JP7323811B2 - Polymerizable ionic liquids, curable compositions, materials for electrochemical devices - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polymerizable ionic liquid , a curable composition, and a material for an electrochemical device.

Ionic liquids, which have both catalytic function and solvent properties, have affinity with specific substances and may function as catalysts, so they are used as reaction solvents, as well as for separation of substances. It has been used for a long time, such as for the purpose of increasing process efficiency.
The ionic liquid depends on the combination of the anion and the cation, but at least one component of the cation and the anion is an organic ion, and the ionic liquid contains at least one polymerizable functional group, i.e., a polymerizable ion Applications to polymers using liquids have been actively studied in recent years. For example, Patent Document 1 discloses a polymerizable ionic liquid containing an imidazolium cation and a sulfonate anion, and Patent Document 2 discloses a polymerizable ionic liquid containing a substituted ammonium cation, a phosphonium cation or a substituted imidazolium cation, and an aromatic carboxylate anion. ionic liquids are disclosed.
Further, Patent Document 3 discloses a polymer electrolyte comprising a polymer having an anionic group in the molecule and a polymer compound having an amidinium cation as an essential structural unit, and Patent Document 4 discloses a polymerizable ionic liquid and a polymerization An ionic conductor for an actuator is disclosed which includes a polymer ion gel having a crosslinked structure obtained by polymerizing a crosslinker containing two or more functional moieties.

WO2011/025847 WO2011/146356 Japanese Patent Application Laid-Open No. 2004-006232 JP 2008-228542 A

However, as a result of examination by the present inventors, it was found that even the polymerizable ionic liquid described above has room for partial improvement in terms of electrical characteristics, such as a narrow potential window and low withstand voltage characteristics. It was found that conventional polymerizable ionic liquids have low polymerizability.
An object of the present invention is to provide a high-performance polymerizable ionic liquid having excellent electrical properties and high polymerizability.

As a result of further studies by the present inventors, it was found that by using a compound containing a polymerizable anion having a predetermined structure having a perfluoroalkyl group and a polymerizable functional group in the molecule and a monovalent cation as a polymerizable ionic liquid, such We have found that the electrical properties of polymerizable ionic liquids are improved.
In addition, among the ionic liquids, by using a compound having a polymerizable site in the cation portion, extremely favorable findings were obtained, such as further improvement in withstand voltage characteristics and improvement in polymerizability.
Furthermore, the present invention provides a polymer using the polymerizable ionic liquid, a curable composition containing the polymerizable ionic liquid, and further, the polymerizable ionic liquid of the present invention has excellent properties as a material for an electrochemical device. The present inventors also found that the present invention was completed.

［上記一般式（Ａ）中、
Ｒ_ｆはフッ素原子、炭素数１～１０の直鎖状、または炭素数３～１２の分岐状もしくは環状のパーフルオロアルキル基を表す。
Ｗは２価の連結基を表し、単結合、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、または－Ｃ（＝Ｏ）－ＮＲ－（Ｒは水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基）を表す。
ｎは０～５の整数を表す。
Ｍ^＋は１価のカチオンを表す。
Ｘは重合性置換基であり、一般式（Ｂ１）に示すビニル基、一般式（Ｂ２）に示すエポキシ基、一般式（Ｂ３）に示すシリル基、一般式（Ｂ４）に示す多価アクリル基、一般式（Ｂ５）に示す多価エポキシ基、または一般式（Ｂ６）に示すノルボルニル基を表す。

上記一般式（Ｂ１）中、Ｒ^Ｂ１は水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表し、炭素原子のいずれかが酸素原子で置換されていてもよく、また、アルキル基の水素原子が酸素原子で置換されていてもよい。
上記一般式（Ｂ２）中、Ｒ^Ｂ２は水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表す。
上記一般式（Ｂ３）中、Ｒ^Ｂ３、Ｒ^Ｂ４およびＲ^Ｂ５はそれぞれ独立に炭素数１～１０の直鎖アルキル基を有するアルコキシ基、炭素数１～１０のアルキル基、炭素数６～１２の芳香環基、水酸基、または塩素原子を表し、少なくとも二つのアルコキシ基、塩素原子、水酸基、またはこれらの組み合わせを含む。
上記一般式（Ｂ４）中、Ｒ^Ｂ６は水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表す。
上記一般式（Ｂ４）および一般式（Ｂ５）中、Ｚ^１およびＺ^２はそれぞれ３価以上の連結基を表し、炭素数１～１８の鎖状または環状の置換アルキル基を表し、いずれかの炭素原子が酸素原子もしくは窒素原子で置換されていてもよく、炭素―炭素結合が不飽和結合を含んでいてもよく、芳香環を含んでもよい。
ｍおよびｌは２～５の整数を表す。］

［上記一般式（Ａ’）中、
Ｒ_ｆはフッ素原子、炭素数１～１０の直鎖状、または炭素数３～１２の分岐状もしくは環状のパーフルオロアルキル基を表す。
Ｌは２価の連結基を表し、単結合、－Ｃ（＝Ｏ）－Ｏ－、または－Ｃ（＝Ｏ）－ＮＲ－（Ｒは水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基）を表す。
Ｒ^Ａ１、Ｒ^Ａ２およびＲ^Ａ３は各々独立に、水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表し、Ｒ^Ａ１、Ｒ^Ａ２およびＲ^Ａ３のうちのいずれか２つ以上が相互に結合して式中の炭素－炭素二重結合と共に環を形成してもよい。
Ｙは２価の連結基を表し、単結合、－Ｏ－Ｃ（＝Ｏ）－、－ＮＲ－Ｃ（＝Ｏ）－（Ｒは水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基）、炭素数６～１２のアリーレン基、または－Ｏ－Ｃ（＝Ｏ）－もしくは－ＮＲ－Ｃ（＝Ｏ）－と炭素数６～１２のアリーレン基とを組み合わせた連結基を表す。
ｍは１～６の整数を表し、ｎは０～５の整数を表す。
Ｍ^＋は１価のカチオンを表す。］According to the present invention, a polymerizable ionic liquid containing a compound represented by at least one of general formula (A) and general formula (A') below is provided.

[In the above general formula (A),
R _f represents a fluorine atom, a linear C 1-10, or a branched or cyclic C 3-12 perfluoroalkyl group.
W represents a divalent linking group, a single bond, -C(=O)-, -C(=O)-O-, or -C(=O)-NR- (R is a hydrogen atom, has 1 carbon atom ~10 alkyl group or substituted alkyl group, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms).
n represents an integer of 0 to 5;
M ⁺ represents a monovalent cation.
X is a polymerizable substituent, a vinyl group represented by general formula (B1), an epoxy group represented by general formula (B2), a silyl group represented by general formula (B3), and a polyvalent acrylic group represented by general formula (B4). , represents a polyepoxy group represented by general formula (B5) or a norbornyl group represented by general formula (B6).

In the above general formula (B1), R ^B1 represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, may be substituted with an oxygen atom, and a hydrogen atom of an alkyl group may be substituted with an oxygen atom.
In general formula (B2) above, R ^{2 B2} represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms.
In the above general formula (B3), R ^B3 , R ^B4 and R ^B5 are each independently an alkoxy group having a straight-chain alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 6 to 12 carbon atoms. represents an aromatic ring group, a hydroxyl group, or a chlorine atom, and contains at least two alkoxy groups, chlorine atoms, hydroxyl groups, or a combination thereof;
In general formula (B4) above, R ^{1 B6} represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms.
In general formula (B4) and general formula (B5) above, Z ¹ and Z ² each represent a trivalent or higher linking group and represent a chain or cyclic substituted alkyl group having 1 to 18 carbon atoms, Carbon atoms may be substituted with oxygen atoms or nitrogen atoms, carbon-carbon bonds may contain unsaturated bonds, and aromatic rings may be contained.
m and l represent an integer of 2-5. ]

[In the above general formula (A′),
R _f represents a fluorine atom, a linear C 1-10, or a branched or cyclic C 3-12 perfluoroalkyl group.
L represents a divalent linking group, a single bond, -C(=O)-O-, or -C(=O)-NR- (R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms).
R ^A1 , R ^A2 and R ^A3 each independently represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, Any two or more of R ^A1 , R ^A2 and R ^A3 may bond together to form a ring together with the carbon-carbon double bond in the formula.
Y represents a divalent linking group, a single bond, -OC(=O)-, -NR-C(=O)- (R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group , or an aromatic ring group or a substituted aromatic ring group having 6 to 12 carbon atoms), an arylene group having 6 to 12 carbon atoms, or -O-C(=O)- or -NR-C(=O)- and the number of carbon atoms It represents a linking group in which 6 to 12 arylene groups are combined.
m represents an integer of 1-6, and n represents an integer of 0-5.
M ⁺ represents a monovalent cation. ]

［上記一般式（ａ）中、
Ｒ_ｆはフッ素原子、炭素数１～１０の直鎖状、または炭素数３～１２の分岐状もしくは環状のパーフルオロアルキル基を表す。
Ｗは２価の連結基を表し、単結合、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、または－Ｃ（＝Ｏ）－ＮＲ－（Ｒは水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基）を表す。
ｎは０～５の整数を表す。
Ｍ^＋は１価のカチオンを表す。
ｘは重合性置換基が反応した下記一般式（ｂ１）、一般式（ｂ２）、一般式（ｂ３）、一般式（ｂ４）、一般式（ｂ５）、または一般式（ｂ６）の構造を表す。

上記一般式（ｂ１）中、Ｒ^ｂ１は水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表し、炭素原子のいずれかが酸素原子で置換されていてもよく、また、アルキル基の水素原子が酸素原子で置換されていてもよい。
上記一般式（ｂ２）中、Ｒ^ｂ２は水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表す。
上記一般式（ｂ３）中、Ｒ^ｂ３は炭素数１～１０の直鎖アルキル基を有するアルコキシ基、炭素数１～１０のアルキル基、炭素数６～１２の芳香環基、水酸基、または塩素原子を表す。
上記一般式（ｂ４）中、Ｒ^ｂ６は水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表す。
上記一般式（ｂ４）および（ｂ５）中、Ｚ^１およびＺ^２はそれぞれ３価以上の連結基を表し、炭素数１～１８の鎖状または環状の置換アルキル基を表し、いずれかの炭素原子が酸素原子もしくは窒素原子で置換されていてもよく、炭素―炭素結合が不飽和結合を含んでいてもよく、芳香環を含んでもよい。
ｍおよびｌは２～５の整数を表す。］

［上記一般式（ａ’）中、
Ｒ_ｆはフッ素原子、炭素数１～１０の直鎖状、または炭素数３～１２の分岐状もしくは環状のパーフルオロアルキル基を表す。
Ｌは２価の連結基を表し、単結合、－Ｃ（＝Ｏ）－Ｏ－、または－Ｃ（＝Ｏ）－ＮＲ－（Ｒは水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基）を表す。
Ｒ^ａ１、Ｒ^ａ２およびＲ^ａ３は各々独立に、水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表し、Ｒ^ａ１、Ｒ^ａ２およびＲ^ａ３のうちのいずれか２つ以上が相互に結合して環状構造を形成してもよい。
Ｙは２価の連結基を表し、単結合、－Ｏ－Ｃ（＝Ｏ）－、－ＮＲ－Ｃ（＝Ｏ）－（Ｒは水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基）、炭素数６～１２のアリーレン基、または－Ｏ－Ｃ（＝Ｏ）－もしくは－ＮＲ－Ｃ（＝Ｏ）－と炭素数６～１２のアリーレン基とを組み合わせた連結基を表す。
ｍは１～６の整数を表し、ｎは０～５の整数を表す。
Ｍ^＋は１価のカチオンを表す。］The present invention also provides a polymer having a repeating structure of structural units represented by at least one of the following general formula (a) and general formula (a').

[In the above general formula (a),
R _f represents a fluorine atom, a linear C 1-10, or a branched or cyclic C 3-12 perfluoroalkyl group.
W represents a divalent linking group, a single bond, -C(=O)-, -C(=O)-O-, or -C(=O)-NR- (R is a hydrogen atom, has 1 carbon atom ~10 alkyl group or substituted alkyl group, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms).
n represents an integer of 0 to 5;
M ⁺ represents a monovalent cation.
x represents the structure of the following general formula (b1), general formula (b2), general formula (b3), general formula (b4), general formula (b5), or general formula (b6) in which the polymerizable substituent has reacted .

In the above general formula (b1), R ^b1 represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, may be substituted with an oxygen atom, and a hydrogen atom of an alkyl group may be substituted with an oxygen atom.
In general formula (b2) above, ^Rb2 represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms.
In the above general formula (b3), R ^b3 is an alkoxy group having a linear alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aromatic ring group having 6 to 12 carbon atoms, a hydroxyl group, or a chlorine atom. represents
In general formula (b4) above, ^Rb6 represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms.
In the above general formulas (b4) and (b5), Z ¹ and Z ² each represent a trivalent or higher linking group, a chain or cyclic substituted alkyl group having 1 to 18 carbon atoms, and any carbon atom may be substituted with an oxygen atom or a nitrogen atom, the carbon-carbon bond may contain an unsaturated bond, and it may contain an aromatic ring.
m and l represent an integer of 2-5. ]

[In the above general formula (a′),
R _f represents a fluorine atom, a linear C 1-10, or a branched or cyclic C 3-12 perfluoroalkyl group.
L represents a divalent linking group, a single bond, -C(=O)-O-, or -C(=O)-NR- (R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms).
R ^a1 , R ^a2 and R ^a3 each independently represent a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, Any two or more of R ^a1 , R ^a2 and R ^a3 may combine with each other to form a cyclic structure.
Y represents a divalent linking group, a single bond, -OC(=O)-, -NR-C(=O)- (R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group , or an aromatic ring group or a substituted aromatic ring group having 6 to 12 carbon atoms), an arylene group having 6 to 12 carbon atoms, or -O-C(=O)- or -NR-C(=O)- and the number of carbon atoms It represents a linking group in which 6 to 12 arylene groups are combined.
m represents an integer of 1-6, and n represents an integer of 0-5.
M ⁺ represents a monovalent cation. ]

Further, according to the present invention, the polymerizable ionic liquid represented by the above formula (A) or formula (A'),
A curable composition is provided comprising a polymerization initiator.
INDUSTRIAL APPLICABILITY According to the present invention, a polymerizable ionic liquid with excellent electrical properties, a polymer and a curable composition with good polymerizability by using the same, an electrochemical device material using these, and an antistatic material are provided. be done.

It is a figure for demonstrating vibration power generation evaluation.

Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments, and can be carried out as appropriate based on the ordinary knowledge of those skilled in the art within the scope of the present invention. can do.

[Ionic liquid]
The polymerizable ionic liquid of the present embodiment contains a compound represented by at least one of general formula (A) and general formula (A') below. This compound contains a polymerizable functional group-containing anion and a monovalent cation. Examples of anionic polymerizable functional groups include cationically polymerizable double bond-containing groups and radically polymerizable double bond-containing groups. These may be used alone or in combination of two or more.

In the above general formula (A),
R _f represents a fluorine atom, a linear C 1-10, or a branched or cyclic C 3-12 perfluoroalkyl group.
W represents a divalent linking group, a single bond, -C(=O)-, -C(=O)-O-, or -C(=O)-NR- (R is a hydrogen atom, has 1 carbon atom ~10 alkyl group or substituted alkyl group, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms).
n represents an integer of 0 to 5;
M ⁺ represents a monovalent cation.
X is a polymerizable substituent, a vinyl group represented by general formula (B1), an epoxy group represented by general formula (B2), a silyl group represented by general formula (B3), and a polyvalent acrylic group represented by general formula (B4). , represents a polyepoxy group represented by general formula (B5) or a norbornyl group represented by general formula (B6).

In the above general formula (B1), R ^B1 represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, may be substituted with an oxygen atom, and a hydrogen atom of an alkyl group may be substituted with an oxygen atom.
In general formula (B2) above, R ^{2 B2} represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms.
In the above general formula (B3), R ^B3 , R ^B4 and R ^B5 are each independently an alkoxy group having a straight-chain alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 6 to 12 carbon atoms. represents an aromatic ring group, a hydroxyl group, or a chlorine atom, and contains at least two alkoxy groups, chlorine atoms, hydroxyl groups, or a combination thereof;
In general formula (B4) above, R ^{1 B6} represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms.
In general formula (B4) and general formula (B5) above, Z ¹ and Z ² each represent a trivalent or higher linking group and represent a chain or cyclic substituted alkyl group having 1 to 18 carbon atoms, Carbon atoms may be substituted with oxygen atoms or nitrogen atoms, carbon-carbon bonds may contain unsaturated bonds, and aromatic rings may be contained.
m and l represent an integer of 2-5.

In the above general formula (A'),
R _f represents a fluorine atom, a linear C 1-10, or a branched or cyclic C 3-12 perfluoroalkyl group.
L represents a divalent linking group, a single bond, -C(=O)-O-, or -C(=O)-NR- (R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms).
R ^A1 , R ^A2 and R ^A3 each independently represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, Any two or more of R ^A1 , R ^A2 and R ^A3 may bond together to form a ring together with the carbon-carbon double bond in the formula.
Y represents a divalent linking group, a single bond, -OC(=O)-, -NR-C(=O)- (R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group , or an aromatic ring group or a substituted aromatic ring group having 6 to 12 carbon atoms), an arylene group having 6 to 12 carbon atoms, or -O-C(=O)- or -NR-C(=O)- and the number of carbon atoms It represents a linking group in which 6 to 12 arylene groups are combined.
m represents an integer of 1-6, and n represents an integer of 0-5.
M ⁺ represents a monovalent cation.

Further, the polymerizable ionic liquid of the present embodiment is specifically a compound represented by at least one of the following general formula (A1), general formula (A2), general formula (A3) and general formula (A4) includes. That is, specific examples of the compound represented by the general formula (A) include compounds represented by the following general formula (A1) or general formula (A2). Specific examples of the compound represented by the general formula (A') include compounds represented by the following general formula (A3) or general formula (A4).

In the above general formula (A1), R _f represents a fluorine atom, a straight chain having 1 to 10 carbon atoms, or a branched or cyclic perfluoroalkyl group having 3 to 12 carbon atoms, and a perfluoroalkyl group having 1 to 4 carbon atoms. Fluoroalkyl groups are preferred, and trifluoromethyl groups are particularly preferred.
In general formula (A1), W ¹ represents a divalent linking group, -C(=O)-, -C(=O)-O-, or -C(=O)-NR- (R is hydrogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms). When W ¹ is -C(=O)-NR-, the alkyl group has 1 to 10 carbon atoms and is linear or branched or cyclic (when the number of carbon atoms is 3 or more). is. Aromatic ring groups having 6 to 12 carbon atoms include aromatic hydrocarbon groups such as phenyl and naphthyl groups, or pyrrolyl groups (including nitrogen-protected groups), pyridyl groups, furyl groups, thienyl groups, indolyl groups (nitrogen-protected aromatic heterocyclic groups containing heteroatoms such as nitrogen, oxygen or sulfur atoms such as quinolyl, benzofuryl and benzothienyl groups. The substituted alkyl group and the substituted aromatic ring group have substituents in any number and in any combination on any carbon atom or nitrogen atom of the above alkyl group and aromatic ring group, respectively. Such substituents include halogen atoms such as fluorine atom, chlorine atom and bromine atom, lower alkyl groups such as methyl group, ethyl group and propyl group, lower haloalkyl groups such as fluoromethyl group, chloromethyl group and bromomethyl group, and methoxy group. , lower alkoxy groups such as ethoxy and propoxy groups; lower haloalkoxy groups such as fluoromethoxy, chloromethoxy and bromomethoxy groups; lower alkoxycarbonyl groups such as cyano, methoxycarbonyl, ethoxycarbonyl and propoxycarbonyl groups; , phenyl group, naphthyl group, anthryl group, pyrrolyl group (including nitrogen-protected compounds), pyridyl group, furyl group, thienyl group, indolyl group (including nitrogen-protected compounds), quinolyl group, benzofuryl group and benzothienyl group, etc. They include aromatic ring groups, carboxyl group protectors, amino group protectors, hydroxyl group protectors, and the like. As used herein, the term “lower” means a linear or branched chain type or cyclic (with 3 or more carbon atoms) having 1 to 6 carbon atoms. In addition, the aromatic ring group of the above ``according substituent'' includes a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a cyano group, a lower alkoxycarbonyl group, and a protected carboxyl group. , an amino group-protected body, a hydroxyl group-protected body, and the like can also be substituted. Further protective groups for pyrrolyl, indolyl, carboxyl, amino and hydroxyl groups are described in Protective Groups in Organic Synthesis, Third Edition, 1999, John Wiley & Sons, Inc. It is a protecting group described in Etc. Among them, -C(=O)- is particularly preferred.
In general formula (A1), n represents an integer of 0 to 5, with 0 and 1 being particularly preferred.
In general formula (A1), M ⁺ represents a monovalent cation.
In the general formula (A1), X is a polymerizable substituent, the vinyl group represented by the general formula (B1), the epoxy group represented by the general formula (B2), the silyl group represented by the general formula (B3), the general formula ( It represents a polyvalent acrylic group represented by B4), a polyvalent epoxy group represented by general formula (B5), or a norbornyl group represented by general formula (B6).

