WO2024038833A1 - 含フッ素芳香族ポリマー及び含フッ素芳香族ポリマーの製造方法 - Google Patents

含フッ素芳香族ポリマー及び含フッ素芳香族ポリマーの製造方法 Download PDF

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WO2024038833A1
WO2024038833A1 PCT/JP2023/029312 JP2023029312W WO2024038833A1 WO 2024038833 A1 WO2024038833 A1 WO 2024038833A1 JP 2023029312 W JP2023029312 W JP 2023029312W WO 2024038833 A1 WO2024038833 A1 WO 2024038833A1
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formula
fluorine
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將 神原
知子 矢島
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Ochanomizu University
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    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
    • C08G64/10—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing halogens
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00

Definitions

  • the present disclosure relates to a fluorine-containing aromatic polymer and a method for producing the fluorine-containing aromatic polymer.
  • Patent Document 1 describes a reaction product of an acid anhydride and an amine including a dimer diamine as a polyimide.
  • fluorine-containing aromatic polymers are used in a wide range of applications, they are desired to have various structures.
  • a independently at each occurrence represents an aliphatic or aromatic imido-diyl group;
  • Ar represents, at each occurrence independently, a divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents;
  • L is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO-
  • R 1 is independently at each occurrence a C 1-16 alkylene group which may have one or more substituents, and a C 1-16 alkylene group which may have one or more substituents;
  • a fluorine-containing aromatic polymer represented by ⁇ 2> The C 2-20 fluorine-containing organic group has the following formula (1A) and formula (1B): R 31 -X 1 -(R F1 ) r -CF 2 -* (1A) *-X 3 -CF 2 -* (1B) [In formula (1A) and formula (1B), R F1 represents -(Rf) p -R F -(O) q -, Rf each independently represents a C 1-16 alkylene group optionally substituted with one or more fluorine atoms; R F represents a divalent fluoro(poly)ether group, X 1 represents a C 1-16 alkylene group or a single bond optionally substituted with one or more halogen atoms, X 3 represents a C 1-16 alkylene group optionally substituted with one or more halogen atoms, R 31 is a C 1-16 alkyl group optionally substituted with one or more halogen atoms, a C 1
  • the C 1-20 fluorine-containing organic group has the following formula (2A) and formula (2B): R 32 -X 1 -(R F1 ) r -CF 2 -* (2A) *-X 1 -CF 2 -* (2B) [In formula (2A) and formula (2B), R F1 represents -(Rf) p -R F -(O) q -, Rf each independently represents a C 1-16 alkylene group optionally substituted with one or more fluorine atoms; R F represents a divalent fluoro(poly)ether group, X 1 represents a C 1-16 alkylene group or a single bond optionally substituted with one or more halogen atoms, R 32 is a C 1-16 alkyl group optionally substituted with one or more halogen atoms, a C 6-20 aromatic hydrocarbon group optionally having one or more substituents , silsesquioxane residue which may have one or more substituents,
  • the fluorine-containing aromatic polymer according to ⁇ 1> which is a group represented by: ⁇ 3>
  • the C 2-20 fluorine-containing organic group has the following formula (1-a), formula (1-b), formula (1-c), and formula (1B): FX 3 -CF 2 -* (1-a) R 31 -X 1 -CF 2 -* (1-b) R 31 -X 1 -R F1 -CF 2 -* (1-c) *-X 3 -CF 2 -* (1B)
  • R F1 represents -(Rf) p -R F -(O) q -
  • Rf each independently represents a C 1-16 alkylene group optionally substituted with one or more fluorine atoms
  • R F represents a divalent fluoro(poly)ether group
  • X 1 represents a C 1-16 alkylene group or a single bond optionally substituted with one or more halogen
  • a group selected from The C 1-20 fluorine-containing organic group has the following formula (2-a), formula (2-b), formula (2-c) and formula (2B): FX 1 -CF 2 -* (2-a) R 32 -X 1 -CF 2 -* (2-b) R 32 -X 1 -R F1 -CF 2 -* (2-c) *-X 1 -CF 2 -* (2B) [In formula (2-a), formula (2-b), formula (2-c) and formula (2B), R F1 represents -(Rf) p -R F -(O) q -, Rf each independently represents a C 1-16 alkylene group optionally substituted with one or more fluorine atoms; R F represents a divalent fluoro(poly)ether group, X 1 represents a C 1-16 alkylene group or a single bond optionally substituted with one or more halogen atoms, R 32 is a C 1-16 alkyl group optionally substituted with one or more
  • the formula (I) is the following formula (I-a): [In formula (I-a), A a independently at each occurrence represents an aliphatic or aromatic imido-diyl group; Ar a represents, at each occurrence independently, a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; na represents an integer of 1 or more, Formula (Ia) has one or more C 1-20 fluorine-containing organic groups.
  • the fluorine-containing aromatic polymer according to any one of ⁇ 1> to ⁇ 3>, which is represented by: ⁇ 5>
  • the formula (I) is the following formula (I-b): [In formula (I-b), Ar b each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; L b is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -, At each occurrence, R 1 is independently a C 1-16 alkylene group which may have a substituent, and a C 3-16 fatty acid which may have one or more substituents.
  • the fluorine-containing aromatic polymer according to any one of ⁇ 1> to ⁇ 3>, which is represented by: ⁇ 6>
  • the formula (I-b) can be represented by the following formulas (I-b1), (I-b2), (I-b3), (I-b4), (I-b5), (I-b6) or (I -b7): [In formula (I-b1), (I-b2), (I-b3), (I-b4), (I-b5), (I-b6) or (I-b7), Ar b each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; nb represents an integer of 1 or more, Formulas (I-b1), (I-b2), (I-b3), (I-b4), (I-b5), (I-b6) and (I-b7) each contain one or It has a C 2-20 fluorine-containing organic group.
  • the fluorine-containing aromatic polymer according to ⁇ 5> which is represented by: ⁇ 7>
  • the formula (I) is the following formula (I-c): [In formula (I-c), Ar c1 each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents; Ar c2 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; L c1 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -, L c2 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-,
  • the fluorine-containing aromatic polymer according to any one of ⁇ 1> to ⁇ 3>, which is represented by: ⁇ 8>
  • the formula (I-c) is the following formula (I-c1), (I-c2) or (I-c3): [In formula (I-c1), (I-c2) or (I-c3), Ar c1 each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents; Ar c2 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; nc independently represents an integer of 1 or more in each occurrence, Formulas (I-c1), (I-c2) and (I-c3) each have one or more C 2-20 fluorine-containing organic groups.
  • the fluorine-containing aromatic polymer according to ⁇ 7> which is represented by: ⁇ 9>
  • the formula (I) is the following formula (I-d): [In formula (I-d), Ar d1 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; Ar d2 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; Ar d3 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; L d1 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -,
  • the fluorine-containing aromatic polymer according to any one of ⁇ 1> to ⁇ 3>, which is represented by: ⁇ 10>
  • the above formula (I-d) is the following formula (I-d1) or (I-d2): [In formula (I-d1) or (I-d2), Ar d1 each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; Ar d2 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; Ar d3 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; nd independently represents an integer of 1 or more in each occurrence, Formulas (I-d1) and (I-d2) each have one or more C 2-20 fluorine-containing organic groups.
