible to provide (a) multiple types of vinyl polymers having different types of functional groups in their side chains, and (b) multiple types of vinyl polymers having polymerizable functional groups at the molecular terminals and different types of functional groups in their side chains.

One embodiment of the present invention will be described below, but the present invention is not limited to this. The present invention is not limited to each of the configurations described below, and various modifications are possible within the scope of the claims. In addition, embodiments or examples obtained by appropriately combining the technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. All academic literature and patent documents described in this specification are incorporated herein by reference. In addition, unless otherwise specified in this specification, "A to B" representing a numerical range intends "A or more (including A and greater than A) and B or less (including B and smaller than B)."

[Technical idea of one embodiment of the present invention]
By introducing various functional groups into a vinyl polymer, it is possible to provide a vinyl polymer having various physical properties according to the type of functional group. However, it has been difficult to introduce various functional groups into a vinyl polymer in the past. This is because, in general, there is a limit to the monomers that can be used depending on the polymerization method, and it is not easy to polymerize a monomer having a desired functional group by a desired polymerization method.

For example, when producing a vinyl polymer by radical polymerization, it was not easy to introduce a (meth)acryloyl group, which is a radically polymerizable group, into the vinyl polymer. Furthermore, in the case of living radical polymerization, there are particular limitations on the monomers that can be used, and it was not easy to use a monomer having a desired functional group in living radical polymerization.

In view of the above problems, the present inventors have conducted extensive research with the objective of providing (a) multiple types of novel vinyl polymers having different types of functional groups in the side chains, and (b) multiple types of novel vinyl polymers having polymerizable functional groups at the molecular terminals and different types of functional groups in the side chains. As a result, the present inventors independently discovered that the above problems can be achieved by using a polymer having halogen groups at the molecular terminals and epoxy groups in the side chains, and have completed the present invention. One embodiment of the present invention will be described in detail below.

[Vinyl polymer]
A vinyl polymer according to one embodiment of the present invention has either: (a) (a-1) 0.5 or more radically polymerizable groups per molecule at their molecular terminals, and (a-2) a structure represented by the following general formula (1) and/or a structure represented by the following general formula (2) in the main chain; or (b) (b-1) 0.5 or more halogen groups per molecule at their molecular terminals, and (b-2) a structure represented by the following general formula (1) in the main chain:

(In the general formula (1), A represents an organic group having one or more selected from the group consisting of an oxycarbonyl group, an alkoxy group, a hydroxyl group, and an amino group, or a halogen group, ^R1 represents hydrogen or an alkyl group having 1 to 20 carbon atoms, and p represents an integer of 0 or more); and

(In the general formula (2), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and p represents an integer of 0 or more).

The "vinyl polymer according to one embodiment of the present invention" is also referred to as the "vinyl polymer" below. The "vinyl polymer having 0.5 or more radical polymerizable groups at the molecular end per molecule and having a structure represented by the general formula (1) and/or a structure represented by the general formula (2) in the main chain" is also referred to as the "first vinyl polymer" below. The "vinyl polymer having 0.5 or more halogen groups at the molecular end per molecule and having a structure represented by the following general formula (1) in the main chain" is also referred to as the "second vinyl polymer" below. The "vinyl polymer" includes the "first vinyl polymer" and the "second vinyl polymer".

Since the vinyl polymer has the above-mentioned structure, it is either (a) a plurality of types of vinyl polymers having different types of functional groups in the side chains, or (b) a plurality of types of vinyl polymers having polymerizable functional groups at the molecular terminals and different types of functional groups in the side chains. Since the vinyl polymer has a variety of types of functional groups in the side chains, it has various physical properties, reactivity, and functions according to the types of functional groups.

As described below, the vinyl polymer can provide a curable resin composition containing the vinyl polymer as one component (e.g., a base resin). A cured product can be obtained by curing the curable resin composition containing the vinyl polymer. The functional groups of the vinyl polymer can also affect the physical properties and functions of the curable resin composition containing the vinyl polymer and the cured product obtained by curing the curable resin composition.

(Main Chain)
The present vinyl polymer contains, as a constituent unit, a constituent unit derived from a vinyl monomer, that is, the main chain of the vinyl polymer is composed of constituent units derived from a vinyl monomer.

The vinyl monomer from which the structural units constituting the main chain are derived is not particularly limited as long as it has a vinyl group. Suitable examples of the vinyl monomer include (meth)acrylic acid monomers, styrene monomers, maleimide monomers, chlorine-containing vinyl monomers, fluorine-containing vinyl monomers, silicon-containing vinyl monomers, nitrile group-containing vinyl monomers, amide group-containing vinyl monomers, vinyl esters, alkenes, and conjugated dienes. In this specification, "(meth)acrylic acid" includes "methacrylic acid" and "acrylic acid".

The (meth)acrylic acid monomer is not particularly limited, but examples thereof include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid, Preferred examples of the acrylate-2-hydroxypropyl acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ-((meth)acryloyloxypropyl)trimethoxysilane, ethylene oxide adduct of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate are mentioned.

Styrenic monomers are not particularly limited, but suitable examples include styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, and salts of styrenesulfonic acid.

The maleimide monomer is not particularly limited, but examples thereof include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide.

The chlorine-containing vinyl monomer is not particularly limited, but examples thereof include vinyl chloride, vinylidene chloride, and allyl chloride.

The fluorine-containing vinyl monomer is not particularly limited, but examples thereof include perfluoroethylene, perfluoropropylene, and vinylidene fluoride.

Silicon-containing vinyl monomers are not particularly limited, but suitable examples include vinyltrimethoxysilane and vinyltriethoxysilane.

The nitrile group-containing vinyl monomer is not particularly limited, but examples thereof include acrylonitrile and methacrylonitrile.

The amide group-containing vinyl monomer is not particularly limited, but examples thereof include acrylamide and methacrylamide.

Vinyl esters are not particularly limited, but suitable examples include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate.

Although there is no particular limitation on alkenes, examples of suitable alkenes include ethylene and propylene.

Conjugated dienes are not particularly limited, but examples thereof include butadiene and isoprene.

Suitable examples of vinyl monomers from which the structural units constituting the main chain are derived include maleic anhydride, maleic acid, monoalkyl esters of maleic acid, dialkyl esters of maleic acid, fumaric acid, monoalkyl esters of fumaric acid, dialkyl esters of fumaric acid, and allyl alcohol.

The vinyl polymer may contain only structural units derived from one of the vinyl monomers described above, or may contain structural units derived from any two or more of the vinyl monomers described above.

The structural units contained in the present vinyl polymer can be appropriately selected from the viewpoints of (a) the glass transition temperature desired for the resulting vinyl polymer, (b) the physical properties such as oil resistance and low-temperature characteristics desired for the resulting vinyl polymer, and (c) the compatibility of the resulting vinyl polymer with compounding agents (e.g., curing agents) contained in the curable composition.

The vinyl polymer is easy to manufacture and has excellent physical properties, and therefore preferably contains structural units derived from one or more vinyl monomers selected from the group consisting of (meth)acrylic acid monomers and styrene monomers, more preferably contains structural units derived from one or more vinyl monomers selected from the group consisting of (meth)acrylic acid monomers, and even more preferably contains structural units derived from n-butyl acrylate.

In view of the excellent processability of the resulting vinyl polymer, the low cost, and the ease of obtaining the monomer, the vinyl polymer preferably contains a structural unit derived from methyl methacrylate. In view of the high glass transition temperature of the resulting vinyl polymer, the vinyl polymer preferably contains a structural unit derived from isobornyl methacrylate, cyclohexyl methacrylate, or the like. In view of the excellent balance between good rubber elasticity and low temperature properties and cost of the resulting vinyl polymer, the vinyl polymer preferably contains a structural unit derived from n-butyl acrylate. In view of the excellent oil resistance of the resulting vinyl polymer, the vinyl polymer preferably contains a structural unit derived from n-butyl acrylate. In view of the excellent balance between oil resistance and low temperature properties of the resulting vinyl polymer, the vinyl polymer preferably contains a structural unit derived from n-ethyl acrylate, n-butyl acrylate, and 2-methoxyethyl acrylate. In view of the excellent low temperature properties of the resulting vinyl polymer, the vinyl polymer preferably contains a structural unit derived from 2-ethylhexyl acrylate.

In addition to the constituent units derived from the vinyl monomers described above, the vinyl polymer may also contain constituent units derived from vinyl monomers other than the vinyl monomers described above. The vinyl polymer preferably contains 40 mol% or more of constituent units derived from one or more vinyl monomers selected from the group consisting of the vinyl monomers described above, more preferably 50 mol% or more, more preferably 60 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more, out of 100 mol% of all constituent units. This configuration has the advantage that the vinyl polymer can be obtained in high yield.