In the above general formula (B1), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, may be substituted with an oxygen atom, and a hydrogen atom of an alkyl group may be substituted with an oxygen atom. The halogen atom is fluorine atom, chlorine atom, bromine atom or iodine atom. The alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the same as the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group represented by R in the compound represented by general formula (A1). be. Among them, a hydrogen atom, a methyl group, an ethyl group, a cyclohexyl group, a chlorine atom, a fluorine atom, a trifluoromethyl group, a methoxy group, an ethoxy group and an acetoxy group are preferred, and a hydrogen atom and a methyl group are particularly preferred.
In general formula (B2) above, R ² represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms. The halogen atom is fluorine atom, chlorine atom, bromine atom or iodine atom. The alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the same as the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group represented by R in the compound represented by general formula (A1). be. Among them, a hydrogen atom, a methyl group, an ethyl group and a phenyl group are preferred, and a hydrogen atom and a methyl group are particularly preferred.
In the above general formula (B3), R ³ , R ⁴ and R ⁵ are each independently an alkoxy group having a linear alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 6 to 12 carbon atoms, represents an aromatic ring group, a hydroxyl group, or a chlorine atom. The alkyl group and aromatic ring group are the same as the alkyl group and aromatic ring group represented by R in the compound represented by general formula (A1). Among them, trichlorosilyl group, methyldimethoxysilyl group, trimethoxysilyl group, phenyldimethoxysilyl group, methyldiethoxysilyl group, triethoxysilyl group, phenyldiethoxysilyl group, methyldiphenoxysilyl group, triphenoxysilyl group and Phenyldiphenoxysilyl groups are preferred, and trichlorosilyl, trimethoxysilyl and triethoxysilyl groups are particularly preferred.
In general formula (B4) above, R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms. The halogen atom is fluorine atom, chlorine atom, bromine atom or iodine atom. The alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the same as the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group represented by R in the compound represented by general formula (A1). be. Among them, a hydrogen atom, a methyl group, an ethyl group, a cyclohexyl group, a chlorine atom, a fluorine atom and a trifluoromethyl group are preferred, and a hydrogen atom and a methyl group are particularly preferred.
In the above general formulas (B4) and (B5), Z ¹ and Z ² each represent a trivalent or higher coupler and represent a chain or cyclic substituted alkyl group having 1 to 18 carbon atoms, Carbon may be substituted with oxygen or nitrogen, the carbon-carbon bond may contain an unsaturated bond, and an aromatic ring may be contained.
Examples are given below.

Among them, a trivalent linking group is particularly preferred.
In general formula (B4), m represents an integer of 2 to 5, with 2 being particularly preferred.
In general formula (B5), l represents an integer of 2 to 5, with 2 being particularly preferred.

Examples of the compound represented by the general formula (A1) include the following.

The compound represented by general formula (A2) represents a compound represented by general formula (A1) in which the connecting group ^W1 is a single bond.
In general formula (A2) above, R _f , X, n and M have the same meanings as R _f , X, n and M in general formula (A1), respectively, and preferred embodiments thereof are also the same.

Examples of the compound represented by the general formula (A2) include the following.

In the above general formula (A3), R _f represents a fluorine atom, a straight chain having 1 to 10 carbon atoms, or a branched or cyclic perfluoroalkyl group having 3 to 12 carbon atoms, and a perfluoroalkyl group having 1 to 4 carbon atoms. Fluoroalkyl groups are preferred, and trifluoromethyl groups are particularly preferred.
In the general formula (A3), L ¹ represents a divalent linking group, -C (=O) -O-, or -C (=O) -NR- (R is a hydrogen atom, having 1 to 10 carbon atoms, an alkyl group or substituted alkyl group, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms).
When L ¹ is -C(=O)-NR-, the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the alkyl represented by R in the compound represented by general formula (A1) group, substituted alkyl group, aromatic ring group and substituted aromatic ring group. Among them, a hydrogen atom is particularly preferred.
In the general formula (A3), Y represents a divalent linking group, a single bond, -OC (= O) -, -NR-C (= O) - (R is a hydrogen atom, has 1 to 10 carbon atoms an alkyl group or substituted alkyl group, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms), an arylene group having 6 to 12 carbon atoms, or -O-C (=O)- or -NR-C ( ═O)— represents a linking group in which an arylene group having 6 to 12 carbon atoms is combined.
When Y is -NR-C(=O)- or a linking group combining -NR-C(=O)- and an arylene group having 6 to 12 carbon atoms, the alkyl group, substituted alkyl group, aromatic ring The group and the substituted aromatic ring group are the same as the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group represented by R in the compound represented by formula (A1). Among them, a hydrogen atom is particularly preferred.
When Y is an arylene group having 6 to 12 carbon atoms or a linking group in which -OC(=O)- or -NR-C(=O)- and an arylene group having 6 to 12 carbon atoms are combined, An arylene group is an aromatic hydrocarbon group or an aromatic heterocyclic group. Any number and any combination of substituents may be present on any carbon atom or nitrogen atom of the aromatic ring group. Such substituents include halogen atoms such as fluorine atom, chlorine atom and bromine atom, lower alkyl groups such as methyl group, ethyl group and propyl group, lower haloalkyl groups such as fluoromethyl group, chloromethyl group and bromomethyl group, and methoxy group. , lower alkoxy groups such as ethoxy and propoxy groups; lower haloalkoxy groups such as fluoromethoxy, chloromethoxy and bromomethoxy groups; lower alkoxycarbonyl groups such as cyano, methoxycarbonyl, ethoxycarbonyl and propoxycarbonyl groups; , phenyl group, naphthyl group, anthryl group, pyrrolyl group (including nitrogen-protected compounds), pyridyl group, furyl group, thienyl group, indolyl group (including nitrogen-protected compounds), quinolyl group, benzofuryl group and benzothienyl group, etc. They include aromatic ring groups, carboxyl group protectors, amino group protectors, hydroxyl group protectors, and the like. Among them, a phenylene group and a perfluorophenylene group are preferred, and a phenylene group is particularly preferred.
In general formula (A3), R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group having 6 to 12 carbon atoms or It represents a substituted aromatic ring group, and any two or more of R ⁷ , R ⁸ and R ⁹ may bond together to form a ring together with the carbon-carbon double bond in the formula. The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the same as the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group represented by R in the compound represented by formula (A1). be. Among them, a hydrogen atom, a fluorine atom, a methyl group and a trifluoromethyl group are preferred, and a hydrogen atom and a methyl group are particularly preferred.
In general formula (A3), m represents an integer of 1 to 6, with 1 being particularly preferred.
In general formula (A3), n represents an integer of 0 to 5, with 2 being particularly preferred.
In general formula (A3), M ⁺ represents a monovalent cation.

Examples of the compound represented by the general formula (A3) include the following.

The compound represented by the general formula (A4) represents a compound represented by the general formula (A3) in which the linking group ^L1 is a single bond and n is 1.
In general formula (A4) above, R _f , R ⁷ , R ⁸ , R ⁹ , Y, m and M correspond to R _f , R ⁷ , R ⁸ , R ⁹ , Y, m and M in general formula (A3). are synonymous with each other, and preferred embodiments are also the same.

Examples of the compound represented by the general formula (A4) include the following.

The above monovalent cations can include, for example, one or more selected from the group consisting of hydrogen ions, ammonium ions, phosphonium ions, imidazolium ions, and pyridinium ions.

Moreover, the monovalent cation can include a polymerizable functional group-containing cation. That is, a monovalent cation having a polymerizable functional group can be used as the monovalent cation.

The monovalent cations include an ammonium cation represented by the following general formula (C1), a phosphonium cation represented by the following general formula (C2), an imidazolium cation represented by the following general formula (C3), and the following general It can contain one or more polymerizable functional group-containing cations selected from the group consisting of pyridinium cations represented by formula (C4). These may be used alone or in combination of two or more.

In general formula (C1) above, each of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ is independently a hydrogen atom, an alkyl group, a substituted alkyl group, an aromatic ring group, a substituted aromatic ring group, or a polymerizable functional group-containing group. represents In addition, two or more of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may combine to form a cyclic structure, and non-aromatic heteroaromatic compounds containing nitrogen atoms such as aziridinium, pyrrolidinium, morpholinium, piperazinium and piperidinium. A ring can be formed.
The alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the same as the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group represented by R in the compound represented by general formula (A1). is.
The polymerizable functional group-containing group is an alkyl group, a substituted alkyl group, an aromatic ring group, or a substituted aromatic ring group containing a polymerizable functional group, and the polymerizable functional group is any number and any combination on any carbon. have in Moreover, you may have substituents other than a polymerizable functional group by arbitrary numbers and arbitrary combinations. The polymerizable functional group includes a radically polymerizable functional group and a cationic polymerizable functional group. The radically polymerizable functional group includes a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl group, an allyl group, a methallyl group, an ethynyl group, an isopropenyl group, a vinyloxy group, an allyloxy group, a methallyloxy group, a vinylthio group, allylthio group, methallylthio group, vinylcarbonyl group, allylcarbonyl group, methallylcarbonyl group, vinyloxycarbonyl group, allyloxycarbonyl group, methallyloxycarbonyl group, vinyloxycarbonyloxy group, allyloxycarbonyloxy group, meta Examples include an allyloxycarbonyloxy group, a vinylamino group, an allylamino group, and a methallylamino group. Cationic polymerizable functional groups include alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiroorthoester groups, vinyloxy groups and the like. The alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the same as the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group represented by R in the compound represented by general formula (A1). be. Among them, an alkyl group having 1 to 8 carbon atoms and an allyl group are preferable, and a methyl group, an ethyl group, a butyl group and an allyl group are particularly preferable.

Examples of compounds represented by the general formula (C1) include ammonium ion, methylammonium ion, n-butylammonium ion, cyclohexylammonium ion, benzylammonium ion, n-octylammonium ion, dimethylammonium ion, diethylammonium ion, Diisopropylammonium ion, di-n-butylammonium ion, dicyclohexylammonium ion, di-n-octylammonium ion, trimethylammonium ion, triethylammonium ion, diisopropylethylammonium ion, tri-n-butylammonium ion, tri-n-octylammonium ion, tetra methylammonium ion, tetraethylammonium ion, tetra-n-butylammonium ion, tetra-n-octylammonium ion, n-butyltrimethylammonium ion, benzyltrimethylammonium ion, n-octyltrimethylammonium ion, tri-n-octylmethylammonium ion, triethyl benzylammonium ion, tri-n-butylbenzylammonium ion, methoxyethyltrimethylammonium ion, diethylmethylmethoxyethylammonium ion, vinyltrimethylammonium ion, allylammonium ion, triallylammonium ion, allyltrimethylammonium ion, triallylmethylammonium ion, triallylethylammonium ion, triallyln-butylammonium ion, triallylbenzylammonium ion, triallyln-octylammonium ion, 2-acryloyloxyethyldimethylammonium ion, 2-acryloyloxyethyltrimethylammonium ion, 2-acryloyl oxyethylbenzyldimethylammonium ion, 2-methacryloyloxyethyldimethylammonium ion, 2-methacryloyloxyethyltrimethylammonium ion, 2-methacryloyloxyethylbenzyldimethylammonium ion, 1-methylpyrrolidinium ion, 1-ethylpyrrolidin um ion, 1-n-butylpyrrolidinium ion, 1-allylpyrrolidinium ion, 1-(2-acryloyloxyethyl)pyrrolidinium ion, 1-(2-methacryloyloxyethyl)pyrrolidinium ion, 1-ethyl- 1-methylpyrrolidinium ion, 1-n-butyl-1-methylpyrrolidinium ion, 1-n-butyl-1-ethylpyrrolidinium ion, 1-allyl-1-methylpyrrolidinium ion, 1-allyl-1- Ethylpyrrolidinium ion, 1-allyl-1-n-butylpyrrolidinium ion, 1-(2-acryloyloxyethyl)-1-methylpyrrolidinium ion, 1-(2-acryloyloxyethyl)-1-ethyl pyrrolidinium ion, 1-(2-acryloyloxyethyl)-1-n-butylpyrrolidinium ion, 1-(2-methacryloyloxyethyl)-1-methylpyrrolidinium ion, 1-ethyl-1-(2 -methacryloyloxyethyl)pyrrolidinium ion, 1-n-butyl-1-(2-methacryloyloxyethyl)pyrrolidinium ion, 1-methylpiperidinium ion, 1-ethylpiperidinium ion, 1-n-butylpipe Lysinium ion, 1-allylpiperidinium ion, 1-(2-acryloyloxyethyl)piperidinium ion, 1-(2-methacryloyloxyethyl)piperidinium ion, 1-ethyl-1-methylpiperidinium ion , 1-n-butyl-1-methylpiperidinium ion, 1-n-butyl-1-ethylpiperidinium ion, 1-allyl-1-methylpiperidinium ion, 1-allyl-1-ethylpiperidinium ion, 1 - allyl-1-n-butylpiperidinium ion, 1-(2-acryloyloxyethyl)-1-methylpiperidinium ion, 1-(2-acryloyloxyethyl)-1-ethylpiperidinium ion, 1- (2-acryloyloxyethyl)-1-n-butylpiperidinium ion, 1-(2-methacryloyloxyethyl)-1-methylpiperidinium ion, 1-ethyl-1-(2-methacryloyloxyethyl) piperidinium ion, 1-n-butyl-1-(2-methacryloyloxyethyl)piperidinium ion, 4-methylmorpholinium ion, 4-ethylmorpholinium ion, 4-n-butylmorpholinium ion, 4-allylmorpholinium ion, 4-(2-acryloyloxyethyl)morpholinium ion, 4-(2-methacryloyloxyethyl)morpholinium ion, 4-ethyl-4-methylmorpholinium ion, 4-n-butyl-4-methylmorpholinium ion, 4-n-butyl-4-ethylmorpholinium ion, 4-allyl-4-methylmorpholinium ion, 4-allyl-4-ethylmol Pholinium ion, 4-allyl-4-n-butylmorpholinium ion, 4-(2-acryloyloxyethyl)-4-methylmorpholinium ion, 4-(2-acryloyloxyethyl)-4- ethylmorpholinium ion, 4-(2-acryloyloxyethyl)-4-n-butylmorpholinium ion, 4-(2-methacryloyloxyethyl)-4-methylmorpholinium ion, 4-ethyl- 4-(2-methacryloyloxyethyl)morpholinium ion and 4-n-butyl-4-(2-methacryloyloxyethyl)morpholinium ion.

In general formula (C2) above, each of R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is independently a hydrogen atom, an alkyl group, a substituted alkyl group, an aromatic ring group, a substituted aromatic ring group, or a polymerizable functional group-containing group. and the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group represented by R in the compound represented by the general formula (A1) Same as cyclic group. The polymerizable functional group-containing group is the same as the polymerizable functional group-containing groups represented by R ¹⁰ , R ¹¹ , R ¹² and R ¹³ in the compound represented by formula (C1). Among them, an alkyl group having 1 to 8 carbon atoms and an allyl group are preferable, and a methyl group, an ethyl group, a butyl group and an allyl group are particularly preferable.

Examples of compounds represented by the general formula (C2) include tri-tert-butylphosphonium ion, di-tert-butylmethylphosphonium ion, tricyclohexylphosphonium ion, tetraethylphosphonium ion, tetra-n-butylphosphonium ion, tetra-n-octylphosphonium ion, ion, tetraphenylphosphonium ion, triethylmethylphosphonium ion, tri-tert-butylmethylphosphonium ion, tri-tert-butylcyanomethylphosphonium ion, triethyloctylphosphonium ion, methyltriphenylphosphonium ion, cyanomethyltriphenylphosphonium ion, triphenylethyl Phosphonium ion, n-butyltriphenylphosphonium ion, tetraphenylphosphonium ion, benzyltriphenylphosphonium ion, allyltriphenylphosphonium ion, triphenylcinnamylphosphonium ion, 2-(1,3-dioxan-2-yl)ethyltri phenylphosphonium ion, 2-(1,3-dioxolan-2-yl)ethyltriphenylphosphonium ion, triphenylvinylphosphonium ion and triphenyl(4-styryl)phosphonium ion.

In the general formula (C3), R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an aromatic ring group, a substituted aromatic ring group, or a polymerizable functional group. Represents a group-containing group, and the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the alkyl group, substituted alkyl group and aromatic ring group represented by R in the compound represented by the general formula (A1) and substituted aromatic ring groups. The polymerizable functional group-containing group is the same as the polymerizable functional group-containing groups represented by R ¹⁰ , R ¹¹ , R ¹² and R ¹³ in the compound represented by formula (C1). Among them, an alkyl group having 1 to 8 carbon atoms and a vinyl group are preferable, and a methyl group, an ethyl group, a butyl group and a vinyl group are particularly preferable.

Examples of the compound represented by the general formula (C3) include 1-methylimidazolium ion, 1-ethylimidazolium ion, 1-n-butylimidazolium ion, 1-n-hexylimidazolium ion, 1-vinyl imidazolium ion, 1,3-dimethylimidazolium ion, 1-ethyl-3-methylimidazolium ion, 1-n-butyl-3-methylimidazolium ion, 1-n-hexyl-3-methylimidazolium ion, 1-n-octyl-3-methylimidazolium ion, 1-(2-hydroxyethyl)-3-methylimidazolium ion, 1-methyl-3-vinylimidazolium ion, 1-ethyl-3-vinylimidazolium ion , 1-n-butyl-3-vinylimidazolium ion, 1-allyl-3-methylimidazolium ion, 1-n-butyl-2,3-dimethylimidazolium ion, 1-(2-acryloyloxyethyl) -3-methylimidazolium ion and 1-(2-methacryloyloxyethyl)-3-methylimidazolium ion.

In general formula (C4) above, each of R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ is independently a hydrogen atom, an alkyl group, a substituted alkyl group, an aromatic ring group, a substituted aromatic ring group, or represents a group containing a polymerizable functional group, and the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the alkyl group, substituted alkyl group, It is the same as the aromatic ring group and the substituted aromatic ring group. The polymerizable functional group-containing group is the same as the polymerizable functional group-containing groups represented by R ¹⁰ , R ¹¹ , R ¹² and R ¹³ in the compound represented by formula (C1). Among them, an alkyl group having 1 to 8 carbon atoms and a vinyl group are preferable, and a methyl group, an ethyl group, a butyl group and a vinyl group are particularly preferable.

Examples of compounds represented by the general formula (C4) include pyridinium ion, 3-methylpyridinium ion, 4-methylpyridinium ion, 2-vinylpyridinium ion, 4-vinylpyridinium ion, 2-(hydroxymethyl)pyridinium ion , 3-(hydroxymethyl)pyridinium ion, 4-(hydroxymethyl)pyridinium ion, 2,6-dimethylpyridinium ion, 2,4,6-trimethylpyridinium ion, 1-ethylpyridinium ion, 1-ethyl-3-methyl pyridinium ion, 1-ethyl-4-methylpyridinium ion, 1-ethyl-2-vinylpyridinium ion, 1-ethyl-4-vinylpyridinium ion, 1-ethyl-2-(hydroxymethyl)pyridinium ion, 1-ethyl- 3-(hydroxymethyl)pyridinium ion, 1-ethyl-4-(hydroxymethyl)pyridinium ion, 1-ethyl-2,6-dimethylpyridinium ion, 1-ethyl-2,4,6-trimethylpyridinium ion, 1- n-butylpyridinium ion, 1-n-butyl-3-methylpyridinium ion, 1-n-butyl-4-methylpyridinium ion, 1-n-butyl-2-vinylpyridinium ion, 1-n-butyl-4- vinylpyridinium ion, 1-n-butyl-2-(hydroxymethyl)pyridinium ion, 1-n-butyl-4-(hydroxymethyl)pyridinium ion, 1-n-butyl-2,6-dimethylpyridinium ion, 1- Examples include n-butyl-2,4,6-trimethylpyridinium ion, 1-(2-acryloyloxyethyl)pyridinium ion, and 1-(2-methacryloyloxyethyl)pyridinium ion.