  • the fluorine-containing aromatic polymer according to ⁇ 9> which is represented by: ⁇ 11>
  • the formula (I) is the following formula (I-e): [In formula (Ie), Ar e1 each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; L e1 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -, L e2 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -
  • the fluorine-containing aromatic polymer according to any one of ⁇ 1> to ⁇ 3>, which is represented by: ⁇ 12>
  • the formula (I-e) is the following formula (I-e1), (I-e2) or (I-e3): [In formula (I-e1), (I-e2) or (I-e3), Ar e1 each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; R 7 is a C 1-16 alkylene group which may have one or more substituents, and a C 3-16 alicyclic group which may have one or more substituents Represents one type selected from divalent groups containing hydrocarbon groups, ne independently represents an integer of 1 or more in each occurrence, Formula (I-e1), (I-e2) or (I-e3) each has one or more C 2-20 fluorine-containing organic groups.
  • the formula (I) is the following formula (Ig): [In formula (Ig), Ar g each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; L g1 represents a divalent group containing a C 3-16 alicyclic hydrocarbon group which may have one or more substituents, mg independently represents an integer of 0 to 4 in each occurrence, ng1 represents an integer of 1 or more, ng2 represents an integer of 1 or more, Formula (Ig) has one or more C 2-20 fluorine-containing organic groups.
  • the fluorine-containing aromatic polymer according to any one of ⁇ 1> to ⁇ 3>, which is represented by: ⁇ 14>
  • the formula (I) is the following formula (Ih): [In formula (Ih), A h independently at each occurrence represents an aliphatic or aromatic imido-diyl group; Ar h at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; L h is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one type selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -, At each occurrence, R 1 is independently a C 1-16 alkylene group which may have a substituent, and a C 3-16 fatty acid which may have one or
  • the fluorine-containing aromatic polymer according to any one of ⁇ 1> to ⁇ 3>, which is represented by: ⁇ 15>
  • the above formula (Ih) is the following formula (Ih1): [In formula (I-h1), A h independently at each occurrence represents an aliphatic or aromatic imido-diyl group; Ar h at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; nh represents an integer of 1 or more independently in each occurrence, In formula (I-h1), each has one or more C 1-20 fluorine-containing organic groups.
  • A is The following formula (A2-I): [In formula (A2-I), A 10 represents a single bond or a divalent organic group, * represents a bond. ] Or the following formula (A2-II) [In formula (A2-II), * represents a bond.
  • a 10 is a single bond and formulas (a-1) to (a-7): [In formulas (a-1) to (a-7), R 3 represents a C 1-16 alkylene group optionally substituted with a fluorine atom, * represents a bond.
  • the fluorine-containing aromatic polymer according to ⁇ 16>, which is one selected from the groups represented by. ⁇ 18> A is the following formula (A1-1) to (A1-19): [In the formulas (A1-1) to (A1-19), * represents a bond.
  • the fluorine-containing aromatic polymer according to any one of ⁇ 1> to ⁇ 17>, which is one selected from the groups represented by. ⁇ 10>
  • R 12 at each occurrence independently represents a C 1-16 alkyl group optionally having a substituent, a C 6-20 aromatic carbonized group optionally having one or more substituents
  • R 12 represents a hydrogen group or hydrogen atom
  • k1 represents an integer from 0 to 4 independently in each occurrence
  • l1 independently represents an integer from 1 to 4 in each occurrence
  • m1 represents an integer from 0 to 4 independently in each occurrence
  • n1 represents an integer of 1 or more
  • Formula (I-1) has one or more C 1-20 fluorine-containing organic groups.
  • a manufacturing method comprising reacting a compound represented by: ⁇ 20> The following formula (I-1): [In formula (I-1), A 1 independently at each occurrence represents an aliphatic or aromatic imido-diyl group; Ar 1 at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; L 1 is independently at each occurrence -R 11 -, -O-, -S-, -NR 12 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one type selected from the group consisting of -O-, -SO 2 -, -NR 12 -CO- and CO-NR 12 -, Each occurrence of R 11 is independently a C 1-16 alky
  • R 12 at each occurrence independently represents a C 1-16 alkyl group optionally having a substituent, a C 6-20 aromatic carbonized group optionally having one or more substituents
  • k1 represents an integer from 0 to 4 independently in each occurrence
  • l1 independently represents an integer from 1 to 4 in each occurrence
  • m1 represents an integer from 0 to 4 independently in each occurrence
  • n1 represents an integer of 1 or more
  • Formula (I-1) has one or more C 1-20 fluorine-containing organic groups.
  • the aromatic monomer has formula (III): R 4 -Ar 3 -R 4 (III)
  • Ar 3 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents;
  • Each occurrence of R 4 independently represents -OH, -NH 2 , a fluorine atom or a chlorine atom.
  • the manufacturing method according to ⁇ 20> which is represented by: ⁇ 22>
  • the second monomer has the following formula (IV): R 5 -L 10 -R 5 (IV) [In formula (IV), R 5 independently represents the following formulas (r-1) to (r-18) at each occurrence: [In formulas (r-1) to (r-18), * represents a bond.
  • L 10 is the following formula (l-1) to (l-11): [In formulas (l-1) to (l-11), R 6 is a C 1-16 alkylene group optionally substituted with one or more fluorine atoms, or one or more substituted represents a divalent C 6-20 aromatic hydrocarbon group which may have a group, * represents a bond. ] Represents one type selected from.
  • the C 1-20 fluorine-containing organic group has the following formulas (2-1A) and (2B): R 33 -X 1 -(R F1 ) r -CF 2 -* (2-1A) *-X 1 -CF 2 -* (2B) [In formulas (2-1A) and (2B), R F1 represents -(Rf) p -R F -(O) q -, Rf each independently represents a C 1-16 alkylene group optionally substituted with one or more fluorine atoms; R F represents a divalent fluoro(poly)ether group, X 1 represents a C 1-16 alkylene group or a single bond optionally substituted with one or more halogen atoms, R 33 is a C 6-20 aromatic hydrocarbon group which may have one or more substituents, a silsesquioxane residue which may have one or more substituents , -COOR f2 , -OR f2 , -SO 2 R
  • the surface treatment agent has the following formula (II-1A) and formula (II-1B): R 32 -X 1 -(R F1 ) r -CF 2 -I (II-1A) I-X 1 -CF 2 -I (II-1B) [In formula (II-1A) and formula (II-1B), R F1 represents -(Rf) p -R F -(O) q -, Rf each independently represents a C 1-16 alkylene group optionally substituted with one or more fluorine atoms; R F represents a divalent fluoro(poly)ether group, X 1 represents a C 1-16 alkylene group or a single bond optionally substituted with one or more halogen atoms, R 32 is a C 1
  • An article containing a compound represented by one or more of the following. ⁇ 27> Including forming a layer on the surface of the base material by reacting the base material and a surface treatment agent, the base material includes an aromatic polymer,
  • the surface treatment agent has the following formula (II-1A) and formula (II-1B): R 32 -X 1 -(R F1 ) r -CF 2 -I (II-1A) I-X 1 -CF 2 -I (II-1B) [In formula (II-1A) and (formula II-1B), R F1 represents -(Rf) p -R F -(O) q -, Rf represents, at each occurrence independently, a C 1-16 alkylene group optionally substituted with one or more fluorine atoms; R F represents a divalent fluoro(poly)ether group, X 1 represents a C 1-16 alkylene group or a single bond optionally substituted with one or more halogen atoms
  • novel fluorine-containing aromatic polymers having various structures can be provided.