The vinyl polymer preferably contains 40 mol% or more of structural units derived from (meth)acrylic acid monomers, more preferably 50 mol% or more, more preferably 60 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more, out of 100 mol% of all structural units. A vinyl polymer having this structure has the advantage of being excellent in weather resistance, heat resistance, oil resistance, and transparency. In this specification, a vinyl polymer containing 50 mol% or more of structural units derived from (meth)acrylic acid monomers out of 100 mol% of all structural units is also referred to as a "(meth)acrylic polymer". It can also be said that the vinyl polymer is preferably a (meth)acrylic polymer.

(Radically polymerizable group)
The first vinyl polymer has 0.5 or more radical polymerizable groups per molecule at the molecular end. In this specification, "the (first) vinyl polymer has 0.5 or more radical polymerizable groups per molecule at the molecular end" means that the assembly of the (first) vinyl polymer has, on average, 0.5 or more radical polymerizable groups per molecule at the molecular end. Each (first) vinyl polymer contained in the assembly of the (first) vinyl polymer has a radical polymerizable group at the molecular end in a natural number value per molecule, for example, 0, 1, or 2. "Each (first) vinyl polymer contained in the assembly of the (first) vinyl polymer" is also referred to as "one (first) vinyl polymer". In this specification, the embodiment of the vinyl polymer will be described as an embodiment of an assembly of multiple vinyl polymers, unless otherwise specified.

The number of radical polymerizable groups at the molecular end of the first vinyl polymer is not particularly limited. The number of radical polymerizable groups at the molecular end of the first vinyl polymer is preferably one or more per molecule, more preferably two or more. This configuration has the advantage that the curable resin composition containing the first vinyl polymer has good curability. When the first vinyl polymer has two or more radical polymerizable groups at the molecular end per molecule, the first vinyl polymer may have, for example, two or more radical polymerizable groups at only one molecular end, or may have one or more radical polymerizable groups at each of both molecular ends.

The number of radical polymerizable groups at the molecular end of the first vinyl polymer is preferably 0.5 or more per molecule, more preferably 0.7 or more, more preferably 1.0 or more, more preferably 1.2 or more, more preferably 1.5 or more, more preferably 1.7 or more, and particularly preferably 2.0 or more, since a curable resin composition having excellent curability can be provided.

The number of radically polymerizable groups at the molecular terminals of the first vinyl polymer is preferably 4.0 or less per molecule, more preferably 3.0 or less, more preferably 2.5 or less, even more preferably 2.3 or less, and particularly preferably 2.0 or less, since this allows for the provision of a curable resin composition with excellent flexibility.

The radical polymerizable group is not particularly limited, but is preferably a functional group having a carbon-carbon double bond, and more preferably a group represented by the following general formula (3). This configuration has the advantage of being able to provide a curable resin composition that cures quickly and at a high reaction rate.

(In the general formula (3), ^R2 represents hydrogen or an alkyl group having 1 to 20 carbon atoms).

In the general formula (3), ^R2 is preferably hydrogen and/or a methyl group. In other words, the radical polymerizable group is preferably an acryloyl group and/or a methacryloyl group. A vinyl polymer having this structure has the advantage of being highly versatile.

(Structure represented by general formula (1))
The first vinyl polymer may have a structure represented by general formula (1) in the main chain.

The structure represented by general formula (1) may be a structure represented by the following general formula (4):

(In the general formula (4), A represents an organic group having one or more selected from the group consisting of an oxycarbonyl group, an alkoxy group, a hydroxyl group, and an amino group, or a halogen group; n represents an integer of 1 or more; ^R1 represents hydrogen or an alkyl group having 1 to 20 carbon atoms; and p represents an integer of 0 or more.)
In the general formulas (1) and (4), R ¹ is preferably a hydrogen atom and/or a methyl group. This structure has the advantage that the monomer from which the structural unit is derived is highly versatile and the resulting vinyl polymer is highly stable.

In general formula (4), n is preferably 1 to 300, more preferably 3 to 150, and particularly preferably 10 to 100. This configuration has the advantage that the characteristics (properties) of the functional group (A in general formula (4)) introduced into the vinyl polymer are fully exhibited in the vinyl polymer, the curable resin composition, and the cured product, and the inherent moldability of the vinyl polymer is not impaired.

In general formulas (1) and (4), p is preferably 0 to 12, more preferably 0 to 6, even more preferably 0 to 3, and particularly preferably 1. A vinyl polymer having this structure has the advantage of being highly versatile.

In general formulas (1) and (4), A is (a) an organic group having one or more selected from the group consisting of an oxycarbonyl group, an alkoxy group, and a hydroxy group, and/or (b) a halogen group, and is preferably an oxycarbonyl group, a hydroxy group, or a halogen group, more preferably an oxycarbonyl group or a halogen group, and particularly preferably an oxycarbonyl group. A vinyl polymer having this structure has the advantage that it can be produced in a short time and with a high yield.

The oxycarbonyl group is not particularly limited, but examples thereof include formyloxy, acetyloxy (also known as acetoxy), propionyloxy, butyryloxy, isobutyryloxy, valeryloxy, isovaleryloxy, pivaloyloxy, caproyloxy, lauroyloxy, myristyloxy, palmityloxy, stearoyloxy, benzoyloxy, toluyloxy, acryloyloxy, methacryloyloxy, propioloyloxy, crotonoyloxy, and maloyloxy, and more preferably acryloyloxy, methacryloyloxy, propioloyloxy, crotonoyloxy, and maloyloxy. A vinyl polymer having this structure has the advantage of having a reactive double bond and the advantage of being highly versatile.

The alkoxy group is not particularly limited, but examples thereof include methoxy, ethoxy, propyloxy, butyloxy, and phenoxy groups. A vinyl polymer having such a structure has the advantage of being highly versatile.

The amino group is not particularly limited. Suitable examples of the amino group include an amino group represented by the following general formula (5) and an ammonium salt represented by the following general formula (6):
-NR ³ ₂ General formula (5)
(In the general formula (5), R ³ is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and the two R ³ may be the same or different, and may be linked to each other at the other end to form a cyclic structure.), and -(NR ³ ₃ ) ⁺ Z _- general formula (6).
(In the general formula (6), R ³ is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and the three R ³ may be the same or different, and may be linked to each other at the other end to form a cyclic structure. In the general formula (5), Z ⁻ is a counter anion.)

In the general formulas (5) and (6), examples of R ³ include hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

The halogen group is not particularly limited, but examples thereof include fluorine, chlorine, bromine, and iodine groups. A vinyl polymer having such a structure has the advantage of being highly versatile.

(Structure represented by general formula (2))
The first vinyl polymer may have a structure represented by general formula (2) in the main chain.

The structure represented by general formula (2) may be a structure represented by the following general formula (7):

In the general formulas (2) and (7), R ¹ is preferably a hydrogen atom and/or a methyl group. This structure has the advantage that the monomer from which the structural unit is derived is highly versatile and the resulting vinyl polymer is highly stable.

In general formula (7), n is preferably 0 to 100, more preferably 0 to 30, and particularly preferably 0 to 10. This configuration has the advantage that the characteristics (properties) of the epoxy group introduced into the vinyl polymer are fully exhibited in the vinyl polymer, the curable resin composition, and the cured product, and the inherent moldability of the vinyl polymer is not impaired.

In general formulas (2) and (7), p is preferably 0 to 12, more preferably 0 to 6, even more preferably 0 to 3, and particularly preferably 1. A vinyl polymer having this structure has the advantage of being highly versatile.

The first vinyl polymer having a structure represented by general formula (2) in the main chain can be said to be a vinyl monomer having an epoxy group in the side chain. The epoxy group can be said to be an organic group having an epoxy ring or a functional group having an epoxy ring. When the first vinyl polymer has a structure represented by general formula (2) in the main chain and p in general formula (2) is 0, the first vinyl polymer can be said to have a 1,2-epoxyethyl group in the side chain. When the first vinyl polymer has a structure represented by general formula (2) in the main chain and p in general formula (2) is 1, the first vinyl polymer can be said to have a 2,3-epoxypropyl group (also known as a glycidyl group) in the side chain.

Epoxy groups are highly reactive and can react with various functional groups. Therefore, when the first vinyl polymer has a structure represented by general formula (2) in the main chain, the first vinyl polymer has the advantage of being highly useful as an intermediate since it can react with various functional groups.

The first vinyl polymer preferably contains a total of 1 mol% or more of the structure (structural unit) represented by general formula (1) and the structure (structural unit) represented by general formula (2) out of 100 mol% of all structural units, more preferably 5 mol% or more, even more preferably 10 mol% or more, and particularly preferably 20 mol% or more. This configuration has the advantage that the characteristics (properties) derived from the structures represented by general formula (1) and general formula (2) are fully exhibited in the vinyl polymer, the curable resin composition, and the cured product.

The first vinyl polymer preferably contains 1 mol % or more of the structure (structural unit) represented by general formula (1) out of 100 mol % of all structural units, more preferably 5 mol % or more, even more preferably 10 mol % or more, and particularly preferably 20 mol % or more. This configuration has the advantage that the characteristics (properties) of the functional group (A in general formula (4)) introduced into the vinyl polymer are fully exhibited in the vinyl polymer, the curable resin composition, and the cured product.

