WO2022004435A1 - Composé éther fluoré, composition durcissable, film durci, élément, et dispositif d'affichage - Google Patents

Composé éther fluoré, composition durcissable, film durci, élément, et dispositif d'affichage Download PDF

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WO2022004435A1
WO2022004435A1 PCT/JP2021/023234 JP2021023234W WO2022004435A1 WO 2022004435 A1 WO2022004435 A1 WO 2022004435A1 JP 2021023234 W JP2021023234 W JP 2021023234W WO 2022004435 A1 WO2022004435 A1 WO 2022004435A1
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group
formula
represented
meth
compound
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岳文 阿部
啓吾 松浦
信行 音澤
薫 鶴岡
早希 武井
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Ａｇｃ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds

Definitions

  • the present disclosure relates to a fluorine-containing ether compound, a curable composition, a cured film, an element, and a display device.
  • the fluorine-containing compound 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.
  • 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.
  • 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).
  • 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.
  • 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
  • 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-
  • 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.
  • 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).
  • Xa independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a methyl group
  • * represents a binding site.
  • 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).
  • 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.
  • 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.
  • 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.
  • the numerical values before and after “-" are included as the minimum value and the maximum value, respectively.
  • 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.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • 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
  • (OX) m represents a continuous (OX).
  • 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
  • Equation (2) -(OX 1- OX 2 ) a-
  • 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
  • a represents an integer of 1 or more. Represented by 2 ⁇ (2 ⁇ a) ⁇ m.
  • 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.
  • 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.
  • 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.
  • 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.
  • curable functional group A examples include the following formulas (A-1) to (A-12). Examples thereof include a curable functional group represented by any of the above.
  • Xa independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a methyl group
  • * represents a binding site
  • 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.
  • 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.
  • Y 1 represents a (r1 + 1) -valent linking group having no fluorine atom
  • 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.
  • 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.
  • 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 further have a substituent.
  • substituents 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.
  • linking group Y examples include linking groups represented by the following formulas (Y-1) to (Y-57).
  • Rf * represents a binding site to a fluoroalkylene group represented by Rf 1 or Rf 2 in the formula (1)
  • * A represents A 1 in the formula (1). or it represents a binding site for curable functional group represented by a 2.
  • n represents an integer of 1 to 6.
  • 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.
  • n represents an integer of 1 to 6
  • Ph represents a phenylene group.
  • 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.
  • 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.
  • the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like.
  • the carbon atom constituting the ring structure include a carbon atom constituting an arylene group and a carbon atom constituting a cycloalkylene group.
  • 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. ..
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the linking group Y may be, for example, any of the formulas (Y-1) to (Y-57).
  • 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.
  • 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.
  • 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.
  • the linking group Y may be, for example, the formula (Y-1).
  • 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.
  • the linking group Y is, for example, a group represented by any of the formulas (Y-1) to (Y-57).
  • 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.
  • 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.
  • the linking group Y is, for example, a group represented by any of the formulas (Y-1) to (Y-57).
  • 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.
  • 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.
  • 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).
  • 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 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.
  • 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.
  • 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.
  • fluoroalkylene group Rf examples 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.
  • the ring structure examples include a cyclobutane structure and a cyclohexane structure.
  • 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.
  • the fluoroalkylene group Rf is preferably a perfluoroalkylene group from the viewpoint of heat resistance.
  • 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.
  • fluoroalkylene group Rf examples 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- * 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- * Y , O * -CH 2 CF 2 CF 2 CF 2 CF 2- * Y , O * -CF 2- * Y , O * -CF 2 CF 2- * Y , O * -CF
  • the fluoroalkylene group Rf is not limited to these specific examples.
  • O * represents a binding site to an oxygen atom in the formula (1)
  • * 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) include 1 to 6, which are 2 to 6 from the viewpoint of improving heat resistance. Is preferable.
  • 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.
  • 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.
  • 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.
  • the fluoroalkylene group X is preferably a perfluoroalkylene group from the viewpoint of heat resistance.
  • 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.
  • 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 * -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 CHF- * 2 , 1 * -CHFCF 2 CF 2 CF 2- * 2 , 1 * -CF 2 CHFCF 2- * 2 , 1 * -CHFCF 2 CHF-
  • the fluoroalkylene group X is not limited to these specific examples.
  • “ 1 *” represents the binding site on the side close to Rf 1 in the formula (1)
  • “* 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-
  • 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
  • a represents an integer of 1 or more.
  • 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.
  • 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.
  • 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.
  • 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 ) a- - (OCHFCF 2 -OCF 2 CHFCF 2) a - - (OCHFCF 2 -OCF 2 CF 2 CHFCF 2) a - - - (OCHFCF 2 -OCF 2 CF 2 CHFCF 2) a - - - (OCHFCF 2 -OCF 2 CF 2 CHF 2) a - - - (OCHFCF 2 -OCF
  • 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.
  • (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 -
  • X 1 and X 2 mean the same groups as X 1 and X 2 in formula (2), respectively.
  • 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).
  • 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.
  • the plurality of a may be the same or different.
  • 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
  • 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).
  • 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