  • the fluorine-containing aromatic polymer of the present disclosure has the following formula (I): [In formula (I), A independently at each occurrence represents an aliphatic or aromatic imido-diyl group; Ar represents, at each occurrence independently, a divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents; L is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO-, -O-CO- Represents one type selected from the group consisting of O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -, R 1 is independently at each occurrence a C 1-16 alkylene group which may have one or more substituents, and a C 1-16 alkylene group which may have one or more substituents; Represents one type selected from divalent groups containing a good C
  • fluorine-containing aromatic polymers can have various structures, which expands the range of structural choices, and improves flexibility, adhesion (reactivity) and affinity with other materials, low dielectric properties, transparency, It will become possible to provide new aromatic polymers (especially super engineering plastics and engineering plastics) with improved properties such as water and oil repellency, low adhesion, stain resistance, solvent solubility, and high surface hardness. Be expected.
  • A independently at each occurrence represents an aliphatic or aromatic imido-diyl group. That is, A is the following formula: It has one or two groups represented by (hereinafter also referred to as "imido-N-yl group"). In the formula, * represents a bond.
  • A preferably represents an aliphatic or aromatic imido-diyl group containing one or more imido rings, said aliphatic or aromatic imido-diyl group having one or more substituents. You may do so.
  • the imide ring is a ring containing an imido-N-yl group, and may be monocyclic or polycyclic, and the number of imide bonds contained in one imide ring may be 1 or 2 or more. It's good.
  • the number of ring members of the imide ring may be preferably 5 or more and 20 or less, more preferably 5 or more and 15 or less, and still more preferably 5 or more and 10 or less.
  • Examples of the imide ring include a 2,5-dioxopyrrolidine ring, a 1,3-dioxohexahydroisoindoline ring, a 1,2,3,4-cyclobutyltetracarboxylic acid diimide ring, and a 1,2,4,5 -Cyclopentyltetracarboxylic acid diimide ring, hexahydropyromellitic acid diimide ring, 1,3-dioxoisoindoline ring, pyromellitic acid diimide ring, 1,4,5,8-naphthalenetetracarboxylic acid diimide ring, etc. , 2,5-dioxopyrrolidine ring, and 1,3-dioxoisoindoline ring are preferred.
  • the number of imide rings contained in the aliphatic or aromatic imido-diyl group is preferably one or two, more preferably two.
  • the substituents that the aliphatic or aromatic imido-diyl group represented by A above may have will be described later.
  • A preferably has the following formula (A1-I): [In formula (A1), A 10 represents a single bond or a divalent organic group, R 10 represents a substituent, n10 represents an integer from 0 to 3, * represents a bond. ] Or The following formula (A1-II): [In formula (A1), R 10 represents a substituent, n10 represents an integer from 0 to 3, * represents a bond. ] It is expressed as
  • A is a group represented by formula (A1-I) or (A1-II), the heat resistance of the fluorine-containing aromatic polymer can be improved.
  • a 10 represents a single bond or a divalent organic group.
  • the above-mentioned organic group includes a divalent C 1-16 alkylene group which may be substituted with a fluorine atom, and a C 6-20 aromatic hydrocarbon group which may have one or more substituents. Examples include groups such as -O-, -CO-, -C ⁇ C-, -SO 2 -, and groups combining these groups.
  • the "C 1-16 alkylene group" in the C 1-16 alkylene group optionally substituted with a fluorine atom may be a straight chain or a branched chain, preferably a straight chain or a branched chain.
  • a methylene group is preferred.
  • the C 1-16 alkylene group optionally substituted with one or more fluorine atoms is preferably -CH 2 -, -C(CH 3 ) 2 -, -CF 2 -, C(CF 3 ) 2 -.
  • the “C 6-20 aromatic hydrocarbon group” in the above divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents is a monocyclic group; may also be polycyclic, and in the case of polycyclic, two or more rings may not form a condensed ring or may form a condensed ring.
  • the number of aromatic hydrocarbon groups contained in the divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents is 1 or more, preferably may be 1 or more and 4 or less, more preferably 1 or more and 3 or less, still more preferably 1 or 2.
  • Such an aromatic hydrocarbon group is preferably a C 6-10 aromatic hydrocarbon group, more preferably a phenylene group, tolylene group, xylylene group, or naphthylene group, and in one embodiment, even more preferably a phenylene group, tolylene group, or naphthylene group. or a xylylene group, and in another embodiment more preferably a naphthylene group.
  • divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents two or more aromatic hydrocarbon groups are connected via a single bond or an organic group. may be combined.
  • organic groups include linear or branched C 1-4 alkyl groups.
  • the substituents in the divalent group represented by A 10 above, which includes a C 6-20 aromatic hydrocarbon group which may have one or more substituents, will be described later.
  • the substituent represented by R 10 will be described later.
  • a 10 preferably has no substituent. That is, A is preferably a group represented by the following formula (A2-I) or (A2-II). In the formula, A 10 has the same meaning as above.
  • a 10 is preferably a single bond and formulas (a-1) to (a-7): [In formulas (a-1) to (a-7), R 3 represents a C 1-16 alkylene group optionally substituted with a fluorine atom, * represents a bond. ] It can be one type selected from the groups represented by.
  • R 3 represents a C 1-16 alkylene group optionally substituted with a fluorine atom.
  • the "C 1-16 alkylene group" in the C 1-16 alkylene group optionally substituted with a fluorine atom may be a straight chain or a branched chain, preferably a straight chain or a branched chain. It is a chain C 1-10 alkylene group, more preferably a straight chain or branched chain C 1-5 alkylene group.
  • groups represented by formula (a-3) and formula (a-7) are preferable.
  • A preferably represents the following formulas (A1-1) to (A1-19): [In the formulas (A1-1) to (A1-19), * represents a bond. ] It can be one type selected from the groups represented by.
  • Each occurrence of Ar independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents.
  • the “C 6-20 aromatic hydrocarbon group” in the above divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents is a monocyclic group; may also be polycyclic, and in the case of polycyclic, two or more rings may or may not form a condensed ring.