The first vinyl polymer preferably contains more structures (structural units) represented by general formula (1) than structures (structural units) represented by general formula (2) in 100 mol% of all structural units. The ratio of structures (structural units) represented by general formula (2) to structures (structural units) represented by general formula (1) in 100 mol% of all structural units of the first vinyl polymer (structure represented by general formula (2)/structure represented by general formula (1)) is preferably less than 1.0, more preferably 0.8 or less, even more preferably 0.5 or less, and particularly preferably 0.3 or less.

(Halogen group)
The second vinyl polymer has 0.5 or more halogen groups per molecule at the molecular end. In this specification, "the (second) vinyl polymer has 0.5 or more halogen groups per molecule at the molecular end" means that the assembly of (second) vinyl polymers has, on average, 0.5 or more halogen groups per molecule at the molecular end. Each (second) vinyl polymer contained in the assembly of (second) vinyl polymers has a halogen group at the molecular end in a natural number value per molecule, for example, 0, 1, or 2. "Each (second) vinyl polymer contained in the assembly of (second) vinyl polymers" is also referred to as "an individual (second) vinyl polymer" below.

The number of halogen groups that the second vinyl polymer has at the molecular end is not particularly limited. The number of halogen groups at the molecular end of the second vinyl polymer is preferably one or more per molecule, and more preferably two or more. This configuration has the advantage that the curable resin composition containing the second vinyl polymer has good curability. When the second vinyl polymer has two or more halogen groups at the molecular end per molecule, the second vinyl polymer may have, for example, two or more halogen groups at only one molecular end, or one or more halogen groups at each of the molecular ends.

The number of halogen groups at the molecular end of the second vinyl polymer is preferably 0.5 or more per molecule, more preferably 0.7 or more, more preferably 1.0 or more, more preferably 1.2 or more, more preferably 1.5 or more, more preferably 1.7 or more, and particularly preferably 2.0 or more, since a curable resin composition having excellent curability can be provided.

The number of halogen groups at the molecular terminals of the second vinyl polymer is preferably 4.0 or less per molecule, more preferably 3.0 or less, more preferably 2.5 or less, even more preferably 2.3 or less, and particularly preferably 2.0 or less, since this provides a curable resin composition with excellent flexibility.

The halogen group is not particularly limited, but examples thereof include chlorine, bromine, and iodine groups. This structure has the advantage that the living radical polymerization of the vinyl polymer having this structure is easy to control.

(Number average molecular weight)
The vinyl polymer preferably has a number average molecular weight of 1000 or more, more preferably 1500 or more, even more preferably 2000 or more, and particularly preferably 2500 or more. This configuration has the advantage that the inherent properties of the vinyl polymer (for example, weather resistance, heat resistance, oil resistance, transparency, etc.) are easily expressed. The vinyl polymer preferably has a number average molecular weight of 100,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less. This configuration has the advantage that the vinyl polymer or the curable resin composition containing the vinyl polymer is easy to handle. The smaller the number average molecular weight of the vinyl polymer, the lower the viscosity of the vinyl polymer, and the larger the number average molecular weight of the vinyl polymer, the higher the viscosity of the vinyl polymer tends to be. Therefore, the number average molecular weight of the vinyl polymer can be appropriately set according to the processing properties required for the vinyl polymer or the curable resin composition containing the vinyl polymer.

(Mw/Mn)
The vinyl polymer has a ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by size exclusion chromatography (SEC) of preferably less than 1.8, more preferably 1.7 or less, more preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.4 or less. This configuration has the advantage that the vinyl polymer or the curable resin composition containing the vinyl polymer is easy to handle.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the vinyl polymer in this specification are values obtained by measurement with SEC. SEC measurement usually uses a silica gel column or the like with chloroform as the mobile phase. In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the vinyl polymer in this specification are values calculated in terms of polystyrene.

When the main chain of the present vinyl polymer is obtained by living radical polymerization, a vinyl polymer having an Mw/Mn value of less than 1.8 can be easily obtained. The main chain of the vinyl polymer can also be said to be the main chain of polymer X in the following [Method for producing vinyl polymer]. The preparation method (polymerization method) of polymer X will be described in detail in [Method for producing vinyl polymer].

[Method for producing vinyl polymer]
A method for producing a vinyl polymer according to one embodiment of the present invention includes: (a) a step of introducing a radically polymerizable group into a molecular terminal of a polymer X having a structure represented by the general formula (2) in its main chain; and/or (b) a step of forming a structure represented by the general formula (1) by reacting the structure represented by the general formula (2) with one or more compounds selected from the group consisting of a carboxylic acid compound, a hydroxy compound, an amine compound, and a hydrogen halide.

The "method of producing a vinyl polymer according to one embodiment of the present invention" is also referred to as "the present production method". The "step of introducing a radical polymerizable group to the molecular end of polymer X having a structure represented by the general formula (2) in the main chain" is also referred to as "radical polymerizable group introduction step". The "step of forming a structure represented by the general formula (1) by reacting the structure represented by the general formula (2) with one or more compounds selected from the group consisting of carboxylic acid compounds, hydroxy compounds, amine compounds, and hydrogen halides" is also referred to as "general formula (1) formation step".

Because this manufacturing method has the above-mentioned configuration, it is possible to provide (a) multiple types of vinyl polymers having different types of functional groups in the side chains, and (b) multiple types of vinyl polymers having polymerizable functional groups at the molecular terminals and different types of functional groups in the side chains. This manufacturing method can provide a variety of vinyl polymers with various physical properties, reactivity, and functions depending on the type of functional group.

In this manufacturing method, the order of the radical polymerizable group introduction step and the general formula (1) formation step is not particularly limited. That is, the radical polymerizable group introduction step may be performed after the general formula (1) formation step.

(Radical Polymerizable Group Introduction Step)
The radical polymerizable group introduction step is a step of reacting the polymer X with a compound having a radical polymerizable group, specifically, a step of reacting a functional group at the molecular end of the polymer X with a radical polymerizable group of a compound having a radical polymerizable group. By carrying out the radical polymerizable group introduction step and introducing a radical polymerizable group into the molecular end of the polymer X, a vinyl polymer having 0.5 or more radical polymerizable groups at the molecular end per molecule can be obtained. When the production method for a vinyl polymer has the radical polymerizable group introduction step but does not have the general formula (1) formation step, the production method provides a vinyl polymer having (a) 0.5 or more radical polymerizable groups at the molecular end per molecule and (b) a structure represented by the general formula (2) in the main chain, i.e., a first vinyl polymer.

In this manufacturing method, if the general formula (1) forming step is not performed or if the radical polymerizable group introduction step is performed prior to the general formula (1) forming step, the polymer X in the radical polymerizable group introduction step has a structure represented by the general formula (2) in the main chain. On the other hand, in this manufacturing method, if the general formula (1) forming step is performed prior to the radical polymerizable group introduction step, the polymer X in the radical polymerizable group introduction step has a structure represented by the general formula (1) in the main chain.

Since radically polymerizable groups can be easily introduced, it is preferable that polymer X has a hydroxy group and/or a halogen group at the molecular end. It is preferable that polymer X has 0.5 or more hydroxy groups and/or halogen groups at the molecular end per molecule, more preferably 0.7 or more, more preferably 1.0 or more, more preferably 1.2 or more, preferably 1.5 or more, more preferably 1.7 or more, and particularly preferably 2.0 or more.

Hereinafter, a method for introducing a radical polymerizable group into the molecular end of polymer X will be described using an example in which polymer X having a hydroxyl group or a halogen group at the molecular end is used and the radical polymerizable group to be introduced is a group represented by general formula (3).

The method for introducing a radical polymerizable group into the molecular terminal of the polymer X is not limited, but examples thereof include the following methods 1 to 3.
Method 1: A method of reacting a polymer X having a halogen group at the molecular terminal with a compound represented by general formula (8).
M ^{+ -OC} (O)C(R ⁴ )=CH ₂ General formula (8)
(In the general formula (8), ^R4 represents hydrogen or an organic group having 1 to 20 carbon atoms, and M ⁺ represents an alkali metal or a quaternary ammonium ion.)
Method 2: A method of reacting a polymer X having a hydroxy group at the molecular terminal with a compound represented by general formula (9).
YC(O)C( ^R4 )= _CH2 General Formula (9)
(In the general formula (9), ^R4 represents hydrogen or an organic group having 1 to 20 carbon atoms, and Y represents a chlorine atom, a bromine atom, or a hydroxyl group.)
Method 3: A method in which a polymer X having a hydroxy group at the molecular terminal is reacted with a diisocyanate compound, and then the remaining isocyanate group is reacted with a compound represented by general formula (10).
HO-R'-OC(O)C( ^R4 )= _CH2 General formula (10)
(In general formula (10), ^R4 represents hydrogen or an organic group having 1 to 20 carbon atoms, and R' represents a divalent organic group having 2 to 20 carbon atoms.)
Each of these methods is described in detail below.