The polymerizable functional group-containing group can have a group represented by the following general formula (C5). That is, the ammonium cation represented by the general formula (C1), the phosphonium cation represented by the general formula (C2), the imidazolium cation represented by the general formula (C3) and the pyridinium represented by the general formula (C4) A monovalent cation selected from the group consisting of cations preferably has a polymerizable functional group-containing group represented by the following general formula (C5).

In the general formula (C5), R ²⁹ , R ³⁰ and R ³¹ are each independently a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group having 6 to 12 carbon atoms or represents a substituted aromatic ring group. The halogen atom is fluorine atom, chlorine atom, bromine atom or iodine atom. The alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the same as the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group represented by R in the compound represented by general formula (A1). be. Also, any two or more of R ²⁹ , R ³⁰ and R ³¹ may bond together to form a ring together with the carbon-carbon double bond in the formula. Among them, a hydrogen atom, a fluorine atom, a methyl group and a trifluoromethyl group are preferred, and a hydrogen atom and a methyl group are particularly preferred.
In the general formula (C5), Z represents a divalent linking group, an alkylene group having 1 to 10 carbon atoms, -O-C(=O)-, -NR-C(=O)- (R is a hydrogen atom , an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms), or -O-C(=O)- or -NR-C(=O) represents a linking group in which - and an arylene group having 6 to 12 carbon atoms are combined. The alkylene group is a linear or branched chain type or cyclic group having 1 to 10 carbon atoms or cyclic (where the number of carbon atoms is 3 or more). The alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the same as the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group represented by R in the compound represented by general formula (A1). be. The arylene group is the same as the arylene group represented by Y in the compound represented by general formula (A3). Among them, a methylene group and -OC(=O)- are preferred, and a methylene group is particularly preferred.

[Method for producing polymerizable ionic liquid]
Next, the production of the polymerizable ionic liquid of this embodiment will be described.
The method for producing the polymerizable ionic liquid of the present embodiment is not particularly limited, and for example, known methods such as an alkyl halide method, a dialkyl carbonate method, an acid neutralization method, and a direct alkylation method can be used. .

Hereinafter, an example of a method for producing the compounds represented by the general formula (A1), general formula (A2), general formula (A3), and general formula (A4) used in the polymerizable ionic liquid of the present embodiment will be described. .

<Manufacturing process of compound represented by general formula (A1)>
First, a method for producing a compound represented by general formula (A1) will be described.
Through the following two steps, the compound represented by general formula (A1) can be easily obtained.

In the presence of a base, a perfluoroalkanesulfonylamide represented by the following general formula (1) and an acid anhydride represented by the general formula (2) or an acid halide represented by the general formula (3) are reacted. A step of reacting to synthesize a compound represented by general formula (4) ([A1]-1: first step).
a compound represented by general formula (4), and an organic salt represented by general formula (5), general formula (6), general formula (7), or general formula (8) or general formula (9), general A step of reacting with an organic base represented by formula (10), general formula (11), or general formula (12) ([A1]-2: second step).

<Regarding the compound used in the process for producing the compound represented by the general formula (A1)>

In the above general formula (1), R _f represents a fluorine atom, a straight chain having 1 to 10 carbon atoms, or a branched or cyclic perfluoroalkyl group having 3 to 12 carbon atoms, and a perfluoroalkyl group having 1 to 4 carbon atoms. Fluoroalkyl groups are preferred, and trifluoromethyl groups are particularly preferred.

In general formula (2) above, W ¹ and X have the same definitions as W ¹ and X in general formula (A1), and the same preferred embodiments can be mentioned.
In general formula (2), n represents an integer of 0 to 5, with 0 and 1 being particularly preferred.

In general formula (3) above, W ¹ and X have the same meanings as W ¹ and X in general formula (A1), respectively, and the same preferred embodiments can be mentioned.
In general formula (3), Hal represents a halogen atom. The halogen atom is fluorine atom, chlorine atom, bromine atom or iodine atom. Among these, a fluorine atom and a chlorine atom are preferred, and a chlorine atom is particularly preferred.
In general formula (3), n represents an integer of 0 to 5, with 0 and 1 being particularly preferred.

In general formula (4) above, R _f has the same definition as R _f in general formula (1), and the same preferred embodiments can be mentioned.
In general formula (4), W ¹ and X have the same meanings as W ¹ and X in general formula (A1), respectively, and preferred embodiments thereof are the same.
In general formula (4), B represents a monovalent cation and is an inorganic ion or an organic ion. Examples of inorganic ions include lithium ions, sodium ions, potassium ions, and cesium ions. Examples of organic ions include trimethylammonium ion (Me ₃ NH ⁺ ), triethylammonium ion (Et ₃ NH ⁺ ), tri-n-propylammonium ion (n-Pr ₃ NH ⁺ ), tri-i-propylammonium ion (i -Pr ₃ NH ⁺ ), tri-n-butylammonium ion (n-Bu ₃ NH ⁺ ), tri-sec-butylammonium ion (sec-Bu ₃ NH ⁺ ), tri-tert-butylammonium ion (t-Bu ₃ NH ⁺ ), diisopropylethylammonium (i-Pr ₂ EtNH ⁺ ), triphenylammonium ion (Ph ₃ NH ⁺ ), dicyclohexylammonium ion, pyridinium ion, 2,6-lutidinium ion, 2,4,6-coli dinium ion, 4-dimethylaminopyridinium ion, ion of 1,5-diazabicyclo[4.3.0]non-5-ene, and ion of 1,8-diazabicyclo[5.4.0]undec-7-ene etc. can be exemplified. Among them, organic ions are preferred, and triethylammonium ion, diisopropylethylammonium ion, dicyclohexylammonium ion, pyridinium ion, 2,6-lutidinium ion, 2,4,6-collidinium ion, and 4-dimethylaminopyridinium ion are preferred. . Among them, triethylammonium ion, dicyclohexylammonium ion and pyridinium ion are particularly preferred.
In general formula (4), n represents an integer of 0 to 5, with 0 and 1 being particularly preferred.

In reaction formula (1), A is an organic salt represented by general formula (5), general formula (6), general formula (7), or general formula (8) or general formula (9) or general formula (10) ), general formula (11), or organic base represented by general formula (12). Organic salts and organic bases are described below, respectively.

In general formula (5) above, R ¹⁰ , R ¹¹ , R ¹² and R ¹³ have the same meanings as R ¹⁰ , R ¹¹ , R ¹² and R ¹³ in general formula (C1), and preferred embodiments are the same. be able to.
In general formula (5), Hal represents a halogen atom. The halogen atom is fluorine atom, chlorine atom, bromine atom or iodine atom. Among them, a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred.

In general formula (6) above, R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ have the same meanings as R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ in general formula (C2), and preferred embodiments are the same. be able to.
In general formula (6), Hal represents a halogen atom. The halogen atom is fluorine atom, chlorine atom, bromine atom or iodine atom. Among them, a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred.

In the above general formula (7), R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are synonymous with R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² in general formula (C3), respectively, and are preferred The aspect can mention the same thing.
In general formula (7), Hal represents a halogen atom. The halogen atom is fluorine atom, chlorine atom, bromine atom or iodine atom. Among them, a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred.

In general formula (8) above, R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are the same as R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ in general formula (C4). Each has the same meaning, and preferred embodiments can include the same ones.
In general formula (8), Hal represents a halogen atom. The halogen atom is fluorine atom, chlorine atom, bromine atom or iodine atom. Among them, a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred.

In general formula (9) above, R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aromatic ring group, a substituted aromatic ring group, or a polymerizable functional group-containing group. Two or more of R ¹⁰ , R ¹¹ and R ¹² may combine to form a cyclic structure, forming a non-aromatic heterocyclic ring containing a nitrogen atom such as aziridine, pyrrolidine, morpholine, piperazine, piperidine, etc. can do.
The alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group represented by R in the compound represented by the general formula (A1). are the same.
The polymerizable functional group-containing group is the same as the polymerizable functional group-containing groups represented by R ¹⁰ , R ¹¹ , R ¹² and R ¹³ in the compound represented by formula (C1). Among them, an alkyl group having 1 to 8 carbon atoms and an allyl group are preferable, and a methyl group, an ethyl group, a butyl group and an allyl group are particularly preferable.

In general formula (10) above, R ¹⁴ , R ¹⁵ and R ¹⁶ have the same meanings as R ¹⁴ , R ¹⁵ and R ¹⁶ in general formula (C2), respectively, and preferred embodiments thereof are the same.

In general formula (11) above, R ¹⁸ , R ¹⁹ , R ²¹ and R ²² have the same meanings as R ¹⁸ , R ¹⁹ , R ²¹ and R ²² in general formula (C3), and preferred embodiments are the same. be able to.

In general formula (12) above, R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are synonymous with R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ in general formula (C4), respectively, and are preferred The aspect can mention the same thing.

[A1]-1: First step <Step of synthesizing a compound represented by general formula (4)>

The amount of the acid anhydride represented by the general formula (2) or the acid halide represented by the general formula (3) to be used is per 1 mol of the perfluoroalkanesulfonylamide represented by the general formula (1). 0.7 mol or more, preferably 0.8 to 5 mol, particularly preferably 0.9 to 3 mol.

bases include inorganic bases such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; and triethylamine, diisopropylethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 2,6-lutidine, 2,4,6-collidine, 4-dimethylaminopyridine, 1,5-diazabicyclo [4.3.0 ]non-5-ene and 1,8-diazabicyclo[5.4.0]undec-7-ene. Among them, organic bases are preferred, and triethylamine, diisopropylethylamine, pyridine, 2,6-lutidine, 2,4,6-collidine and 4-dimethylaminopyridine are particularly preferred. These bases can be used alone or in combination.

The amount of the base used may be 0.35 mol or more, preferably 0.4 to 20 mol, particularly preferably 0.45 to 15 mol, per 1 mol of the perfluoroalkanesulfonylamide represented by the general formula (1). .

The order of addition of the base is not particularly limited, and the perfluoroalkanesulfonylamide represented by the general formula (1) and the acid anhydride represented by the general formula (2) or the acid anhydride represented by the general formula (3) are added to the reaction solvent. Good results may be obtained by adding the desired acid halide and finally adding the base.

Reaction solvents include aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as toluene and xylene, halogens such as methylene chloride and 1,2-dichloroethane, tetrahydrofuran and tert-butyl methyl ether. esters such as ethyl acetate and n-butyl acetate, N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide and 1,3-dimethyl-2-imidazolidinone amide systems such as acetonitrile and propionitrile, nitrile systems such as acetonitrile and propionitrile, dimethylsulfoxide and water. Among them, n-heptane, toluene, methylene chloride, tetrahydrofuran, ethyl acetate, N,N-dimethylformamide, acetonitrile, dimethylsulfoxide and water are preferable, and toluene, methylene chloride, tetrahydrofuran, ethyl acetate, N,N-dimethylformamide and acetonitrile. and water are particularly preferred. These reaction solvents can be used alone or in combination. When used in combination with water, the reaction can also be carried out in a two-phase system.

The amount of the reaction solvent used may be 0.05 L (liter) or more, preferably 0.1 to 20 L, and 0.15 to 1 mol per 1 mol of the perfluoroalkanesulfonylamide represented by the general formula (1). 10L is particularly preferred. This reaction can also be carried out in a neat state without using a reaction solvent.

The reaction temperature may be in the range of -80 to +200°C, preferably -60 to +150°C, particularly preferably -40 to +100°C.

The reaction time may be within 240 hours, and varies depending on the raw material substrate, reactants and reaction conditions. It is preferable to set the end point at the time when the decrease in the raw material substrate is hardly observed.

Work-up can be carried out to obtain compounds represented by general formula (4) by employing common procedures in organic synthesis. The crude product can be purified to a high degree of purity by treatment with activated carbon, recrystallization, or the like, if necessary.

[A1]-2: Second step <Step of obtaining a compound represented by general formula (A1)>

In the above formula, A is an organic salt represented by general formula (5), general formula (6), general formula (7), or general formula (8) or general formula (9), general formula (10), general It represents an organic base represented by formula (11) or general formula (12).
Organic salts represented by the above general formula (5), general formula (6), general formula (7), or general formula (8), or general formula (9), general formula (10), and general formula (11) , or the organic base represented by the general formula (12) may be used in an amount of 0.7 mol or more, preferably 0.8 to 5 mol, and 0.7 mol or more per 1 mol of the compound represented by the general formula (4). 9-3 mol is particularly preferred.

The reaction solvent is the same as the reaction solvent described in the step of obtaining the compound represented by general formula (4), and the "preferred" and "particularly preferred" reaction solvents are also the same. These reaction solvents can be used alone or in combination. When used in combination with water, the reaction can also be carried out in a two-phase system.

The amount of the reaction solvent used may be 0.05 L (liter) or more, preferably 0.1 to 20 L, particularly preferably 0.15 to 10 L, per 1 mol of the compound represented by formula (4). This reaction can also be carried out in a neat state without using a reaction solvent.

The reaction temperature may be in the range of -80 to +200°C, preferably -60 to +150°C, particularly preferably -40 to +100°C.

The reaction time may be within 240 hours, and varies depending on the raw material substrate, reactants and reaction conditions. It is preferable to set the end point at the time when the decrease in the raw material substrate is hardly observed.

For post-treatment, a compound represented by general formula (A1) can be obtained by employing a general operation in organic synthesis. The crude product can be purified to a high degree of purity by treatment with activated carbon, recrystallization, or the like, if necessary.

<Manufacturing process of compound represented by general formula (A2)>
Next, a method for producing the compound represented by formula (A2) will be described. Through the following two steps, the compound represented by general formula (A2) can be easily obtained.

In the presence of a base, an amine represented by the following general formula (13) and a perfluoroalkanesulfonic anhydride represented by the general formula (14) or a perfluoroalkanesulfonic acid represented by the general formula (15) A step of reacting with a halide to synthesize a compound represented by the general formula (16) ([A2]-1: first step).
A compound represented by the general formula (16) and an organic salt represented by the general formula (5), general formula (6), general formula (7), or general formula (8) or general formula (9), general A step of reacting with an organic base represented by formula (10), general formula (11), or general formula (12) ([A2]-2: second step).

<Regarding the compound used in the process for producing the compound represented by the general formula (A2)>

In general formula (13) above, X has the same definition as X in general formula (A1), and the same preferred embodiments can be mentioned.
In general formula (13), n represents an integer of 0 to 5, with 1 being particularly preferred.

In general formula (14) above, R _f has the same definition as R _f in general formula (1), and the same preferred embodiments can be mentioned.

In general formula (15) above, R _f has the same definition as R _f in general formula (1), and the same preferred embodiments can be mentioned.
In general formula (15), Hal represents a halogen atom. The halogen atom is fluorine atom, chlorine atom, bromine atom or iodine atom. Among them, fluorine and chlorine atoms are preferred, and chlorine is particularly preferred.

In general formula (16) above, R _f has the same definition as R _f in general formula (1), and the same preferred embodiments can be mentioned.
In general formula (16), X has the same definition as X in general formula (A1), and preferred embodiments thereof are the same.
In general formula (16), B has the same definition as B in general formula (4), and preferred embodiments thereof are the same.
In general formula (16), n represents an integer of 0 to 5, with 1 being particularly preferred.

In Reaction Formula (2), A has the same definition as A in Reaction Formula (1).

[A2]-1: First Step <Step of Obtaining Compound Represented by General Formula (16)>

The amount of the perfluoroalkanesulfonic anhydride represented by the general formula (14) or the perfluoroalkanesulfonic acid halide represented by the general formula (15) is the amine represented by the general formula (13). It may be used in an amount of 0.7 mol or more, preferably 0.8 to 5 mol, particularly preferably 0.9 to 3 mol, per 1 mol of the compound.

The base is the same as the base described in the step of obtaining the compound represented by general formula (4), and the "preferred" and "particularly preferred" bases are also the same. These bases can be used alone or in combination.

The amount of the base to be used may be 0.35 mol or more, preferably 0.4 to 20 mol, particularly preferably 0.45 to 15 mol, per 1 mol of the amine represented by the general formula (13).

The order of addition of the base is not particularly limited, and the reaction solvent is the amine represented by the general formula (13) and the perfluoroalkanesulfonic anhydride represented by the general formula (14) or the general formula (15). Good results may be obtained by adding the perfluoroalkanesulfonic acid halide and finally adding the base.

The reaction solvent is the same as the reaction solvent described in the step of obtaining the compound represented by general formula (4), and the "preferred" and "particularly preferred" reaction solvents are also the same. These reaction solvents can be used alone or in combination. When used in combination with water, the reaction can also be carried out in a two-phase system.

The amount of the reaction solvent used may be 0.05 L (liter) or more, preferably 0.1 to 20 L, particularly preferably 0.15 to 10 L, per 1 mol of the amine represented by the general formula (13). This reaction can also be carried out in a neat state without using a reaction solvent.

The reaction temperature may be in the range of -80 to +200°C, preferably -60 to +150°C, particularly preferably -40 to +100°C.

The reaction time may be within 240 hours, and varies depending on the raw material substrate, reactants and reaction conditions. It is preferable to set the end point at the time when the decrease in the raw material substrate is hardly observed.

Workup can be carried out to obtain compounds of general formula (16) by employing common procedures in organic synthesis. The crude product can be purified to a high degree of purity by treatment with activated carbon, recrystallization, or the like, if necessary.

[A2]-2: Second step <Step of obtaining general formula (A2)>

In the above formula, A has the same definition as A in reaction formula (1).
Organic salts represented by the above general formula (5), general formula (6), general formula (7), or general formula (8), or general formula (9), general formula (10), and general formula (11) , or the organic base represented by the general formula (12) may be used in an amount of 0.7 mol or more, preferably 0.8 to 5 mol, and 0.7 mol or more per 1 mol of the compound represented by the general formula (16). 9-3 mol is particularly preferred.

The reaction solvent is the same as the reaction solvent described in the step of obtaining the compound represented by general formula (4), and the "preferred" and "particularly preferred" reaction solvents are also the same. These reaction solvents can be used alone or in combination. When used in combination with water, the reaction can also be carried out in a two-phase system.

The amount of the reaction solvent used may be 0.05 L (liter) or more, preferably 0.1 to 20 L, particularly preferably 0.15 to 10 L, per 1 mol of the compound represented by the general formula (16). This reaction can also be carried out in a neat state without using a reaction solvent.

The reaction temperature may be in the range of -80 to +200°C, preferably -60 to +150°C, particularly preferably -40 to +100°C.

The reaction time may be within 240 hours, and varies depending on the raw material substrate, reactants and reaction conditions. It is preferable to set the end point at the time when the decrease in the raw material substrate is hardly observed.

For post-treatment, a compound represented by general formula (A2) can be obtained by employing a general operation in organic synthesis. The crude product can be purified to a high degree of purity by treatment with activated carbon, recrystallization, or the like, if necessary.

<Manufacturing process of compound represented by general formula (A3)>
Next, a method for producing a compound represented by general formula (A3) will be described.
The compound represented by general formula (A3) can be easily obtained by the following steps.

A step of synthesizing a compound represented by the general formula (19) by reacting an ester compound represented by the following general formula (17) with a compound represented by the following general formula (18) ([A3] -1: first step).
A compound represented by the general formula (19) and an organic salt represented by the general formula (5), general formula (6), general formula (7), or general formula (8) or general formula (9), general A step of reacting with an organic base represented by formula (10), general formula (11), or general formula (12) ([A3]-2: second step).

The compound represented by general formula (A3) can also be easily obtained through the following three steps.

A step of synthesizing a compound represented by the general formula (21) by reacting an ester compound represented by the following general formula (17) with a compound represented by the general formula (20) ([A3]- 1': first step).
A compound represented by the general formula (21) is reacted with an acid anhydride represented by the general formula (22) or an acid halide represented by the general formula (23) to obtain a compound represented by the general formula (19). A step of synthesizing a compound obtained ([A3]-2′: second step).
A compound represented by the general formula (19) and an organic salt represented by the general formula (5), general formula (6), general formula (7), or general formula (8) or general formula (9), general formula (10), a step of reacting with an organic base represented by general formula (11) or general formula (12) ([A3]-3′: third step).

