WO2022004435A1 - Fluorine-containing ether compound, curable composition, cured film, element, and display device - Google Patents

Abstract

A fluorine-containing ether compound represented by formula (1). A¹ and A² represent curable functional groups, r1 and r2 represent integers of 1 or more, Y¹ and Y² represent linking groups that do not have a fluorine atom, Rf¹ represents a fluoroalkylene group in which a fluorine atom is bonded to a carbon atom and which bonds to Y¹, Rf² represents a fluoroalkylene group in which a fluorine atom is bonded to a carbon atom and which bonds to Y², X represents a fluoroalkylene group, m represents an integer of 2 or more, (OX)_m includes a structure represented by formula (2), X¹ represents a C2-6 fluoroalkylene group, X² represents a C2-6 fluoroalkylene group different from X¹, a represents an integer of 1 or more, and 2≤(2×a)≤m. Formula (1): A¹ _r1-Y¹-Rf¹-(OX)_m-O-Rf²-Y²-A² _r2, formula (2): -(OX¹-OX²)_a-

Description

Fluorine-containing ether compounds, curable compositions, cured films, devices, and display devices

The present disclosure relates to a fluorine-containing ether compound, a curable composition, a cured film, an element, and a display device.

Since the fluorine-containing compound has high transparency, light resistance, and insulating property, it is suitably used as a material for a sealing layer and an insulating layer for encapsulating elements such as sensors and LEDs.
Among the fluorine-containing compounds, the fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain in which an ether bond is present in the middle of the fluoroalkylene chain has a low viscosity, is fluid, and is soluble in a solvent, and thus is wet. Suitable for curable compositions for coating.
It has been proposed that such a fluorine-containing ether compound be used, for example, as a fluorine-based adhesive used in the manufacture of a pressure sensor device, or as a material for a fluorine-based gel forming a protective member for a pressure sensor (specially). Kai 2001-09937A, JP-A-2001-153746, and JP-A-2005-283587).

As described above, the fluorine-containing ether compound is suitably used as a material for a curable composition that forms a sealing layer or the like for sealing an element.
Therefore, the fluorine-containing ether compound used in the curable composition for forming a sealing layer or the like is required to have further excellent curability and heat resistance.

The present disclosure has been made in view of the above circumstances, and is a fluorine-containing ether compound having excellent curability and heat resistance, a curable composition containing the fluorine-containing ether compound, and curing using the curable composition. It is an object of the present invention to provide a film, an element, and a display device.

Specific means for achieving the above-mentioned problems are as follows.
<1>
A fluorine-containing ether compound represented by the following formula (1).
Equation ^{_{(1): A 1 r1 -Y}} 1 -Rf 1 - (OX) m -O-Rf 2 -Y 2 -A 2 r2
However, in the above formula (1),
A ¹ and A ² each independently represent a curable functional group.
r1 and r2 each independently represent an integer of 1 or more.
Y ¹ represents a (r1 + 1) valent linking group that does not have a fluorine atom.
Rf ¹ represents a fluoroalkylene group in which a fluorine atom is bonded to a carbon atom bonded to Y ^1.
Each of X independently represents a fluoroalkylene group, and (OX) _m contains a structure represented by the following formula (2).
m represents an integer of 2 or more,
Rf ² represents a fluoroalkylene group in which a fluorine atom is bonded to a carbon atom bonded to Y ^2.
Y ² represents a (r2 + 1) valent linking group that does not have a fluorine atom.
Equation (2):-(OX ^{1- OX 2} ) _a-
However, in the above formula (2),
X ¹ represents a fluoroalkylene group having 2 to 6 carbon atoms.
X ² represents a fluoroalkylene group having 2 to 6 carbon atoms, which is different from X ^1.
a represents an integer of 1 or more, and 2 ≦ (2 × a) ≦ m.
<2>
The linking group represented by linking groups and Y ² is represented by Y ¹ in the formula (1) are each independently a single bond or an alkylene group, an arylene group, -C (= O) A linking group containing at least one selected from the group consisting of-, -O-, -S-, -NH-, -N <, _{-SiH 2-,> SiH-, and> Si <, <1.} > The fluorine-containing ether compound.
<3>
The curable functional group represented by ^{A 1 and the curable functional group represented by A 2} in the formula (1) are independently any of the following formulas (A-1) to (A-12). The fluorine-containing ether compound according to <1> or <2>, which is a curable functional group represented by.

In the formulas (A-1) to (A-3), Xa independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a methyl group, and * represents a binding site.
<4>
The curable functional group represented by ^{A 1 and the curable functional group represented by A 2} in the formula (1) are independently curable functional groups represented by the formula (A-1). In addition, the atom bonded to ^{A 1} in the linking group represented by ^{Y 1 and the atom bonded to A 2} in the linking group represented by ^{Y 2} in the above formula (1) are independently heteroatoms or rings. It is a carbon atom that constitutes a structure, or it is
The curable functional group represented by ^{A 1 and the curable functional group represented by A 2} in the formula (1) are independently one of the formulas (A-2) to (A-12). The fluorine-containing ether compound according to <3>, which is a curable functional group represented by.
<5>
The fluorine-containing ether compound according to any one of <1> to <4>, which has a fluorine atom content of 53% by mass or more.
<6>
The fluorine-containing ether compound according to any one of <1> to <5> and
At least one selected from the group consisting of a polymerization initiator, a solvent, and a curing agent, and
Curable composition containing.
<7>
A cured film which is a cured product of the curable composition according to <6>.
<8>
The element having the cured film according to <7>.
<9>
The element according to <8>, which is for a sensor.
<10>
The element according to <8>, which is for optics.
<11>
A display device including an optical element which is the element according to <10>.

According to the present disclosure, a fluorine-containing ether compound having excellent curability and heat resistance, a curable composition containing the fluorine-containing ether compound, and a cured film, an element, and a display device using the curable composition are provided. Will be done.

Hereinafter, embodiments according to the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to the numerical values and their ranges, and does not limit this disclosure.

In the numerical range indicated by using "-" in the present specification, the numerical values before and after "-" are included as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. good. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.

[Fluorine-containing ether compound]
The fluorine-containing ether compound of the present disclosure is a compound represented by the following formula (1) (hereinafter, also referred to as “compound (1)”).
Equation ^{_{(1): A 1 r1 -Y}} 1 -Rf 1 - (OX) m -O-Rf 2 -Y 2 -A 2 r2
However, in the above formula (1), A ¹ and A ² each independently represent a curable functional group, r1 and r2 each independently represent an integer of 1 or more, and Y ¹ does not have a fluorine atom (r1 + 1). ^{Rf 1} represents a valence linking group, Rf 1 represents a fluoroalkylene group in which a fluorine atom is bonded to a carbon atom bonded to Y ¹ _{, X represents a fluoroalkylene group independently, and (OX) m} represents a continuous (OX). There comprises a structure represented by the following formula (2), m is integer of 2 or more, Rf ² represents a fluoroalkylene group in which a fluorine atom to carbon atom is bond to Y ^2, Y ² is a fluorine atom Represents a (r2 + 1) valence linking group that does not have.

Equation (2):-(OX ^{1- OX 2} ) _a-
However, in the above formula (2), X ¹ represents a fluoroalkylene group having 2 to 6 carbon atoms, X ² represents a fluoroalkylene group having 2 to 6 carbon atoms different from X ^1, and a represents an integer of 1 or more. Represented by 2 ≦ (2 × a) ≦ m.

Here, the "fluorine-containing ether compound" means a compound having an oxyfluoroalkylene structure.
Since the compound (1) has a structure represented by the formula (1), it is excellent in curability and heat resistance. The reason is not clear, but it is presumed as follows. First, the compound (1) _{contains a structure in which (OX) m} in the formula (1) is represented by the formula (2), so that X ¹ or X ² in the formula (2) is a fluorocarbon having 1 carbon atom. It is presumed that the heat resistance is superior to that of the alkylene group. ^{Further, since the compound (1) has a curable functional group represented by A 1} and A ² in the formula (1), it is said that the compound (1) is superior in curability as compared with the case where both ends are fluoroalkyl groups, for example. Guessed.
Hereinafter, each group in the formula (1) will be described.

(Curable functional group A)
^{A 1} and A ² in the formula (1) independently represent a curable functional group. In the formula (1), r1 A ¹ and r2 A ² may all represent the same curable functional group, or may represent different curable functional groups. From the viewpoint of ease of synthesis and curability, r2 amino curable functional groups represented by r1 one curable functional group and A ² represented by A ¹ in the formula (1) is, that all the same Is preferable.

^{Examples of the curable functional group represented by A 1} or A ² in the formula (1) (hereinafter, also referred to as “curable functional group A”) include the following formulas (A-1) to (A-12). Examples thereof include a curable functional group represented by any of the above.

In the formulas (A-1) to (A-3), Xa independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a methyl group, and * represents a binding site.

From the viewpoint of curability, the curable functional group A has a formula (A-1), a formula (A-6), a formula (A-7), a formula (A-8), and a formula (A-9). ), The formula (A-10), the formula (A-11), or the curable functional group represented by the formula (A-12) is preferable, and the formula (A-1), the formula (A-6), the formula ( A curable functional group represented by A-7), formula (A-8), formula (A-9), or formula (A-10) is more preferable.
Further, Xa in the formulas (A-1) to (A-3) is preferably a hydrogen atom, a fluorine atom or a methyl group, and more preferably a hydrogen atom.

R1 and r2 in the equation (1) independently represent an integer of 1 or more. The integer represented by r1 and the integer represented by r2 in the equation (1) may be the same or different. From the viewpoint of ease of synthesis and cross-linking efficiency, it is preferable that the integer represented by r1 and the integer represented by r2 in the formula (1) are the same. The average value of r1 and r2 is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and 1 from the viewpoint of storage stability and viscosity. Is particularly preferable.

(Connecting group Y)
In the formula (1), Y ¹ represents a (r1 + 1) -valent linking group ^{having no fluorine atom, and Y 2} represents a (r2 + 1) -valent linking group having no fluorine atom. ^{The linking group represented by Y 1} and the linking group represented by Y ² in the formula (1) may be the same or different. From the viewpoint of ease of synthesis, the linking group represented by the linking group and Y ² represented by Y ¹ in the formula (1), it is preferably the same. Here, the fact ^{that the linking group represented by Y 1} and the linking group represented by Y ² are the same means that the structure of Y ^{1 from the binding site with Rf 1} to the binding site with A ^{1 is Rf.} means that the binding sites of ² is the same as the structure of the Y ² in toward the binding site of the a ^2.