Method 1 will now be described. In method 1, the polymer X preferably has a structure represented by the following general formula (11) at the molecular terminal.
-CR ⁵ R ⁶ Z General formula (11)
(In formula (11), R ⁵ and R ⁶ represent groups bonded to the ethylenically unsaturated group of the vinyl monomer, and Z represents chlorine, bromine or iodine).

A vinyl polymer having a structure represented by general formula (11) at the molecular end is obtained by polymerizing a vinyl monomer using an organic halide or a sulfonyl halide compound described later as an initiator and a transition metal complex as a catalyst. A vinyl polymer having a structure represented by general formula (11) at the molecular end can also be obtained by polymerizing a vinyl monomer using a halogen compound as a chain transfer agent. A vinyl polymer having a structure represented by general formula (11) at the molecular end is preferably obtained by polymerizing a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst.

The compound represented by the general formula (8) is not particularly limited. Specific examples of R ⁴ in the general formula (8) include, for example, -H, -CH ₃ , -CH ₂ CH ₃ , -(CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), -C ₆ H ₅ , -CH ₂ OH, -CN, and the like, and are preferably -H and -CH _3. M ⁺ in the general formula (8) is a counter cation of the oxyanion. The type of M ⁺ in the general formula (8) includes an alkali metal ion, specifically a lithium ion, a sodium ion, a potassium ion, and a quaternary ammonium ion. The quaternary ammonium ion includes a tetramethylammonium ion, a tetraethylammonium ion, a tetrabenzylammonium ion, a trimethyldodecylammonium ion, a tetrabutylammonium ion, and a dimethylpiperidinium ion, and the like, and is preferably a sodium ion or a potassium ion.

The ratio of the amount of the polymer X having a halogen group at the molecular end to the compound represented by general formula (8) when reacting the polymer X with the compound represented by general formula (8) will be described. The amount of the compound represented by general ^formula (8) used is preferably 1.0 to 5.0 equivalents, more preferably 1.0 to 3.0 equivalents, still more preferably 1.0 to 1.8 equivalents, and particularly preferably 1.0 to 1.2 equivalents, relative to 1 equivalent of the halogen group of the polymer X, in the compound represented by general formula (8). This configuration has the advantage that the obtained vinyl polymer has an excellent balance between the number of radical polymerizable groups at the molecular end per molecule and the production cost.

In Method 1, the solvent in which the above reaction is carried out is not particularly limited, but since this is a nucleophilic substitution reaction, a polar solvent is preferred, and examples of suitable solvents include tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, and acetonitrile.

In method 1, the temperature at which the above reaction is carried out (reaction temperature) is not limited, but is generally 0°C to 120°C, preferably 50°C or less in order to maintain the radically polymerizable terminal group, and more preferably room temperature (e.g., 15°C to 30°C).

Method 2 will now be described. In Method 2, the compound represented by general formula (9) is not particularly limited. Specific examples of R ⁴ in general formula (9) include, for example, -H, -CH ₃ , -CH ₂ CH ₃ , -(CH ₂ ) _n CH ₃ (n is an integer of 2 to 19), -C ₆ H ₅ , -CH ₂ OH, -CN, and the like, and are preferably -H or -CH ₃ .

A vinyl polymer having a hydroxyl group at the molecular end is obtained by polymerizing a vinyl monomer using an organic halide or a sulfonyl halide compound described below as an initiator and a transition metal complex as a catalyst. A vinyl polymer having a hydroxyl group at the molecular end can also be obtained by polymerizing a vinyl monomer using a compound having a hydroxyl group as a chain transfer agent. A vinyl polymer having a hydroxyl group at the molecular end is preferably obtained by polymerizing a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst.

In method 2, the method described in paragraphs [0060] to [0064] of JP-A-2000-072816 is also suitable as a method for obtaining a vinyl polymer having a hydroxyl group at the molecular end.

The following describes the ratio of the amount of polymer X having a hydroxyl group at the molecular end to the compound represented by general formula (9) when the polymer X is reacted with the compound represented by general formula (9). The amount of the compound represented by general formula (9) used is preferably 1.0 to 5.0 equivalents, more preferably 1.0 to 3.0 equivalents, still more preferably 1.0 to 1.8 equivalents, and particularly preferably 1.0 to 1.2 equivalents, of Y in the compound represented by general formula (9) relative to 1 equivalent of the hydroxyl group of the polymer X. This configuration has the advantage that the resulting vinyl polymer has an excellent balance between the number of radically polymerizable groups at the molecular end per molecule and the production cost.

In method 2, the solvent for carrying out the above reaction is not particularly limited, but from the viewpoint of converting the by-product halogen acid into a neutral salt, for example, dehydrated triethylamine, dehydrated tributylamine, dehydrated pyridine, dehydrated picoline, etc. are preferably used.

In method 2, the temperature (reaction temperature) at which the above reaction is carried out is not limited, but since the above reaction is an exothermic reaction, for example, a temperature of -10°C to 50°C is preferable, and a temperature of 0°C to 30°C is even more preferable.

Method 2 will be described. In Method 2, the compound represented by general formula (10) is not particularly limited. Specific examples of R ⁴ in general formula (10) include, for example, -H, -CH ₃ , -CH ₂ CH ₃ , -(CH ₂ ) _n CH ₃ (n is an integer of 2 to 19), -C ₆ H ₅ , -CH ₂ OH, -CN, and the like, and preferably -H or -CH _3. A specific example of the compound represented by general formula (10) is 2-hydroxypropyl methacrylate.

For the vinyl polymer having a hydroxyl group at the molecular end in method 3, the explanation for the vinyl polymer having a hydroxyl group at the molecular end in method 2 can be used, including preferred embodiments.

The diisocyanate compound in method 3 is not particularly limited, and any of the conventionally known compounds can be used. Examples of the diisocyanate compound include isocyanate compounds such as toluylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethyl diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate. These diisocyanate compounds may be used alone or in combination of two or more. Blocked isocyanates may also be used as the diisocyanate compound.

To take advantage of better weather resistance, it is preferable to use a diisocyanate compound that does not have an aromatic ring, such as hexamethylene diisocyanate or hydrogenated diphenylmethane diisocyanate, as the polyfunctional isocyanate compound.

The following describes the ratio of the amount of polymer X having hydroxyl groups at the molecular end to the amount of diisocyanate compound when the polymer X is reacted with the diisocyanate compound. The amount of diisocyanate compound used is preferably 1.0 to 5.0 equivalents, more preferably 1.0 to 3.0 equivalents, even more preferably 1.0 to 1.8 equivalents, and particularly preferably 1.0 to 1.2 equivalents, per equivalent of hydroxyl groups in polymer X. This configuration has the advantage that the resulting vinyl polymer has an excellent balance between the number of residual isocyanate groups at the molecular end per molecule and the production cost.

In method 3, the solvent used when reacting polymer X having a hydroxy group at the molecular end with a diisocyanate compound is not particularly limited, but since they do not have active hydrogen that can cause side reactions, for example, dehydrated pyridine, dehydrated tetrahydrofuran, dehydrated toluene, dehydrated dimethylformamide, dehydrated dimethylsulfoxide, and dehydrated dimethylacetamide are preferably used.

In method 3, the temperature (reaction temperature) when reacting polymer X having a hydroxy group at the molecular end with a diisocyanate compound is not limited, but since the above reaction is an exothermic reaction, for example, a temperature of -10°C to 50°C is preferable, and 0°C to 30°C is even more preferable.

In method 3, the ratio of the amount of polymer X to the compound represented by general formula (10) when the remaining isocyanate groups in polymer X after the reaction with the diisocyanate compound are reacted with the compound represented by general formula (10) will be described. The amount of the compound represented by general formula (10) used is preferably 1.0 to 5.0 equivalents, more preferably 1.0 to 3.0 equivalents, still more preferably 1.0 to 1.8 equivalents, and particularly preferably 1.0 to 1.2 equivalents, relative to 1 equivalent of the remaining isocyanate groups in polymer X. This configuration has the advantage that the resulting vinyl polymer has an excellent balance between the number of radically polymerizable groups at the molecular end per molecule and the production cost.

In method 3, the solvent used when reacting polymer X after reacting with the diisocyanate compound with the compound represented by general formula (10) is not particularly limited, but since they do not have active hydrogen that can undergo side reactions, for example, dehydrated pyridine, dehydrated tetrahydrofuran, dehydrated toluene, dehydrated dimethylformamide, dehydrated dimethylsulfoxide, dehydrated dimethylacetamide, etc. are preferably used.

In method 3, the temperature (reaction temperature) when reacting polymer X after reacting with the diisocyanate compound with the compound represented by general formula (10) is not limited, but since the above reaction is an exothermic reaction, for example, a temperature of -10°C to 50°C is preferable, and 0°C to 30°C is even more preferable.