  • the number of aromatic hydrocarbon groups is 1 or more, preferably 1. The number may be 4 or more, more preferably 1 or more and 3 or less, and even more preferably 1 or 2.
  • Such an aromatic hydrocarbon group is preferably a C 6-10 aromatic hydrocarbon group, more preferably a phenylene group, tolylene group, xylylene group or naphthylene group, even more preferably a phenylene group, tolylene group or xylylene group. It can be.
  • divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents
  • two or more aromatic hydrocarbon groups are bonded to a single bond or a divalent organic It may be bonded via a group.
  • organic groups include linear or branched C 1-4 alkyl groups.
  • Ar preferably has the following formula (Ar1): [In formula (Ar1), Ar 11 represents a divalent C 6-10 aromatic hydrocarbon group which may have one or more substituents, Ar 12 at each occurrence independently represents a divalent C 6-10 aromatic hydrocarbon group optionally having one or more substituents; X 10 represents a single bond, -O-, -CO-, -SO 2 - or a C 1-4 alkylene group, n11 represents an integer from 0 to 3, * represents a bond, The total number of carbon atoms in formula (Ar1) is 6 or more and 20 or less. ] It is expressed as
  • Ar 11 represents a divalent C 6-10 aromatic hydrocarbon group which may have one or more substituents.
  • the "bivalent C 6-20 aromatic hydrocarbon group" in the above divalent C 6-20 aromatic hydrocarbon group which may have one or more substituents is a monocyclic may also be polycyclic, and in the case of polycyclic, two or more rings may not form a condensed ring or may form a condensed ring.
  • the "divalent C 6-20 aromatic hydrocarbon group” in the divalent C 6-20 aromatic hydrocarbon group which may have one or more substituents is preferably a divalent C 6-20 aromatic hydrocarbon group.
  • aromatic hydrocarbon group more preferably a divalent C 6-10 aromatic hydrocarbon group, still more preferably a phenylene group, tolylene group, xylylene group or naphthylene group, still more preferably phenylene group. group, tolylene group or xylylene group.
  • the substituents that the divalent C 6-10 aromatic hydrocarbon group represented by Ar 11 may have will be described later.
  • Ar 12 at each occurrence independently represents a divalent C 6-10 aromatic hydrocarbon group optionally having one or more substituents.
  • the "bivalent C 6-20 aromatic hydrocarbon group" in the above divalent C 6-20 aromatic hydrocarbon group which may have one or more substituents is a monocyclic may also be polycyclic, and in the case of polycyclic, two or more rings may not form a condensed ring or may form a condensed ring.
  • the "divalent C 6-20 aromatic hydrocarbon group” in the divalent C 6-20 aromatic hydrocarbon group which may have one or more substituents is preferably a divalent C 6-20 aromatic hydrocarbon group.
  • aromatic hydrocarbon group more preferably a divalent C 6-10 aromatic hydrocarbon group, still more preferably a phenylene group, tolylene group, xylylene group or naphthylene group, still more preferably phenylene group. group, tolylene group or xylylene group.
  • the substituents that the divalent C 6-10 aromatic hydrocarbon group represented by Ar 12 may have will be described later.
  • X 10 represents a single bond, -O-, -CO-, -SO 2 -, or a C 1-4 alkylene group.
  • the C 1-4 alkylene group may be a straight chain or a branched chain, and is preferably a straight chain or branched C 1-3 alkylene group, specifically -CH 2 -, -C(CH 3 ) 2 -.
  • the substituents that the divalent group containing a C 6-20 aromatic hydrocarbon group represented by Ar may have will be described later.
  • Ar is preferably a phenylene group, tolylene group, xylylene group, hydroxyphenylene group, hydroxyxylylene group, naphthylene group, biphenylene group, 3,3'-dimethylbiphenylene group, 2,2'-dimethylbiphenylene group, 2,2 '-dimethoxybiphenylene group, 3,3',5,5'-tetramethylbiphenylene group, 3,3',5,5'-tetraethylbiphenylene group, 2,2-diphenylpropane-4,4'-diyl group, 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, diphenylsulfone-4,4'-diyl group or oxybisphenyl-4,4'-diyl group, and more
  • L is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO- Represents one selected from the group consisting of O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -.
  • R 1 at each occurrence independently represents a C 1-16 alkylene group which may have one or more substituents, and a C 1-16 alkylene group which may have one or more substituents; Represents one type selected from divalent groups containing a good C 3-16 alicyclic hydrocarbon group.
  • C 1-16 alkylene group in the above-mentioned C 1-16 alkylene group which may have one or more substituents may be linear or branched, and is preferably is a straight-chain or branched C 1-10 alkylene group, more preferably a straight-chain or branched C 1-5 alkylene group, and in one embodiment, a straight-chain or branched C 1-5 alkylene group.
  • -3 alkylene group specifically, it can be -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -.
  • R 1 is preferably a C 1-16 fluoroalkylene group substituted with one or more fluorine atoms, more preferably a C 1-16 perfluoroalkylene group, and further Preferably it is a C 1-6 perfluoroalkylene group, and even more preferably a C 1-3 perfluoroalkylene group.
  • the above C 1-16 perfluoroalkylene group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkylene group, more preferably a straight chain.
  • a chain or branched C 1-3 perfluoroalkylene group specifically -CF 2 -, -CF 2 CF 2 -, -CF 2 CF 2 CF 2 -, -CF 2 CF (CF 3 ) -, -C(CF 3 ) 2 -.
  • R 1 may have will be described later.
  • the “C 3-16 alicyclic hydrocarbon group” in the above divalent group containing a C 3-16 alicyclic hydrocarbon group which may have one or more substituents is a monocyclic group. In the case of a polycyclic ring, two or more rings may form a bridged ring or may not form a bridged ring.
  • the number of alicyclic hydrocarbon groups is 1 or more, preferably may be 1 or more and 4 or less, more preferably 1 or more and 3 or less, even more preferably 1 or 2.
  • a divalent group containing such an alicyclic hydrocarbon group preferably a divalent C 3-16 alicyclic hydrocarbon group, more preferably a divalent C 6-12 alicyclic hydrocarbon group More preferably, it may be a cyclohexanediyl group, a decahydronaphthyl group, an isobornyl group, a tricyclo[5.2.1.0 2,6 ]decanediyl group, or an adamantyl group.
  • two or more alicyclic hydrocarbon groups are a single bond or a divalent group. may be bonded via an organic group.
  • organic groups include linear or branched C 1-4 alkyl groups.
  • the divalent group containing a C 3-16 alicyclic hydrocarbon group represented by R 1 above is a divalent group containing a C 3-16 alicyclic hydrocarbon group having no substituent. In another embodiment, it is a divalent group containing a C 3-16 alicyclic hydrocarbon group having a substituent.
  • the substituents that the divalent group containing a C 3-16 alicyclic hydrocarbon group represented by R 1 may have will be described later.