^{Examples of the linking group represented by Y 1} or Y ² in the formula (1) (hereinafter, also referred to as “linking group Y”) include a single bond, an alkylene group, an arylene group, and −C (= O) −. , -O-, -S-, _{-NH-, -N <, -SiH 2} -,> SiH-, and> Si <. Hereinafter, an alkylene group, an arylene group, -C (= O)-, _{-O-, -S-, -NH-, -N <, -SiH 2} -,> SiH-, and> Si <are unit-connected. Also called "group".
The alkylene group as a unit linking group may be a linear alkylene group, a branched alkylene group, or a cyclic alkylene group (that is, a cycloalkylene group). The carbon number of the alkylene group as the unit linking group is, for example, 1 to 10, preferably 1 to 6, and more preferably 1 to 4.
Examples of the arylene group as the unit linking group include a phenylene group and a naphthylene group. Examples of the phenylene group include an o-phenylene group, an m-phenylene group, and a p-phenylene group. Of these, the phenylene group is preferable as the arylene group as the unit linking group.

The linking group Y may contain only one unit linking group, or may contain a combination of two or more. Examples of combinations of two or more types include -C (= O) -NH-, -NH-C (= O)-, -C (= O) -O-, -S-S-, and -OC. (= O) -NH-, -NH-C (= O) -O-, -NH-C (= O) -NH-, -Ry-O-, -O-Ry-, -Ry-O-Ry -, -Ry-Ary-, -O-Ry-Ary-, -Ry-O-Ry-Ary-, _{-O-SiH 2-} , -SiH ₂ -O-, -O-SiH <,> SiH-O -, -O-Si (CH ₃ ) _2- , -Si (CH ₃ ) _2- O-, the following formula (YA), the following formula (YB), the following formula (YC), the following formula (YD), the following formula (YE), the following formula (YF) and the like can be mentioned. Here, Ry represents an alkylene group as a unit linking group, Rz represents an alkyl group as a substituent described later, and Ary represents an arylene group as a unit linking group.

 

The linking group Y may further have a substituent. Examples of the substituent that the linking group Y may further include include an alkyl group, an alkoxy group, a hydroxy group, an amino group, a thiol group, and a hydrosilyl group (SiH). The alkyl group and the alkoxy group as the substituent may be linear or branched. The number of carbon atoms of the alkyl group and the alkoxy group as the substituent is, for example, 1 to 6, preferably 1 to 4, and more preferably 1.

The linking group Y is preferably a linking group containing an arylene group.
The linking group Y is selected from the group consisting of an arylene group, an alkylene group, -C (= O)-, _{-O-, -S-, -N <, -SiH 2} -,> SiH-, and> Si <. It is preferable to contain at least one of the above, and more preferably to contain an arylene group, an alkylene group, and —O—.

Examples of the linking group Y include linking groups represented by the following formulas (Y-1) to (Y-57).
Here, in the following formula, " ^Rf *" represents a binding site to a fluoroalkylene group represented by ^{Rf 1} or Rf ^{2 in the formula (1), and "* A " represents A 1} in the formula (1). or it represents a binding site for curable functional group represented by a ^2.
Further, in the following formulas, ^{B 1} is a group directly bonded to a fluoroalkylene group represented by Rf ¹ or Rf ² in the formula (1), a single _{^{bond, Rf * -C n H 2n -O-}} , ^Rf * -O-, ^Rf * -C (= O) -NH-, ^Rf * -NH-C (= O)-, ^Rf * -C (= O) -O-, ^Rf * -OC (= O)-, ^Rf * -S-, ^Rf * -S-S-, ^Rf * -OC (= O) -NH-, ^Rf * -NH-C (= O) -O-, or ^Rf *- Represents NH-C (= O) -NH-. However, n represents an integer of 1 to 6.
Further, in the following formula, B ² is a group that directly binds to the curable functional group represented by ^{A 1} or A ² in the formula (1) _{, and is independently single-bonded and −OC n} H, respectively. _2n- * ^A , -O- * ^A , -C (= O) -NH- * ^A , -NH-C (= O)-* ^A , -C (= O) -O- * ^A , -O- C (= O)-* ^A , -S- * ^A , -S-S- * ^A , -OC (= O) -NH- * ^A , -NH-C (= O) -O- * ^A , -NH-C (= O) -NH- * ^A , -Ph- * ^A , or -O-CH _2- Ph- * ^A. However, n represents an integer of 1 to 6, and Ph represents a phenylene group.

 

 

 

In the above equation, B ¹ is a single bond, ^Rf * -C _n H _2n- O-, ^Rf * -O-, ^Rf * -C _n H _2n- NH-, ^Rf * -C _n H _2n- NH. -CO- is preferable. Further, in the above formula, B ² is -O- * ^A , -C (= O) -NH- * ^A , -C (= O) -O- * ^A , -S- * ^A , -SS. -* ^A , -OC (= O) -NH- * ^A , -NH-C (= O) -O- * ^A , NH-C (= O) -NH- * ^A , -Ph- * ^A , Or -O-CH _2- Ph- * ^A is preferable.

When the curable functional group A is a group represented by the formula (A-1), the atom directly bonded to the curable functional group A in the linking group Y is a heteroatom or a carbon atom constituting a ring structure. Is preferable. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like. Examples of the carbon atom constituting the ring structure include a carbon atom constituting an arylene group and a carbon atom constituting a cycloalkylene group.
When the curable functional group A is a group represented by the formula (A-1), the atoms directly bonded to the curable functional group A in the linking group Y are, among them, an oxygen atom, a nitrogen atom, and an arylene group. The carbon atom constituting the phenylene group is preferable, the oxygen atom, the nitrogen atom, and the carbon atom constituting the phenylene group are more preferable, the oxygen atom and the carbon atom constituting the phenylene group are further preferable, and the carbon atom constituting the phenylene group is particularly preferable. ..

In particular, when the curable functional group is represented by the formula (A-1) and Xa in the formula (A-1) is a hydrogen atom, the atom directly bonded to the curable functional group A in the linking group Y is hetero. It is preferably an atom or a carbon atom constituting a ring structure, and more preferably a carbon atom constituting a ring structure. On the other hand, when the curable functional group A is represented by the formula (A-1) and Xa in the formula (A-1) is a fluorine atom, a chlorine atom, a bromine atom or a methyl group, the curability in the linking group Y is said. Examples of the atom directly bonded to the functional group A include a hetero atom, a carbon atom constituting a ring structure, a carbon atom constituting an alkylene group, and a carbon atom constituting a carbonyl group.

Further, in particular, when the curable functional group A is a group represented by the formula (A-1) and all m Xs in the formula (1) represent a perfluoroalkylene group, the above-mentioned in the linking group Y. The atom directly bonded to the curable functional group A is preferably a heteroatom or a carbon atom constituting a ring structure, and more preferably a carbon atom constituting the ring structure. On the other hand, when the curable functional group A is a group represented by the formula (A-1) and at least one of the m Xs in the formula (1) represents a fluoroalkylene group having a hydrogen atom. Examples of the atom directly bonded to the curable functional group A in the linking group Y include a hetero atom, a carbon atom constituting a ring structure, a carbon atom constituting an alkylene group, and a carbon atom constituting a carbonyl group.

When the curable functional group is a group represented by the formula (A-1), the linking group Y is represented by, for example, any of the formulas (Y-1) to (Y-31) and the curable functional group. Examples thereof include a group in which the atom bonded to the group A is a heteroatom or a carbon atom constituting a ring structure, and among them, a group represented by any of the formulas (Y-1) to (Y-20) is preferable. A group represented by any of the formulas (Y-1) to (Y-6), the formulas (Y-7) to the formula (Y-9), and the formulas (Y-17) to the formula (Y-18). Is more preferable, and a group represented by any of the formulas (Y-1) to (Y-6) is further preferable.

When the curable functional group A is a group represented by any of the formulas (A-2) to (A-5), the atom directly bonded to the curable functional group A in the linking group Y is hetero. Examples thereof include an atom, a carbon atom constituting a ring structure, a carbon atom constituting an alkylene group, and a carbon atom constituting a carbonyl group, and among them, a hetero atom is preferable.
When the curable functional group is a group represented by the formula (A-2) or the formula (A-3), the linking group Y may be, for example, any of the formulas (Y-1) to (Y-57). Among them, the group represented by any of the formulas (Y-1) to (Y-20) and the formulas (Y-32) to (Y-57) is preferable. Groups represented by any of the formulas (Y-7) to (Y-9) and the formulas (Y-17) to (Y-18) are more preferable.

When the curable functional group A is a group represented by any of the formulas (A-6) and the formulas (A-9) to (A-12), it is directly attached to the curable functional group A in the linking group Y. Examples of the atom to be bonded include a hetero atom, a carbon atom constituting a ring structure, a carbon atom constituting an alkylene group, and a carbon atom constituting a carbonyl group, and among them, a carbon atom constituting an alkylene group is preferable.
When the curable functional group is a group represented by any of the formula (A-6) and the formulas (A-9) to (A-12), the linking group Y may be, for example, the formula (Y-1). ) To a group represented by any of the formulas (Y-57), among which the formulas (Y-32) to the formula (Y-45) and the formulas (Y-52) to the formula (Y-57) are listed. Preferably, the formulas (Y-32) to (Y-34) are more preferable.

When the curable functional group A is a group represented by the formula (A-7), the atom directly bonded to the curable functional group A in the linking group Y includes a hetero atom, a carbon atom constituting a ring structure, and the like. Examples thereof include a carbon atom constituting an alkylene group and a carbon atom constituting a carbonyl group, and among them, a carbon atom constituting a ring structure and a carbon atom constituting an alkylene group are preferable.
When the curable functional group is a group represented by the formula (A-7), the linking group Y is, for example, a group represented by any of the formulas (Y-1) to (Y-57). Among them, formulas (Y-1) to formulas (Y-6), formulas (Y-32) to formulas (Y-45), and formulas (Y-52) to formulas (Y-57) are preferable. Formulas (Y-1) to (Y-6) and formulas (Y-32) to formulas (Y-34) are more preferable.

When the curable functional group A is a group represented by the formula (A-8), the atom directly bonded to the curable functional group A in the linking group Y includes a hetero atom, a carbon atom constituting a ring structure, and the like. Examples thereof include a carbon atom constituting an alkylene group and a carbon atom constituting a carbonyl group, and among them, a carbon atom constituting a ring structure and a carbon atom constituting an alkylene group are preferable.
When the curable functional group is a group represented by the formula (A-8), the linking group Y is, for example, a group represented by any of the formulas (Y-1) to (Y-57). Among them, formulas (Y-1) to formulas (Y-6), formulas (Y-32) to formulas (Y-45), and formulas (Y-52) to formulas (Y-57) are preferable. Formulas (Y-1) to (Y-6) and formulas (Y-32) to formulas (Y-34) are more preferable.

In the combination of the curable functional group A and the linking group Y, the curable functional group A is a curable functional group represented by the formula (A-1) and is bonded to the curable functional group A in the linking group Y. The atom is a heteroatom or a carbon atom constituting a ring structure, or the curable functional group A is a curable functional group represented by any of the formulas (A-2) to (A-12). It is preferable to have.