(Formula (1) Forming Step)
The general formula (1) forming step is a step of reacting the structure represented by general formula (2) in the main chain of polymer X with one or more compounds selected from the group consisting of carboxylic acid compounds, hydroxy compounds, amine compounds and hydrogen halides. The general formula (1) forming step can provide a vinyl polymer having the structure represented by general formula (1) in the main chain.

By reacting the structure represented by general formula (2) in the main chain of polymer X with a carboxylic acid compound, it is possible to obtain a vinyl polymer having (a) a structure represented by general formula (1) in the main chain and (b) a structure in which A is an organic group having an oxycarbonyl group.

Suitable carboxylic acid compounds include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, acrylic acid, propiolic acid, methacrylic acid, crotonic acid, oleic acid, maleic acid, fumaric acid, glycolic acid, lactic acid, glyceric acid, malic acid, glyoxylic acid, pyruvic acid, acetoacetic acid, benzoic acid, toluic acid, anisic acid, naphthoic acid, cinnamic acid, nicotinic acid, phthalic acid, terephthalic acid, salicylic acid, furoic acid, thenoic acid, potassium acetate, potassium acrylate, and sodium methacrylate. Among these carboxylic acid compounds, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, propiolic acid, methacrylic acid, benzoic acid, and potassium acrylate are more preferred due to their high versatility. These carboxylic acid compounds may be used alone or in combination of two or more.

By reacting the structure represented by general formula (2) in the main chain of polymer X with a hydroxy compound, it is possible to obtain a vinyl polymer having (a) a structure represented by general formula (1) in the main chain and (b) a structure in which A is an organic group having a hydroxy group.

Preferred examples of hydroxy compounds include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, hexanol, decanol, cyclohexanol, phenol, grezol, xylenol, ethylene glycol, propylene glycol, pinacol, glycerin, hydroquinone, naltol, sodium ethoxide, and potassium butoxide. Among these hydroxy compounds, methanol, ethanol, propanol, isopropanol, butanol, and phenol are preferred because of their high versatility. These hydroxy compounds may be used alone or in combination of two or more.

By reacting the structure represented by general formula (2) in the main chain of polymer X with an amine compound, it is possible to obtain a vinyl polymer having (a) a structure represented by general formula (1) in the main chain and (b) a structure in which A is an organic group having an amino group.

Suitable examples of amine compounds include dipromylamine, butylamine, dibutylamine, propanediamine, aniline, and triidine. Among these amine compounds, dipromylamine, butylamine, and dibutylamine are preferred due to their high versatility. These amine compounds may be used alone or in combination of two or more.

By reacting the structure represented by general formula (2) in the main chain of polymer X with hydrogen halide, it is possible to obtain a vinyl polymer having (a) a structure represented by general formula (1) in the main chain and (b) A being a halogen group.

Examples of hydrogen halides include hydrogen chloride, hydrogen fluoride, hydrogen bromide, and hydrogen iodide. These hydrogen halides may be used alone or in combination of two or more.

The following describes the ratio of the amount of the structure represented by general formula (2) in polymer X to the amount of one or more compounds selected from the group consisting of carboxylic acid compounds, hydroxy compounds, amine compounds, and hydrogen halides when the structure represented by general formula (2) in the main chain of polymer X is reacted with one or more compounds selected from the group consisting of carboxylic acid compounds, hydroxy compounds, amine compounds, and hydrogen halides. The amount of one or more compounds selected from the group consisting of carboxylic acid compounds, hydroxy compounds, amine compounds, and hydrogen halides used is preferably 1 equivalent or more, more preferably 2 equivalents or more, and even more preferably 5 equivalents or more relative to 1 equivalent of the structure represented by general formula (2) in polymer X, since this can suppress the occurrence of a crosslinked structure due to a side reaction of the reaction.

The solvent used when reacting the structure represented by general formula (2) in the main chain of polymer X with one or more compounds selected from the group consisting of carboxylic acid compounds, hydroxy compounds, amine compounds, and hydrogen halides is not particularly limited, and the reaction may be carried out without a solvent. When a solvent is used, the solvent preferably used is, for example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, acetonitrile, etc., because they have excellent solubility for polymer X, carboxylic acid compounds, hydroxy compounds, and amine compounds.

The temperature (reaction temperature) when reacting the structure represented by general formula (2) in the main chain of polymer X with one or more compounds selected from the group consisting of carboxylic acid compounds, hydroxy compounds, amine compounds, and hydrogen halides is not limited, but since the reaction proceeds quickly, for example, a temperature of 50°C to 150°C is preferred, 70°C to 130°C is more preferred, and 80°C to 120°C is even more preferred.

(Polymer X Preparation Step)
The present production method preferably further comprises a step of preparing a polymer X. In this specification, the "step of preparing a polymer X" may also be referred to as a "polymer X preparation step".

The method for producing polymer X is not particularly limited. Polymer X is preferably obtained by controlled polymerization. Examples of controlled polymerization include living anionic polymerization, radical polymerization using a chain transfer agent, and living radical polymerization.

The polymer X is preferably obtained by living radical polymerization. In other words, the present production method preferably further includes a polymer X preparation step in which the polymer X is prepared by living radical polymerization. With this configuration, a vinyl polymer having a small ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), for example less than 1.8, can be easily obtained.

Examples of living radical polymerization include (a) a polymerization method using a chain transfer agent such as polysulfide, (b) a polymerization method using a radical scavenger such as a cobalt porphyrin complex and/or a nitroxide compound, and (c) atom transfer radical polymerization (ATRP) using an organic halide or the like as an initiator and a transition metal complex as a catalyst. In one embodiment of the present invention, there is no particular limitation on which of these methods is used as the living radical polymerization.

Atom transfer radical polymerization is generally a radical polymerization with a very high polymerization rate, and while it is prone to termination reactions such as coupling between radicals, the polymerization can proceed in a living manner. In atom transfer radical polymerization, a polymer with a narrow molecular weight distribution, for example, Mw/Mn = less than 1.8 or Mw/Mn = about 1.1 to 1.5, can be obtained. In atom transfer radical polymerization, the molecular weight of the resulting polymer can be freely controlled by the ratio of the monomer and initiator charged. In one embodiment of the present invention, it is preferable that the living radical polymerization is atom transfer radical polymerization, since it is easier to obtain a vinyl-based polymer with a small Mw/Mn, for example, less than 1.8. In other words, it is preferable that the present production method further includes a step of preparing polymer X by atom transfer radical polymerization.

The initiator used in the polymer X preparation step is not particularly limited, and examples thereof include organic halides and halogenated sulfonyl compounds that can be used in atom transfer radical polymerization. Conventionally known substances can be used as the organic halides and halogenated sulfonyl compounds.

The catalyst used in the polymer X preparation step is not particularly limited, and may be, for example, a metal complex having a central metal of an element of Group 8, 9, 10, or 11 of the periodic table, which may be used in atom transfer radical polymerization. Hereinafter, a "metal complex having a central metal of an element of Group 8, 9, 10, or 11 of the periodic table" is also referred to as a "transition metal complex."

The transition metal complex is not particularly limited, but preferred examples include complexes of monovalent and zero-valent copper, divalent ruthenium, divalent iron, and divalent nickel. Among these, copper complexes are preferred from the standpoint of cost and reaction control.

Examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, and cuprous perchlorate. When a copper compound is used, 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, and polyamines such as tetramethylethylenediamine (TMEDA), pentamethyldiethylenetriamine, and hexamethyl(2-aminoethyl)amine can be added as ligands to enhance catalytic activity. In addition, a tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also preferred as a catalyst.

When using ruthenium compound as catalyst, aluminum alkoxides can be added as activator.Furthermore, bistriphenylphosphine complex of divalent iron ( _FeCl2 ( _PPh3 ) ₂ ), bistriphenylphosphine complex of divalent nickel ( _NiCl2 ( _PPh3 ) ₂ ) and bistributylphosphine complex of divalent nickel ( _NiBr2 ( _PBu3 ) ₂ ) can also be preferably used as catalyst.The amount of catalyst, ligand and activator used is not particularly limited, but can be appropriately determined based on the relationship between the amount of initiator, monomer and solvent used and the required reaction rate.

In the polymer X preparation step of this manufacturing method, it is preferable to use one or more complexes selected from the group consisting of copper complexes, nickel complexes, ruthenium complexes, and iron complexes as a catalyst.

The solvent that can be used in the polymer X preparation process is not particularly limited. Atom transfer radical polymerization can be carried out without a solvent (bulk polymerization) or in various solvents. Examples of solvents that can be used in the polymer X preparation process include hydrocarbon solvents, ether solvents, halogenated hydrocarbon solvents, ketone solvents, alcohol solvents, nitrile solvents, ester solvents, and carbonate solvents.