<Regarding the compound used in the process for producing the compound represented by the general formula (A3)>

In general formula (17) above, R _f has the same definition as R _f in general formula (1), and the same preferred embodiments can be mentioned.
In general formula (17), R ³² is a hydrogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms. The alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the same as the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group represented by R in the compound represented by general formula (A1). is. Among them, a hydrogen atom, a methyl group and an ethyl group are preferred, and a hydrogen atom and a methyl group are particularly preferred.
In general formula (17), m represents an integer of 1 to 6, with 1 being particularly preferred.
In general formula (17), B has the same definition as B in general formula (4), and preferred embodiments thereof are the same.

In the above general formula (18), L ² represents a divalent linking group, -O- or -NR- (R is a hydrogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or 6 to 12 aromatic ring groups or substituted aromatic ring groups). When L ² is -NR-, the alkyl group, substituted alkyl group, aromatic ring group and substituted aromatic ring group are the alkyl group, substituted alkyl group represented by R in the compound represented by the general formula (A1) group, aromatic ring group and substituted aromatic ring group. Among them, a hydrogen atom is particularly preferred.
In general formula (18), Y, R ⁷ , R ⁸ and R ⁹ have the same definitions as Y, R ⁷ , R ⁸ and R ⁹ in general formula (A3), and the same preferred embodiments can be mentioned. .
In general formula (18), n represents an integer of 0 to 5, with 0 and 1 being particularly preferred.

In general formula (19) above, R _f has the same definition as R _f in general formula (1), and the same preferred embodiments can be mentioned.
In general formula (19), L ¹ , Y, R ⁷ , R ⁸ and R ⁹ have the same definitions as L ¹ , Y, R ⁷ , R ⁸ and R ⁹ in general formula (A3), and preferred embodiments are the same. things can be mentioned.
In general formula (19), m represents an integer of 1 to 6, with 1 being particularly preferred.
In general formula (19), n represents an integer of 0 to 5, with 0 and 1 being particularly preferred.
In general formula (19), B has the same definition as B in general formula (4), and preferred embodiments thereof are the same.

In general formula (20), L ² has the same definition as L ² in general formula (18), and the same preferred embodiments can be mentioned.
In general formula (20), n represents an integer of 0 to 5, with 2 being particularly preferred.

In general formula (21) above, R _f has the same definition as R _f in general formula (1), and the same preferred embodiments can be mentioned.
In general formula (21), L ¹ has the same definition as L ¹ in general formula (A3), and preferred embodiments thereof are the same.
In general formula (21), L ² has the same definition as L ² in general formula (18), and preferred embodiments thereof are the same.
In general formula (21), m represents an integer of 1 to 6, with 1 being particularly preferred.
In general formula (21), n represents an integer of 0 to 5, with 2 being particularly preferred.
In general formula (21), B has the same definition as B in general formula (4), and preferred embodiments thereof are the same.

In general formula (22) above, R ⁷ , R ⁸ and R ⁹ have the same meanings as R ⁷ , R ⁸ and R ⁹ in general formula (A3), respectively, and preferred embodiments thereof are the same.
In general formula (22), Y ¹ represents a divalent linking group, and represents a linking group obtained by combining -C(=O)- or -C(=O)- with an arylene group having 6 to 12 carbon atoms. . The arylene group is the same as the arylene group represented by Y in the compound represented by general formula (A3). Among them, a phenylene group and a perfluorophenylene group are preferred, and a phenylene group is particularly preferred.

In general formula (23) above, R ⁷ , R ⁸ and R ⁹ have the same meanings as R ⁷ , R ⁸ and R ⁹ in general formula (A3), respectively, and preferred embodiments thereof are the same.
In general formula (23), Y ¹ has the same definition as Y ¹ in general formula (22), and the same preferred embodiments can be mentioned.
In general formula (23), Hal represents a halogen atom. The halogen atom is fluorine atom, chlorine atom, bromine atom or iodine atom. Among them, chlorine is particularly preferred.

In Reaction Formulas (3) and (4), A has the same definition as A in Reaction Formula (1).

[A3]-1: First Step <Step of Obtaining Compound Represented by General Formula (19)>

The amount of the compound represented by the general formula (18) to be used may be 0.7 mol or more, preferably 0.8 to 5 mol, and 0.7 mol or more per 1 mol of the ester represented by the general formula (17). 9-3 mol is particularly preferred.

The reaction solvent is the same as the reaction solvent excluding water described in the step of obtaining the compound represented by general formula (4), and the "preferred" and "particularly preferred" reaction solvents are also the same excluding water. These reaction solvents can be used alone or in combination.

The amount of the reaction solvent used may be 0.05 L (liter) or more, preferably 0.1 to 20 L, particularly preferably 0.15 to 10 L, per 1 mol of the ester represented by the general formula (17). . This reaction can also be carried out in a neat state without using a reaction solvent.

The reaction temperature may be in the range of -80 to +200°C, preferably -60 to +150°C, particularly preferably -20 to +120°C.

The reaction time may be within 240 hours, and varies depending on the raw material substrate, reactants and reaction conditions. It is preferable to set the end point at the time when the decrease in the raw material substrate is hardly observed.

Work-up can be carried out to obtain compounds represented by general formula (19) by employing common procedures in organic synthesis. The crude product can be purified to a high degree of purity by treatment with activated carbon, recrystallization, or the like, if necessary.

[A3]-2: Second step <Step of obtaining a compound represented by general formula (A3)>

In the above formula, A has the same definition as A in reaction formula (1).
Organic salts represented by the above general formula (5), general formula (6), general formula (7), or general formula (8), or general formula (9), general formula (10), and general formula (11) , or the organic base represented by the general formula (12) may be used in an amount of 0.7 mol or more, preferably 0.8 to 5 mol, and 0.7 mol or more per 1 mol of the compound represented by the general formula (22). 9-3 mol is particularly preferred.

The reaction solvent is the same as the reaction solvent described in the step of obtaining the compound represented by general formula (4), and the "preferred" and "particularly preferred" reaction solvents are also the same. These reaction solvents can be used alone or in combination. When used in combination with water, the reaction can also be carried out in a two-phase system.

The amount of the reaction solvent used may be 0.05 L (liter) or more, preferably 0.1 to 20 L, particularly preferably 0.15 to 10 L, per 1 mol of the compound represented by the general formula (19). This reaction can also be carried out in a neat state without using a reaction solvent.

The reaction temperature may be in the range of -80 to +200°C, preferably -60 to +150°C, particularly preferably -40 to +100°C.

The reaction time may be within 240 hours, and varies depending on the raw material substrate, reactants and reaction conditions. It is preferable to set the end point at the time when the decrease in the raw material substrate is hardly observed.

For post-treatment, a compound represented by general formula (A3) can be obtained by employing a general operation in organic synthesis. The crude product can be purified to a high degree of purity by treatment with activated carbon, recrystallization, or the like, if necessary.

[A3]-1': First step <Step of obtaining a compound represented by general formula (21)>

The amount of the compound represented by the general formula (20) to be used may be 0.7 mol or more, preferably 0.8 to 5 mol, and 0.7 mol or more per 1 mol of the ester represented by the general formula (17). 9-3 mol is particularly preferred.

The reaction solvent is the same as the reaction solvent excluding water described in the step of obtaining the compound represented by general formula (4), and the "preferred" and "particularly preferred" reaction solvents are also the same excluding water. These reaction solvents can be used alone or in combination.

The amount of the reaction solvent used may be 0.05 L (liter) or more, preferably 0.1 to 20 L, particularly preferably 0.15 to 10 L, per 1 mol of the ester represented by the general formula (17). . This reaction can also be carried out in a neat state without using a reaction solvent.

The reaction temperature may be in the range of -80 to +200°C, preferably -60 to +150°C, particularly preferably -20 to +120°C.

The reaction time may be within 240 hours, and varies depending on the raw material substrate, reactants and reaction conditions. It is preferable to set the end point at the time when the decrease in the raw material substrate is hardly observed.

Work-up can afford compounds of general formula (21) by employing common procedures in organic synthesis. The crude product can be purified to a high degree of purity by treatment with activated carbon, recrystallization, or the like, if necessary.

[A3]-2': Second step <Step of obtaining a compound represented by general formula (19)>

The amount of the carboxylic anhydride represented by the general formula (22) or the carboxylic acid halide represented by the general formula (23) to be used is 0.00 per 1 mol of the compound represented by the general formula (21). It may be used in an amount of 7 mol or more, preferably 0.8 to 5 mol, particularly preferably 0.9 to 3 mol.

The base is the same as the base described in the step of obtaining the compound represented by general formula (4), and the "preferred" and "particularly preferred" bases are also the same. These bases can be used alone or in combination.

The amount of the base to be used may be 0.35 mol or more, preferably 0.4 to 20 mol, particularly preferably 0.45 to 15 mol, per 1 mol of the compound represented by formula (21).

The order of addition of the base is not particularly limited, and the compound represented by the general formula (21) and the carboxylic acid anhydride represented by the general formula (22) or the carboxylic acid represented by the general formula (23) are added to the reaction solvent. Adding the halide and finally the base may give good results.

The reaction solvent is the same as the reaction solvent excluding water described in the step of obtaining the compound represented by general formula (4), and the "preferred" and "particularly preferred" reaction solvents are also the same excluding water. These reaction solvents can be used alone or in combination.

The amount of the reaction solvent used may be 0.05 L (liter) or more, preferably 0.1 to 20 L, particularly preferably 0.15 to 10 L, per 1 mol of the compound represented by the general formula (21). This reaction can also be carried out in a neat state without using a reaction solvent.

The reaction temperature may be in the range of -80 to +200°C, preferably -60 to +150°C, particularly preferably -40 to +100°C.

The reaction time may be within 240 hours, and varies depending on the raw material substrate, reactants and reaction conditions. It is preferable to set the end point at the time when the decrease in the raw material substrate is hardly observed.

Work-up can be carried out to obtain compounds represented by general formula (19) by employing common procedures in organic synthesis. The crude product can be purified to a high degree of purity by treatment with activated carbon, recrystallization, or the like, if necessary.

[A3]-3': Third step <Step of obtaining a compound represented by general formula (A3)>
[A3]-2: The same as the second step <the step of obtaining the compound represented by the general formula (A3)>.

<Manufacturing process of compound represented by general formula (A4)>
Next, a method for producing the compound represented by general formula (A4) will be described.
Through the following three steps, the compound represented by general formula (A4) can be easily obtained.

A step of reducing a compound represented by the following general formula (24) with a reducing agent to synthesize a compound represented by the general formula (25) ([A4]-1: first step).
A compound represented by the general formula (25) is reacted with an acid anhydride represented by the general formula (22) or an acid halide represented by the general formula (23) to obtain a compound represented by the general formula (26). A step of synthesizing the compound obtained ([A4]-2: second step).
a compound represented by general formula (26) and an organic salt represented by general formula (5), general formula (6), general formula (7), or general formula (8) or general formula (9), general A step of reacting with an organic base represented by formula (10), general formula (11), or general formula (12) ([A4]-3: third step).

<Regarding the compound used in the manufacturing process of the compound represented by the general formula (A4)>

In general formula (24) above, R _f has the same definition as R _f in general formula (1), and the same preferred embodiments can be mentioned.
In general formula (24), R ³³ has the same definition as R ³² in general formula (17), and preferred embodiments thereof are the same.
In general formula (24), L ³ represents a divalent linking group and represents —O— or —NH—. Among them, -O- is particularly preferred.
In general formula (24), m represents an integer of 1 to 6, with 1 being particularly preferred.
In general formula (24), B has the same definition as B in general formula (4), and preferred embodiments thereof are the same.

In general formula (25) above, R _f has the same definition as R _f in general formula (1), and the same preferred embodiments can be mentioned.
In general formula (25), L ² has the same definition as L ² in general formula (18), and preferred embodiments thereof are the same.
In general formula (25), m represents an integer of 1 to 6, with 1 being particularly preferred.
In general formula (25), B has the same definition as B in general formula (4), and preferred embodiments thereof are the same.

In general formula (26) above, R _f has the same definition as R _f in general formula (1), and the same preferred embodiments can be mentioned.
In general formula (26), Y, R ⁷ , R ⁸ and R ⁹ have the same definitions as Y, R ⁷ , R ⁸ and R ⁹ in general formula (A3), and the same preferred embodiments can be mentioned. .
In general formula (26), m represents an integer of 1 to 6, with 1 being particularly preferred.
In general formula (26), B has the same definition as B in general formula (4), and preferred embodiments thereof are the same.

In Reaction Formula (5), A has the same definition as A in Reaction Formula (1).

[A4]-1: First step <Step of obtaining a compound represented by general formula (25)>

Reducing agents can include sodium borohydride, lithium aluminum hydride, diborane, and the like. Among them, sodium borohydride and diborane are particularly preferred.

The amount of the reducing agent to be used may be 0.35 mol or more, preferably 0.4 to 5 mol, particularly preferably 0.45 to 3 mol, per 1 mol of the compound represented by the general formula (24).

The reaction solvent is the same as the reaction solvent described in the step of obtaining the compound represented by general formula (4), preferably water, methanol and tetrahydrofuran, particularly preferably methanol and tetrahydrofuran. These reaction solvents can be used alone or in combination.

The amount of the reaction solvent used may be 0.05 L (liter) or more, preferably 0.1 to 20 L, particularly preferably 0.15 to 10 L, per 1 mol of the compound represented by the general formula (24).

The reaction temperature may be in the range of -80 to +200°C, preferably -60 to +150°C, particularly preferably -40 to +100°C.

The reaction time may be within 24 hours, and varies depending on the raw material substrate, reactants and reaction conditions. It is preferable to set the end point at the time when the decrease in the raw material substrate is hardly observed.

Work-up can afford compounds of general formula (25) by employing common procedures in organic synthesis. The crude product can be purified to a high degree of purity by treatment with activated carbon, recrystallization, or the like, if necessary.

[A4]-2: Second step <Step of obtaining a compound represented by general formula (26)>

The amount of the carboxylic acid anhydride represented by the general formula (22) or the carboxylic acid halide represented by the general formula (23) to be used is 0.7 mol or more per 1 mol of the compound represented by the general formula (25). 0.8 to 5 mol is preferable, and 0.9 to 3 mol is particularly preferable.

The base is the same as the base described in the step of obtaining the compound represented by general formula (4), and the "preferred" and "particularly preferred" bases are also the same. These bases can be used alone or in combination.

The amount of the base to be used may be 0.35 mol or more, preferably 0.4 to 20 mol, particularly preferably 0.45 to 15 mol, per 1 mol of the compound represented by formula (25).

The order of addition of the base is not particularly limited, and the compound represented by the general formula (25) and the carboxylic acid anhydride represented by the general formula (22) or the carboxylic acid represented by the general formula (23) are added to the reaction solvent. Adding the halide and finally the base may give good results.

The reaction solvent is the same as the reaction solvent excluding water described in the step of obtaining the compound represented by general formula (4), and the "preferred" and "particularly preferred" reaction solvents are also the same excluding water. These reaction solvents can be used alone or in combination.

The amount of the reaction solvent used may be 0.05 L (liter) or more, preferably 0.1 to 20 L, particularly preferably 0.15 to 10 L, per 1 mol of the compound represented by the general formula (25). This reaction can also be carried out in a neat state without using a reaction solvent.

The reaction temperature may be in the range of -80 to +200°C, preferably -60 to +150°C, particularly preferably -40 to +100°C.

The reaction time may be within 240 hours, and varies depending on the raw material substrate, reactants and reaction conditions. It is preferable to set the end point at the time when the decrease in the raw material substrate is hardly observed.

Work-up can afford compounds of general formula (26) by employing common procedures in organic synthesis. The crude product can be purified to a high degree of purity by treatment with activated carbon, recrystallization, or the like, if necessary.

[A4]-3: Third Step <Step of Obtaining Compound Represented by General Formula (A4)>

In the above formula, A has the same definition as A in reaction formula (1).
Organic salts represented by the above general formula (5), general formula (6), general formula (7), or general formula (8), or general formula (9), general formula (10), and general formula (11) , or the organic base represented by the general formula (12) may be used in an amount of 0.7 mol or more, preferably 0.8 to 5 mol, and 0.7 mol or more per 1 mol of the compound represented by the general formula (26). 9-3 mol is particularly preferred.

The reaction solvent is the same as the reaction solvent described in the step of obtaining the compound represented by general formula (4), and the "preferred" and "particularly preferred" reaction solvents are also the same. These reaction solvents can be used alone or in combination. When used in combination with water, the reaction can also be carried out in a two-phase system.

The amount of the reaction solvent used may be 0.05 L (liter) or more, preferably 0.1 to 20 L, particularly preferably 0.15 to 10 L, per 1 mol of the compound represented by the general formula (26). This reaction can also be carried out in a neat state without using a reaction solvent.

The reaction temperature may be in the range of -80 to +200°C, preferably -60 to +150°C, particularly preferably -40 to +100°C.

The reaction time may be within 24 hours, and varies depending on the raw material substrate, reactants and reaction conditions. It is preferable to set the end point at the time when the decrease in the raw material substrate is hardly observed.

For post-treatment, a compound represented by general formula (A4) can be obtained by employing a general operation in organic synthesis. The crude product can be purified to a high degree of purity by treatment with activated carbon, recrystallization, or the like, if necessary.

[polymer]
Next, the polymer of this embodiment will be described.
The polymer of this embodiment has a repeating structure of structural units represented by at least one of the following general formula (a) and general formula (a'). These may be used alone or in combination of two or more.

In general formula (a) above, R _f , W, n and M have the same meanings as R _f , W, n and M in general formula (A) above.
x is the following general formula (b1), general formula (b2), general formula (b3), general formula (b4), general formula (b5), or general formula (b6) in which X in general formula (A) is polymerized represents the structure of

In general formula (b1), general formula (b2), general formula (b3) and general formula (b4), R ^b1 , R ^b2 , R ^b3 and R ^b6 are ), the descriptions of R ^B1 , R ^B2 , R ^B3 and R ^B6 in general formulas (B3) and (B4) apply.
In general formulas (b4) and (b5), Z ¹ , Z ² , m and l are synonymous with Z ¹ , Z ² , m and l in general formulas (B4) and (B5), respectively. is.

In general formula (a') above, R _f , L, Y, m, n and M have the same meanings as R _f , L, Y, m, n and M in general formula (A') above. The description of R ^A1 , R ^A2 and R ^A3 in the general formula (A′) applies to R ^a1 , R ^a2 and R ^a3 .

Further, the polymer of the present embodiment specifically has a repeating structure of at least one structural unit represented by the following general formula (a1), general formula (a2), general formula (a3) and general formula (a4) A polymer having a That is, as a specific example of the polymer having a repeating structure of the structural unit represented by the general formula (a), a polymer having a repeating structure of the structural unit represented by the following general formula (a1) or general formula (a2) are mentioned. Specific examples of the polymer having a repeating structure of structural units represented by the general formula (a′) include polymers having a repeating structure of structural units represented by the following general formula (a3) or general formula (a4). mentioned.

A polymer having a repeating structure of structural units represented by general formula (a1) below is formed by polymerizing the polymerizable substituent in the compound represented by general formula (A1) above. In the polymerization reaction, the structure other than the polymerizable substituent is not changed, and the original structure is maintained.

In general formula (a1) above, R _f , W ¹ , n and M have the same meanings as R _f , W ¹ , n and M in general formula (A1) above, and preferred embodiments are the same. .
x is the following general formula (b1), general formula (b2), general formula (b3), general formula (b4), general formula (b5), or general formula (b6) in which X in general formula (A1) is polymerized represents the structure of

In general formula (b1), general formula (b2), general formula (b3) and general formula (b4), R ^b1 , R ^b2 , R ^b3 and R ^b6 are represented by general formula (B1) and general formula (B2). , R ^B1 , R ^B2 , R ^B3 and R ^B6 in general formulas (B3) and (B4), and the same preferred embodiments can be mentioned.
In general formulas (b4) and (b5), Z ¹ , Z ² , m and l are synonymous with Z ¹ , Z ² , m and l in general formulas (B4) and (B5), respectively. and preferred embodiments are the same.