Further, in the combination of the curable functional group A and the linking group Y, the curable functional group A is a curable functional group represented by the formula (A-1), and the linking group Y is the formula (Y-1). )-The atom bonded to the curable functional group A represented by any of the formula (Y-31) is a hetero atom or a linking group which is a carbon atom constituting a ring structure, or the curable functional group A is It is a curable functional group represented by any of the formulas (A-2) to (A-12), and the linking group Y is any of the formulas (Y-1) to (Y-57). It is preferably a linking group represented, and the curable functional group A is a formula (A-1), a formula (A-6), a formula (A-7), a formula (A-8), a formula (A-9). ), The formula (A-10), the formula (A-11), or the curable functional group represented by the formula (A-12), and the linking group Y is the formula (Y-1) to the formula (Y-1) to It is more preferable that the atom represented by any of the formula (Y-31) and bonded to the curable functional group A is a hetero atom or a linking group which is a carbon atom constituting a ring structure.

(Fluoroalkylene group Rf)
^{Rf 1} and Rf ² in the formula (1) each independently represent a fluoroalkylene group in which a fluorine atom is bonded to a carbon atom bonded to the linking group Y. ^{The fluoroalkylene group represented by Rf 1} and the fluoroalkylene group represented by Rf ² in the formula (1) may be the same or different. From the viewpoint of easiness of synthesis, it is preferable that the fluoroalkylene group represented by ^{Rf 1 and the fluoroalkylene group represented by Rf 2 in the formula (1) are the same.} Here, the fact ^{that the fluoroalkylene group represented by Rf 1} and the fluoroalkylene group represented by Rf ² are the same means that the structure of Rf ¹ from the binding site with the O atom to the binding site with Y ¹ is the same. , It means that the structure is the same as that of Rf ² from the binding site with the O atom to the binding site with Y ^2.

^{Examples of the carbon number of the fluoroalkylene group represented by Rf 1} or Rf ² in the formula (1) (hereinafter, also referred to as “fluoroalkylene group Rf”) include 1 to 6, and from the viewpoint of improving heat resistance. It is preferably 2 to 6, and more preferably 3 to 6.
The fluoroalkylene group Rf may be a linear fluoroalkylene group, a branched fluoroalkylene group, or a fluoroalkylene group containing a ring structure. Examples of the ring structure include a cyclobutane structure and a cyclohexane structure.

As the fluoroalkylene group Rf, a linear fluoroalkylene group and a branched fluoroalkylene group are preferable from the viewpoint of viscosity before curing, and a linear fluoroalkylene group is preferable from the viewpoint of easiness of synthesis.
Further, the fluoroalkylene group Rf is preferably a perfluoroalkylene group from the viewpoint of heat resistance. On the other hand, the fluoroalkylene group Rf may contain a hydrogen atom from the viewpoint of compatibility with other components in the curable composition. The bond position and number of hydrogen atoms in the fluoroalkylene group Rf containing a hydrogen atom are not particularly limited as long as the fluorine atom is bonded to the carbon atom bonded to the linking group Y.

Specific examples of the fluoroalkylene group Rf include, for example,
^O * -CHF- * ^Y ,
^O * -CF ₂ CHF- * ^Y ,
^O * -CHFCF _2- * ^Y ,
^O * -CH ₂ CF _2- * ^Y ,
^O * -CF ₂ CF ₂ CHF- * ^Y ,
^O * -CHFCF ₂ CF _2- * ^Y ,
^O * -CH ₂ CF ₂ CF _2- * ^Y ,
^O * -CH ₂ CF ₂ CF ₂ CF _2- * ^Y ,
^O * -CH ₂ CF ₂ CF ₂ CF ₂ CF _2- * ^Y ,
^O * -CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- * ^Y ,
^O * -CF _2- * ^Y ,
^O * -CF ₂ CF _2- * ^Y ,
^O * -CF ₂ CF ₂ CF _2- * ^Y ,
^O * -CF (CF ₃ ) CF _2- * ^Y ,
^O * -CF ₂ CF ₂ CF ₂ CF _2- * ^Y ,
^O * -CF (CF ₃ ) CF ₂ CF _2- * ^Y ,
^O * -CF ₂ CF ₂ CF ₂ CF ₂ CF _2- * ^Y ,
^O * -CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- * ^Y ,
Groups represented by the following equations (Rf-1) to (Rf-9),
Examples thereof include those in which a part of the fluorine atom in the group represented by the following formulas (Rf-1) to (Rf-9) is replaced with hydrogen. The fluoroalkylene group Rf is not limited to these specific examples. Here, " ^O *" represents a binding site to an oxygen atom in the formula (1), and "* ^Y " represents a binding site to a linking group represented by ^{Y 1} or Y ² in the formula (1). show.

 

(Fluoroalkylene group X)
Each of X in the formula (1) independently represents a fluoroalkylene group. _{Further, (OX) m} in the equation (1) includes a structure in which continuous (OX) is represented by the equation (2), and m represents an integer of 2 or more.
Equation (2):-(OX ^{1- OX 2} ) _a-
However, in the above formula (2), X ¹ represents a fluoroalkylene group having 2 to 6 carbon atoms, X ² represents a fluoroalkylene group having 2 to 6 carbon atoms different from X ^1, and a represents an integer of 1 or more. Represented by 2 ≦ (2 × a) ≦ m.

Examples of the carbon number of the fluoroalkylene group represented by X in the formula (1) (hereinafter, also referred to as “fluoroalkylene group X”) include 1 to 6, which are 2 to 6 from the viewpoint of improving heat resistance. Is preferable.
_{Of the m fluoroalkylene groups X contained in (OX) m} in the formula (1), the ratio of the fluoroalkylene group X having 2 or more carbon atoms is 50% by number with respect to the total of m fluoroalkylene groups X. The above is preferable, 70% by number or more is more preferable, and 100% by number is further preferable. When the ratio of the fluoroalkylene group X having 2 or more carbon atoms is in the above range, the heat resistance is improved. That is, the proportion of the fluoroalkylene group having 1 carbon atom is preferably small, and it is preferable that the fluoroalkylene group does not exist. In particular, it is preferable from the viewpoint of heat resistance that there is no continuous fluoroalkylene group having 1 carbon atom.

The fluoroalkylene group X may be a linear fluoroalkylene group, a branched fluoroalkylene group, or a fluoroalkylene group containing a ring structure. Examples of the ring structure include a cyclobutane structure and a cyclohexane structure.
The fluoroalkylene group X is preferably a linear fluoroalkylene group or a branched fluoroalkylene group from the viewpoint of viscosity before curing, and more preferably a linear fluoroalkylene group whose molecular weight can be easily increased from the viewpoint of insulating property after curing. ..

_{The ratio of the branched fluoroalkylene group X among the m fluoroalkylene groups X contained in (OX) m} in the formula (1) is less than 50% by number with respect to the total of m fluoroalkylene groups X. It is preferable, it is more preferably less than 30% by number, and even more preferably 0% by number. Further, the ratio of the linear fluoroalkylene group X among the m fluoroalkylene groups X contained in _{(OX) m} in the formula (1) is 50% by number with respect to the total of m fluoroalkylene groups X. The above is preferable, 70% by number or more is more preferable, and 100% by number is further preferable.
_{Since the proportion of the branched fluoroalkylene group X contained in (OX) m} in the formula (1) is small and the proportion of the linear fluoroalkylene group X is large, it becomes easy to increase the molecular weight at the time of polymerization. Therefore, the insulating property after curing is improved.

Further, the fluoroalkylene group X is preferably a perfluoroalkylene group from the viewpoint of heat resistance. On the other hand, the fluoroalkylene group X may contain a hydrogen atom from the viewpoint of compatibility with other components in the curable composition. The bond position and number of hydrogen atoms in the fluoroalkylene group X containing hydrogen atoms are not particularly limited.

Specific examples of the fluoroalkylene group X include, for example,
¹ * -CHF- * ² ,
¹ * -CF ₂ CHF- * ² ,
¹ * -CHFCF _2- * ² ,
¹ * -CH ₂ CF _2- * ² ,
¹ * -CF ₂ CH _2- * ² ,
¹ * -CF ₂ CF ₂ CHF- * ² ,
¹ * -CF ₂ CHFCF _2- * ² ,
¹ * -CHFCF ₂ CF _2- * ² ,
¹ * -CH ₂ CF ₂ CF _2- * ² ,
¹ * -CF ₂ CH ₂ CF _2- * ² ,
¹ * -CF ₂ CF ₂ CH _2- * ² ,
¹ * -CHFCF ₂ CHF- * ² ,
¹ * -CHFCF ₂ CF ₂ CF _2- * ² ,
¹ * -CF ₂ CHFCF ₂ CF _2- * ² ,
¹ * -CF ₂ CF ₂ CHFCF _2- * ² ,
¹ * -CF ₂ CF ₂ CF ₂ CHF- * ² ,
¹ * -CH ₂ CF ₂ CF ₂ CF _2- * ² ,
¹ * -CF ₂ CF ₂ CF ₂ CH _2- * ² ,
¹ * -CH ₂ CF ₂ CF ₂ CF ₂ CF _2- * ² ,
¹ * -CF ₂ CF ₂ CF ₂ CF ₂ CH _2- * ² ,
¹ * -CH ₂ CF ₂ CF ₂ CF ₂ CH _2- * ² ,
¹ * -CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- * ² ,
¹ * -CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH _2- * ² ,
¹ * -CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH _2- * ² ,
¹ * -CF _2- * ² ,
¹ * -CF ₂ CF _2- * ² ,
¹ * -CF ₂ CF ₂ CF _2- * ² ,
¹ * -CF (CF ₃ ) CF _2- * ² ,
¹ * -CF ₂ CF ₂ CF ₂ CF _2- * ² ,
¹ * -CF (CF ₃ ) CF ₂ CF _2- * ² ,
¹ * -CF ₂ CF ₂ CF ₂ CF ₂ CF _2- * ² ,
¹ * -CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- * ² ,
Groups represented by the following equations (X-1) to (X-9),
Examples thereof include those in which a part of the fluorine atom in the group represented by the following formulas (X-1) to (X-9) is replaced with hydrogen. The fluoroalkylene group X is not limited to these specific examples. Here, " ¹ *" represents the binding site on the side close to ^{Rf 1} in the formula (1) ^{, and "* 2} " represents the binding site on the side close to ^{Rf 2} in the formula (1).

 

M in the formula (1) is an integer of 2 or more, preferably 2 to 400, more preferably 2 to 200, and even more preferably 2 to 100.

_{(OX) m} in the formula (1) includes a structure in which continuous (OX) is represented by the formula (2) (hereinafter, also referred to as “structure (2)”), and (OX) other than the structure (2). May include.
Equation (2):-(OX ^{1- OX 2} ) _a-
In the formula (2), X ¹ represents a fluoroalkylene group having 2 to 6 carbon atoms, X ² represents a fluoroalkylene group having 2 to 6 carbon atoms different from X ^1, and a represents an integer of 1 or more. ≦ (2 × a) ≦ m.