The above-mentioned solvents may be used alone or in combination of two or more. When the polymer X preparation step is carried out without a solvent, the polymer X is prepared by bulk polymerization. On the other hand, when the polymer X preparation step is carried out using a solvent, the amount of solvent used can be appropriately determined based on the relationship between the viscosity of the entire system and the required stirring efficiency (i.e., reaction rate).

The temperature in the polymer X preparation process, in other words the polymerization temperature of polymer X, can be in the range of room temperature to 200°C, preferably 50 to 150°C.

[Curable resin composition]
The curable resin composition according to one embodiment of the present invention contains the vinyl polymer described in the section [Vinyl polymer] or the vinyl polymer produced by the production method described in the section [Production method of vinyl polymer].

The "curable resin composition according to one embodiment of the present invention" is also referred to as "the composition" below. The vinyl polymer or the vinyl polymer produced by the production method is also referred to as the "main component" of the composition.

The present composition is not particularly limited in other aspects as long as it contains the present vinyl polymer or a vinyl polymer produced by the present production method. The present composition preferably contains 30% by weight or more of the present vinyl polymer or a vinyl polymer produced by the present production method, more preferably 50% by weight or more, even more preferably 70% by weight or more, and particularly preferably 80% by weight or more, of the 100% by weight of the composition. This configuration has the advantage of being able to provide a cured product with good mechanical properties such as strength and flexibility.

In addition to the main component, the present composition may contain polymerizable monomers and/or oligomers other than the main component depending on the purpose. In order to eliminate odor problems caused by residual monomers, it is preferable that the present composition does not contain other polymerizable monomers. As the polymerizable monomers and/or oligomers other than the main component, monomers and/or oligomers having a radical polymerizable group and monomers and/or oligomers having an anion polymerizable group are preferable. Examples of the monomers having a radical polymerizable group include monomers having a (meth)acryloyl-based group such as a (meth)acryloyl group, a styrene-based group, an acrylonitrile-based group, a vinyl ester-based group, an N-vinylpyrrolidone-based group, an acrylamide-based group, a conjugated diene-based group, a vinyl ketone-based group, a vinyl chloride-based group, and the like. Among the monomers having a radical polymerizable group described above, a monomer having a (meth)acryloyl-based group similar to the preferred embodiment of the present vinyl polymer is preferable. Examples of monomers having an anionically polymerizable group include monomers having a (meth)acryloyl group, a styrene group, an acrylonitrile group, an N-vinylpyrrolidone group, an acrylamide group, a conjugated diene group, a vinyl ketone group, and the like. Among the above-mentioned monomers having an anionically polymerizable group, monomers having a (meth)acryloyl group similar to the preferred embodiment of the present vinyl polymer are preferred. Examples of polymerizable monomers and/or oligomers other than the main component include the monomers and oligomers described in paragraphs [0068] to [0074] of JP-A-2000-072816. The polymerizable monomers and/or oligomers other than the main component contained in the present composition can be appropriately selected depending on the initiator that the composition may contain and the curing conditions of the composition.

The composition may contain a curing agent and a curing catalyst. The curing agent and curing catalyst contained in the composition may be appropriately selected depending on the type of functional group possessed by the vinyl polymer contained in the composition.

The present composition will be described below in the case where the vinyl monomer contains a vinyl polymer having (a) 0.5 or more radical polymerizable groups at the molecular end per molecule, and (b) a structure represented by the general formula (1) in the main chain. In this case, the present composition contains a vinyl polymer having an epoxy group in the side chain. In this case, the present composition can contain a curing agent and a curing catalyst that have been conventionally used in epoxy resins as a curing agent and a curing catalyst. Examples of curing agents and curing catalysts that have been conventionally used in epoxy resins include polyamines, modified polyamines, acid anhydrides, polyphenols, polymercaptans, isocyanates, organic acids, tertiary amines, imidazoles, Lewis acids, and Bronsted acid salts. Polyamines, modified polyamines, acid anhydrides, polyphenols, polymercaptans, isocyanates, and organic acids themselves react with epoxy groups to crosslink. Tertiary amines, imidazoles, Lewis acids, and Bronsted acid salts serve as polymerization catalysts between epoxy groups. In this case, the composition may contain the substances described in paragraphs [0107] to [0118] of JP-A-2002-060449 as a curing agent and a curing catalyst.

The present composition will be described below with respect to a case where the present composition contains, as a vinyl monomer, a vinyl polymer having (a) (a-1) 0.5 or more radical polymerizable groups per molecule at the molecular end and (a-2) a structure in the main chain represented by the following general formula (1) in which A is an organic group having an oxycarbonyl group, or (b) (b-1) 0.5 or more halogen groups per molecule at the molecular end and (b-2) a structure in the main chain represented by the following general formula (1) in which A is an organic group having an oxycarbonyl group. In this case, the present composition contains a vinyl polymer having an oxycarbonyl group in the side chain. In this case, the present composition can contain, as a curing agent and a curing catalyst, for example, polyamine, modified polyamine, acid anhydride, polyphenol, polymercaptan, isocyanate, polycarboxylic acid, tertiary amine, imidazole, etc.

The present composition will be described below in the case where the vinyl monomer contains a vinyl polymer having (a) (a-1) 0.5 or more radical polymerizable groups per molecule at the molecular end and (a-2) a structure in the main chain represented by the following general formula (1) in which A is an organic group having an alkoxy group, or (b) (b-1) 0.5 or more halogen groups per molecule at the molecular end and (b-2) a structure in the main chain represented by the following general formula (1) in which A is an organic group having an alkoxy group. In this case, the present composition contains a vinyl polymer having an alkoxy group in the side chain. In this case, the present composition can contain, for example, an acid anhydride, polymercaptan, isocyanate, polycarboxylic acid, etc. as a curing agent and a curing catalyst.

The present composition will be described below in the case where the vinyl monomer contains a vinyl polymer having (a) (a-1) 0.5 or more radical polymerizable groups per molecule at the molecular end and (a-2) a structure in the main chain represented by the following general formula (1) where A is a halogen group, or (b) (b-1) 0.5 or more halogen groups per molecule at the molecular end and (b-2) a structure in the main chain represented by the following general formula (1) where A is a halogen group. In this case, the present composition contains a vinyl polymer having a halogen group in the side chain. In this case, the present composition can contain, for example, polyamine, modified polyamine, polycarboxylate, polyalkoxide, etc. as a curing agent and curing catalyst.

The present composition will be described below with respect to a case where the present composition contains, as a vinyl monomer, a vinyl polymer having (a) (a-1) 0.5 or more radical polymerizable groups at the molecular end per molecule, and (a-2) a structure in the main chain represented by the following general formula (1) in which A is an organic group having a hydroxyl group, or (b) (b-1) 0.5 or more halogen groups at the molecular end per molecule, and (b-2) a structure in the main chain represented by the following general formula (1) in which A is an organic group having a hydroxyl group. In this case, the present composition contains a vinyl polymer having a hydroxyl group in the side chain. In this case, the present composition can contain, as a curing agent and a curing catalyst, a curing agent and a curing catalyst that have traditionally been used in polyurethane resins. Examples of curing agents that have traditionally been used in polyurethane resins include polyisocyanates, resol-type phenolic resins, methylol group-containing urea resins, and methylol group-containing melamine resins. These curing agents undergo a condensation reaction with hydroxyl groups. Examples of the curing catalysts that have been used conventionally in urethane resins include tertiary amines and amine salts. In this case, the composition may contain the substances described in paragraphs [0119] to [0121] of JP-A-2002-060449 as the curing agent and curing catalyst.

The present composition will be described with respect to a case where the present composition contains, as a vinyl monomer, a vinyl polymer having (a) (a-1) 0.5 or more radical polymerizable groups per molecule at the molecular end and (a-2) a structure in the main chain represented by the following general formula (1) in which A is an organic group having an amino group, or (b) (b-1) 0.5 or more halogen groups per molecule at the molecular end and (b-2) a structure in the main chain represented by the following general formula (1) in which A is an organic group having an amino group. In this case, the present composition contains a vinyl polymer having an amino group in the side chain. In this case, the present composition may contain, as a curing agent, a polyfunctional organic acid, a bifunctional glycidyl ether type epoxy resin, a polyfunctional glycidyl ether type epoxy resin, or a glycidyl amine type epoxy resin. In this case, the present composition may contain, as a curing agent and a curing catalyst, a substance described in paragraphs [0122] to [0125] of JP-A 2002-060449.

As regards the embodiment of the curing agent and curing catalyst in this composition, the description in paragraphs [0126] to [0129] of JP 2002-060449 can be appropriately cited.

The composition may contain various compounding agents to improve the physical properties depending on the desired physical properties. The compounding agents are not particularly limited, but suitable examples include known thermoplastic resins, rubbers, thermoplastic elastomers, composite rubber particles, stabilizers, plasticizers, lubricants, flame retardants, pigments, and fillers.