A polymer having a repeating structure of structural units represented by general formula (a2) below is formed by polymerizing a polymerizable substituent in a compound represented by general formula (A2). In the polymerization reaction, the structure other than the polymerizable substituent is not changed, and the original structure is maintained.

In general formula (a2) above, R _f , n and M have the same meanings as R _f , n and M in general formula (A2) above, and preferred embodiments thereof are the same.
x has the same meaning as x in the general formula (a1), and the same preferred embodiments can be mentioned.

A polymer having a repeating structure of structural units represented by general formula (a3) below is formed by cleavage of the polymerizable double bond of the compound represented by general formula (A3). In the polymerization reaction, the structure other than the polymerizable double bond is not changed and the original structure is maintained.

In general formula (a3) above, R _f , L ¹ , Y, R ⁷ , R ⁸ , R ⁹ , m, n and M are R _f , L ¹ , Y, R ⁷ and R in general formula (A3) above. ⁸ , R ⁹ , m, n and M have the same meanings, and preferred embodiments are the same.

A polymer having a repeating structure of structural units represented by general formula (a4) is formed by cleavage of the polymerizable double bond of the compound represented by general formula (A4). In the polymerization reaction, the structure other than the polymerizable double bond is not changed and the original structure is maintained.

In general formula (a4) above, R _f , Y, R ⁷ , R ⁸ , R ⁹ , m and M are R _f , Y, R ⁷ , R ⁸ , R ⁹ , m and M in general formula (A4) above. are synonymous with each other, and preferred embodiments are the same.

Polymers having a repeating structure of at least one structural unit represented by general formula (a1), general formula (a2), general formula (a3) and general formula (a4) are represented by general formula (a1) and general formula (a2 ), one of the structural units represented by general formula (a3) or general formula (a4) may form a homopolymer. Alternatively, two or more of the structural units represented by general formula (a1), general formula (a2), general formula (a3), or general formula (a4) are combined to form a copolymer. good too. Alternatively, two or more structural units represented by general formula (a1), general formula (a2), general formula (a3) or general formula (a4) may be combined to form a copolymer.

[Copolymer]
The polymer of the present embodiment has, in the molecule, a repeating structure of structural units represented by at least one of the above general formula (a) and general formula (a′), specifically the above general formula (a1), It may be composed of a copolymer having a repeating structure of at least one structural unit represented by general formula (a2), general formula (a3) and general formula (a4), and other repeating units. .

Examples of the other repeating units include acrylic acid esters, methacrylic acid esters, fluorine-containing acrylic acid esters, fluorine-containing methacrylic acid esters, styrene compounds, fluorine-containing styrene compounds, olefins, fluorine-containing olefins, norbornene compounds, and vinyl ethers. Examples thereof include repeating structures of structural units derived from at least one selected from the group consisting of fluorine vinyl ethers, oxiranes and silane compounds.

The copolymer of the present embodiment includes a copolymer of an ionic compound represented by at least one of general formula (A) and general formula (A') and a polymerizable compound.
Specific examples of the ionic compound include ionic compounds represented by at least one of the general formula (A1), general formula (A2), general formula (A3), or general formula (A4). .
The polymerizable compound may self-polymerize with each other, or may react with anions and/or cations of the polymerizable compound. The polymerizable compound may contain a monomer (hereinafter referred to as "secondary monomer") whose double bond is cleaved to form a secondary repeating unit. As a result, the curing treatment cleaves the double bonds of each other to form a copolymer ( copolymers).

As the polymerizable compound, a compound having a polymerizable functional group in the molecule, a monomer, a dimer thereof, an oligomer, a polymer, or a mixture thereof is used.

Specifically, examples of the polymerizable compound include acrylic acid esters, methacrylic acid esters, fluorine-containing acrylic acid esters, fluorine-containing methacrylic acid esters, styrene compounds, fluorine-containing styrene compounds, olefins, fluorine-containing olefins, norbornene compounds, vinyl ethers, At least one compound selected from the group consisting of fluorine-containing vinyl ethers, oxiranes and silane compounds can be used.
One of these may be used alone, or two or more of them may be mixed and used in any combination and ratio according to the application.

The repeating structure after polymerization in the compounds exemplified above will be described.
When the monomer is an oxirane, it becomes a repeating structure with an ether bond obtained by ring-opening polymerization of the oxirane after polymerization, and when the monomer is a silane, the silanol produced by hydrolyzing the silane after polymerization is It becomes a repeating structure having a siloxane bond (--Si--O--) obtained by dehydration condensation. When the monomer is any of the other exemplified compounds, it becomes a repeating structure formed by cleavage of the polymerizable double bond contained in the molecule after polymerization. In this case, the structure other than the polymerizable double bond does not change before and after the polymerization, and the original structure is maintained.

Each compound for synthesizing the copolymer will be described below.
As the acrylic acid ester or methacrylic acid ester, the ester side chain can be used without any particular limitation. Examples of known compounds include methyl acrylate or methacrylate, ethyl acrylate or methacrylate, n-propyl acrylate or methacrylate, and isopropyl acrylate. or methacrylate, n-butyl acrylate or methacrylate, isobutyl acrylate or methacrylate, n-hexyl acrylate or methacrylate, n-octyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, lauryl acrylate or methacrylate, 2-hydroxyethyl acrylate or methacrylate, 2 - alkyl esters of acrylic or methacrylic acid such as hydroxypropyl acrylate or methacrylate, acrylates or methacrylates containing ethylene glycol, propylene glycol, tetramethylene glycol groups, acrylic or methacrylate esters containing alkoxysilyl groups, tert-butyl acrylate or methacrylate, 3-oxocyclohexyl acrylate or methacrylate, adamantyl acrylate or methacrylate, alkyladamantyl acrylate or methacrylate, cyclohexyl acrylate or methacrylate, tricyclodecanyl acrylate or methacrylate, acrylate or methacrylate having a ring structure such as lactone ring or norbornene ring , polyethylene glycol diacrylate (e.g., Shin-Nakamura Chemical Co., Ltd. product names: A-200, A-400, A-600), urethane acrylate (e.g., Shin-Nakamura Chemical Co., Ltd. product name: UA- 122P, UA-4HA, UA-6HA, UA-6LPA, UA-11003H, UA-53H, UA-4200, UA-200PA, UA-33H, UA-7100, UA-7200) and the like.
Moreover, as said acrylic acid ester or methacrylic acid ester, bifunctional acrylate or bifunctional methacrylate, trifunctional or more polyfunctional acrylate or polyfunctional methacrylate can be used. As an example of these, the following compounds may be used.

Unsaturated amides such as acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide and diacetoneacrylamide, and acryloyl group-containing compounds such as acrylonitrile and methacrylonitrile can also be used. In addition, maleic acid, fumaric acid, maleic anhydride, etc. can also be used.

As the fluorine-containing acrylic acid ester or fluorine-containing methacrylic acid ester, for example, an acrylic acid ester or a methacrylic acid ester having a group having a fluorine atom at the α-position or ester site of an acryloyl group can be used. For example, monomers in which a fluorine-containing alkyl group is introduced at the α-position include a trifluoromethyl group, a trifluoroethyl group, a nonafluoro-n A monomer substituted with a -butyl group or the like is preferably employed.

On the other hand, in the case of a fluorine-containing acrylic ester or fluorine-containing methacrylic ester having a fluorine-containing group in the ester moiety, the fluorine-containing group is a perfluoroalkyl group or a fluoroalkyl group, and the ring carbon is a fluorine atom or a trifluoro A fluorine-containing cyclic group substituted with a methyl group, such as a fluorine-containing benzene ring, a fluorine-containing cyclopentane ring, a fluorine-containing cyclohexane ring, and a fluorine-containing cycloheptane ring.

Among the fluorine-containing allyl ester or fluorine-containing methacrylic acid ester units, particularly representative examples include 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, heptafluoroisopropyl acrylate, 1,1-dihydroheptafluoro-n-butyl acrylate, 1,1,5-trihydrooctafluoro-n-pentyl acrylate , 1,1,2,2-tetrahydrotridecafluoro-n-octyl acrylate, 1,1,2,2-tetrahydroheptadecafluoro-n-decyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2, 2,3,3-tetrafluoropropyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, heptafluoroisopropyl methacrylate, 1,1-dihydroheptafluoro-n-butyl methacrylate, 1,1, 5-trihydrooctafluoro-n-pentyl methacrylate, 1,1,2,2-tetrahydrotridecafluoro-n-octyl methacrylate, 1,1,2,2-tetrahydroheptadecafluoro-n-decyl methacrylate, perfluoro cyclohexylmethyl acrylate, perfluorocyclohexylmethyl methacrylate and the like. Also included are esters of acrylic acid or methacrylic acid in which the fluorine-containing group in the ester moiety is a fluorine atom-containing t-butyl group.

In addition, in the acrylic acid ester or fluorine-containing acrylic acid ester described above, an acrylic acid ester or fluorine-containing acrylic acid ester having a cyano group introduced at the α-position can also be used.

Examples of the styrene-based compound or fluorine-containing styrene-based compound include styrene, fluorinated styrene, hydroxystyrene, etc., styrene-based compounds obtained by adding hexafluoroacetone to the benzene ring, and hydrogen atoms of the benzene ring substituted with a trifluoromethyl group. Styrene, hydroxystyrene, the above styrenic compounds or fluorine-containing styrenic compounds having a halogen atom, an alkyl group, or a fluorine-containing alkyl group bonded to the α-position can be used.
Preferred monomers for polystyrene compounds include styrene, 4-hydroxystyrene, pentafluorostyrene, 2-trifluoromethylstyrene, 4-trifluoromethylstyrene, 3,5-bistrifluoromethylstyrene, 4-(1,1 , 1,3,3,3-hexafluoro-2-propanol)styrene and 3,5-bis(1,1,1,3,3,3-hexafluoro-2-propanol)styrene.

Examples of the olefin include ethylene and propylene, and examples of the fluoroolefin include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and hexafluoroisobutene.

The norbornene compound or fluorine-containing norbornene compound is a norbornene monomer having a mononuclear or plural nucleus structures, and these can be used without particular limitation. At this time, allyl alcohol, fluorine-containing allyl alcohol, acrylic acid, α-fluoroacrylic acid, methacrylic acid, all acrylic acid esters or methacrylic acid esters described herein, fluorine-containing acrylic acid esters or methacrylic acid esters, etc. A norbornene compound obtained by a Diels Alder addition reaction using an unsaturated compound, cyclopentadiene, and cyclohexadiene can be preferably used.

The above vinyl ether or fluorine-containing vinyl ether may have an alkyl group that may contain a hydroxy group such as, for example, a methyl group, an ethyl group, a hydroxyethyl group, a hydroxybutyl group, etc. Some or all of the atoms may be substituted with fluorine. In addition, cyclic vinyl ethers having an oxygen atom or a carbonyl bond in the cyclic structure, and monomers in which some or all of the hydrogen atoms of these cyclic vinyl ethers are substituted with fluorine atoms, such as cyclohexyl vinyl ether, can also be used. . Allyl ethers, vinyl esters, and vinyl silanes can also be used without particular limitations as long as they are known compounds. Preferred vinyl ethers are ethyl vinyl ether, butyl vinyl ether, diethyl vinyl orthoformate and diethylene glycol vinyl ether.

Specific examples of the oxiranes include ethylene oxide, epifluorohydrin, epichlorohydrin, epibromohydrin, 1,2-propylene oxide, 1,3-propylene oxide, 3,3,3-trifluoro- 1,2-propylene oxide, 1,2-epoxy-2-methylpropane, 1,2-epoxybutane, 3,4-epoxy-1-butene, 1,2-epoxypentane, 1,2-epoxyhexane, 1 , 2-epoxy-5-hexene, 1,2-epoxyoctane, 1,2-epoxytetradecane, 1,2-epoxydodecane, (2,2,3,3,4,4,5,5,6,6 ,7,7,8,8,9,9,9-heptadecafluorononyl) oxirane, cyclopentene oxide, cyclohexene oxide, glycidol, 2,3-dimethyloxirane, ethyl glycidyl ether, glycidyl propargyl ether, glycidyl isopropyl ether, allyl glycidyl ether, butyl glycidyl ether, diglycidyl ether, glycidyl phenyl ether, glycidyl (4-methoxyphenyl) ether, glycidyl (2-methylphenyl) ether, glycidyl (2,2,3,3-tetrafluoropropyl) ether, glycidyl (2,2,3,3,4,4,5,5-octafluoropentyl) ether, glycidyl octyl ether, glycidyl decyl ether, 2,3-dimethyl-2,3-epoxybutane, 3,3-dimethyl- 1,2-epoxybutane, glycidaldehyde diethyl acetal, 2-(4-fluorophenyl)oxirane, 2-(4-chlorophenyl)oxirane, 2-(4-bromophenyl)oxirane, 1,2-epoxyoctane, 3 ,4-epoxy-2-phenyl-1,1,1-trifluoro-2-butanol, benzyl glycidyl ether, 2-ethylhexyl glycidyl ether, epoxynorbornane, styrene oxide, 1,2,7,8-diepoxyoctane, Neopentyl glycol diglycidyl ether, bis[4-(glycidyloxy)phenyl]methane, sulfuryl glycidyl ether, 1,3-butanediene diepoxide, 1,4-butanediol diglycidyl ether, 2-methyl-2-vinyl Oxirane, resorcinol diglycidyl ether, trimethylene oxide, 3-methyl-3-oxetanemethanol, 3-ethyl-3-oxetanemethanol, 3,3-dimethyloxetane, 3-bromomethyl-3-methyloxetane, 3-oxetanone, 3 -bromooxetane, 3-iodooxetane and the like.
Oxiranes are preferably ethylene oxide, epifluorohydrin, epichlorohydrin, 1,2-propylene oxide, 1,3-propylene oxide, 3,3,3-trifluoro-1,2-propylene oxide, trimethylene oxide, more preferably ethylene oxide, 1,2-propylene oxide, 3,3,3-trifluoro-1,2-propylene oxide and trimethylene oxide, particularly preferably ethylene oxide and 1,2-propylene oxide is.

Trifunctional silanes are preferably used as the silanes. Phenyltrimethoxysilane, (4-methylphenyl)trimethoxysilane, (4-methoxyphenyl)trimethoxysilane, (4-methylbenzyl)trimethoxysilane, (4-methylbenzyl)trimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyl(tri-n-propoxy)silane, methyl(tri-iso-propoxy)silane, methyl(tri-n-butoxy)silane, methyl(tri-sec-butoxy)silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyl(tri-n-propoxy)silane, ethyl(tri-iso-propoxy)silane, ethyl(tri-n-butoxy)silane, ethyl(tri-sec-butoxy)silane, (n-propyl)trimethoxysilane, (n-propyl)triethoxysilane, (n-propyl)(tri-n-propoxy)silane, (n-propyl)(tri-iso-propoxy)silane, (n-propyl) ) (tri-n-butoxy)silane, (n-propyl)(tri-sec-butoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane.

Further, specific examples of silanes other than the above include bifunctional silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl(di-n-propoxy)silane, dimethyl(di-iso-propoxy)silane, dimethyl ( Di-n-butoxy)silane, dimethyl(di-sec-butoxy)silane, dimethyl(di-tert-butoxy)silane, dimethyldiphenoxysilane and the like can be mentioned. Among them, dimethyldimethoxysilane and dimethyldiethoxysilane are preferred.

Other specific examples of silanes include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, and tetra-sec-butoxysilane. , tetra-tert-butoxysilane, tetraphenoxysilane, tetrachlorosilane, and the like. Among them, tetramethoxysilane and tetraethoxysilane are preferred.
When trifunctional silanes or tetrafunctional silanes are used as the silanes, the polymer obtained after polymerization has a network structure as a whole.

Thus, the polymer of the present embodiment is an ionic compound represented by at least one of the general formula (A1), general formula (A2), general formula (A3), or general formula (A4), and the above-exemplified In the case of a copolymer with at least one polymerizable compound selected from the group consisting of compounds, at least one of general formula (a1), general formula (a2), general formula (a3) or general formula (a4) The content of the repeating structure represented by is, for the entire polymer, preferably 0.1 to 70% by mass, more preferably 0.3 to 50% by mass, particularly 0.5 to 30% by mass. preferable. By making it 0.1% by mass or more, there is a tendency to suppress deterioration in performance (capacitance) derived from the compound represented by at least one of the general formula (A) and the general formula (A'). , 70% by mass or less tends to suppress a decrease in the tensile strength of the polymer.

When the polymer of the present embodiment is the above copolymer, it may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. It may be a polymer. A random copolymer is preferable from the viewpoint of dispersing each characteristic appropriately rather than locally.

The molecular weight of the copolymer is a weight average molecular weight measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and is preferably 1,000 to 1,000,000, and preferably 3,000 to 100,000. is more preferred. By setting the weight average molecular weight to 1,000 or more, it is possible to suppress the decrease in strength as a polymer. On the other hand, by making it 1,000,000 or less, there is a tendency to suppress the decrease in capacitance presumed to be caused by the structure of the polymer.

The dispersity (Mw/Mn) is preferably 1.01 to 5.00, more preferably 1.01 to 4.00, and particularly preferably 1.01 to 3.00.
In the present specification, "-" means including the upper limit and the lower limit, unless otherwise specified.

[About mixing (blending) with other resins]
Using the polymer of the present embodiment by mixing (blending) it with "another resin" is one of the excellent aspects of the present embodiment.

The mixing (blending) will be described in detail below. As described in the above [copolymer], the molecular structure corresponding to the "other resin component" is in the form of "copolymer" of the present embodiment, general formula (a1), general formula (a2), general formula ( It may be incorporated into a polymer having a repeating structure of at least one structural unit represented by a3) and general formula (a4). It can be said that it is simple because it is not necessary to consider even the optimum conditions. A person skilled in the art can appropriately select whether to take the form of a copolymer or the form of a blend. In addition, this embodiment also includes a mode in which a copolymer is used as a polymer and other resins are blended separately.

When mixed and used in this way, the total mass of the entire polymer after mixing is represented by general formula (a1), general formula (a2), general formula (a3) and general formula (a4) of the present embodiment. The weight percent of the repeating structure of at least one structural unit of the is usually 0.1 to 70 weight percent, more preferably 0.3 to 50 weight percent, and particularly preferably 0.5 to 30 weight percent. The remainder is "other resins" to be described later. By making it 0.1% by mass or more, there is a tendency to suppress deterioration in performance (capacitance) derived from the compound represented by at least one of the general formula (A) and the general formula (A'). , 70 mass or less, there is a tendency that the decrease in the tensile strength of the resin can be suppressed.

The molecular weight of the "other resin" used in the above mixture (blend) is preferably 1,000 to 1,000,000 as a weight average molecular weight measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and 3 ,000 to 100,000 is more preferred. By setting the weight-average molecular weight to 1,000 or more, a decrease in strength as a polymer can be suppressed. On the other hand, by setting the weight average molecular weight to 1,000,000 or less, the entanglement of the polymer chains increases, and it is possible to suppress the decrease in the capacitance which is presumed to be caused by the aggregation of ions in the polymer.

The dispersity (Mw/Mn) is preferably 1.01 to 5.00, more preferably 1.01 to 4.00, and particularly preferably 1.01 to 3.00.

"Other resins" used for mixing include acrylic acid esters, methacrylic acid esters, fluorine-containing acrylic acid esters, fluorine-containing methacrylic acid esters, styrene compounds, fluorine-containing styrene compounds, olefins, fluorine-containing olefins, norbornene compounds, vinyl ethers, etc. Resins having a repeating structure of structural units derived from at least one selected from the group consisting of fluorine vinyl ethers, oxiranes and silane compounds can be mentioned.

Specific resins include resins having a repeating structure of structural units derived from the compounds (monomers) exemplified in the above [copolymer].

[Curable composition]
The curable composition of this embodiment contains the polymerizable ionic liquid and a polymerization initiator. As the polymerizable ionic liquid, the polymerizable ionic liquid represented by at least one of the general formula (A) and the general formula (A'), specifically, the general formula (A1), the general formula (A2 ), a polymerizable ionic liquid represented by general formula (A3) or general formula (A4) is used. This curable composition can further contain a compound having a polymerizable functional group in the molecule (polymerizable compound), if necessary.

A radical polymerization initiator or a cationic polymerization initiator can be used as the polymerization initiator. Each polymerization initiator can be used alone or in combination. In addition, by using an additive together with the polymerization initiator, it is possible to carry out living polymerization in some cases, and known additives can be used.