^{X 1} and X ² in the formula (2) represent different fluoroalkylene groups, and each independently represents a fluoroalkylene group having 2 to 6 carbon atoms. ^{The fluoroalkylene group represented by X 1} or X ² in the formula (2) may be a linear fluoroalkylene group, a branched fluoroalkylene group, or a fluoroalkylene group containing a ring structure. ^{Specific examples of the fluoroalkylene group represented by X 1} or X ² in the formula (2) include fluoroalkylene groups having 2 to 6 carbon atoms among those listed as specific examples of the fluoroalkylene group X. .. ^{The fluoroalkylene group represented by X 1} or X ² in the formula (2) is not limited to these specific examples.

Examples of the fluoroalkylene groups different from each other include fluoroalkylene groups having different carbon atoms, fluoroalkylene groups having the same carbon number and different structures, and fluoroalkylene groups having the same carbon number and structure but different numbers of hydrogen atoms.
The fluoroalkylene groups different from each other are preferably fluoroalkylene groups having different carbon atoms or fluoroalkylene groups having the same carbon number but different structures, and more preferably fluoroalkylene groups having different carbon atoms.

The combinations of different carbon numbers include a combination of 2 carbon atoms and 3 carbon atoms, a combination of 2 carbon atoms and 4 carbon atoms, a combination of 2 carbon atoms and 5 carbon atoms, and a combination of 2 carbon atoms and 6 carbon atoms. Combination, combination of 3 carbons and 4 carbons, 3 carbons and 5 carbons, 3 carbons and 6 carbons, 4 carbons and 5 carbons, 4 carbons Examples thereof include a combination with 6 carbon atoms and a combination with 5 carbon atoms and 6 carbon atoms. Among these, the combination of different carbon atoms is a combination of 2 carbon atoms and 3 carbon atoms, a combination of 2 carbon atoms and 4 carbon atoms, and a combination of 2 carbon atoms and 6 carbon atoms from the viewpoint of ease of synthesis. Is preferable, and a combination of 2 carbon atoms and 4 carbon atoms is more preferable.
The combination of fluoroalkylene groups having different carbon atoms may have different numbers of hydrogen atoms in addition to the carbon atoms.

Examples of combinations of fluoroalkylene groups having different structures include a combination of a linear fluoroalkylene group and a branched fluoroalkylene group, a combination of a linear fluoroalkylene group and a fluoroalkylene group containing a ring structure, and a branched fluoro. Examples thereof include a combination of an alkylene group and a fluoroalkylene group containing a ring structure, a combination of two types of branched fluoroalkylene groups having different structures, a combination of a fluoroalkylene group containing two types of ring structures having different structures, and the like.
The combination of fluoroalkylene groups having different structures may have different numbers of hydrogen atoms in addition to the structure.

The combination of X ¹ and X ² is a combination of a fluoroalkylene group having 2 carbon atoms and a fluoroalkylene group having 3 carbon atoms, a combination of a fluoroalkylene group having 2 carbon atoms and a fluoroalkylene group having 4 carbon atoms, or a carbon number of carbon atoms. A combination of a fluoroalkylene group of 2 and a fluoroalkylene group having 6 carbon atoms is more preferable, a combination of a fluoroalkylene group having 2 carbon atoms and a fluoroalkylene group having 4 carbon atoms is further preferable, and a linear linear group having 2 carbon atoms is preferable. A combination of a fluoroalkylene group and a linear fluoroalkylene group having 4 carbon atoms is particularly preferable.

Among the examples of the structure (2), as a specific example in which X ¹ and X ² are a combination of a linear fluoroalkylene group having 2 carbon atoms and a linear fluoroalkylene group having 4 carbon atoms, for example,
_{- (OCF 2 CF 2 -OCF 2} CF 2 CF 2 CF 2) a -
_{- (OCHFCF 2 -OCF 2 CF 2} CF 2 CF 2) a -
-(OCHFCF ₂ -OCHFCF ₂ CF ₂ CF ₂ ) _a-
-(OCHFCF ₂ -OCF ₂ CHFCF ₂ CF ₂ ) <sub>a-
- (OCHFCF 2 -OCF 2 CF 2</sub> CHFCF 2) a -
_{- (OCHFCF 2 -OCF 2 CF 2} CF 2 CHF) a -
_{- (OCHFCF 2 -OCH 2 CF 2} CF 2 CF 2) a -
-(OCHFCF ₂ -OCF ₂ CH ₂ CF ₂ CF ₂ ) <sub>a-
- (OCHFCF 2 -OCF 2 CF 2</sub> CH 2 CF 2) a -
_{- (OCHFCF 2 -OCF 2 CF 2} CF 2 CH 2) a -
-(OCH ₂ CF ₂ -OCF ₂ CF ₂ CF ₂ CF ₂ ) _a-
-(OCH ₂ CF _2- OCH FCF ₂ CF ₂ CF ₂ ) _a-
-(OCH ₂ CF _2- OCF ₂ CHFCF ₂ CF ₂ ) _a-
-(OCH ₂ CF ₂ -OCF ₂ CF ₂ CHFCF ₂ ) _a-
-(OCH ₂ CF _2- OCF ₂ CF ₂ CF ₂ CHF) <sub>a-
- (OCH 2 CF 2 -OCH 2</sub> CF 2 CF 2 CF 2) a -
-(OCH ₂ CF ₂ -OCF ₂ CH ₂ CF ₂ CF ₂ ) _a-
-(OCH ₂ CF ₂ -OCF ₂ CF ₂ CH ₂ CF ₂ ) _a-
-(OCH ₂ CF ₂ -OCF ₂ CF ₂ CF ₂ CH ₂ ) _a-
Can be mentioned. The structure (2) is not limited to these specific examples.

A in the formula (2) is an integer of 1 or more and satisfies the condition of 2 ≦ (2 × a) ≦ m.
The a in the formula (2) is preferably 1 to 200, more preferably 1 to 100, and even more preferably 1 to 50.
When a in the formula (2) is 1, (OX) _m in the formula (1) has a structure in which continuous (OX) is represented by the formula (2-1) or the formula (2-2). You may have.
Equation (2-1): -OX ¹ -OX ^{2 --OX 1-}
Equation ^{(2-2): - OX 2 -OX} 1 -OX 2 -
In formulas (2-1) and (2-2), X ¹ and X ² mean the same groups as ^{X 1} and X ^{2 in} formula (2), respectively.
In addition, a in the formula (2) may be an integer of 2 or more.

_{(OX) m} in the formula (1) may include two or more structures (2). Examples of the form including two or more structures (2) include a form including two or more types of structures (2) in which at least one ^{of X 1} and X ^{2 is different in the formula (2), and X 1 in the formula (2).} And X ² include two or more structures (2) having the same structure (2) via (OX) other than the structure (2).
_{The number of structures (2) contained in (OX) m} in the formula (1) is preferably 1 to 10, more preferably 1 to 6, and even more preferably 2 to 4.
_{When (OX) m} in the formula (1) includes a plurality of structures (2), the plurality of a may be the same or different.

(Preferable form of compound (1), specific example)
Examples of the compound (1) include a compound represented by the following formula (3).
Equation (3): A ¹ _r1- Y ^1- Rf ^1- (OX ³¹ ) _b1- (OX ^{11- OX 21} ) _a1- (OX ³² ) _b2- (OX ^{22- OX 12} ) _a2- (OX ³³ ) _b3 -O-Rf ^2- Y ^2- A ² _r2
In the formula (3), A ¹ , r1, Y ¹ , Rf ¹ , Rf ² , Y ² , A ^{2 and r 2 are the A 1} , r ¹ , Y 1, Rf ¹ and Rf 1 in the formula (1). It means the same group or number as ^{Rf 2} , Y ² , A ^{2 and r 2.}
In the above formula (3), X ³¹ , X ³² , and X ³³ each independently represent a fluoroalkylene group, b1, b2, and b3 each independently represent an integer of 0 or more, and X ¹¹ has 2 to 2 carbon atoms. 6 represents a fluoroalkylene group, X ²¹ represents a fluoroalkylene group having 2 to 6 carbon atoms different from X ¹¹ , a1 represents an integer of 2 or more, a2 represents an integer of 0 or 2 or more, and X ^{12 represents an integer of 0 or 2 or more.} It represents a fluoroalkylene group having 2 to 6 carbon atoms, and X ²² represents a fluoroalkylene group having 2 to 6 carbon atoms which is different from X ^12.
The total of b1, 2 × a1, b2, 2 × a2, and b3 in the formula (3) corresponds to m in the formula (1).

^{The fluoroalkylene group represented by X 31} , X ³² , or X ³³ in the formula (3) corresponds to the above-mentioned fluoroalkylene group X. ^{The fluoroalkylene group represented by X 31} in the formula (3), the fluoroalkylene group represented by X ³² , and the ^{fluoroalkylene group represented by X 33} may be the same or different. .. From the viewpoint of easiness of synthesis, it is preferable that the fluoroalkylene group represented by ^{X 31 and the fluoroalkylene group represented by X 33 in the formula (3) are the same.}

Each of b1 and b3 in the formula (3) is preferably an integer of 0 to 20, more preferably an integer of 0 to 10, and even more preferably 0 or 1. The integer represented by b1 and the integer represented by b3 in the equation (3) may be the same or different. From the viewpoint of ease of synthesis, it is preferable that the integer represented by b1 and the integer represented by b3 in the equation (3) are the same.
The b2 in the formula (3) is preferably 0 to 20, more preferably 0 to 10, and even more preferably 0-1. ^{However, when (OX 11- OX 21} ) and (OX ^{12- OX 22} ) in the equation (3) have the same structure, b2 is an integer of 1 or more.

^{The fluoroalkylene group represented by X 11} or X ¹² in the formula (3) corresponds to the fluoroalkylene group represented by ^{X 1} in the above-mentioned formula (2), and ^{is represented by X 21} or X ^22. fluoroalkylene groups correspond to the fluoroalkylene group represented by X ² in the above formula (2).
^{The fluoroalkylene group represented by X 11} and the fluoroalkylene group represented by X ²¹ in the formula (3) are the same as the fluoroalkylene group represented by X ¹² or the fluoroalkylene group represented by ^{X 22.} It may be different from any of them. From the viewpoint of easiness of synthesis, the compound represented by the formula (3) has a fluoroalkylene group represented by ^{X 11 as one of a fluoroalkylene group represented by X 12} and a fluoroalkylene group represented by ^{X 22.} It is preferable that the fluoroalkylene group represented by ^{X 21} is the same as the other of the fluoroalkylene ^{group represented by X 12} and the fluoroalkylene group ^{represented by X 22.}

A1 and a2 in the formula (3) correspond to a in the above-mentioned formula (2).
The integer represented by a1 and the integer represented by a2 in the equation (3) may be the same or different. From the viewpoint of ease of synthesis, it is preferable that the integer represented by a1 and the integer represented by a2 in the equation (3) are the same.