When the composition contains a filler as an additive, the composition has the advantage of having excellent reinforcing effect and reduced cost. When the composition contains a thermoplastic resin as an additive, the composition has the advantage of being able to provide a cured product having excellent hardness and modulus. When the composition contains a plasticizer and/or unvulcanized rubber as an additive, the composition has the advantage of being able to provide a cured product having excellent hardness and modulus. The composition may contain a combination of multiple additives in order to obtain a curable resin composition having an excellent balance of physical properties.

The content of the compounding agent in the present composition is not particularly limited. As the content (wt%) of the compounding agent in the curable resin composition increases, the content (wt%) of the vinyl polymer in the curable resin composition may decrease. The higher the content (wt%) of the vinyl polymer in the curable resin composition, the higher the effect of improving heat resistance, compression set, stability, etc. due to the vinyl polymer tends to be, and the higher the content (wt%) of the compounding agent in the curable resin composition, the easier it is to obtain the effect of improving physical properties due to the compounding agent. Therefore, the content of the vinyl polymer or compounding agent in the curable resin composition can be appropriately set according to the desired effect and physical properties for the curable resin composition or the cured product of the curable resin composition. For example, the present composition preferably contains 5 wt% to 100 wt% of the compounding agent in 100 wt% of the curable resin composition, more preferably contains 10 wt% to 90 wt% of the compounding agent, even more preferably contains 20 wt% to 80 wt% of the compounding agent, and particularly preferably contains 30 wt% to 70 wt% of the compounding agent.

The composition may contain, as a compounding agent, a substance listed as compounding agent (b) in paragraphs [0132] to [0140] of JP 2002-060449.

(Method for producing curable resin composition)
The composition can be produced by mixing (a) the main component, and (b) polymerizable monomers and/or oligomers other than the main component, curing agents, curing catalysts, and various compounding agents as necessary, by a known method. Suitable devices for producing the composition include a Banbury mixer, a roll mill, and a twin-screw extruder. The composition can also be produced by using an existing method such as a method of mechanically mixing (a) the main component, and (b) polymerizable monomers and/or oligomers other than the main component, curing agents, curing catalysts, and various compounding agents as necessary, using the above-mentioned known device, and forming the resulting mixture into pellets. The pellets obtained by forming the composition can be molded in a wide temperature range. A normal injection molding machine, blow molding machine, extrusion molding machine, compression molding machine, etc. can be used to mold the pellets.

(Method of curing curable resin composition)
A cured product can be obtained by curing the composition. The composition is preferably cured by active energy rays such as UV and/or electron beams. The composition preferably contains a photopolymerization initiator so that it can be cured by active energy rays.

The photopolymerization initiator is not particularly limited, but a photoradical initiator and/or a photoanionic initiator are preferred, with a photoradical initiator being particularly preferred. Suitable examples of the photopolymerization initiator include acetophenone, propiophenone, benzophenone, xanthol, fluorene, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis(4-dimethylaminophenyl)ketone, benzyl methoxyketal, and 2-chlorothioxanthone. These initiators may be used alone or in combination of two or more, or in combination of one or more of these initiators with other compounds. When the above-mentioned initiators are used in combination with other compounds, specific examples of the other compounds include amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine. It is more preferable to use the above-mentioned initiators and the above-mentioned amines in combination with an iodonium salt such as phenyliodonium chloride, and it is also more preferable to use the above-mentioned initiators in combination with the above-mentioned amines and a dye such as methylene blue.

The composition may contain a near-infrared light absorbing cationic dye as a near-infrared light polymerization initiator. As the near-infrared light absorbing cationic dye, it is preferable to use a near-infrared light absorbing cationic dye-borate anion complex, which is excited by light energy in the 650 to 1500 nm region, as disclosed in, for example, JP-A-3-111402 and JP-A-5-194619, and it is even more preferable to use a near-infrared light absorbing cationic dye-borate anion complex in combination with a boron-based sensitizer.

The content of the photopolymerization initiator in the present composition is not particularly limited, since an amount sufficient to slightly photofunctionalize the system is sufficient. The present composition preferably contains 0.001 to 10 parts by weight of the photopolymerization initiator per 100 parts by weight of the composition.

The method for curing the composition is not particularly limited. Suitable methods for curing the composition include light and electron beam irradiation methods using a high-pressure mercury lamp, low-pressure mercury lamp, electron beam irradiation device, halogen lamp, light-emitting diode, semiconductor laser, etc., depending on the properties of the photopolymerization initiator contained in the curable resin composition.

The cured product obtained by curing this composition is also one embodiment of the present invention.

[Application]
Specific applications of the vinyl polymer, the composition, and the cured product obtained by curing the composition include sealing materials, adhesives, pressure sensitive adhesives, elastic adhesives, paints, powder paints, foams, potting materials for electric and electronic applications, films, gaskets, resists, various molding materials, photopolymerization, artificial marble, etc.

Below, one embodiment of the present invention will be specifically described using examples. The present invention is not limited to the following examples.

[Analysis Method]
First, the analytical methods for the vinyl copolymers obtained in the examples will be described below.

(Polymerization Conversion Rate)
The conversion rate of monomers to polymer in the production of polymer X was measured using a gas chromatograph (GC (GC-2000, manufactured by Shimadzu Corporation)). The column used was a GC column HP-1 manufactured by Agilent J&W. Decane was used as the standard.

(Qualitative and quantitative analysis of functional groups)
Qualitative and quantitative analysis of functional groups in the vinyl polymer was carried out using ¹ H NMR (Bruker 400 MHz NMR). 30 mg of the vinyl polymer was dissolved in 0.8 g of deuterated chloroform to obtain a solution, which was used as a sample for analysis.

(Weight average molecular weight (Mw) and number average molecular weight (Mn))
The weight average molecular weight and number average molecular weight of polymer X were analyzed using SEC (HLC-8420GPC). TOSOH TSKgel Super HM-L was used as the column, and a polystyrene standard sample was used as the standard. The dissolved matter obtained by dissolving 3 mg of vinyl polymer in 3 ml of chloroform was used as the sample for analysis. The weight average molecular weight (Mw) and number average molecular weight (Mn) values of polymer X are almost the same as the weight average molecular weight (Mw) and number average molecular weight (Mn) values of the vinyl polymer, so they can be considered as the weight average molecular weight (Mw) and number average molecular weight (Mn) values of the vinyl polymer.

(Terminal bromine content analysis)
The amount of terminal bromine in the vinyl polymer was obtained by replacing the bromine group with potassium acrylate, and then calculating the amount of H at the base of the substituent by ¹ H NMR. The method of replacing the terminal bromine group is as follows. A large excess of dimethylacetamide and potassium acrylate was added to the vinyl polymer, and the resulting solution was stirred at 50° C. for 30 minutes. An excess of ethyl acetate and water was added to the resulting solution, and only the organic layer was collected from the resulting mixture. The organic layer was then concentrated to obtain a vinyl polymer in which the terminal bromine group was replaced with potassium acrylate. The resulting vinyl polymer was dissolved in deuterated chloroform, and the resulting solution was used as an analytical sample, and ¹ H NMR measurement was performed. As a result, the signal of H at the base of the substituent replaced with potassium acrylate was confirmed in the range of 4.8 to 5.2 ppm, and the amount of terminal bromine in the vinyl polymer was calculated from the integral value of the signal.

(Analysis of Terminal Radical Polymerizable Group Amount)
The amount of terminal radical polymerizable groups of the vinyl polymer was calculated by calculating the amount of H at the base of the substituent by ¹ H NMR. That is, the obtained vinyl polymer was dissolved in deuterated chloroform, and the solution obtained was used as an analytical sample, and ¹ H NMR measurement was performed. As a result, a signal of H at the base where the terminal radical polymerizable group was introduced was confirmed in the range of 4.8 to 5.2 ppm, and a signal of H of the double bond of the radical polymerizable group was confirmed in the range of 5.5 to 7.0 ppm, and the amount of terminal radical polymerizable groups of the vinyl polymer was calculated from their integral values.

Production Example 1: Production of a polymer (Polymer X) having at least one bromine group at the molecular end per molecule and an epoxy group in the main chain 18 g of methanol, 3 g of glycidyl methacrylate, 31 g of 2-methoxyethyl acrylate, 3 g of ethyl 2-bromoisobutyrate, 0.3 g of triethylamine, 15 mg of cupric bromide, and 15 mg of tris[2-(dimethylamino)ethyl]amine were added to a flask. Nitrogen was then bubbled through the flask. The term "nitrogen bubbling" refers to the process of removing oxygen from an object such as a flask or a solution by flowing nitrogen into the object.

The mixture in the flask was then heated to 45°C. 26 g of methanol, 0.3 g of ascorbic acid, and 0.3 g of triethylamine were then mixed to obtain a methanol solution. The methanol solution was then dripped into the flask.