  • R 1 may be a C 1-16 alkylene group having no substituent. In another embodiment, R 1 may be a C 1-16 alkylene group having a substituent. In yet another embodiment, R 1 may be a divalent C 1-16 alicyclic hydrocarbon group having no substituents.
  • R 2 at each occurrence independently represents a C 1-16 alkyl group optionally having one or more substituents, a C 1-16 alkyl group optionally having one or more substituents; 6-20 represents an aromatic hydrocarbon group or a hydrogen atom.
  • the "C 1-16 alkyl group" in the above C 1-16 alkyl group which may have one or more substituents may be linear or branched, preferably A straight-chain or branched C 1-10 alkyl group, more preferably a straight-chain or branched C 1-5 alkyl group, and in one embodiment, a straight-chain or branched C 1-5 alkyl group .
  • R 2 can be an unsubstituted C 1-16 alkyl group. In another embodiment, R 2 can be a C 1-16 alkyl group with substituents.
  • a C 1-16 alkyl group which may have one or more substituents may be substituted with one or more fluorine atoms.
  • R 2 is preferably a C 1-16 fluoroalkyl group substituted with one or more fluorine atoms, more preferably a C 1-16 perfluoroalkyl group, and Preferably it is a C 1-6 perfluoroalkyl group, even more preferably a C 1-4 perfluoroalkyl group, specifically -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF( CF3 ) 2 , -CF2CF2CF2CF3 , -CF2CF ( CF3 ) 2 , -CF( CF3 ) 3 .
  • Other substituents that the C 1-16 alkyl group represented by R 2 may have will be described later.
  • the "C 6-20 aromatic hydrocarbon group" in the C 6-20 aromatic hydrocarbon group which may have one or more substituents may be monocyclic or polycyclic. In the case of a polycyclic ring, two or more rings may not necessarily form a condensed ring, but may form a condensed ring.
  • the above C 6-20 aromatic hydrocarbon group which may have one or more substituents is preferably a C 6-10 aromatic hydrocarbon group, more preferably a phenylene group, a tolylene group, It can be a xylylene group or a naphthylene group, more preferably a phenylene group, a tolylene group or a xylylene group in one embodiment, and even more preferably a naphthylene group in another embodiment.
  • Examples of substituents that the C 6-20 aromatic hydrocarbon group may have include a hydroxyl group.
  • L is preferably one selected from the group consisting of -O-, -S-, -CO-, -O-CO-O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 - It is.
  • Aliphatic or aromatic imido-diyl group represented by A divalent group containing a C 6-20 aromatic hydrocarbon group represented by Ar, C 6-20 aromatic hydrocarbon group represented by A 10
  • the alkylene group and the C 1-16 alkyl group represented by R 2 may have a substituent.
  • Aliphatic or aromatic imido-diyl group represented by A divalent group containing a C 6-20 aromatic hydrocarbon group represented by Ar, C 6-20 aromatic hydrocarbon group represented by A 10 a substituent that the C 6-10 aromatic hydrocarbon group represented by Ar 11 and the C 6-10 aromatic hydrocarbon group represented by Ar 12 may have;
  • the substituent represented by R 10 includes a C 1-20 fluorine-containing organic group or a C 2-20 fluorine-containing organic group; a C 1-16 alkyl group optionally substituted with one or more fluorine atoms; ; C 6-20 aromatic hydrocarbon group optionally substituted with one or more fluorine atoms; C 1-16 alkoxy group; C 1-16 hydroxyalkyl group; hydroxyl group; carboxy group; glycidyl group; One or more types selected from fluorine atoms can be mentioned.
  • substituents include one or more selected from a C 1-20 fluorine-containing organic group or a C 2-20 fluorine-containing organic group; a C 6-20 aromatic hydrocarbon group; a hydroxyl group; and a fluorine atom. It will be done.
  • the group hydrocarbon group may be modified with oils such as cashew oil, linseed oil, castor oil, and linseed oil.
  • the above C 1-20 fluorine-containing organic group or C 2-20 fluorine-containing organic group is an organic group containing a fluorine atom, and may contain a hydrogen atom or an oxygen atom in addition to a fluorine atom and a carbon atom.
  • the above C 2-20 fluorine-containing organic group is preferably the following formula (1A) and formula (1B): R 31 -X 1 -(R F1 ) r -CF 2 -* (1A) *-X 3 -CF 2 -* (1B)
  • R F1 represents -(Rf) p -R F -(O) q -
  • Rf each independently represents a C 1-16 alkylene group optionally substituted with one or more fluorine atoms
  • R F represents a divalent fluoro(poly)ether group
  • a group represented by one or more selected from The C 1-20 fluorine-containing organic group is preferably The following formula (2A) and formula (2B): R 32 -X 1 -(R F1 ) r -CF 2 -* (2A) *-X 1 -CF 2 -* (2B)
  • R F1 represents -(Rf) p -R F -(O) q -
  • Rf each independently represents a C 1-16 alkylene group optionally substituted with one or more fluorine atoms
  • R F represents a divalent fluoro(poly)ether group
  • the fluorine-containing organic group has the above structure, it has flexibility, adhesion (reactivity) and affinity with other materials, low dielectric properties, transparency, water and oil repellency, low adhesion, stain resistance, A fluorine-containing aromatic polymer having excellent various properties such as solvent solubility and high surface hardness can be provided.
  • the fluorine-containing organic group has a structure represented by formula (2B), it has rigidity, low coefficient of thermal expansion, low dielectric properties, transparency, water and oil repellency, low adhesiveness, antifouling property, and solvent solubility. It is possible to provide a fluorine-containing aromatic polymer having excellent various properties such as hardness and high surface hardness.
  • R F1 represents -(Rf) p -R F -(O) q -.
  • Rf at each occurrence independently represents a C 1-16 alkylene group optionally substituted with one or more fluorine atoms.
  • the “C 1-16 alkylene group” in the C 1-16 alkylene group optionally substituted with one or more fluorine atoms may be linear or branched, and is preferably is a straight-chain or branched C 1-6 alkylene group, more preferably a straight-chain C 1-3 alkylene group.
  • Rf is preferably a C 1-16 fluoroalkylene group substituted with one or more fluorine atoms, more preferably a C 1-16 perfluoroalkylene group, and still more preferably a C 1-16 perfluoroalkylene group. 6 perfluoroalkylene group, and even more preferably a C 1-3 perfluoroalkylene group.
  • the above C 1-16 perfluoroalkylene group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkylene group, more preferably a straight chain.
  • a chain or branched C 1-3 perfluoroalkylene group specifically -CF 2 -, -CF 2 CF 2 -, CF 2 CF 2 CF 2 -, CF 2 CF (CF 3 ) - .
  • R F represents a divalent fluoro(poly)ether group.
  • a fluoro(poly)ether group means a fluoroether group and/or a fluoropolyether group.
  • the fluoropolymer of the present disclosure can be imparted with the properties of a fluoro(poly)ether group, and can have good flexibility, heat resistance, friction properties, antifouling properties, and water and oil repellency.