The compound (1) is preferably a compound represented by the following formula (4).
Equation (4): A ¹ _r1- Y ^1- Rf ^1- (OX ³¹ ) _b1- (OX ^{1- OX 2} ) _a1- (OX ³² ) _b2- (OX ^{2- OX 1} ) _a2- (OX ³³ ) _b3 -O-Rf ^2- Y ^2- A ² _r2
In the formula (4), A ¹ , r1, Y ¹ , Rf ¹ , Rf ² , Y ² , A ^{2 and r 2 are the A 1} , r ¹ , Y 1, Rf ¹ and Rf 1 in the formula (1). It means the same group or number as ^{Rf 2} , Y ² , A ^{2 and r 2.}
In the formula (4), X ¹ and X ² mean the same group as ^{X 1} and X ² in the formula (2).
In the formula (4), X ³¹ , b1, a1, X ³² , b2, a2, X ³³ , and b3 are the X ³¹ , b1, a1, X ³² , b2, a2, X in the formula (3). ^It means the same group or integer as 33 and b3. However, b2 represents an integer of 1 or more.
The total of b1, 2 × a1, b2, 2 × a2, and b3 in the equation (4) corresponds to m in the equation (1).

It is preferable that the compound (1) has ^{a chemical structure in which the A 1} side and the A ² side in the formula (1) are symmetrical from the viewpoint of easiness of synthesis. Compound (1), among the compounds represented by formula (4), ^{A 1} and ^A 2, r1 and r2, ^{Y 1} and ^Y 2, Rf ¹ and ^{Rf 2, X 31} and ^{X 33,} and b1 and b3 Is preferably the same compound, and more preferably a1 and a2 are the same compound.

Specific examples of the compound represented by the formula (4) include compounds represented by the following (4-1) to (4-16). The compound represented by the formula (4) is not limited to these specific examples. Further, the compound (1) is not limited to the compound represented by the formula (4).

 

 

 

(Characteristics of compound (1))
The number average molecular weight of compound (1) is, for example, 500 to 100,000, preferably 500 to 50,000, preferably 500 to 50,000, from the viewpoint of viscosity before curing, insulation after curing, and heat resistance. 000 is more preferable.
The number average molecular weight is calculated by obtaining the number of units of a constituent unit from the integrated values of ¹ H-NMR and ^{19 F-NMR.}

The fluorine atom content in the compound (1) is preferably 25% by mass or more, more preferably 30% by mass or more, and further preferably 35% by mass or more from the viewpoint of insulating property after curing. It is preferably 53% by mass or more, particularly preferably 55% by mass or more, and most preferably 57% by mass or more. The upper limit of the fluorine atom content in the compound (1) is not particularly limited, and examples thereof include 75% by mass. That is, the fluorine atom content in the compound (1) is preferably 25% by mass to 75% by mass, more preferably 30% by mass to 75% by mass, further preferably 35% by mass to 70% by mass, and 53% by mass to 70%. The mass% is particularly preferable, 55% by mass to 70% by mass is extremely preferable, and 57% by mass to 70% by mass is most preferable.
Here, the fluorine atom content is a value obtained by the following formula when the number of fluorine atoms constituting the compound (1) is NF and the number average molecular weight of the compound (1) is MA.
Formula: Fluorine atom content (% by mass) = (19 x NF / MA) x 100
The fluorine atom content is determined by the above formula after determining the chemical structure of compound (1) from the integrated values of ¹ H-NMR and ^{19 F-NMR.}

The thermosetting film of compound (1) is heated from room temperature (25 ° C) to 450 ° C at 10 ° C / min under a nitrogen flow by a thermogravimetric differential thermal analyzer (manufactured by Hitachi High-Tech Science Co., Ltd .: STA7200). The weight loss rate when heated is preferably 70% by mass or less, more preferably 50% by mass or less, and further preferably 30% by mass or less. The lower limit of the weight loss rate of the compound (1) is not particularly limited, and the closer it is to 0% by mass, the more preferable.
Here, in the heat-cured film, specifically, the compound (1) is coated on a quartz glass substrate that has been subjected to a mold release treatment, and another quartz that has been subjected to a mold release treatment via a 100 μm spacer. It is obtained by heating the material sandwiched between glass substrates at 250 ° C. for 1 hour under a nitrogen flow and then removing the mold from the quartz glass substrate.
Further, the weight reduction rate is a value obtained by the following formula when the mass of the compound (1) before heating is Wb and the mass of the compound after heating is Wa.
Formula: Weight loss rate (% by mass) = ((Wb-Wa) / Wb) × 100

Regarding the thermosetting film of compound (1), the refractive index obtained by the following method is preferably 1.3 to 1.7, more preferably 1.3 to 1.6, from the viewpoint of light extraction from the optical element. .3 to 1.5 are more preferable.
Specifically, a refractive index measuring device (product name "prism coupler: 2010 / M", manufactured by Metricon Co., Ltd.) is used to measure the refractive index for light having a wavelength of 473 nm, 594 nm, and 658 nm at a temperature of 25 ° C. The refractive index is calculated as the refractive index for light having a wavelength of 589 nm using the Mercon Fit attached to the device.

(Method for producing compound (1))
As an example of the manufacturing method of the compound (1), among the compounds represented by formula (4), an r1 and r2 is 1, b1 and b3 are ^0, A 2, ^{Y 2,} and Rf ² are each An example of a method for producing a compound which is the same as A ¹ , Y ¹ , and Rf ^{1 will be described.} The production of the above compound is carried out, for example, as follows.
Specifically, first, the precursor compound represented by the following formula (53) is obtained by reacting the compound represented by the following formula (51) with the compound represented by the following formula (52). obtain.
Equation _{^{(51): HO-X 2}} - (OX 32) b2 -O-X 2 -OH
Equation (52): X ^O1- O-X ^2- OH
Equation _{^{(53): HO-X 2}} - (OX 1 -OX 2) a1 - (OX 32) b2 - (OX 2 -OX 1) a2 -O-X 2 -OH
^{Wherein, X 1, X 2, X} 32, a1, a2, and b2 in equation (51) - (53), ^X 1 in the formula ^{(4), X 2, X} 32, a1, a2 and, It is the same as b2. ^{Further, X O1} in the formula (52) represents a fluoroalkendiyl group in which the carbon-carbon bond at the terminal of the fluoroalkylene group represented by ^{X 1} in the formula (4) is replaced with a double bond.

Next, by reacting the precursor compound represented by the formula (53) with the compound represented by the following formula (54), the compound represented by the following formula (55) which is the compound (1). Is obtained.
Equation (54): Ay-Cl
Equation (55): Ay- ^{OX 2-} (OX ^{1- OX 2} ) _a1- (OX ³² ) _b2- (OX ^{2- OX 1} ) _a2- O-X ^2- O-Ay
Here, ^{X 1, X 2, X 32} , a1, a2, and b2 in equation (55) is the same as ^{X 1, X 2, X 32} , a1, a2, and b2 in equation (4) be. Further, Ay in the formulas (54) and (55) is a group containing the above-mentioned curable functional group A, and "Ay-O-X ^2- " in the formula (55) is a group in the formula (4). Corresponds to "A ^1- Y ^1- Rf ^1-".

Examples of the method for producing the compound represented by the formula (51) include the following methods when X ^{32 of the} formula (51) is a fluoroalkylene group represented by the formula (X-1).
Specifically, by heating the compound represented by the following formula (56), the compound represented by the following formula (57) can be obtained.

 

Here, ^{X 2} in the formula (56) and (57) is the same as ^{X 2} in the formula (4).

^{When all of X 1} and X ² in the formula (4) are perfluoroalkylene groups, even if the precursor compound is subjected to a step of perfluoroization before the compound represented by the formula (54) is reacted. good.

As another example of the manufacturing method of the compound (1), among the compounds represented by the formula (4), r1 and r2 are 1, b1 and b3 are ^1, A 2, ^{Y 2,} and Rf ² There will be described one example of a manufacturing method of each ^{a 1, Y} 1, and the same, compound with Rf ^1. The production of the above compound is carried out, for example, as follows.
Specifically, first, the precursor compound represented by the following formula (63) is obtained by reacting the compound represented by the following formula (61) with the compound represented by the following formula (62). obtain.
Equation (61): HO- (OX ³² ) _b2- OH
Equation (62): X ^O2- O-X ^1- OH
Equation ^{(63): HO-X 1} -OX 2 - (OX 1 -OX 2) a1 - (OX 32) b2 - (OX 2 -OX 1) a2 -OX 2 -O-X 1 -OH
^{Wherein, X 1, X 2, X} 32, a1, a2, and b2 in equation (61) - (63), ^X 1 in the formula ^{(4), X 2, X} 32, a1, a2 and, It is the same as b2. ^{Further, X O2} in the formula (62) represents a fluoroalkendiyl group in which the carbon-carbon bond at the end of the fluoroalkylene group represented by ^{X 2} in the formula (4) is replaced with a double bond.

Next, by reacting the precursor compound represented by the formula (63) with the compound represented by the following formula (64), the compound represented by the following formula (65), which is the compound (1). Is obtained.
Equation (64): Ay-Cl
Equation ^{(65): Ay-OX 1} -OX 2 - (OX 1 -OX 2) a1 - (OX 32) b2 - (OX 2 -OX 1) a2 -OX 2 -O-X 1 -Ay
Here, ^{X 1, X 2, X 32} , a1, a2, and b2 in equation (65) is the same as ^{X 1, X 2, X 32} , a1, a2, and b2 in equation (4) be. Further, Ay in the formulas (64) and (65) is a group containing the above-mentioned curable functional group A, and "Ay-O-X ^1- " in the formula (65) is in the formula (4). Corresponds to "A ^1- Y ^1- Rf ^1-".

^{When all of X 1} and X ² in the formula (4) are perfluoroalkylene groups, even if the precursor compound is subjected to a step of perfluoroization before the compound represented by the formula (64) is reacted. good.

[Curable composition]
The curable composition of the present disclosure (hereinafter, also referred to as “the present composition”) is selected from the group consisting of the above-mentioned fluorine-containing ether compound (that is, compound (1)), a polymerization initiator, a solvent, and a curing agent. At least one of them may be contained, and other components may be contained if necessary. Since the present composition contains the compound (1), it is excellent in curability and heat resistance after curing.
The composition may contain a polymerization initiator, a solvent, or a curing agent, may contain a polymerization initiator and a solvent, may contain a polymerization initiator and a curing agent, may contain a solvent and a curing agent, and may be polymerized. It may contain an initiator, a solvent, and a curing agent.

The present composition may contain only one kind of compound (1), or may contain two or more kinds. Examples of the content of the compound (1) with respect to the entire composition include, for example, 30% by mass to 100% by mass, preferably 50% by mass to 99% by mass, and more preferably 70% by mass to 98% by mass.
The present composition may contain a fluorine-containing ether compound other than the compound (1). However, the content of the compound (1) with respect to the entire fluorine-containing ether compound contained in the present composition is preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass or more. Is even more preferable.

<Polymerization initiator>
When the present composition contains a polymerization initiator, the polymerization initiator contained in the present composition may be one kind or two or more kinds.
The polymerization initiator is appropriately selected depending on the curing method (photo-curing or thermosetting) and the like. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator.
Examples of the photopolymerization initiator include a photoradical initiator and a photoacid generator, and examples of the thermal polymerization initiator include a thermal radical initiator.