Radical polymerization initiators include photoradical polymerization initiators (photopolymerization initiators) that generate radicals by irradiation with energy rays such as ultraviolet rays, or thermal radical polymerization initiators that generate radicals by heating (thermal polymerization initiators). can be used.

As the photopolymerization initiator, known ones can be used. For example, intramolecular cleavage type in which intramolecular bonds are cleaved by absorption of high energy rays to generate radicals, tertiary amines, ethers, and the like. There is a hydrogen abstraction type that generates radicals by using a hydrogen donor in combination, and any of them may be used. For example, intramolecularly cleaved 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Darocur 1173) is irradiated with light (especially light in the ultraviolet region). , the carbon-carbon bond is cleaved to generate a radical. As for the hydrogen-abstraction type, benzophenone, methyl orthobenzoinbenzoate, 4-benzoyl-4'-methyldiphenylsulfide, camphorquinone, and the like generate radicals through a bimolecular reaction with a hydrogen donor.

The thermal radical polymerization initiator is a compound that generates radicals by cleaving the bond in the molecule by heating, and known ones can be used. Alternatively, benzoyl peroxide (BPO), which is an organic peroxide, can be exemplified.

As the cationic polymerization initiator, a compound that generates acid by irradiation with energy rays such as ultraviolet rays (photoacid generator) or a compound that generates acid by heating (thermal acid generator) can be used.

Compounds (photoacid generators) that generate acids upon irradiation with energy rays such as ultraviolet rays include aromatic sulfonic acids, aromatic iodoniums, aromatic diazoniums, aromatic ammoniums, thianthreniums, thioxanthoniums, (2, At least one cation selected from the group consisting of 4-cyclopentadien-1-yl)(1-methylethylbenzene)iron and from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, and pentafluorophenylborate It is an onium salt consisting of at least one selected anion pair. These photoacid generators can be used alone or in combination of two or more.

Photoacid generators include bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, and diphenyliodonium hexafluorophosphate. Especially preferred.

Commercially available photoacid generators include, for example, San-Apro product names: CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S, Dow Chemical Japan Co., Ltd. product names: Cyracure photocuring initiator UVI-6990, Cyracure photocuring initiator UVI-6992, Cyracure photocuring initiator UVI-6976, product names manufactured by ADEKA Co., Ltd.: Adeka Optomer SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP-172, Adeka Optomer SP-300, product names manufactured by Nippon Soda Co., Ltd.: CI-5102, CI-2855, product names manufactured by Sanshin Chemical Industry Co., Ltd.: San-Aid SI -60L, San-Aid SI-80L, San-Aid SI-100L, San-Aid SI-110L, San-Aid SI-180L, San-Aid SI-110, San-Aid SI-180, Lamberti product names: Esacure 1064, Esacure 1187, Chiba Specialty - Product name manufactured by Chemicals Co., Ltd.: Irgacure 250 and the like.

Examples of compounds that generate acids by heating (thermal acid generators) include benzylsulfonium salts, thiophenium salts, thiolanium salts, benzylammonium salts, pyridinium salts, hydrazinium salts, carboxylic acid esters, sulfonic acid esters, and amine imides. can do. Commercially available thermal acid generators include, for example, product names of ADEKA Corporation: Adeka Opton CP77 and Adeka Opton CP66, product names of Nippon Soda Co., Ltd.: CI-2639 and CI-2624, and products of Sanshin Chemical Industry Co., Ltd. Product names: San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L can also be used.

The amount of the polymerization initiator used is, for example, 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of the polymerizable ionic liquid.
Further, it is, for example, 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, with respect to a total of 100 parts by mass of the polymerizable ionic liquid and the polymerizable compound.

Examples of the polymerizable compound include acrylic acid esters, methacrylic acid esters, fluorine-containing acrylic acid esters, fluorine-containing methacrylic acid esters, styrene compounds, fluorine-containing styrene compounds, olefins, fluorine-containing olefins, norbornene compounds, vinyl ethers, fluorine-containing It can contain one or more compounds selected from the group consisting of vinyl ethers, oxiranes and silane compounds. These may be used alone or in combination of two or more.
Specific polymerizable compounds include the polymerizable compounds exemplified in the above [Copolymer].

The weight average molecular weight of the polymerizable compound is, for example, 1,000 to 1,000,000, preferably 3,000 to 500, as measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. 000, more preferably 5,000 to 300,000.

In addition to the polymerizable ionic liquid and the polymerization initiator, the curable composition of the present embodiment may contain other components, if necessary.
Such other components include, for example, reactive functional group-containing low-molecular-weight organic compounds and polymer compounds, but are not particularly limited thereto.

Examples of the reactive functional group-containing low-molecular-weight organic compounds include compounds that are widely used as main agents, curing agents, etc. in the field of adhesives and paints. Unsaturated nitrile group, conjugated diene, carboxylic acid vinyl ester group, carboxyl group, carbonyl group, epoxy group, isocyanate group, hydroxy group, amide group, cyano group, amino group, chloromethyl group, glycidyl ether group, ester group, formyl group, nitrile group, nitro group, carbodiimide group, oxazoline group, carbon-carbon double bond-containing group, carbon-carbon triple bond-containing group and the like.

Specific examples of the reactive functional group-containing low-molecular-weight organic compounds include (meth)acrylic acid, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl acrylate, methyl (meth)acrylate and the like (meth) ) acrylic acid-based low-molecular-weight compounds; nitrile-based low-molecular-weight compounds such as acrylonitrile, methacrylonitrile, ethacrylonitrile, maleonitrile, fumaronitrile; amide-based low-molecular-weight compounds such as (meth)acrylamide, N-methyl(meth)acrylamide, and methylolacrylamide Compound; isocyanate-based low-molecular-weight compounds such as toluene diisocyanate and hexamethylene diisocyanate; carbon-carbon double-bond-containing low-molecular-weight compounds such as styrene, butadiene, vinyl chloride and vinyl acetate; 1-butyn-1-ol, 1,6- carbon-carbon triple bond-containing low-molecular-weight compounds such as heptadiyne;

As the polymer compound, for example, at least one selected from fluorine resins, acrylic resins, polyester resins, epoxy resins, melamine resins, silicone resins, polyurethane resins, and the like can be used. These polymer compounds may or may not have reactive functional groups.

Examples of polymer compounds having reactive functional groups include polyether-based polymer compounds. The polyether-based polymer compound is a polymer compound having a polymerizable functional group at the molecular terminal, at the side chain, or at the molecular terminal and the side chain. As the polyether polymer compound, those having two or more, preferably three or more polymerizable functional groups in the molecule can be used.
Examples of the polymerizable functional group include alkenyl groups such as (meth)acryloyl group ((meth)acrylic acid residue), vinyl group, propenyl group, and (meth)allyl group.
Although the molecular weight (Mw) of the polyether polymer compound is not particularly limited, it is usually about 500-500,000, preferably about 2000-300,000.

As the polymerizable compound, a compound having a polymerizable functional group at the molecular end, such as the polyether polymer compound, can be used.

The polymerizable ionic liquid, polymer, copolymer, and curable composition of the present embodiment can be applied to various uses as electrochemical materials. For example, it can be applied to electrochemical devices such as electric double layer capacitors (capacitors), lithium ion batteries, fuel cells, solar cells, actuators, and transparent conductive films. It is also expected to be applied to antistatic materials, solvents, _CO2 absorbents, lubricants, ion exchange membranes, gas separation membranes, acid catalysts, toners, antibacterial agents, adhesives, sensors, etc.

Moreover, the curable composition may contain various additives according to each application. Examples of additives include inorganic fillers such as silica, alumina, titania, aluminum nitride and boron nitride, fillers such as carbon nanotubes, polymerization inhibitors, antifoaming agents, leveling agents, solvents and pigments. One of these may be used, or two or more may be used in combination. Since such a curable composition can exhibit a desired function with an additive, it is expected to be utilized as a functional composite material in which a polymerizable ionic liquid and an additive are combined.
The amount of these additives used is 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, particularly preferably 3 to 10% by mass, based on 100% by mass of the curable composition.

The curable composition can be used in various forms such as varnish (solution), paste, film, and particles. The cured composition can be shaped to give it a suitable shape, depending on the application.

The polymerizable ionic liquid can have compatibility with various organic compounds. In addition, the polymerizable ionic liquid can also have the ability to dissolve various inorganic compounds. Therefore, the curable composition can use various components together with the polymerizable ionic liquid.

[Materials for electrochemical devices]
The polymer, resin mixture, and cured product of the curable composition of the present invention described above can be used as materials for electrochemical devices. As the electrochemical device, for example, it can be applied to electric devices such as a power generation device, a capacitive device, and a sensor device, particularly micro devices (semiconductor devices).

One form of an electrochemical device material is obtained by a curing step in which the curable composition is subjected to a curing treatment. That is, the electrochemical device exemplified here includes a cured product of the curable composition described above.

As the curing treatment, known curing/polymerization means can be used, and for example, at least one of light irradiation and heat treatment can be included. The curable composition can have at least one of photocurable and thermosetting properties. Appropriate means for the curing treatment are selected according to the curing properties of the curable composition.

By the above light irradiation, it is possible to photo-cure the curable composition by promoting the polymerization reaction using the light energy of the ultraviolet light. The polymerization reaction can proceed efficiently by containing a photopolymerization initiator. A heat treatment may be performed along with the light irradiation. In addition, the above heat treatment can be performed by heating at 50° C. to 150° C., for example.

Further, in the method for producing a material for an electrochemical device, the curing treatment can be performed while an electric field is applied to the curable composition. This makes it possible to provide an electrochemical device material with excellent properties. In addition, depending on the composition, it is possible to stably realize an electrochemical device material having electric polarization inside.

Further, as an example of the method for producing the material for an electrochemical device, there is a step of sandwiching a curable composition containing a polymerizable ionic liquid between a pair of counter electrodes, and applying a voltage to the counter electrodes to cure the curable composition. and a curing step of performing a curing treatment on the adhesive composition. This polymerizable ionic liquid contains at least one compound represented by the general formula (A1), general formula (A2), general formula (A3) or general formula (A4).

Further, in the above method for producing a material for an electrochemical device, one of the opposing electrodes may be a transparent electrode that transmits light. Thereby, the curing step can be performed in a state in which the curable composition is sandwiched between the counter electrodes. As a result, lot-to-lot variation can be reduced and manufacturing yield can be increased.
Further, in the method for producing a material for an electrochemical device, the curing step can be performed by sandwiching the curable composition between opposing electrodes and heating the electrodes together while applying an electric field for polarization treatment. As a result, lot-to-lot variation can be reduced and manufacturing yield can be increased.

［上記一般式（Ａ）中、
Ｒ _ｆ はフッ素原子、炭素数１～１０の直鎖状、または炭素数３～１２の分岐状もしくは環状のパーフルオロアルキル基を表す。
Ｗは２価の連結基を表し、単結合、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、または－Ｃ（＝Ｏ）－ＮＲ－（Ｒは水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基）を表す。
ｎは０～５の整数を表す。
Ｍ ^＋ は１価のカチオンを表す。
Ｘは重合性置換基であり、一般式（Ｂ１）に示すビニル基、一般式（Ｂ２）に示すエポキシ基、一般式（Ｂ３）に示すシリル基、一般式（Ｂ４）に示す多価アクリル基、一般式（Ｂ５）に示す多価エポキシ基、または一般式（Ｂ６）に示すノルボルニル基を表す。

上記一般式（Ｂ１）中、Ｒ ^Ｂ１ は水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表し、炭素原子のいずれかが酸素原子で置換されていてもよく、また、アルキル基の水素原子が酸素原子で置換されていてもよい。
上記一般式（Ｂ２）中、Ｒ ^Ｂ２ は水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表す。
上記一般式（Ｂ３）中、Ｒ ^Ｂ３ 、Ｒ ^Ｂ４ およびＲ ^Ｂ５ はそれぞれ独立に炭素数１～１０の直鎖アルキル基を有するアルコキシ基、炭素数１～１０のアルキル基、炭素数６～１２の芳香環基、水酸基、または塩素原子を表し、少なくとも二つのアルコキシ基、塩素原子、水酸基、またはこれらの組み合わせを含む。
上記一般式（Ｂ４）中、Ｒ ^Ｂ６ は水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表す。
上記一般式（Ｂ４）および一般式（Ｂ５）中、Ｚ ^１ およびＺ ^２ はそれぞれ３価以上の連結基を表し、炭素数１～１８の鎖状または環状の置換アルキル基を表し、いずれかの炭素原子が酸素原子もしくは窒素原子で置換されていてもよく、炭素―炭素結合が不飽和結合を含んでいてもよく、芳香族環を含んでもよい。
ｍおよびｌは２～５の整数を表す。］

［上記一般式（Ａ'）中、
Ｒ _ｆ はフッ素原子、炭素数１～１０の直鎖状、または炭素数３～１２の分岐状もしくは環状のパーフルオロアルキル基を表す。
Ｌは２価の連結基を表し、単結合、－Ｃ（＝Ｏ）－Ｏ－、または－Ｃ（＝Ｏ）－ＮＲ－（Ｒは水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基）を表す。
Ｒ ^Ａ１ 、Ｒ ^Ａ２ およびＲ ^Ａ３ は各々独立に、水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表し、Ｒ ^Ａ１ 、Ｒ ^Ａ２ およびＲ ^Ａ３ のうちのいずれか２つ以上が相互に結合して式中の炭素－炭素二重結合と共に環を形成してもよい。
Ｙは２価の連結基を表し、単結合、－Ｏ－Ｃ（＝Ｏ）－、－ＮＲ－Ｃ（＝Ｏ）－（Ｒは水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基）、炭素数６～１２のアリーレン基、または－Ｏ－Ｃ（＝Ｏ）－もしくは－ＮＲ－Ｃ（＝Ｏ）－と炭素数６～１２のアリーレン基とを組み合わせた連結基を表す。
ｍは１～６の整数を表し、ｎは０～５の整数を表す。
Ｍ ^＋ は１価のカチオンを表す。］
２． １．に記載の重合性イオン液体であって、
前記１価のカチオンが、水素イオン、アンモニウムイオン、ホスホニウムイオン、イミダゾリウムイオン、およびピリジニウムイオンのカチオンからなる群から選択される一種以上を含む、重合性イオン液体。
３． １．または２．に記載の重合性イオン液体であって、
前記１価のカチオンが、重合性官能基含有カチオンを含む、重合性イオン液体。
４． １．から３．のいずれか１つに記載の重合性イオン液体であって、
前記１価のカチオンが、下記一般式（Ｃ１）で表されるアンモニウムカチオン、下記一般式（Ｃ２）で表されるホスホニウムカチオン、下記一般式（Ｃ３）で表されるイミダゾリウムカチオン、および下記一般式（Ｃ４）で表されるピリジニウムカチオンからなる群から選択される一種以上を含む、重合性イオン液体。

［上記一般式（Ｃ１）中、Ｒ ^１０ 、Ｒ ^１１ 、Ｒ ^１２ およびＲ ^１３ は各々独立に、水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、炭素数６～１２の芳香環基もしくは置換芳香環基、または重合性官能基含有基を表す。また、Ｒ ^１０ 、Ｒ ^１１ 、Ｒ ^１２ およびＲ ^１３ のうち二つ以上が結合し、環状構造を形成していてもよい。］

［上記一般式（Ｃ２）中、Ｒ ^１４ 、Ｒ ^１５ 、Ｒ ^１６ およびＲ ^１７ は各々独立に、水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、炭素数６～１２の芳香環基もしくは置換芳香環基、または重合性官能基含有基を表す。］

［上記一般式（Ｃ３）中、Ｒ ^１８ 、Ｒ ^１９ 、Ｒ ^２０ 、Ｒ ^２１ およびＲ ^２２ は各々独立に、水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、炭素数６～１２の芳香環基もしくは置換芳香環基、または重合性官能基含有基を表す。］

［上記一般式（Ｃ４）中、Ｒ ^２３ 、Ｒ ^２４ 、Ｒ ^２５ 、Ｒ ^２６ 、Ｒ ^２７ およびＲ ^２８ は各々独立に、水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、炭素数６～１２の芳香環基もしくは置換芳香環基、または重合性官能基含有基を表す。］
５． ４．に記載の重合性イオン液体であって、
上記重合性官能基含有基が、下記の一般式（Ｃ５）で表される基を備える、重合性イオン液体。

［上記一般式（Ｃ５）中、
Ｒ ^２９ 、Ｒ ^３０ およびＲ ^３１ は各々独立に、水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表し、Ｒ ^２９ 、Ｒ ^３０ およびＲ ^３１ のうちのいずれか２つ以上が相互に結合して式（Ｃ５）中の炭素－炭素二重結合と共に環を形成してもよい。
Ｚは２価の連結基を表し、炭素数１～１０のアルキレン基、－Ｏ－Ｃ（＝Ｏ）－、－ＮＲ－Ｃ（＝Ｏ）－（Ｒは水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基）、または－Ｏ－Ｃ（＝Ｏ）－もしくは－ＮＲ－Ｃ（＝Ｏ）－と炭素数６～１２のアリーレン基とを組み合わせた連結基を表す。］
６． 下記一般式（ａ）、および一般式（ａ'）の少なくとも一つで表される構造単位の繰り返し構造を有する、ポリマー。

［上記一般式（ａ）中、
Ｒ _ｆ はフッ素原子、炭素数１～１０の直鎖状、または炭素数３～１２の分岐状もしくは環状のパーフルオロアルキル基を表す。
Ｗは２価の連結基を表し、単結合、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、または－Ｃ（＝Ｏ）－ＮＲ－（Ｒは水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基）を表す。
ｎは０～５の整数を表す。
Ｍ ^＋ は１価のカチオンを表す。
ｘは重合性置換基が反応した下記一般式（ｂ１）、一般式（ｂ２）、一般式（ｂ３）、一般式（ｂ４）、一般式（ｂ５）、または一般式（ｂ６）の構造を表す。

上記一般式（ｂ１）中、Ｒ ^ｂ１ は水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表し、炭素原子のいずれかが酸素原子で置換されていてもよく、また、アルキル基の水素原子が酸素原子で置換されていてもよい。
上記一般式（ｂ２）中、Ｒ ^ｂ２ は水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表す。
上記一般式（ｂ３）中、Ｒ ^ｂ３ は炭素数１～１０の直鎖アルキル基を有するアルコキシ基、炭素数１～１０のアルキル基、炭素数６～１２の芳香環基、水酸基、または塩素原子を表す。
上記一般式（ｂ４）中、Ｒ ^ｂ６ は水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表す。
上記一般式（ｂ４）および（ｂ５）中、Ｚ ^１ およびＺ ^２ はそれぞれ３価以上の連結基を表し、炭素数１～１８の鎖状または環状の置換アルキル基を表し、いずれかの炭素原子が酸素原子もしくは窒素原子で置換されていてもよく、炭素―炭素結合が不飽和結合を含んでいてもよく、芳香族環を含んでもよい。
ｍおよびｌは２～５の整数を表す。］

［上記一般式（ａ'）中、
Ｒ _ｆ はフッ素原子、炭素数１～１０の直鎖状、または炭素数３～１２の分岐状もしくは環状のパーフルオロアルキル基を表す。
Ｌは２価の連結基を表し、単結合、－Ｃ（＝Ｏ）－Ｏ－、または－Ｃ（＝Ｏ）－ＮＲ－（Ｒは水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基）を表す。
Ｒ ^ａ１ 、Ｒ ^ａ２ およびＲ ^ａ３ は各々独立に、水素原子、ハロゲン原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基を表し、Ｒ ^ａ１ 、Ｒ ^ａ２ およびＲ ^ａ３ のうちのいずれか２つ以上が相互に結合して環状構造を形成してもよい。
Ｙは２価の連結基を表し、単結合、－Ｏ－Ｃ（＝Ｏ）－、－ＮＲ－Ｃ（＝Ｏ）－（Ｒは水素原子、炭素数１～１０のアルキル基もしくは置換アルキル基、または炭素数６～１２の芳香環基もしくは置換芳香環基）、炭素数６～１２のアリーレン基、または－Ｏ－Ｃ（＝Ｏ）－もしくは－ＮＲ－Ｃ（＝Ｏ）－と炭素数６～１２のアリーレン基とを組み合わせた連結基を表す。
ｍは１～６の整数を表し、ｎは０～５の整数を表す。
Ｍ ^＋ は１価のカチオンを表す。］
７． ６．に記載のポリマーであって、
アクリル酸エステル、メタクリル酸エステル、含フッ素アクリル酸エステル、含フッ素メタクリル酸エステル、スチレン化合物、含フッ素スチレン化合物、オレフィン、含フッ素オレフィン、ノルボルネン化合物、ビニルエーテル、含フッ素ビニルエーテル、オキシラン類及びシラン化合物からなる群から選択される少なくとも一種由来の構造単位の繰り返し構造を有する、ポリマー。
８． １．～５．のいずれか一つに記載の重合性イオン液体と、
重合開始剤と、
を含む、硬化性組成物。
９． ８．に記載の硬化性組成物であって、さらに重合性化合物を含む、硬化性組成物。
１０． ９．に記載の硬化性組成物であって、
前記重合性化合物が、
アクリル酸エステル、メタクリル酸エステル、含フッ素アクリル酸エステル、含フッ素メタクリル酸エステル、スチレン化合物、含フッ素スチレン化合物、オレフィン、含フッ素オレフィン、ノルボルネン化合物、ビニルエーテル、含フッ素ビニルエーテル、オキシラン類及びシラン化合物からなる群より選ばれる一種以上を含む、硬化性組成物。
１１． ９．または１０．に記載の硬化性組成物であって、
前記重合性化合物の重量平均分子量が、１，０００以上１，０００，０００以下である、硬化性組成物。
１２． ９．から１１．のいずれか１つに記載の硬化性組成物であって、
前記重合性化合物が、末端に重合性官能基を有する、硬化性組成物。
１３． ８．から１２．のいずれか１つに記載の硬化性組成物の硬化物からなる電気化学素子用材料。
１４． １．～５．のいずれか一つに記載の重合性イオン液体を含む、帯電防止材料。
[Antistatic material]
The polymerizable ionic liquid, polymer, copolymer and curable composition of this embodiment can be applied to antistatic materials.
As compared with the polymerizable ionic liquid and the non-polymerizable ionic liquid of the present embodiment, the durability as an antistatic material is excellent at high temperatures. Although the detailed mechanism is not clear, it is considered that the polymerizable anion is immobilized in the polymer by copolymerization, which increases the durability and leads to suppression of bleeding out and the like.
In addition, in the examples described later, the reason why the immobilization does not cause the loss of conductivity and antistatic performance is considered to be that cations are immobilized or ions are supplemented from moisture in the atmosphere.
The antistatic material is not particularly limited, and may be used in the form of a sheet, film, solution, powder, or the like. Specifically, the antistatic material may be used, for example, as an antistatic agent, which is one of additives, or may be used as a single-layer or multi-layered antistatic layer or antistatic film. Antistatic agents can be used in combination with other components, and antistatic layers and antistatic films can be used by laminating with other layers and films.
Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than those described above can also be adopted.
Examples of reference forms are added below.
1. A polymerizable ionic liquid containing a compound represented by at least one of the following general formula (A) and general formula (A').