  • R F preferably has the formula: -(OC 4 F 8 ) c - (OC 3 R Fa 6 ) d - (OC 2 F 4 ) e - (OCF 2 ) f -
  • R Fa is each independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence
  • c, d, e and f are each independently an integer of 0 to 200, and the sum of c, d, e and f is 1 or more.
  • the repeating units appended with c, d, e, or f and enclosed in parentheses can be present in any order in the formula.
  • all R Fa are hydrogen atoms or chlorine atoms, at least one of c, e, and f is 1 or more.
  • PFPE group represented by
  • R Fa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. However, when all R Fa are hydrogen atoms or chlorine atoms, at least one of c, e, and f is 1 or more.
  • c, d, e and f may each independently be an integer of 0 to 100 or an integer of 0 to 20.
  • the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more.
  • the sum of c, d, e and f is preferably 200 or less, more preferably 100 or less, still more preferably 60 or less, and may be, for example, 50 or less, or 30 or less, and even 20 or less.
  • repeating units may be linear or branched.
  • -(OC 4 F 8 )- is -(OCF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF(CF 3 ))-, -(OCF 2 C(CF 3 ) 2 )-, -(OCF(CF 3 ) It may be any of CF(CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and -(OCF 2 CF(C 2 F 5 ))-.
  • -(OC 3 F 6 )- (that is, in the above formula, R Fa is a fluorine atom) represents -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )- and -( It may be OCF 2 CF(CF 3 ))-, and preferably either -(OCF(CF 3 )CF 2 )- or -(OCF 2 CF(CF 3 ))-.
  • -(OC 2 F 4 )- may be either -(OCF 2 CF 2 )- or -(OCF(CF 3 ))-.
  • each occurrence of R F is independently a group represented by the following formula (f1). -(OC 3 F 6 ) d - (OCF 2 ) f - (f1) [In the formula, d is an integer from 0 to 200, and f is an integer from 1 to 200. ];
  • OC3F6 in the above formula (f1) is preferably ( OCF2CF2CF2 ), (OCF( CF3 ) CF2 ) or ( OCF2CF ( CF3 )), more preferably, (OCF 2 CF (CF 3 )).
  • d is preferably an integer of 0 to 100, more preferably 0 to 50, and still more preferably 0 to 10. In one embodiment, d is 0. In another embodiment, d is preferably 1-100, more preferably 2-50, even more preferably 3-10.
  • f is preferably 1 to 100, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. In one embodiment, f is 1.
  • p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1. q is 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1. r is 0 or 1. In one embodiment, r is 0. In another embodiment, r is 1.
  • X 1 represents a C 1-16 alkylene group or a single bond which may be substituted with one or more halogen atoms.
  • the “C 1-16 alkylene group” in the above C 1-16 alkylene group optionally substituted with one or more halogen atoms may be a straight chain or a branched chain, preferably A straight chain or branched C 1-10 alkylene group, more preferably a straight chain or branched C 1-5 alkylene group, and in one embodiment, a branched C 2-4 alkylene group. In another embodiment, it is preferably a linear C 2-5 alkylene group.
  • halogen atom in the C 1-16 alkylene group optionally substituted with one or more halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a fluorine atom and an iodine atom. can be mentioned.
  • the C 1-16 alkylene group optionally substituted with one or more halogen atoms is preferably -CF 2 -, -CF 2 CF 2 -, -CF(CF 3 )-, -CF 2 CF 2 CF 2 -, -CF 2 CF (CF 3 )-, -CF 2 CF 2 CF 2 CF 2 -, -CF 2 CF 2 CF 2 CF 2 - or CHI-CH 2 -CF 2 CF 2 -, more preferably -CF 2 CF 2 -, -CF(CF 3 )-, -CF 2 CF(CF 3 )-, -CF 2 CF 2 CF 2 CF 2 - or CHI-CH 2 -CF 2 CF 2 -.
  • X 1 is preferably a linear or branched C 1-10 alkylene group or a single bond which may be substituted with one or more halogen atoms, more preferably a fluorine atom and an iodine atom. It is a linear or branched C 1-5 alkylene group or a single bond which may be substituted with one or more selected ones.
  • X 3 represents a C 1-16 alkylene group or a single bond which may be substituted with one or more halogen atoms.
  • the “C 1-16 alkylene group” in the above C 1-16 alkylene group optionally substituted with one or more halogen atoms may be a straight chain or a branched chain, preferably A straight chain or branched C 1-10 alkylene group, more preferably a straight chain or branched C 1-5 alkylene group, and in one embodiment, a branched C 2-4 alkylene group. In another embodiment, it is preferably a linear C 2-5 alkylene group.
  • halogen atom in the C 1-16 alkylene group optionally substituted with one or more halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a fluorine atom and an iodine atom. can be mentioned.
  • the C 1-16 alkylene group optionally substituted with one or more halogen atoms is preferably -CF 2 -, -CF 2 CF 2 -, -CF(CF 3 )-, -CF 2 CF 2 CF 2 -, -CF 2 CF (CF 3 )-, -CF 2 CF 2 CF 2 CF 2 -, -CF 2 CF 2 CF 2 CF 2 - or CHI-CH 2 -CF 2 CF 2 -, more preferably -CF 2 CF 2 -, -CF(CF 3 )-, -CF 2 CF(CF 3 )-, -CF 2 CF 2 CF 2 CF 2 CF 2 - or CHI-CH 2 - CF 2 CF 2 -.
  • X 3 is preferably a linear or branched C 1-10 alkylene group optionally substituted with one or more halogen atoms, more preferably 1 selected from fluorine atoms and iodine atoms.
  • a straight or branched chain C 1-5 alkylene group optionally substituted by one or more of the following species.
  • the “C 1-16 alkyl group” in the C 1-16 alkyl group optionally substituted with one or more halogen atoms represented by R 31 and R 32 above may be a linear or branched It may be a chain, preferably a straight or branched C 1-10 alkyl group, more preferably a straight or branched C 1-6 alkyl group, and in one embodiment, A linear or branched C 1-4 alkyl group, specifically -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 It can be CH 2 CH 2 CH 3 , -CH 2 CH(CH 3 ) 2 , -CH(CH 3 ) 3 .
  • halogen atom in the C 1-16 alkyl group optionally substituted with one or more halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a fluorine atom and an iodine atom. can be mentioned.
  • the C 1-16 alkyl group optionally substituted with one or more halogen atoms is a C 1-16 alkyl group that is not substituted with a halogen atom.
  • the C 1-16 alkyl group optionally substituted with one or more halogen atoms is C 1-16 fluoroalkyl, preferably substituted with one or more fluorine atoms. group, more preferably a C 1-16 perfluoroalkyl group, even more preferably a C 1-6 perfluoroalkyl group.
  • the above C 1-16 perfluoroalkyl group may be linear or branched, preferably a linear or branched C 1-10 perfluoroalkyl group, more preferably , a linear or branched C 1-6 perfluoroalkyl group, specifically -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -CF2CF2CF2CF3 , -CF2CF ( CF3 ) 2 , -CF ( CF3 ) 3 .