Examples of the photoradical polymerization initiator include an acetophenone-based photopolymerization initiator, a benzoin-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, a thioxanthone-based photopolymerization initiator, an α-aminoketone-based photopolymerization initiator, and an α-hydroxyl. Ketone-based photopolymerization initiator, α-acyloxime ester, benzyl- (o-ethoxycarbonyl) -α-monooxime, acylphosphine oxide, glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylthiumam Examples include sulfides, azobisisobutyronitrile, benzoyl peroxides, dialkyl peroxides, and tert-butyl peroxypivalates. Among them, the photoradical polymerization initiator is an acetophenone-based photopolymerization initiator, a benzoin-based photopolymerization initiator, an α-aminoketone-based photopolymerization initiator, or a benzophenone-based photopolymerization initiator from the viewpoint of sensitivity and compatibility. Is preferable, and it is more preferable that the acetophenone-based photopolymerization initiator is used.

As the photoacid generator, a known photoacid generator can be used. For example, various compounds which are suitable in JP-A-2017-90515 can be mentioned, but the present invention is not particularly limited thereto. Examples of the photoacid generator that can be preferably used in one embodiment of the present invention include sulfonate esters, carboxylic acid esters, and onium salts, and onium salts are preferably used.

Examples of the onium salts which can be used in an embodiment of the present invention, tetrafluoroborate (BF ₄ ^-), hexafluorophosphate (PF ₆ ^-), hexafluoroantimonate (SbF ₆ ^-), hexafluoroarsenate (AsF ₆ ^- ), hexa-chloro antimonate (SbCl ₆ ^-), tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluorophenyl methylphenyl) borate, perchlorate ion (ClO ₄ ^-), trifluoromethanesulfonate ion ( CF 3 _SO 3 ^_-), fluoro sulfonic acid ion (FSO 3 ^_-), can be used toluenesulfonic acid ion, trinitrobenzene sulfonic acid anion, a sulfonium salt or iodonium salt having an anion such as trinitrotoluene sulfonate anion.

Examples of the sulfonium salt include triphenylsulfonium hexafluoroacylnate, triphenylsulfonium hexahexafluoroborate, triphenylsulfoniumtetrafluoroborate, triphenylsulfoniumtetrakis (pentafluobenzyl) borate, methyldiphenylsulfoniumtetrafluoroborate, and methyldiphenyl. Sulfonium Sulfonium (Pentafluorobenzyl) Borate, dimethylphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenylnaphthylsulfonium hexafluoroarsenate, tritoylsulfonium hexafluorophosphate, anisyldiphenylsulfonium Hexahexafluorantimonate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 4-butoxyphenyldiphenylsulfoniumtetrakis (pentafluorobenzyl) borate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, tris (4-phenoxyphenyl) sulfonium hexa Fluorophosphate, di (4-ethoxyphenyl) methylsulfonium hexafluoroarsenate, 4-acetylphenyldiphenylsulfonium tetrafluoroborate, 4-acetylphenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, tris (4-thiomethoxyphenyl) sulfonium Hexafluorophosphate, di (methoxysulfonylphenyl) methylsulfonium hexafluoroantimonate, di (methoxynaphthyl) methylsulfonium tetrafluoroborate, di (methoxynaphthyl) methylsulfonium tetrakis (pentafluorobenzyl) borate, di (carbomethoxyphenyl) methyl Sulfonium Hexafluorophosphate, (4-octyloxyphenyl) diphenylsulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, tris (dodecylphenyl) sulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, 4-Acetamide phenyldiphenylsulfonium tetrafluoroborate, 4-acetamidophenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, di Methylnaphthylsulfonium hexafluorophosphate, trifluoromethyldiphenylsulfonium tetrafluoroborate, trifluoromethyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, phenylmethylbenzylsulfonium hexafluorophosphate, 10-methylphenoxatiinium hexafluorophosphate, 5- Methylthiantrenium Hexafluorophosphate, 10-Phenyl-9,9-Dimethylthioxanthenium Hexafluorophosphate, 10-Phenyl-9-oxothioxanthenium xantenium Tetrafluoroborate, 10-Phenyl-9-oxothio Xanthenium tetrakis (pentafluorobenzyl) borate, 5-methyl-10-oxothiatrenium tetrafluoroborate, 5-methyl-10-oxothiatrenium tetrakis (pentafluorobenzyl) borate, and 5-methyl-10,10- Examples thereof include dioxothiatrenium hexafluorophosphate. These can be used alone or in combination of two or more.

Examples of the iodonium salt that can be used in one embodiment of the present invention include (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate and [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluoro. Antimonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium trifluorosulfonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluorophosphate, [4- (2-Hydroxy-n-tetradecyloxy) Phenyl] Phenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium hexafluoro Phosphate, bis (4-t-butylphenyl) iodonium trifluorosulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoro Borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium trifluoromethyl sulphonate, di (dodecylphenyl) iodonium hexafluoroantimonate, di (dodecylphenyl) iodonium trifurate, diphenyl iodonium bisulfate, 4,4'-Dichlorodiphenyliodonium bisulfate, 4,4'-dibromodiphenyliodonium bisulfate, 3,3'-dinitrodiphenyliodonium bisulfate, 4,4'-dimethyldiphenyliodonium bisulfate, 4,4'-bis Succinimidediphenyliodonium bisulfate, 3-nitrodiphenyliodonium bisulfate, 4,4'-dimethoxydiphenyliodonium bisulfate, bis (dodecylphenyl) iodinenium tetrakis (pentafluorophenyl) borate, (4-octyloxyphenyl) phenyliodonium tetrakis (4-octyloxyphenyl) 3,5-bis-trifluoromethylphenyl) borate, (trilucmil) iodonium tetrakis (pentafluorophenyl) borate, (CH ₃ C ₆ H) disclosed in US Pat. No. 5,554,664. ^{_{4) 2 I - (SO 2}} CF 3) 3, it is disclosed in U.S. Patent No. ^{_{5,514,728 (C 6 H 5) 2}} I - B (C 6 F 5) 4, and U.S. Patent No. 5 , 340, 898, and the like. These can be used alone or in combination of two or more.

As the other onium salt, an aromatic diazonium salt can be used, for example, p-methoxybenzenediazonium hexafluoroantimonate or the like can be used.

As the thermal radical initiator, a known polymerization initiator can be used. For example, azo compounds and organic peroxides can be mentioned. Examples of the azo compound include 2,2'-azobis (isobutyronitrile), and examples of the organic peroxide include benzoyl peroxide, but the present invention is not particularly limited thereto.

When the present composition contains a polymerization initiator, the content of the polymerization initiator in the entire composition may be, for example, 0.5% by mass to 10% by mass, and may be 1% by mass to 8% by mass. It is preferably 1% by mass to 6% by mass, more preferably 1% by mass.

<Solvent>
When the present composition contains a solvent, the solvent contained in the present composition may be one kind or two or more kinds.
Examples of the solvent include organic solvents. The organic solvent may be a fluorine-containing organic solvent, a non-fluorine-containing organic solvent, or may contain both a fluorine-containing organic solvent and a non-fluorine-containing organic solvent.

Examples of the fluorine-containing organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
Examples of the fluorinated alkane include fluorinated alkanes having 4 to 8 carbon atoms. Specific examples of the fluorinated alkane include C ₆ F ₁₃ H, C ₆ F ₁₃ C ₂ H ₅ , and C ₂ F ₅ CHFCHFCF ₃ .
Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis (trifluoromethyl) benzene.
Examples of the fluoroalkyl ether include fluoroalkyl ethers having 4 to 12 carbon atoms. Specific examples of the fluoroalkyl ether include, for example, CF ₃ CH ₂ OCF ₂ CF ₂ H, C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ Can be mentioned.
Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol and hexafluoroisopropanol.
Examples of the non-fluorine organic solvent include hydrocarbons, alcohols, ketones, ethers and esters.

<Curing agent>
Examples of the curing agent include compounds having two or more curable functional groups and no oxyfluoroalkylene group (hereinafter, also referred to as “polyfunctional compound”). Examples of the polyfunctional compound include a polyfunctional (meth) acrylate compound, a polyfunctional maleimide, and a polyfunctional vinyl ether, a polyfunctional amine, and a polyfunctional alcohol. Among them, the polyfunctional compound is preferably at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional maleimide from the viewpoint of curability, and is preferably a polyfunctional (meth) acrylate. More preferred. These compounds may have a fluorine atom.
Here, in the present specification, "(meth) acrylate" means at least one of acrylate and methacrylate. Further, "(meth) acryloyl group" means at least one of acryloyl group and methacrylic group, and "(meth) acrylic" means at least one of acrylic and methacrylic.

The number of curable functional groups of the polyfunctional compound is preferably 3 or more from the viewpoint of curability. Further, the number of curable functional groups contained in the polyfunctional compound is preferably 6 or less, and more preferably 4 or less, from the viewpoint of reducing the viscosity of the curable composition.

Examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate. , Dipropylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, Butylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, Neopentyl glycol di (meth) ) Acrylate, 3-Methyl-1,5-pentanediol di (meth) acrylate, hexanediol di (meth) acrylate, heptanediol di (meth) acrylate, EO-modified neopentyl glycol di (meth) acrylate, PO-modified neopentyl Glycoldi (meth) acrylate, EO-modified hexanediol di (meth) acrylate, PO-modified hexanediol di (meth) acrylate, octanediol di (meth) acrylate, nonanediol di (meth) acrylate, decanediol di (meth) acrylate , Dodecanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl Etherdi (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylol ethanetri (meth) acrylate, trimethylol propanetri (meth) acrylate, trimethylol propane EO-added tri (trimethylol propane EO-added tri) Meta) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acrylate ) Acryloyloxyethoxytrimethylol propane, glycerin polyglycidyl ether poly (meth) acrylate and tris (2-acryloyloxyethyl) isocyanurate.

Further, the polyfunctional (meth) acrylate may be urethane (meth) acrylate which is a reaction product of the bifunctional isocyanate compound and the hydroxyl group-containing polyfunctional (meth) acrylate.

Further, the polyfunctional (meth) acrylate may be an epoxy (meth) acrylate which is a reaction product of (meth) acrylic acid and an epoxy resin. Examples of the epoxy resin include bisphenol A type epoxy resin and cresol novolac type epoxy resin.

Examples of the polyfunctional maleimide include 1,2-bis (maleimide) ethane, 1,4-bis (maleimide) butane, 1,6-bis (maleimide) hexane, and 4,4'-bismaleimide diphenylmethane. ..

Examples of the polyfunctional vinyl ether include 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, and hexanediol di. Vinyl ether, 1,4-cyclohexanedimethanol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylol ethane trivinyl ether, trimethylol propanetrivinyl ether, ditrimethylol propanetetravinyl ether, glycerin trivinyl ether, pentaerythritol Tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, EO-added trimethylol propanetrivinyl ether, PO-added trimethylolpropanetrivinyl ether, EO-added ditrimethylolpropane tetravinyl ether, PO-added ditrimethylolpropanetetravinyl ether, EO-added penta Examples thereof include erythritol tetravinyl ether, PO-added pentaerythritol tetravinyl ether, EO-added dipentaerythritol hexavinyl ether and PO-added dipentaerythritol hexavinyl ether.