[In the above general formula (A),
R _f represents a fluorine atom, a linear C 1-10, or a branched or cyclic C 3-12 perfluoroalkyl group.
W represents a divalent linking group, a single bond, -C(=O)-, -C(=O)-O-, or -C(=O)-NR- (R is a hydrogen atom, has 1 carbon atom ~10 alkyl group or substituted alkyl group, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms).
n represents an integer of 0 to 5;
M ⁺ represents a monovalent cation.
X is a polymerizable substituent, a vinyl group represented by general formula (B1), an epoxy group represented by general formula (B2), a silyl group represented by general formula (B3), and a polyvalent acrylic group represented by general formula (B4). , represents a polyepoxy group represented by general formula (B5) or a norbornyl group represented by general formula (B6).

In the above general formula (B1), R ^B1 represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, may be substituted with an oxygen atom, and a hydrogen atom of an alkyl group may be substituted with an oxygen atom.
In general formula (B2) above, R ^{2 B2} represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms.
In the above general formula (B3), R ^B3 , R ^B4 and R ^B5 are each independently an alkoxy group having a straight-chain alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 6 to 12 carbon atoms. represents an aromatic ring group, a hydroxyl group, or a chlorine atom, and contains at least two alkoxy groups, chlorine atoms, hydroxyl groups, or a combination thereof;
In general formula (B4) above, R ^{1 B6} represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms.
In general formula (B4) and general formula (B5) above, Z ¹ and Z ² each represent a trivalent or higher linking group and represent a chain or cyclic substituted alkyl group having 1 to 18 carbon atoms, Carbon atoms may be substituted with oxygen atoms or nitrogen atoms, carbon-carbon bonds may contain unsaturated bonds, and aromatic rings may be contained.
m and l represent an integer of 2-5. ]

[In the above general formula (A′),
R _f represents a fluorine atom, a linear C 1-10, or a branched or cyclic C 3-12 perfluoroalkyl group.
L represents a divalent linking group, a single bond, -C(=O)-O-, or -C(=O)-NR- (R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms).
R ^A1 , R ^A2 and R ^A3 each independently represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, Any two or more of R ^A1 , R ^A2 and R ^A3 may bond together to form a ring together with the carbon-carbon double bond in the formula.
Y represents a divalent linking group, a single bond, -OC(=O)-, -NR-C(=O)- (R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group , or an aromatic ring group or a substituted aromatic ring group having 6 to 12 carbon atoms), an arylene group having 6 to 12 carbon atoms, or -O-C(=O)- or -NR-C(=O)- and the number of carbon atoms It represents a linking group in which 6 to 12 arylene groups are combined.
m represents an integer of 1-6, and n represents an integer of 0-5.
M ⁺ represents a monovalent cation. ]
2. 1. The polymerizable ionic liquid according to
A polymerizable ionic liquid, wherein the monovalent cations include one or more selected from the group consisting of hydrogen ions, ammonium ions, phosphonium ions, imidazolium ions, and pyridinium ions.
3. 1. or 2. The polymerizable ionic liquid according to
A polymerizable ionic liquid, wherein the monovalent cation includes a polymerizable functional group-containing cation.
4. 1. to 3. The polymerizable ionic liquid according to any one of
The monovalent cation is an ammonium cation represented by the following general formula (C1), a phosphonium cation represented by the following general formula (C2), an imidazolium cation represented by the following general formula (C3), and the following general A polymerizable ionic liquid containing one or more selected from the group consisting of pyridinium cations represented by formula (C4).

[In the above general formula (C1), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, an aromatic ring group having 6 to 12 carbon atoms, Alternatively, it represents a substituted aromatic ring group or a polymerizable functional group-containing group. Also, two or more of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may combine to form a cyclic structure. ]

[In the above general formula (C2), R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, an aromatic ring group having 6 to 12 carbon atoms, Alternatively, it represents a substituted aromatic ring group or a polymerizable functional group-containing group. ]

[In the above general formula (C3), R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, represents an aromatic ring group, a substituted aromatic ring group, or a polymerizable functional group-containing group. ]

[In the general formula (C4), R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are each independently a hydrogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, 1 to 12 aromatic ring groups or substituted aromatic ring groups, or polymerizable functional group-containing groups. ]
5. 4. The polymerizable ionic liquid according to
A polymerizable ionic liquid, wherein the polymerizable functional group-containing group comprises a group represented by the following general formula (C5).

[In the above general formula (C5),
R ²⁹ , R ³⁰ and R ³¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, Any two or more of R 29 , R 30 and R 31 may bond together to form a ring together with the carbon-carbon double bond in ^formula ( ^C5 ) ^.
Z represents a divalent linking group, an alkylene group having 1 to 10 carbon atoms, -O-C(=O)-, -NR-C(=O)- (R is a hydrogen atom, a alkyl group or substituted alkyl group, or aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms), or -OC(=O)- or -NR-C(=O)- and 6 to 12 carbon atoms represents a linking group in combination with an arylene group of ]
6. A polymer having a repeating structure of structural units represented by at least one of the following general formula (a) and general formula (a').

[In the above general formula (a),
R _f represents a fluorine atom, a linear C 1-10, or a branched or cyclic C 3-12 perfluoroalkyl group.
W represents a divalent linking group, a single bond, -C(=O)-, -C(=O)-O-, or -C(=O)-NR- (R is a hydrogen atom, has 1 carbon atom ~10 alkyl group or substituted alkyl group, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms).
n represents an integer of 0 to 5;
M ⁺ represents a monovalent cation.
x represents the structure of the following general formula (b1), general formula (b2), general formula (b3), general formula (b4), general formula (b5), or general formula (b6) in which the polymerizable substituent has reacted .

In the above general formula (b1), R ^b1 represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, may be substituted with an oxygen atom, and a hydrogen atom of an alkyl group may be substituted with an oxygen atom.
In general formula (b2) above, Rb2 ^represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms.
In the above general formula (b3), R ^b3 is an alkoxy group having a linear alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aromatic ring group having 6 to 12 carbon atoms, a hydroxyl group, or a chlorine atom. represents
In general formula (b4) above, Rb6 ^represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms.
In the above general formulas (b4) and (b5), Z ¹ and Z ² each represent a trivalent or higher linking group, a chain or cyclic substituted alkyl group having 1 to 18 carbon atoms, and any carbon atom may be substituted with an oxygen atom or a nitrogen atom, the carbon-carbon bond may contain an unsaturated bond, or it may contain an aromatic ring.
m and l represent an integer of 2-5. ]

[In the above general formula (a′),
R _f represents a fluorine atom, a linear C 1-10, or a branched or cyclic C 3-12 perfluoroalkyl group.
L represents a divalent linking group, a single bond, -C(=O)-O-, or -C(=O)-NR- (R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms).
R ^a1 , R ^a2 and R ^a3 each independently represent a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, Any two or more of R ^a1 , R ^a2 and R ^a3 may combine with each other to form a cyclic structure.
Y represents a divalent linking group, a single bond, -OC(=O)-, -NR-C(=O)- (R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group , or an aromatic ring group or a substituted aromatic ring group having 6 to 12 carbon atoms), an arylene group having 6 to 12 carbon atoms, or -O-C(=O)- or -NR-C(=O)- and the number of carbon atoms It represents a linking group in which 6 to 12 arylene groups are combined.
m represents an integer of 1-6, and n represents an integer of 0-5.
M ⁺ represents a monovalent cation. ]
7. 6. A polymer according to
Consisting of acrylic acid ester, methacrylic acid ester, fluorine-containing acrylic acid ester, fluorine-containing methacrylic acid ester, styrene compound, fluorine-containing styrene compound, olefin, fluorine-containing olefin, norbornene compound, vinyl ether, fluorine-containing vinyl ether, oxiranes and silane compounds A polymer having a repeating structure of structural units derived from at least one selected from the group.
8. 1. ~ 5. The polymerizable ionic liquid according to any one of
a polymerization initiator;
A curable composition comprising:
9. 8. The curable composition according to 1, further comprising a polymerizable compound.
10. 9. A curable composition according to
The polymerizable compound is
Consisting of acrylic acid ester, methacrylic acid ester, fluorine-containing acrylic acid ester, fluorine-containing methacrylic acid ester, styrene compound, fluorine-containing styrene compound, olefin, fluorine-containing olefin, norbornene compound, vinyl ether, fluorine-containing vinyl ether, oxiranes and silane compounds A curable composition comprising one or more selected from the group.
11. 9. or 10. A curable composition according to
The curable composition, wherein the polymerizable compound has a weight average molecular weight of 1,000 or more and 1,000,000 or less.
12. 9. to 11. The curable composition according to any one of
The curable composition, wherein the polymerizable compound has a polymerizable functional group at its terminal.
13. 8. to 12. A material for an electrochemical device comprising a cured product of the curable composition according to any one of .
14. 1. ~ 5. An antistatic material comprising the polymerizable ionic liquid according to any one of.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to the description of these Examples. Moreover, the present invention is not limited to the above-described embodiments, and includes modifications, improvements, etc. within the scope of achieving the object of the present invention.
<Preparation of ionic liquid>
[Example 1]
A dropping funnel and a condenser (refrigerant temperature: -5°C) were attached to a 200 ml three-necked flask, 5.00 g (33.5 mmol) of trifluoromethanesulfonylamide and 66 ml of acetonitrile were added, and 7.12 g (70.4 mmol) of triethylamine was added. rice field. While cooling with an ice bath, 3.18 g (35.2 mmol) of acrylic acid chloride was added dropwise thereto, and after the dropwise addition, the temperature was raised to room temperature and the mixture was stirred for 1 hour. After the reaction, 50 g of water was added, and concentrated hydrochloric acid was added so as to adjust the pH to 1. The aqueous layer was extracted with 50 ml of MTBE three times, and the resulting organic layer was concentrated under reduced pressure and then dried in vacuo to obtain 6.92 g of the compound represented by the following formula as white crystals. The obtained crude product was directly used for the next reaction without being purified.

6.92 g of the acrylamides obtained above, 7 mg of phenothiazine, and 45 ml of acetonitrile were placed in a 100 ml flask, and 4.61 g (32.2 mmol) of [2-(acryloyloxy)ethyl]dimethylamine was added and stirred at room temperature for 30 minutes. bottom. After the reaction, the reaction mixture was concentrated under reduced pressure at 40° C. or less and vacuum-dried to obtain 10.44 g (30.15 mmol) of a compound represented by the following formula as a pale yellow oil with a yield of 90%. ¹ H-NMR and ¹⁹ F-NMR are shown below.

¹ H-NMR (reference substance; Me ₄ Si, heavy solvent; CDCl ₃ ), δ ppm; 3.02 (s, 6H), 3.58 (t, 2H), 4.57 (t, 2H), 5 .67 (m, 1H), 6.03 (m, 1H), 6.24-6.32 (3H), 6.52 (m, 1H).
¹⁹ F-NMR (reference substance; CFCl ₃ , deuterated solvent; CDCl ₃ ) δ ppm; −78.75 (s, 3F).

[Example 2]
3.70 g (35.4 mmol) of methacrylic acid chloride instead of acrylic acid chloride, 5.11 g (32.5 mmol) of [2-(methacryloyloxy)ethyl]dimethylamine instead of [2-(acryloyloxy)ethyl]dimethylamine 11.54 g (30.8 mmol) of the compound represented by the following formula was obtained in a yield of 92% by performing the same reaction as in Example 1 except that ) was used. ¹ H-NMR and ¹⁹ F-NMR are shown below.

¹ H-NMR (reference material; Me ₄ Si, heavy solvent; CD ₃ OD), δ ppm; 1.87 (s, 3H), 1.95 (s, 3H), 2.97 (s, 6H), 3.53 (t, 2H), 4.50 (t, 2H), 5.38 (m, 1H), 5.70 (m, 1H), 5.98 (m, 1H), 6.18 (m , 1H).
¹⁹ F-NMR (reference substance; CFCl ₃ , deuterated solvent; CD ₃ OD) δ ppm; −78.96 (s, 3F).

[Example 3]
A 25 ml flask was charged with 5.04 g (10.02 mmol) of the imidic acid derivative represented by the following formula and 10 ml of ethyl acetate, followed by adding 0.63 g (10.31 mmol) of ethanolamine and stirring at room temperature for 5 hours.

After the reaction, the solvent was distilled off by concentration under reduced pressure, and then vacuum drying was performed to obtain 5.44 g of a compound represented by the following formula as pale yellow crystals. The obtained crude product was directly used for the next reaction without being purified.

Subsequently, a nitrogen introduction line and a condenser (refrigerant temperature: -5°C) were attached to a 50 ml three-necked flask, 5.44 g of the alcohol obtained above and 10 ml of chloroform were added, and nitrogen was bubbled. 1.28 g (14.14 mmol) of acrylic acid chloride was added thereto, heated to 75° C., and stirred for 8 hours. After the reaction, the solvent was distilled off by concentration under reduced pressure to obtain 5.57 g of a compound represented by the following formula as a pale yellow oil. The obtained crude product was directly used for the next reaction without being purified.

5.57 g of the acrylic acid ester obtained above and 36 ml of ethyl acetate were placed in a 100 ml flask, 1.84 g (9.85 mmol) of 1-butyl-3-vinylimidazolium chloride was added thereto, and the mixture was stirred at room temperature for 16 hours. bottom. After the reaction, insoluble matter was removed by filtration, and the filtrate was concentrated. The resulting crude product was washed with 10 ml of MTBE three times, added with 15 ml of ethyl acetate, and then washed with 10 ml of distilled water three times. After adding 3.0 mg of MEHQ to the collected organic layer, the mixture was concentrated under reduced pressure and dried in vacuo to obtain 3.88 g (6.99 mmol) of a compound represented by the following formula with a yield of 70%. ¹ H-NMR and ¹⁹ F-NMR are shown below.

¹ H-NMR (reference material; Me ₄ Si, heavy solvent; CD ₃ OD), δ ppm; 0.98 (t, 3H), 1.39 (m, 2H), 1.89 (m, 2H), 3.57 (t, 2H), 4.23-4.27 (4H), 5.42 (m, 1H), 5.85-5.92 (2H), 6.15 (m, 1H), 6 .40 (m, 1H), 7.23 (m, 1H), 7.74 (s, 1H), 7.98 (s, 1H) 9.25 (s, 1H).
¹⁹ F-NMR (reference substance; CFCl ₃ , deuterated solvent; CD ₃ OD) δ ppm; −111.42 (s, 2F), −80.04 (s, 3F).

[Example 4]

Using 3.83 g (7.62 mmol) of the imidic acid derivative represented by the above formula as a raw material, [2-(acryloyloxy)ethyl]trimethylammonium chloride aqueous solution (80 wt%) instead of 1-butyl-3-vinylimidazolium chloride By performing the same reaction as in Example 3 except that 1.69 g (6.98 mmol) was used, 2.55 g (4.55 mmol) of the compound represented by the following formula was obtained with a yield of 60%. ¹ H-NMR and ¹⁹ F-NMR are shown below.

¹ H-NMR (reference substance; Me ₄ Si, heavy solvent; DMF-d7), δ ppm; 3.43 (s, 9H), 3.61 (t, 2H), 4.00 (t, 2H), 4.28 (t, 2H), 4.73 (t, 2H), 5.94 (m, 1H), 6.04 (m, 1H) 6.13-6.28 (2H), 6.36- 6.44 (2H), 8.91 (br, 1H).
¹⁹ F-NMR (reference substance; CFCl ₃ , heavy solvent; DMF-d7) δ ppm; −111.27 (s, 2F), −80.50 (s, 3F).

[Example 5]

1.21 g (2.41 mmol) of the imide acid derivative represented by the above formula was used as a raw material, and 0.39 g (2.26 mmol) of triallylamine hydrochloride was used instead of 1-butyl-3-vinylimidazolium chloride. By performing the same reaction as in Example 3, 0.71 g (1.32 mmol) of the compound represented by the following formula was obtained with a yield of 55%. ¹ H-NMR and ¹⁹ F-NMR are shown below.

¹ H-NMR (reference substance; Me ₄ Si, heavy solvent; CDCl ₃ ), δ ppm; 3.66 (t, 2H), 3.71 (d, 6H), 4.29 (t, 2H), 5 .52 (m, 3H), 5.61 (m, 3H), 5.85 (m, 1H) 5.93 (m, 3H) 6.12 (m, 1H), 6.43 (m, 1H) , 7.93 (br, 1H).
¹⁹ F-NMR (reference substance; CFCl ₃ , heavy solvent; CDCl ₃ ) δ ppm; −112.16 (s, 2F), −79.91 (s, 3F)

[Example 6]

Using 4.92 g (9.79 mmol) of the imide acid derivative represented by the above formula as a starting material, the same reaction as in Example 3 was carried out except that 1.58 g (15.12 mmol) of methacrylic acid chloride was used instead of acrylic acid chloride. 4.13 g (7.05 mmol) of a compound represented by the following formula was obtained with a yield of 72%. ¹ H-NMR and ¹⁹ F-NMR are shown below.

¹ H-NMR (reference substance; Me ₄ Si, heavy solvent; CDCl ₃ ), δ ppm; 0.95 (t, 3H), 1.37 (m, 2H), 1.86 (m, 2H), 1 .93 (s, 3H), 3.65 (m, 2H), 4.23-4.29 (4H), 5.38 (m, 1H), 5.58 (d, 1H), 5.74 ( m, 1H), 6.14 (d, 1H), 7.23 (m, 1H), 7.40 (s, 1H), 7.58 (s, 1H), 9.14 (s, 1H).
¹⁹ F-NMR (reference substance; CFCl ₃ , deuterated solvent; CDCl ₃ ) δ ppm; −111.75 (s, 2F), −79.98 (s, 3F).