  • the “C 6-20 aromatic hydrocarbon group” in the C 6-20 aromatic hydrocarbon group which may have one or more substituents represented by R 31 and R 32 above is a monocyclic group. It may be polycyclic, and in the case of polycyclic, two or more rings may not form a condensed ring or may form a condensed ring.
  • the "C 6-20 aromatic hydrocarbon group” in the C 6-20 aromatic hydrocarbon group which may have one or more substituents is preferably a C 6-15 aromatic hydrocarbon group. More preferably, it is a C 6-10 aromatic hydrocarbon group, and still more preferably a phenyl group.
  • Substituents in the above C 6-20 aromatic hydrocarbon group which may have one or more substituents include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; C 1- 4 alkyl group; C 1-4 alkoxy group; R 20 -O-CO- (wherein R 20 represents a C 1-4 alkyl group), preferably a halogen atom, particularly preferably a fluorine atom It is.
  • R 20 may be a straight chain or branched chain, preferably a straight chain or branched C 1-3 alkyl group, and specifically, -CH 3 and -CH 2 CH 3 are preferred.
  • the C 6-20 aromatic hydrocarbon group represented by R 31 and R 32 above is preferably a C 6-10 aromatic hydrocarbon group which may have one or more substituents. , more preferably a C 6-10 aromatic hydrocarbon group which may have one or more substituents. In one embodiment, the C 6-20 aromatic hydrocarbon group represented by R 31 and R 32 described above preferably has a substituent, and in another embodiment, the C 6-20 aromatic hydrocarbon group represented by R 31 and R 32 described above preferably has a substituent. The 6-20 aromatic hydrocarbon group preferably has no substituents.
  • silsesquioxane residue in the silsesquioxane residue that may have one or more substituents represented by R 31 and R 32 above refers to It is a monovalent group from which one substituent has been removed, and may have any of a cage-shaped structure, a ladder-shaped structure, and a random structure.
  • the substituent in the silsesquioxane residue which may have one or more substituents is preferably a C 1-10 alkyl group which may be substituted with one or more halogen atoms. ; a phenyl group, more preferably a C 1-6 alkyl group optionally substituted with one or more halogen atoms; a phenyl group.
  • the “C 1-10 alkyl group” in the C 1-10 alkyl group optionally substituted with one or more halogen atoms as a substituent of the above-mentioned silsesquioxane residue is a straight chain It may also be a branched chain, preferably a straight or branched C 1-8 alkyl group, more preferably a straight chain C 1-6 alkyl group.
  • halogen atom in the C 1-10 alkyl group which may be substituted with one or more halogen atoms as a substituent of the silsesquioxane residue include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • halogen atoms include atoms, preferably fluorine atoms and iodine atoms.
  • the C 1-10 alkyl group optionally substituted with one or more halogen atoms as a substituent of the silsesquioxane residue is preferably -CHI-CH 2 -CF 2 CF 2 CF 2 -I.
  • a phenyl group and an isobutyl group are preferable.
  • R f2 at each occurrence independently represents a C 1-16 alkyl group or a hydrogen atom optionally substituted by one or more fluorine atoms, preferably one or more fluorine atoms represents a C 1-16 alkyl group which may be substituted with
  • the “C 1-16 alkyl group” in the above C 1-16 alkyl group optionally substituted with one or more fluorine atoms may be linear or branched, and is preferably is a straight-chain or branched C 1-10 alkyl group, more preferably a straight-chain or branched C 1-5 alkyl group, particularly preferably a C 1-2 alkyl group.
  • the C 1-16 alkyl group optionally substituted with one or more fluorine atoms is preferably a methyl group, ethyl group, trifluoromethyl group, or pentafluoroethyl group.
  • R f3 represents a C 1-16 alkyl group optionally substituted with one or more halogen atoms, a fluorine atom, or a hydrogen atom.
  • the "C 1-16 alkyl group" in the above-mentioned C 1-16 alkyl group optionally substituted with one or more halogen atoms may be linear or branched, preferably A straight-chain or branched C 1-10 alkyl group, more preferably a straight-chain or branched C 1-5 alkyl group, particularly preferably a C 1-2 alkyl group.
  • halogen atom in the C 1-16 alkyl group optionally substituted with one or more halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a fluorine atom.
  • the C 1-16 alkyl group optionally substituted with one or more fluorine atoms is preferably a methyl group, ethyl group, trifluoromethyl group, or pentafluoroethyl group.
  • R f3 is preferably a C 1-5 alkyl group, phenyl group, alkoxy group, hydroxy group, ONa, OK, chlorine atom or fluorine atom, which may be substituted with one or more halogen atoms, More preferred is a fluorine atom.
  • R f4 each independently represents a hydrogen atom or a fluorine atom at each occurrence.
  • R f4 is a hydrogen atom
  • R f4 is a fluorine atom.
  • R 31 and R 32 are iodine atoms, in the unit represented by formula (I), R 31 and R 32 are replaced with bonds, and X 1 bonded to R 31 and R 32 is Aromatic ring (the above R 31 and R 32 are aromatic rings other than the group bonded via -X 1 -(R F1 ) r -CF 2 -, for example, other groups represented by formula (I)) may be bonded to an aromatic ring contained in the unit.
  • Aromatic ring the above R 31 and R 32 are aromatic rings other than the group bonded via -X 1 -(R F1 ) r -CF 2 -, for example, other groups represented by formula (I)
  • the above structure can be considered as follows.
  • the iodine atom of the compound represented by formula (II) is extracted to become a reaction point, and is bonded to the aromatic ring of the unit represented by formula (I-1). It is thought that the structure represented by formula (I) can be obtained by doing so.
  • R 31 and R 32 are iodine atoms, it is considered that the iodine atoms corresponding to R 31 and R 32 can be similarly extracted and bonded to other aromatic rings.
  • the substituents of the groups represented by R 31 and R 32 include an I atom, and the group bonded to the I atom may be bonded to another aromatic ring.
  • the total number of carbon atoms in formula (1A) is 2 or more and 20 or less, preferably 3 or more and 15 or less, and more preferably 4 or more and 15 or less. It is considered that the smaller the number of carbon atoms, the easier it is to maintain the properties of the aromatic polymer, and the larger the number of carbon atoms, the easier it is to exhibit the properties of the fluorine-containing organic group.
  • the total number of carbon atoms in formula (1B) is 2 or more and 20 or less, preferably 3 or more and 10 or less, and more preferably 3 or more and 5 or less.
  • the total number of carbon atoms in formula (2A) may be 1 or more and 20 or less, preferably 1 or more and 15 or less. It is considered that the smaller the number of carbon atoms, the easier it is to maintain the properties of the aromatic polymer, and the larger the number of carbon atoms, the easier it is to exhibit the properties of the fluorine-containing organic group.