When the curable composition contains a polyfunctional compound, the content of the polyfunctional compound in the entire curable composition may be, for example, in the range of 5% by mass to 40% by mass.

<Other ingredients>
The composition may contain other components other than the fluorine-containing ether compound, the polymerization initiator, the solvent, and the curing agent, if necessary.
Examples of other components include a compound having one curable functional group and no oxyfluoroalkylene group (hereinafter, also referred to as “monofunctional compound”), a silane coupling agent, and a metal catalyst (for example, platinum catalyst, tin). Catalysts, etc.) and other additives.

(Monofunctional compound)
Examples of the monofunctional compound include monofunctional (meth) acrylate, monofunctional maleimide, monofunctional (meth) acrylamide, monofunctional aromatic vinyl compound, monofunctional vinyl ether, and monofunctional N-vinyl compound. Among them, from the viewpoint of curability, the monofunctional compound is preferably at least one selected from the group consisting of monofunctional (meth) acrylate and monofunctional maleimide, and more preferably monofunctional (meth) acrylate. .. These compounds may have a fluorine atom.

Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Butyl-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) Acrylate, 4-n-Butylcyclohexyl (meth) acrylate, 4-tert-Butylcyclohexyl (meth) acrylate, Bornyl (meth) acrylate, Isobornyl (meth) acrylate, 2-ethylhexyldiglycol (meth) acrylate, Butoxyethyl ( Meta) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoethyl (meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluoro Decyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, 2-phenoxymethyl (meth) Acrylate, 2-phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2 -Hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) ) Acrylate, Cyclic Trimethylol Propaneformal (meth) Acrylate, Phylglycidyl Ether (Meta) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate , Polyethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxyethyl Succinic acid, 2-methacryloyloxyhexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropylphthalate, ethoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (Meta) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ethylene oxide (EO) modified phenol (meth) acrylate, EO-modified cresol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, propylene oxide (PO) Modified nonylphenol (meth) acrylate, EO-modified -2-ethylhexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (3-ethyl- Examples thereof include 3-oxetanylmethyl) (meth) acrylate, phenoxyethylene glycol (meth) acrylate, 2-carboxyethyl (meth) acrylate and 2- (meth) acryloyloxyethyl succinate.

Examples of the monofunctional maleimide include N-phenylmaleimide.

Examples of the monofunctional (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and Nn-butyl (meth) acrylamide. Nt-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl Examples include (meth) acrylamide and (meth) acryloylmorpholin.

Examples of the monofunctional aromatic vinyl compound include styrene, dimethylstyrene, trimethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, and 3-methyl. Styrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene,3-octyl Styrene, 4-octyl styrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allyl styrene, isopropenyl styrene, butenyl styrene, octenyl styrene, 4-t-butoxycarbonyl styrene and 4- Included is t-butoxystyrene.

Examples of the monofunctional vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether and 4-methyl. Cyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, tetrahydro Full frill vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chlorethyl vinyl ether, chlorbutyl vinyl ether, chlorethoxyethyl vinyl ether , Phenylethyl vinyl ether and phenoxypolyethylene glycol vinyl ether.

Examples of the monofunctional N-vinyl compound include N-vinyl-ε-caprolactam and N-vinylpyrrolidone.

When the curable composition contains a monofunctional compound, the content of the monofunctional compound in the entire curable composition may be, for example, in the range of 5% by mass to 50% by mass.

(Silane coupling agent)
Examples of the silane coupling agent include a silane coupling agent having a curable functional group. Examples of the silane coupling agent having a curable functional group include a silane coupling agent having a vinyl group, a silane coupling agent having a (meth) acryloyl group, and a silane coupling agent having a vinyl phenyl group. Among them, the silane coupling agent having a curable functional group is preferably a silane coupling agent having a (meth) acryloyl group.

Examples of the silane coupling agent having a curable functional group include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldi. Examples thereof include ethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and p-styryltrimethoxysilane.

When the curable composition contains a silane coupling agent, the content of the silane coupling agent in the entire curable composition is, for example, 1% by mass to 10% by mass, and 2% by mass to 8% by mass. It is preferable to have.

[Hardened film]
The cured film of the present disclosure is a cured product of the above-mentioned curable compound. The cured film of the present disclosure is manufactured by, for example, the following manufacturing method.

<Manufacturing method of cured film>
The cured film of the present disclosure is produced by a production method including, for example, a step of applying the curable composition onto a substrate and a step of irradiating the curable composition with active energy rays. May be good.
Further, the cured film of the present disclosure is, for example, a step of applying the above-mentioned curable composition on a substrate, a step of irradiating the curable composition with active energy rays, and a curable composition irradiated with active energy rays. It may be manufactured by a manufacturing method including a step of heating an object.
Further, the cured film of the present disclosure is produced by a production method including, for example, a step of applying the curable composition on a substrate and a step of heating the curable composition applied on the substrate. It may be the one.
The cured film of the present disclosure may include, if necessary, other steps (for example, a step of releasing the cured film from the substrate) in addition to the above steps.

(Step of applying the curable composition)
The method for applying the curable composition onto the substrate is not particularly limited, and examples thereof include a spin coating method, a roll coating method, a spray coating method, a dipping method, and an inkjet method.
The type of the base material is not particularly limited, and examples thereof include a quartz glass substrate, a silicon substrate, a SiN substrate, a PET substrate, a PEN substrate, and a polyimide substrate.

(Step of irradiating the curable composition with active energy rays)
Examples of the active energy ray include α-ray, γ-ray, X-ray, ultraviolet ray, visible light and electron beam. Above all, from the viewpoint of safety and cost, the active energy ray is more preferably ultraviolet rays.
Exposure of ultraviolet rays ^is preferably 100mJ / cm 2 ~ 8000mJ / cm 2, more preferably 500mJ / cm 2 ~ 5000mJ / cm 2.
Examples of the light source for ultraviolet irradiation include a mercury lamp, a gas laser, a solid-state laser, a metal halide lamp, an ultraviolet fluorescent lamp, a UV-LED (light emitting diode) and a UV-LD (laser diode). Above all, the light source for ultraviolet irradiation is preferably a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or a UV-LED.

(Step of heating the curable composition applied on the substrate)
The heating temperature and heating time in the step of heating the curable composition applied on the substrate are not particularly limited as long as the curable composition is thermally cured.
The heating temperature in the step of heating the curable composition applied on the substrate is, for example,
The range of 150 ° C. to 350 ° C. is mentioned, the range of 180 ° C. to 330 ° C. is preferable, and the range of 200 ° C. to 300 ° C. is more preferable. The heating time in the step of heating the curable composition applied onto the substrate may be, for example, in the range of 1 minute to 300 minutes, preferably in the range of 30 minutes to 180 minutes, and preferably in the range of 30 minutes to 120 minutes. The minute range is more preferred.
Examples of the heat source used in the step of heating the curable composition applied on the substrate include a hot plate and an oven.

(Step of heating the curable composition irradiated with active energy rays)
The heating temperature and heating time in the step of heating the curable composition irradiated with the active energy rays are not particularly limited, and are, for example, 70 ° C. to 120 ° C. for 1 minute to 3 hours.

<Physical characteristics of cured film>
(Dielectric constant)
The dielectric constant of the cured film of the present disclosure is preferably 3.3 or less, more preferably 2.8 or less, and even more preferably 2.6 or less.
The permittivity can be obtained as a relative permittivity at 100 kHz by performing CV (capacity-voltage) measurement using, for example, a mercury prober (product name "SSM-495", manufactured by SSM).
The dielectric constant may be obtained, for example, by measuring the relative permittivity at 10 GHz at room temperature (25 ° C.) using an SPDR method dielectric constant measuring device (manufactured by QEWD).

(Refractive index)
The refractive index of the cured film of the present disclosure is preferably 1.3 to 1.7, more preferably 1.3 to 1.5.
The refractive index is measured by the following method using, for example, a refractive index measuring device. First, using a refractive index measuring device (product name "prism coupler: 2010 / M", manufactured by Metricon), the refractive index of the cured film at 25 ° C. for wavelengths of 473 nm, 594 nm, and 658 nm is measured. The refractive index is calculated as the refractive index for light having a wavelength of 589 nm using the Mercon Fit attached to the device.

(Transmittance)
The transmittance of the cured film of the present disclosure is preferably, for example, 80% to 100%, more preferably 90% to 100%.
The transmittance is calculated as the light transmittance for light having a wavelength of 410 nm using, for example, an ultraviolet / visible / near-infrared spectrophotometer (product name “Solid Spec-3700”, manufactured by Shimadzu Corporation).

[element]
The device of the present disclosure has the above-mentioned cured film.
Examples of the element include an OLED organic layer including a light emitting layer and an element provided with a thin film encapsulating layer arranged on the OLED organic layer and containing the above-mentioned cured film. In the thin film sealing layer, for example, the SiN film and the cured film are alternately laminated.
The elements of the present disclosure are suitable for sensors. For example, a touch panel can be formed by arranging the touch sensor electrode on the thin film sealing layer of the element.
The elements of the present disclosure are also suitable for optical use.

[Display device]
The display device of the present disclosure has the above-mentioned optical element.
Examples of the display device include a liquid crystal display device and an organic light emitting element display device.

Hereinafter, embodiments of the present disclosure will be described in detail with reference to Examples and Reference Examples. However, the present disclosure is not limited to the following examples. In the following description, "parts" and "%" are based on mass unless otherwise specified. The structure of the compound obtained by synthesis was ^{confirmed by measuring 1 1} H-NMR and ¹⁹ F-NMR.

[Example 1]
(Example 1-1)
Compound (1A) was obtained according to the method described in Example 1-1 of Examples of International Publication No. 2013-121984.
CF ₂ = CF-O-CF ₂ CF ₂ CF ₂ CH _2- OH (1A)

(Example 1-2)
100 g of the compound (1A) obtained in Example 1-1 was placed in a 100 mL stainless steel reactor, and the mixture was stirred at 175 ° C. for 200 hours. The obtained organic phase was concentrated to obtain 62 g of compound (2A).

 

(Example 1-3)
In a 500 mL eggplant flask, 10 g of the compound (2A) obtained in Example 1-2 and 2.4 g of potassium carbonate were placed, stirred at 120 ° C., 50 g of the compound (1A) was added, and the mixture was stirred at 120 ° C. for 2 hours. did. The inside of the eggplant flask was returned to 25 ° C., and 1,1,1,2,2,3,4,4,5,5,6-tridecafluorohexane (product name: Asahiclean AC-2000, AGC stock). 60 g each of a company-made product (hereinafter also referred to as "AC-2000") and hydrochloric acid was added, and the liquid was separated to concentrate the organic phase. The obtained crude reaction solution was purified by column chromatography to obtain 42 g of compound (3A). The average value of the number of units m + n in the following formula (3A) was 10.