[Example 7]

In a 25 ml flask, 3.01 g (5.99 mmol) of the imidic acid derivative represented by the above formula and 6 ml of methanol were added, and 0.29 g (7.67 mmol) of sodium borohydride was added in three portions. After that, the mixture was stirred at room temperature for 3 hours. After the reaction, 1.5 ml of 6N hydrochloric acid was added under ice-cooling, 6 ml of acetonitrile was added thereto, and the insoluble matter was filtered under reduced pressure. 73 g was obtained. The crude product was directly used for the next reaction without purification.

A nitrogen introduction line and a condenser (refrigerant temperature: -5°C) were attached to a 30 ml three-necked flask, 2.73 g of the alcohol obtained above and 5 ml of acetonitrile were added, and nitrogen was bubbled. 1.08 g (11.93 mmol) of acrylic acid chloride was added thereto, heated to 85° C., and stirred for 4 hours. After the reaction, the solvent was distilled off by concentration under reduced pressure to obtain 3.16 g of a compound represented by the following formula as pale yellow oil. The obtained crude product was directly used for the next reaction without being purified.

3.16 g of the acrylates obtained above, 5 ml of acetonitrile and 15 ml of MTBE were added to a 50 ml flask, and 1.01 g (5.41 mmol) of 1-butyl-3-vinylimidazolium chloride was added thereto. Stirred for 7 hours. After the reaction, insoluble matter was removed by filtration, and the filtrate was concentrated. The resulting crude product was washed three times with 7 ml of MTBE, added with 15 ml of ethyl acetate, and then washed with 7 ml of distilled water three times. After adding 2.0 mg of MEHQ to the collected organic layer, the mixture was concentrated under reduced pressure and dried in vacuo to obtain 1.82 g (3.65 mmol) of a compound represented by the following formula with a yield of 61%. ¹ H-NMR and ¹⁹ F-NMR are shown below.

¹ H-NMR (reference substance; Me ₄ Si, heavy solvent; CD ₃ OD), δ ppm; 0.97 (t, 3H), 1.38 (m, 2H), 1.88 (m, 2H), 4.24 (t, 2H), 4.80 (t, 2H), 5.40 (m, 1H), 5.74 (m, 1H), 5.96 (m, 1H), 6.20 (m , 1H), 6.47 (m, 1H), 7.20 (m, 1H), 7.70 (s, 1H), 7.93 (s, 1H), 9.14 (s, 1H).
¹⁹ F-NMR (reference substance; CFCl ₃ , deuterated solvent; CD ₃ OD) δ ppm; −113.19 (t, 2F), −80.05 (s, 3F).

[Example 8]

Using 3.12 g (6.21 mmol) of the imidic acid derivative represented by the above formula as a starting material, the same reaction as in Example 7 was carried out except that 2.01 g (19.22 mmol) of methacrylic acid chloride was used instead of acrylic acid chloride. 1.66 g (3.25 mmol) of a compound represented by the following formula was obtained with a yield of 52%. ¹ H-NMR and ¹⁹ F-NMR are shown below.

¹ H-NMR (reference material; Me ₄ Si, heavy solvent; CDCl ₃ ), δ ppm; 0.95 (t, 3H), 1.37 (m, 2H), 1.87 (m, 2H), 1 .95 (s, 3H), 4.24 (t, 2H), 4.82 (t, 2H), 5.40 (m, 1H), 5.65 (d, 1H), 5.78 (m, 1H), 6.22 (d, 1H), 7.17 (m, 1H), 7.46 (s, 1H), 7.66 (s, 1H), 9.11 (s, 1H).
¹⁹ F-NMR (reference substance; CFCl ₃ , deuterated solvent; CDCl ₃ ) δ ppm; −113.25 (t, 2F), −79.93 (s, 3F).

[Example 9]
In a 25 ml flask, 1.21 g (2.41 mmol) of the imidic acid derivative represented by the following formula and 10 ml of chloroform were charged, and 0.06 g (0.52 mmol) of N,N-dimethyl-4-aminopyridine and 4- 0.57 g (4.78 mmol) of aminostyrene was added and stirred at room temperature for 6 days.

After the reaction, insoluble matter was removed by filtration, and then the solvent was removed by vacuum concentration, followed by vacuum drying to obtain 1.70 g of a crude product containing 1.53 mmol of a mixture of compounds represented by the following formulas. The obtained crude product was directly used for the next reaction without being purified.

1.70 g of the crude product obtained above and 10 ml of ethyl acetate were placed in a 25 ml flask, 0.30 g (1.61 mmol) of 1-butyl-3-vinylimidazolium chloride was added thereto, and the mixture was stirred at room temperature for 2 days. After the reaction, insoluble matter was removed by filtration, and the filtrate was concentrated. The resulting crude product was washed with 5 ml of MTBE three times, added with 10 ml of ethyl acetate, and then washed with 5 ml of distilled water three times. The obtained organic layer was concentrated under reduced pressure and dried in vacuo to obtain 0.77 g (1.38 mmol) of the compound represented by the following formula with a yield of 57%. ¹ H-NMR and ¹⁹ F-NMR are shown below.

¹ H-NMR (reference material; Me ₄ Si, heavy solvent; CD ₃ OD), δ ppm; 0.95 (t, 3H), 1.37 (m, 2H), 1.87 (m, 2H), 4.24 (t, 2H), 5.19 (m, 1H), 5.40 (m, 1H), 5.73 (m, 1H), 5.74 (m, 1H), 6.69 (m , 1H), 7.22 (m, 1H), 7.39-7.41 (2H), 7.45 (s, 1H), 7.50-7.54 (2H), 7.62 (s, 1H), 9.23 (s, 1H).
¹⁹ F-NMR (reference substance; CFCl ₃ , deuterated solvent; CD ₃ OD) δ ppm; −111.11 (s, 2F), −80.08 (s, 3F).

[Comparative Example 1]
1.50 g (3.14 mmol) of bistrifluoromethanesulfonylimidic acid aqueous solution (59 wt %) and 3 ml of distilled water were placed in a 10 ml flask, and 0.33 g (3.25 mmol) of triethylamine was added thereto and stirred at room temperature for 1 hour. . After the reaction, extraction was performed three times with 5 ml of chloroform, and the recovered organic layer was concentrated under reduced pressure and dried in vacuo to obtain 1.04 g (2.73 mmol) of the compound represented by the following formula with a yield of 87%.

[Comparative Example 2]
Put 1.32 g (2.77 mmol) of bistrifluoromethanesulfonylimidic acid aqueous solution (59 wt%) and 3 ml of distilled water in a 10 ml flask, add 0.11 g (2.75 mmol) of sodium hydroxide, and stir at room temperature for 30 minutes. bottom. After stirring, 0.66 g (2.73 mmol) of [2-(acryloyloxy)ethyl]trimethylammonium chloride aqueous solution (80 wt %) was added and further stirred at room temperature for 1 hour. After the reaction, the mixture was extracted with 5 ml of chloroform three times, and the organic layer was washed with 4 ml of water twice. After adding 1.1 mg of MEHQ to the collected organic layer, the mixture was concentrated under reduced pressure and dried in vacuo to obtain 0.91 g (2.07 mmol) of a compound represented by the following formula with a yield of 75%.

The obtained ionic liquid was evaluated based on the following evaluation items.

<Electrochemical measurement>
For the compounds obtained in Examples 1, 3, 4, 5, 6, 7 and 8, potentials at which oxidation and reduction currents start to flow were measured by CV measurement. Acetonitrile was used as the solvent, 0.1 M tetrabutylammonium perchlorate was used as the electrolyte, a platinum disk (φ3 mm) was used as the working electrode, and a platinum wire (φ0.5 mm) was used as the counter electrode. The reference was Ag+/Ag and the sweep rate was 250 mV/s.
In addition, as a comparison of compounds having polymerizability in cations and anions, the results of a commercially available vinylsulfonic acid in the form of a triallylamine salt (Reference Example 1) are also described.
For the measurement, a precision source/measuring unit (model: B2901A, manufactured by KEYSIGHT TECHNOLOGIES) was used. Table 1 shows the measurement results.

As shown in Table 1, all of the compounds obtained in Examples 1, 3, 4, 5, 6, 7 and 8 had a wider potential than the triallylamine salt of vinylsulfonic acid of Reference Example 1. Confirmed to have windows.

<Evaluation of vibration power generation>
Next, using the compound obtained in Example 6, a material for an electrochemical device was produced, and vibration power generation was evaluated.

(Preparation of material for electrochemical device)
A mixture was obtained by mixing 0.1 g of the compound obtained in Example 6, 1.0 g of trimethylolpropane triacrylate, and 0.01 g of azobisisobutyronitrile. The resulting mixture was sandwiched between a pair of gold electrodes via a 0.5 mm spacer. A voltage of 1.5 to 3.5 V was applied between the gold electrodes, and the mixture was heated in a constant temperature bath at 70° C. for 30 minutes to cure the mixture, thereby obtaining a material for an electrochemical device.

(Procedure for evaluation of vibration power generation)
The vibration power generation evaluation was performed using the device 100 shown in FIG.
The device 100 includes a pair of pedestals (pedestal 10, pedestal 20), electrodes (electrode 30, electrode 40) provided on adjacent surfaces of the pair of pedestals, and an electrochemical device material 50 provided between the electrodes. (Plate-shaped member produced in (Preparation of material for electrochemical device) above), wiring connecting a pair of electrodes, and an oscilloscope (voltmeter) arranged in the wiring.
In the device 100, changes over time in the voltage generated by vibrating the pair of pedestals (pedestal 10, pedestal 20) at 1 Hz were measured using an oscilloscope (model: DSOX3052T, manufactured by KEYSIGHT TECHNOLOGIES).
The maximum current density (V/(Ω·S)) was calculated based on the maximum voltage (V) and resistance value (Ω) of the generated voltage measured with an oscilloscope and the surface area (S) of the electrochemical device material 50. . Table 2 shows the measurement results. In Table 2, the applied voltage indicates the applied voltage at the time of preparation, and the maximum current density was calculated from the generated voltage observed in the vibration power generation evaluation of the electrets prepared at each applied voltage and compared.

As shown in Table 2, it was observed that as the applied voltage increased, the power generation performance also tended to improve. The compounds obtained in the Examples have a wide potential window, that is, they can be applied with a high voltage within a range that does not involve an electrolytic reaction, so they can be said to be excellent materials for electrochemical devices.

In addition, using the compounds obtained in Examples 1 to 9 and the compounds obtained in Comparative Examples 1 and 2, preparation of materials for electrochemical devices and evaluation of vibration power generation were carried out in the same manner as <Evaluation of vibration power generation>. gone. However, the vibration power generation evaluation was the same except that the applied voltage was fixed at 3V. Table 3 shows the evaluation results.

As shown in Table 3, the compounds of Examples 1 to 9 having at least an anion with a polymerizable functional group exhibited a higher maximum current density than the compounds of Comparative Examples 1 and 2 containing anions having no polymerizable functional group. Indicated. That is, the compounds of Examples 1 to 9 exhibited excellent properties as materials for electrochemical devices due to their good polymerizability.

<Evaluation of antistatic performance>
In order to evaluate the performance as an antistatic material, as Example 10, a resin film A was produced from the ionic liquid having an anion obtained in Example 2, and the surface resistance was measured. In consideration of the performance as an antistatic material, tributylmethylammonium, which does not have polymerizability, was used as the cation. Further, as Reference Example 2, a resin film B containing no ionic liquid, and as Comparative Example 3, a resin film C using an ionic liquid whose anion is non-polymerizable TFSI (bistrifluoromethanesulfonylimide) were also measured. .

(Preparation of resin film)
[Reference example 2]
Dipentaerythritol hexaacrylate (DPHA) as a cross-linking agent was mixed with triethylene glycol methyl ether acrylate monomer (TEGMEA) at a ratio of 98:2, and 0.02 g of 1-hydroxycyclohexylphenyl ketone was added to 2 g of this mixture. mixed as an initiator. The resulting liquid monomer composition was applied to a glass substrate (5 cm×5 cm) and irradiated with UV light for 5 minutes to form a film having a thickness of about 5 mm. (Resin film A)

[Example 10]
DPHA, a crosslinker, was mixed with TEGMEA in a ratio of 98:2, and 0.06 g of 1-hydroxycyclohexylphenyl ketone was mixed as an initiator with 4.32 g of this mixture. Furthermore, the liquid monomer composition obtained by adding 1.98 g (15% solution) of N-methacryl-N-trifluoromethanesulfonylimide/tributylmethylammonium represented by the following formula was applied to a glass substrate (5 cm x 5 cm). and irradiated with UV light for 5 minutes to form a film with a thickness of about 5 mm. (Resin film B)

[Comparative Example 3]
DPHA, a crosslinker, was mixed with TEGMEA in a ratio of 98:2, and 0.06 g of 1-hydroxycyclohexylphenyl ketone was mixed as an initiator with 6.00 g of this mixture. Furthermore, a liquid monomer composition obtained by adding 0.30 g of bistrifluoromethanesulfonylimide tributylmethylammonium (FC4400 manufactured by 3M) represented by the following formula was applied to a glass substrate (5 cm × 5 cm), and UV light was applied. was irradiated for 5 minutes to form a film with a thickness of about 5 mm. (Resin film C)

(Surface resistance measurement)
The surface resistance values of the resin films A to C immediately after film formation were measured using a high resistivity meter Hiresta UX manufactured by Mitsubishi Chemical Analytech. In addition, the surface resistance value of each resin film was measured after storage in a constant temperature bath at 120° C. for three days. Table 4 shows the evaluation results.

As shown in Table 4, the sample of Example 10, which contains a polymerizable anion, has a lower resistance value than the sample of Reference Example 2, which does not contain an ionic liquid, immediately after preparation, and is suitable as an antistatic material. there is In addition, it can be confirmed that the sample of Example 10 after the storage test maintains the performance remarkably compared to the sample of Comparative Example 3 using an ionic liquid that does not have polymerizability, and is excellent in durability. That is, the compound of Example 10 exhibited excellent properties as an antistatic material. Therefore, a polymerizable ionic liquid containing a polymerizable anion can be suitably used as an antistatic material.

This application claims priority based on Japanese Patent Application No. 2018-151186 filed on August 10, 2018, and the entire disclosure thereof is incorporated herein.

Claims (10)

A polymerizable ionic liquid used for forming an electrochemical device material having electric polarization inside,
A polymerizable ionic liquid containing a compound represented by at least one of the following general formula (A) and general formula (A').

[In the above general formula (A),
R _f represents a fluorine atom, a linear C 1-10, or a branched or cyclic C 3-12 perfluoroalkyl group.
W represents a divalent linking group, a single bond, -C(=O)-, -C(=O)-O-, or -C(=O)-NR- (R is a hydrogen atom, has 1 carbon atom ~10 alkyl group or substituted alkyl group, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms).
n represents an integer of 0 to 5;
M ⁺ represents monovalent cations , including polymerizable functional group-containing cations .
X is a polymerizable substituent, a vinyl group represented by general formula (B1), an epoxy group represented by general formula (B2), a silyl group represented by general formula (B3), and a polyvalent acrylic group represented by general formula (B4). , represents a polyepoxy group represented by general formula (B5) or a norbornyl group represented by general formula (B6).

In the above general formula (B1), R ^B1 represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, may be substituted with an oxygen atom, and a hydrogen atom of an alkyl group may be substituted with an oxygen atom.
In general formula (B2) above, R ^{2 B2} represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms.
In the above general formula (B3), R ^B3 , R ^B4 and R ^B5 are each independently an alkoxy group having a straight-chain alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 6 to 12 carbon atoms. represents an aromatic ring group, a hydroxyl group, or a chlorine atom, and contains at least two alkoxy groups, chlorine atoms, hydroxyl groups, or a combination thereof;
In general formula (B4) above, R ^{1 B6} represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms.
In general formula (B4) and general formula (B5) above, Z ¹ and Z ² each represent a trivalent or higher linking group and represent a chain or cyclic substituted alkyl group having 1 to 18 carbon atoms, Carbon atoms may be substituted with oxygen atoms or nitrogen atoms, carbon-carbon bonds may contain unsaturated bonds, and aromatic rings may be contained.
m and l represent an integer of 2-5. ]

[In the above general formula (A′),
R _f represents a fluorine atom, a linear C 1-10, or a branched or cyclic C 3-12 perfluoroalkyl group.
L represents a divalent linking group, a single bond, -C(=O)-O-, or -C(=O)-NR- (R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms).
R ^A1 , R ^A2 and R ^A3 each independently represents a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, Any two or more of R ^A1 , R ^A2 and R ^A3 may bond together to form a ring together with the carbon-carbon double bond in the formula.
Y represents a divalent linking group, a single bond, -OC(=O)-, -NR-C(=O)- (R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group , or an aromatic ring group or a substituted aromatic ring group having 6 to 12 carbon atoms), an arylene group having 6 to 12 carbon atoms, or -O-C(=O)- or -NR-C(=O)- and the number of carbon atoms It represents a linking group in which 6 to 12 arylene groups are combined.
m represents an integer of 1-6, and n represents an integer of 0-5.
M ⁺ represents a monovalent cation. ] The polymerizable ionic liquid according to claim 1,
A polymerizable ionic liquid, wherein the monovalent cations include one or more selected from the group consisting of hydrogen ions, ammonium ions, phosphonium ions, imidazolium ions, and pyridinium ions. The polymerizable ionic liquid according to claim 1 or 2 ,
The monovalent cation is an ammonium cation represented by the following general formula (C1), a phosphonium cation represented by the following general formula (C2), an imidazolium cation represented by the following general formula (C3), and the following general A polymerizable ionic liquid containing one or more selected from the group consisting of pyridinium cations represented by formula (C4).

[In the above general formula (C1), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, an aromatic ring group having 6 to 12 carbon atoms, Alternatively, it represents a substituted aromatic ring group or a polymerizable functional group-containing group. Also, two or more of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may combine to form a cyclic structure. ]

[In the above general formula (C2), R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, an aromatic ring group having 6 to 12 carbon atoms, Alternatively, it represents a substituted aromatic ring group or a polymerizable functional group-containing group. ]

[In the above general formula (C3), R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, represents an aromatic ring group, a substituted aromatic ring group, or a polymerizable functional group-containing group. ]

[In the general formula (C4), R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are each independently a hydrogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, 1 to 12 aromatic ring groups or substituted aromatic ring groups, or polymerizable functional group-containing groups. ] The polymerizable ionic liquid according to claim 3 ,
A polymerizable ionic liquid, wherein the polymerizable functional group-containing group comprises a group represented by the following general formula (C5).

[In the above general formula (C5),
R ²⁹ , R ³⁰ and R ³¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group or substituted alkyl group having 1 to 10 carbon atoms, or an aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms, Any two or more of R ²⁹ , R ³⁰ and R ³¹ may bond together to form a ring together with the carbon-carbon double bond in formula (C5).
Z represents a divalent linking group, an alkylene group having 1 to 10 carbon atoms, -O-C(=O)-, -NR-C(=O)- (R is a hydrogen atom, a alkyl group or substituted alkyl group, or aromatic ring group or substituted aromatic ring group having 6 to 12 carbon atoms), or -OC(=O)- or -NR-C(=O)- and 6 to 12 carbon atoms represents a linking group in combination with an arylene group of ] The polymerizable ionic liquid according to any one of claims 1 to 4 ,
a polymerization initiator;
A curable composition comprising: 6. The curable composition of claim 5 , further comprising a polymerizable compound. A curable composition according to claim 6 ,
The polymerizable compound is
Consisting of acrylic acid ester, methacrylic acid ester, fluorine-containing acrylic acid ester, fluorine-containing methacrylic acid ester, styrene compound, fluorine-containing styrene compound, olefin, fluorine-containing olefin, norbornene compound, vinyl ether, fluorine-containing vinyl ether, oxiranes and silane compounds A curable composition comprising one or more selected from the group. A curable composition according to claim 6 or 7 ,
The curable composition, wherein the polymerizable compound has a weight average molecular weight of 1,000 or more and 1,000,000 or less. A curable composition according to any one of claims 6 to 8 ,
The curable composition, wherein the polymerizable compound has a polymerizable functional group at its terminal. A material for an electrochemical device comprising a cured product of the curable composition according to any one of claims 5 to 9 .

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