  • 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
  • X 12 represents an integer of 0 or 2 or more.
  • 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.
  • 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
  • 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.
  • X 1 and X 2 mean the same group as X 1 and X 2 in the formula (2).
  • 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.
  • 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).
  • 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.
  • the compound (1) is not limited to the compound represented by the formula (4).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a refractive index measuring device product name "prism coupler: 2010 / M", manufactured by Metricon Co., Ltd.
  • 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, 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.
  • 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.
  • 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
  • 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.
  • Ay in the formulas (54) and (55) is a group containing the above-mentioned curable functional group A
  • "Ay-O-X 2- " in the formula (55) is a group in the formula (4).
  • 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.
  • X 2 in the formula (56) and (57) is the same as X 2 in the formula (4).
  • 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.
  • 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.
  • 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
  • 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.
  • 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-".
  • 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).
  • 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.
  • 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.
  • the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator.
  • 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 ⁇ -aminoketone-based photopolymerization initiator, and an ⁇ -hydroxyl.
  • Ketone-based photopolymerization initiator ⁇ -acyloxime ester, benzyl- (o-ethoxycarbonyl) - ⁇ -monooxime, acylphosphine oxide, glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylthiumam
  • sulfides include sulfides, azobisisobutyronitrile, benzoyl peroxides, dialkyl peroxides, and tert-butyl peroxypivalates.
  • the photoradical polymerization initiator is an acetophenone-based photopolymerization initiator, a benzoin-based photopolymerization initiator, an ⁇ -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.
  • the photoacid generator a known photoacid generator can be used.
  • various compounds which are suitable in JP-A-2017-90515 can be mentioned, but the present invention is not particularly limited thereto.
  • 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.
  • 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
  • sulfonium salt examples include triphenylsulfonium hexafluoroacylnate, triphenylsulfonium hexahexafluoroborate, triphenylsulfoniumtetrafluoroborate, triphenylsulfoniumtetrakis (pentafluobenzyl) borate, methyldiphenylsulfoniumtetrafluoroborate, and methyldiphenyl.
  • 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.
  • an aromatic diazonium salt can be used, for example, p-methoxybenzenediazonium hexafluoroantimonate or the like can be used.
  • thermal radical initiator a known polymerization initiator can be used.
  • 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.
  • 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.
  • the solvent contained in the present composition may be one kind or two or more kinds.
  • 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.
  • fluorine-containing organic solvent examples include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
  • fluorinated alkane examples 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 .
  • fluorinated aromatic compound examples include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis (trifluoromethyl) benzene.
  • fluoroalkyl ether examples 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.
  • the curing agent examples include compounds having two or more curable functional groups and no oxyfluoroalkylene group (hereinafter, also referred to as “polyfunctional compound”).
  • the polyfunctional compound examples include a polyfunctional (meth) acrylate compound, a polyfunctional maleimide, and a polyfunctional vinyl ether, a polyfunctional amine, and a polyfunctional alcohol.
  • 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.
  • (meth) acrylate means at least one of acrylate and methacrylate.
  • (meth) acryloyl group means at least one of acryloyl group and methacrylic group
  • (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.
  • polyfunctional (meth) acrylate examples 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.
  • 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.
  • the polyfunctional (meth) acrylate may be an epoxy (meth) acrylate which is a reaction product of (meth) acrylic acid and an epoxy resin.
  • the epoxy resin include bisphenol A type epoxy resin and cresol novolac type epoxy resin.
  • polyfunctional maleimide examples include 1,2-bis (maleimide) ethane, 1,4-bis (maleimide) butane, 1,6-bis (maleimide) hexane, and 4,4'-bismaleimide diphenylmethane. ..
  • polyfunctional vinyl ether examples 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.
  • 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.
  • the composition may contain other components other than the fluorine-containing ether compound, the polymerization initiator, the solvent, and the curing agent, if necessary.
  • 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.
  • the monofunctional compound examples include monofunctional (meth) acrylate, monofunctional maleimide, monofunctional (meth) acrylamide, monofunctional aromatic vinyl compound, monofunctional vinyl ether, and monofunctional N-vinyl compound.
  • 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.
  • 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.
  • 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.
  • Examples of the monofunctional N-vinyl compound include N-vinyl- ⁇ -caprolactam and N-vinylpyrrolidone.
  • 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 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.
  • the silane coupling agent having a curable functional group is preferably a silane coupling agent having a (meth) acryloyl group.
  • silane coupling agent having a curable functional group examples include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldi. Examples thereof include ethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and p-styryltrimethoxysilane.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 include ⁇ -ray, ⁇ -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.
  • the light source for ultraviolet irradiation examples 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).
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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).
  • the device of the present disclosure has the above-mentioned cured film.
  • 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.
  • 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.
  • 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.
  • 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.
  • Example 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.
  • Octane product name: AC-6000, manufactured by AGC Co., Ltd.
  • 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.
  • 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 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 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.
  • 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 ⁇ m 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 ⁇ m.
  • thermogravimetric differential thermal analyzer manufactured by Hitachi High-Tech Science Co., Ltd .: STA7200
  • Table 1 shows the measurement results of the obtained weight loss rate (mass%). The lower the weight loss rate, the higher the heat resistance.
  • 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