 

(Example 1-4)
In a 200 mL four-necked flask, 10 g of the compound (3A) obtained in Example 1-3, 1,1,1,2,2,3,4,4,5,6,6-tridecafluoro 10 mL of Octane (product name: AC-6000, manufactured by AGC Co., Ltd.) and 2.1 g of cesium carbonate were added, and the mixture was stirred at 60 ° C. for 30 minutes. Then, the temperature of the reaction system was cooled to room temperature (25 ° C.), 1.2 g of chloromethylstyrene (meth, paramix: manufactured by Tokyo Kasei) was added, and the mixture was stirred at 70 ° C. for 12 hours. Then, after adding methanol, the fluorous layer was separated, the obtained fluorolas layer was further washed, and the obtained fluorolas layer was concentrated. The obtained crude product was purified by silica gel column chromatography to obtain 5.9 g of compound (A-1). The average value of the number of units m + n in the following formula (A-1) was 10.

 

[Example 2]
(Example 2-1)
In a 50 mL eggplant flask connected to a reflux condenser, 20 g of the compound (3A) obtained in Example 1-3, 7.1 g of sodium fluoride powder, 20 g of AC-2000, CF ₃ CF ₂ CF ₂ OCF (CF). ₃ ) 20 g of COF was added. The mixture was stirred at 50 ° C. for 24 hours under a nitrogen atmosphere. After cooling the eggplant flask to room temperature (25 ° C.), the sodium fluoride powder was removed with a pressure filter. Then, excess CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF and AC-2000 were distilled off under reduced pressure to obtain 24 g of compound (1B). The average value of the number of units m + n in the following formula (1B) was 10.

 

(Example 2-2)
_{250 mL of ClCF 2} CFClCF ₂ OCF ₂ CF ₂ Cl (hereinafter referred to as "CFE-419") was placed in a 500 mL nickel reactor, and nitrogen gas was bubbled. After the oxygen gas concentration was sufficiently lowered, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled for 1 hour. A CFE-419 solution of compound (1B) obtained in Example 2-1 (concentration: 10%, compound (1B): 20 g) was added over 3 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in compound (1B) (mol / hour) was controlled to be 2: 1. After the addition of the compound (1B) was completed, a CFE-419 solution of benzene (concentration: 0.1%, benzene: 0.1 g) was added intermittently. After the addition of benzene was completed, the fluorine gas was bubbled for 1 hour, and finally the inside of the reactor was sufficiently replaced with nitrogen gas. The solvent was distilled off to obtain 21 g of compound (2B). The average value of the number of units m + n in the following formula (2B) was 10.

 

(Example 2-3)
In a 50 mL eggplant flask, 20 g of the compound (2B) obtained in Example 2-2, 1.8 g of sodium fluoride and 20 mL of AC-2000 were placed and stirred in an ice bath. 1.4 g of methanol was added, and the mixture was stirred at 25 ° C. for 1 hour. After filtration, the filtrate was purified by column chromatography. 14 g of compound (3B) was obtained. The average value of the number of units m + n in the following formula (3B) was 10.

 

(Example 2-4)
To a 500 mL three-necked eggplant flask, 14 g of the compound (3B) obtained in Example 2-3, 20 mL of THF, 20 mL of AC-2000, and 1.0 g of sodium borohydride were added and stirred, and methanol was added to 0. 4 mL was added and the mixture was stirred overnight at room temperature (25 ° C.). Then, a 1 mol / L hydrochloric acid aqueous solution and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (product name: Asahiclean AE-3000, manufactured by AGC Co., Ltd.) were added to separate the liquids. The obtained organic phase was concentrated. The obtained crude product was purified by silica gel column chromatography to obtain 14 g of compound (4B). The average value of the number of units m + n in the following formula (4B) was 10.

 

(Example 2-5)
Compound (B-1) was obtained by using the same method as in Example 1-4 except that compound (4B) was used instead of compound (3A). The average value of the number of units m + n in the following formula (B-1) was 10.

 

[Example 3]
(Example 3-1)
Compound (C-1) was used in the same manner as in Example 1-3 and Example 1-4 except that 2,2,3,3-tetrafluorobutane-1,4-diol was used instead of compound (2A). ) Was obtained. The average value of the number of units m + n in the following formula (C-1) was 10.

 

[Example 4]
(Example 4-1)
Examples 1-3, Example 2-1 and Example 2-2, Example 2-3, except that 2,2,3,3-tetrafluorobutane-1,4-diol was used instead of compound (2A). Compound (D-1) was obtained in the same manner as in Example 2-4 and Example 2-5. The average value of the number of units m + n in the following formula (D-1) was 10.

 

[Example 5]
(Example 5-1)
Compound (E-2) was obtained by using the same method as in Example 1-4 except that FomblinD2 (manufactured by Solvay) was used instead of compound (3A). The average value of the number of units m + n in the following formula (E-2) was 15.

 

[Measurement and evaluation]
The following measurements and evaluations were carried out on the obtained compound (A-1), compound (B-1), compound (C-1), compound (D-1), and compound (E-2).

(Measurement of number average molecular weight and fluorine atom content)
By the above-mentioned method, the number average molecular weight and the fluorine atom content of the obtained compound were measured. The results are shown in Table 1.

(Method for producing cured product)
The compound obtained by the above-mentioned method is applied onto a quartz glass substrate that has undergone a mold release treatment, and the compound sandwiched between another quartz glass substrate that has undergone a mold release treatment via a 100 μm spacer is curable. It was used as an evaluation sample. The obtained curability evaluation sample was heat-treated at 250 ° C. for 1 hour in a nitrogen atmosphere, and then the cured product was separated from a quartz glass substrate to obtain a cured product having a thickness of 100 μm.

(Evaluation of heat resistance)
The cured product obtained by the above method is subjected to a thermogravimetric differential thermal analyzer (manufactured by Hitachi High-Tech Science Co., Ltd .: STA7200) at 10 ° C. per minute from room temperature (25 ° C.) to 450 ° C. under a nitrogen flow. It was heated by raising the temperature, and the weight loss rate was measured. Table 1 shows the measurement results of the obtained weight loss rate (mass%). The lower the weight loss rate, the higher the heat resistance.

(Evaluation of curability)
The obtained compound was spin-coated on a silicon substrate and heated at 250 ° C. for 1 hour in a nitrogen atmosphere to obtain a cured product having a thickness of 1.5 μm.
Infrared spectroscopy was performed on the obtained compound and the thermosetting product obtained by the above method, and the curability was evaluated according to the following criteria from the reduction rate of the curable functional groups before and after curing. The results are shown in Table 1.
Curability A: The peak derived from the curable functional group disappears from the infrared absorption spectrum after curing, or the peak height derived from the curable functional group in the infrared absorption spectrum after curing is cured in the infrared absorption spectrum before curing. Reduced to less than 30% of the peak height derived from the sex functional group Curability B: The peak height derived from the curable functional group in the infrared absorption spectrum after curing is the curable functional group in the infrared absorption spectrum before curing. More than 30% remains with respect to the peak height of origin

(Refractive index)
The refractive index of compound (1) with respect to light having a wavelength of 589 nm was measured by the above-mentioned method. The results are shown in Table 1.

 

As can be seen from the results shown in Table 1, the compounds (A-1), (B-1), (C-1) and (D-1) have excellent curability and the compound (E-2). It can be seen that the heat resistance is superior to that of.

The entire disclosure of Japanese Patent Application No. 2020-11346 filed on June 30, 2020 is incorporated herein by reference in its entirety. Also, all documents, patent applications and technical standards described herein are to the same extent as if the individual documents, patent applications and technical standards were specifically and individually stated to be incorporated by reference. , Incorporated by reference herein.

Claims (11)

1. A fluorine-containing ether compound represented by the following formula (1).
   Equation ^{_{(1): A 1 r1 -Y}} 1 -Rf 1 - (OX) m -O-Rf 2 -Y 2 -A 2 r2
   However, in the above formula (1),
   A ¹ and A ² each independently represent a curable functional group.
   r1 and r2 each independently represent an integer of 1 or more.
   Y ¹ represents a (r1 + 1) valent linking group that does not have a fluorine atom.
   Rf ¹ represents a fluoroalkylene group in which a fluorine atom is bonded to a carbon atom bonded to Y ^1.
   Each of X independently represents a fluoroalkylene group, and (OX) _m contains a structure represented by the following formula (2).
   m represents an integer of 2 or more,
   Rf ² represents a fluoroalkylene group in which a fluorine atom is bonded to a carbon atom bonded to Y ^2.
   Y ² represents a (r2 + 1) valent linking group that does not have a fluorine atom.
   Equation (2):-(OX ^{1- OX 2} ) _a-
   However, in the above formula (2),
   X ¹ represents a fluoroalkylene group having 2 to 6 carbon atoms.
   X ² represents a fluoroalkylene group having 2 to 6 carbon atoms, which is different from X ^1.
   a represents an integer of 1 or more, and 2 ≦ (2 × a) ≦ m.
2. The linking group represented by linking groups and Y ² is represented by Y ¹ in the formula (1) are each independently a single bond or an alkylene group, an arylene group, -C (= O) A linking group comprising at least one selected from the group consisting of-, -O-, -S-, -NH-, -N <, _{-SiH 2-,> SiH-, and> Si <.} The fluorine-containing ether compound according to 1.
3. The curable functional group represented by ^{A 1 and the curable functional group represented by A 2} in the formula (1) are independently any of the following formulas (A-1) to (A-12). The fluorine-containing ether compound according to claim 1 or 2, which is a curable functional group represented by.
   

   

   
   
   In the formulas (A-1) to (A-3), Xa independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a methyl group, and * represents a binding site.
4. The curable functional group represented by ^{A 1 and the curable functional group represented by A 2} in the formula (1) are independently curable functional groups represented by the formula (A-1). In addition, the atom bonded to ^{A 1} in the linking group represented by ^{Y 1 and the atom bonded to A 2} in the linking group represented by ^{Y 2} in the above formula (1) are independently heteroatoms or rings. It is a carbon atom that constitutes a structure, or it is
   The curable functional group represented by ^{A 1 and the curable functional group represented by A 2} in the formula (1) are independently one of the formulas (A-2) to (A-12). The fluorine-containing ether compound according to claim 3, which is a curable functional group represented by.
5. The fluorine-containing ether compound according to any one of claims 1 to 4, wherein the fluorine atom content is 53% by mass or more.
6. The fluorine-containing ether compound according to any one of claims 1 to 5.
   At least one selected from the group consisting of a polymerization initiator, a solvent, and a curing agent, and
   Curable composition containing.
7. A cured film which is a cured product of the curable composition according to claim 6.
8. The element having the cured film according to claim 7.
9. The element according to claim 8, which is for a sensor.
10. The element according to claim 8, which is for optics.
11. A display device including an optical element which is the element according to claim 10.