Here, 13 g of glycidyl methacrylate and 47 g of 2-methoxyethyl acrylate were mixed to prepare an acrylic ester mixture. Three hours after the start of dripping the methanol solution, the acrylic ester mixture bubbled with nitrogen was dripped into the flask over 1.5 hours. Six hours after the start of dripping the methanol solution, it was confirmed by gas chromatography that the conversion rates of glycidyl methacrylate, 2-methoxyethyl acrylate, and ethyl 2-bromoisobutyrate reached 98% or more, respectively, and dripping of the methanol solution was stopped. The reaction solution in the flask was then concentrated at 80°C under vacuum for 1 hour. 100 g of butyl acetate, 1 g of Kyoward 500 (Kyowa Chemical), and 1 g of Kyoward 700 (Kyowa Chemical) were added to the concentrated reaction solution. The resulting reaction solution was stirred at 80°C for 1 hour. Next, the resulting reaction solution was filtered. The resulting filtrate was concentrated at 100°C under vacuum for 2 hours. Through this procedure, approximately 70 g of polymer X was obtained, which (a) had 0.8 or more bromine groups per molecule as halogen groups at the molecular terminals, and (b) had a structure represented by general formula (2) in the main chain.

Production Example 1 can be said to be a process for preparing polymer X. It was confirmed by 1 H NMR that the epoxy groups contained in the main chain of the obtained polymer X accounted for 20 mol% of all acrylic acid ester units (100 mol%). It was confirmed by ^SEC that the number average molecular weight of the obtained polymer X was 5700 and the molecular weight distribution was 1.51.

Example 1
5 g of polymer X, 0.2 g of potassium acrylate, 0.5 mg of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 5 g of N,N'-dimethylacetamide were mixed, and the mixture was stirred at 70°C for 2 hours. The mixture was then concentrated at 100°C under vacuum for 1 hour. The concentrate was then dissolved in 10 g of butyl acetate to obtain a solution. The solution was then filtered, and the filtrate was further concentrated at 100°C under vacuum for 1 hour. This operation yielded a vinyl polymer (E1). ¹ H NMR measurement of the vinyl polymer (E1) confirmed that the amount of epoxy groups in the side chains did not change, while 1.1 acryloyl groups were introduced to the molecular terminals per polymer molecule. That is, the vinyl polymer (E1) obtained in Example 1 is a vinyl polymer having (a) 1.1 acryloyl groups per molecule as radical polymerizable groups at the molecular terminals, and (b) a structure represented by general formula (2) in the main chain. The vinyl polymer (E1) can be said to be a first vinyl polymer.

Example 2
5 g of vinyl polymer (E1), 5 g of acetic acid and 1 mg of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl were mixed, and the resulting mixture was stirred at 120° C. for 2 hours. The resulting mixture was then concentrated at 100° C. under vacuum for 1 hour. By this operation, vinyl polymer (E2) was obtained. ¹ H NMR measurement of vinyl polymer (E2) confirmed that the epoxy groups in the side chains had completely disappeared, acetoxy groups had been introduced in the side chains, and 0.9 acryloyl groups were maintained at the molecular terminals per polymer molecule. That is, vinyl polymer (E2) is a vinyl polymer having (a) 0.9 acryloyl groups per molecule as radical polymerizable groups at the molecular terminals, and (b) a structure represented by the general formula (1) in the main chain, in which A is an acetoxy group, R ¹ is a methyl group, and p is 1. Vinyl polymer (E2) can be said to be a first vinyl polymer.

Example 3
5 g of vinyl polymer (E1), 7 g of crotonic acid, 10 g of N,N'-dimethylacetamide and 1 mg of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl were mixed, and the mixture was stirred at 120°C for 2 hours. The mixture was then concentrated at 100°C under vacuum for 1 hour. This operation yielded vinyl polymer (E2). ¹ H NMR measurement of vinyl polymer (E3) confirmed that the epoxy groups in the side chains had completely disappeared, crotonoyloxy groups had been introduced in the side chains, and that the number of acryloyl groups at the molecular terminals was maintained at 1.0 per polymer molecule. That is, vinyl polymer (E3) is (a) a vinyl polymer having 1.0 acryloyl groups per molecule as radical polymerizable groups at the molecular terminals, and (b) a vinyl polymer having a structure represented by the general formula (1) in the main chain, in which A is a crotonoyloxy group, R ¹ is a methyl group, and p is 1. The vinyl polymer (E3) can be said to be the first vinyl polymer.

( Reference Example 4)
5 g of polymer X and 5 g of acetic acid were mixed, and the resulting mixture was stirred at 70° C. for 2 hours. The resulting mixture was then concentrated at 80° C. under vacuum for 1 hour to obtain a vinyl polymer (E4-1). ¹ H NMR measurement of the vinyl polymer (E4-1) confirmed that the epoxy groups in the side chains had completely disappeared and that acetoxy groups had been introduced into the side chains. That is, the vinyl polymer (E4-1) is a vinyl polymer that (a) has 0.8 or more bromine groups per molecule as halogen groups at the molecular terminals, and (b) has a structure represented by the general formula (1) in the main chain, in which A is an acetoxy group, R ¹ is a methyl group, and p is 1. The vinyl polymer (E4-1) can be said to be a second vinyl polymer.

Next, 5 g of vinyl polymer (E4-1), 0.2 g of potassium acrylate, 0.5 mg of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 5 g of N,N'-dimethylacetamide were mixed, and the resulting mixture was stirred at 70°C for 2 hours. Thereafter, the resulting mixture was concentrated at 100°C under vacuum for 1 hour. Next, the resulting concentrate was dissolved in 10 g of butyl acetate to obtain a solution. Next, the resulting solution was filtered, and the obtained filtrate was further concentrated at 100°C under vacuum for 1 hour. By this operation, vinyl polymer (E4-2) was obtained. ¹ H NMR measurement of vinyl polymer (E4-2) confirmed that 0.6 acryloyl groups were introduced per polymer molecule at the molecular terminal. That is, the vinyl polymer (E4-2) is a vinyl polymer which (a) has 0.6 acryloyl groups per molecule as radically polymerizable groups at the molecular terminals, and (b) has in its main chain a structure represented by the general formula (1) in which A is an acetoxy group, R ¹ is a methyl group, and p is 1. The vinyl polymer (E4-2) can be said to be a first vinyl polymer.

According to one embodiment of the present invention, it is possible to provide (a) a plurality of types of vinyl polymers having different types of functional groups in the side chains, and (b) a plurality of types of vinyl polymers having polymerizable functional groups at the molecular terminals and different types of functional groups in the side chains. Therefore, the vinyl polymers, curable resin compositions, and cured products according to one embodiment of the present invention can be suitably used in sealing materials, adhesives, pressure sensitive adhesives, elastic adhesives, paints, powder paints, foams, potting materials for electrical and electronic applications, films, gaskets, resists, various molding materials, photopolymerization, artificial marble, and the like.

Claims (8)

(a) (a-1) a vinyl polymer having at least 0.7 radical polymerizable groups at molecular terminals per molecule, and (a-2) a structure represented by the following general formula (1) in the main chain:
(In the general formula (1), A represents an organic group having one or more selected from the group consisting of an oxycarbonyl group, an alkoxy group, a hydroxyl group, and an amino group, or a halogen group; ^R1 represents hydrogen or an alkyl group having 1 to 20 carbon atoms; and p represents an integer of 0 or more.) The vinyl polymer according to claim 1, wherein the radical polymerizable group is a group represented by the following general formula (3):
(In the general formula (3), ^R2 represents hydrogen or an alkyl group having 1 to 20 carbon atoms). The vinyl polymer according to claim 1 or 2, having a number average molecular weight of 1,000 or more. The vinyl polymer according to any one of claims 1 to 3, in which the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by size exclusion chromatography is less than 1.8. A curable resin composition comprising the vinyl polymer according to any one of claims 1 to 4. (a) introducing a radical polymerizable group into a molecular terminal of a polymer X having a structure represented by the following general formula (2) in its main chain; and
(b) a step of reacting a structure represented by the following general formula (2) with one or more compounds selected from the group consisting of a carboxylic acid compound, a hydroxy compound, an amine compound and a hydrogen halide to form a structure represented by the following general formula (1), in this order :
(In the general formula (2), R ¹ represents hydrogen or an alkyl group having 1 to 20 carbon atoms, and p represents an integer of 0 or more); and
(In the general formula (1), A represents an organic group having one or more selected from the group consisting of an oxycarbonyl group, an alkoxy group, a hydroxyl group, and an amino group, or a halogen group; ^R1 represents hydrogen or an alkyl group having 1 to 20 carbon atoms; and p represents an integer of 0 or more.) The method for producing a vinyl polymer according to claim 6, further comprising a polymer X preparation step of preparing the polymer X by living radical polymerization. The method for producing a vinyl polymer according to claim 7, wherein the polymer X preparation step uses one or more complexes selected from the group consisting of copper complexes, nickel complexes, ruthenium complexes, and iron complexes as a catalyst.