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Abstract

L'invention concerne un composé éther fluoré représenté par la formule (1). Ａ１ et Ａ２ représentent un groupe fonctionnel durcissable. ｒ１ et ｒ２ représentent un nombre entier supérieur ou égal à 1. Ｙ１ et Ｙ２ représentent un groupe de liaison exempt d'atome de fluor. Ｒｆ１ représente un groupe fluoroalkylène dans lequel un atome de fluor est lié à un atome de carbone à son tour lié à Ｙ１. Ｒｆ２ représente un groupe fluoroalkylène dans lequel un atome de fluor est lié à un atome de carbone à son tour lié à Ｙ２. X représente un groupe fluoroalkylène. m représente un nombre entier supérieur ou égal à 2. （ＯＸ）ｍ contient une structure représentée par la formule (2). Ｘ１ représente un groupe fluoroalkylène de 2 à 6 atomes de carbone. Ｘ２ représente un groupe fluoroalkylène de 2 à 6 atomes de carbone différent de Ｘ１. a représente un nombre entier supérieur ou égal à 1.２≦（２×ａ）≦ｍ est satisfait. Formule（１）：Ａ１ ｒ１－Ｙ１－Ｒｆ１－（ＯＸ）ｍ－Ｏ－Ｒｆ２－Ｙ２－Ａ２ ｒ２ Formule（２）：－（ＯＸ１－ＯＸ２）ａ－
PCT/JP2021/023234 2020-06-30 2021-06-18 Composé éther fluoré, composition durcissable, film durci, élément, et dispositif d'affichage WO2022004435A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015022871A1 (fr) * 2013-08-13 2015-02-19 旭硝子株式会社 Composé polyéther fluoré, lubrifiant, composition liquide, et article
WO2019039341A1 (fr) * 2017-08-22 2019-02-28 Ａｇｃ株式会社 Composé éther contenant du fluor, composition éther contenant du fluor, liquide de revêtement, article et procédé de fabrication de celui-ci
WO2019044479A1 (fr) * 2017-08-31 2019-03-07 Ａｇｃ株式会社 Composé éther contenant du fluor, composition d'éther contenant du fluor, solution de revêtement, article et procédé de production associé
WO2019049753A1 (fr) * 2017-09-05 2019-03-14 Ａｇｃ株式会社 Composé éther contenant du fluor, composition et article
WO2020111010A1 (fr) * 2018-11-28 2020-06-04 Ａｇｃ株式会社 Composé éther fluoré, composition, et article

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015022871A1 (fr) * 2013-08-13 2015-02-19 旭硝子株式会社 Composé polyéther fluoré, lubrifiant, composition liquide, et article
WO2019039341A1 (fr) * 2017-08-22 2019-02-28 Ａｇｃ株式会社 Composé éther contenant du fluor, composition éther contenant du fluor, liquide de revêtement, article et procédé de fabrication de celui-ci
WO2019044479A1 (fr) * 2017-08-31 2019-03-07 Ａｇｃ株式会社 Composé éther contenant du fluor, composition d'éther contenant du fluor, solution de revêtement, article et procédé de production associé
WO2019049753A1 (fr) * 2017-09-05 2019-03-14 Ａｇｃ株式会社 Composé éther contenant du fluor, composition et article
WO2020111010A1 (fr) * 2018-11-28 2020-06-04 Ａｇｃ株式会社 Composé éther fluoré, composition, et article

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