  • the total number of carbon atoms in formula (2B) is 1 or more and 20 or less, preferably 3 or more and 10 or less, and more preferably 3 or more and 5 or less. It is considered that the smaller the number of carbon atoms, the easier it is to maintain the properties of the aromatic polymer, and the larger the number of carbon atoms, the easier it is to exhibit the properties of the fluorine-containing organic group.
  • the C 2-20 fluorine-containing organic group represented by the above formula (1A) is a C 4-20 fluoroalkyl group, a C 2-20 fluorine-containing organic group having a functional group, or a C 4-20 fluoro(poly) An ether group is preferred.
  • formula (1A) and formula (1B) can be replaced by the following formula (1-a), formula (1-b), formula (1-c), and formula (1B): FX 3 -CF 2 -* (1-a) R 31 -X 1 -CF 2 -* (1-b) R 31 -X 1 -R F1 -CF 2 -* (1-c) *-X 3 -CF 2 -* (1B) [In formula (1-a), formula (1-b), formula (1-c) and formula (1B), R F1 represents -(Rf) p -R F -(O) q -, Rf each independently represents a C 1-16 alkylene group optionally substituted with one or more fluorine atoms; R F represents a divalent fluoro(poly)ether group, X 1 represents a C 1-16 alkylene group or a single bond optionally substituted with one or more halogen atoms, X 2 represents a C 1-16 alkylene group optionally substituted with one or
  • the C 4-20 fluorine organic group represented by the above formula (1A) is a group represented by the formula (1-a)
  • properties derived from the fluoroalkyl group are imparted to the fluorine-containing aromatic polymer.
  • the C 4-20 fluorine organic group represented by the above formula (1A) is a group represented by the formula (1-b)
  • the fluorine-containing aromatic polymer has characteristics derived from a specific functional group.
  • the C 4-20 fluorine organic group represented by the above formula (1A) is a group represented by the formula (1-c)
  • the fluoro(poly)ether can be imparted to the fluoroaromatic polymer. properties derived from the group.
  • the C 1-20 fluorine-containing organic group represented by the above formula (2A) and formula (2B) is a C 1-20 fluoroalkyl group, a C 1-20 fluorine-containing organic group having a functional group, or a C 1-20 fluorine-containing organic group having a functional group.
  • 20 fluoro(poly)ether groups are preferred.
  • formula (2A) and formula (2B) can be replaced by the following formula (2-a), formula (2-b), formula (2-c), and formula (2B): FX 1 -CF 2 -* (2-a) R 32 -X 1 -CF 2 -* (2-b) R 32 -X 1 -R F1 -CF 2 -* (2-c) *-X 1 -CF 2 -* (2B) [In formula (2-a), formula (2-b), formula (2-c) and formula (2B), R F1 represents -(Rf) p -R F -(O) q -, Rf each independently represents a C 1-16 alkylene group optionally substituted with one or more fluorine atoms; R F represents a divalent fluoro(poly)ether group, X 1 represents a C 1-16 alkylene group or a single bond optionally substituted with one or more halogen atoms, R 32 is a C 1-16 alkyl group optionally substituted with one or more
  • the C 4-20 fluorine organic group represented by the above formula (2A) is a group represented by the formula (2-a)
  • properties derived from the fluoroalkyl group are imparted to the fluorine-containing aromatic polymer.
  • the C 4-20 fluorine organic group represented by the above formula (2A) is a group represented by the formula (2-b)
  • the fluorine-containing aromatic polymer has characteristics derived from a specific functional group.
  • the C 4-20 fluorine organic group represented by the above formula (2A) is a group represented by the formula (2-c)
  • fluoro(poly)ether can be imparted to the fluorine-containing aromatic polymer. properties derived from the group.
  • X 3 has the same meaning as above, and is preferably a linear or branched C 3-10 alkylene group optionally substituted with one or more halogen atoms, more preferably a fluorine atom and a straight chain or branched C 3-5 alkylene group optionally substituted with one or more of one selected from iodine atoms.
  • a divalent group containing a hydrogen group, a substituent that the C 6-10 aromatic hydrocarbon group represented by Ar 11 and the C 6-10 aromatic hydrocarbon group represented by Ar 12 may have; and
  • the C 1-16 alkyl group in the C 1-16 alkyl group optionally substituted with one or more fluorine atoms as a substituent represented by R 10 is It may be a branched chain, preferably a straight or branched C 1-10 alkyl group, more preferably a straight or branched C 1-5 alkyl group, and in one embodiment , a linear or branched C 1-4 alkyl group, specifically -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -CH
  • the C 1-16 alkyl group substituted with one or more fluorine atoms is preferably a C 1-16 fluoroalkyl group, more preferably a C 1-16 perfluoroalkyl group, even more preferably is a straight-chain or branched C 1-19 perfluoroalkyl group, more preferably a straight-chain or branched C 1-5 perfluoroalkyl group, such as -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ) 2 , -C(CF 3 ) 3 could be.
  • the C 1-16 alkyl group optionally substituted with one or more fluorine atoms is a C 1-16 alkyl group that is not substituted with a fluorine atom, and in another embodiment, the C 1-16 alkyl group optionally substituted with one or more fluorine atoms is It can be a 1-16 fluoroalkyl group.
  • the C 6-20 aromatic hydrocarbon group which may have one or more substituents is preferably a C 6-10 aromatic hydrocarbon group, more preferably a phenylene group, a tolylene group, It can be a xylylene group or a naphthylene group, more preferably a phenylene group, a tolylene group or a xylylene group in one embodiment, and even more preferably a naphthylene group in another embodiment.
  • Examples of the substituent that the C 6-20 aromatic hydrocarbon group may have include a hydroxyl group and a fluorine-containing organic group.
  • the fluorine-containing organic group is preferably a group represented by the above formula (1A), formula (1B), formula (2A) or formula (2B), and is preferably a group represented by the above formula (1-a) or formula (1-a).
  • b) a group represented by any one of formula (1-c), formula (1B), formula (2-a), formula (2-b), formula (2-c) and formula (2B); It is more preferable that there be.
  • the fluorine-containing organic group is preferably a group represented by the formula (1A) or (2A), and the fluorine-containing organic group is preferably a group represented by the formula (1-a), (1-b), or ( 1-c), formula (2-a), formula (2-b) and formula (2-c).
  • a divalent group containing a hydrogen group, a substituent that the C 6-10 aromatic hydrocarbon group represented by Ar 11 and the C 6-10 aromatic hydrocarbon group represented by Ar 12 may have; and , the C 1-16 alkoxy group as a substituent represented by R 10 may be a straight chain or a branched chain, and preferably a straight chain or branched C 1-10 alkoxy group.
  • a linear or branched C 1-5 alkoxy group and in one embodiment a linear or branched C 1-4 alkoxy group, specifically - O-CH 3 , -O-CH 2 CH 3 , -O-CH 2 CH 2 CH 3 , -O-CH(CH 3 ) 2 , -O-CH 2 CH 2 CH 2 CH 3 , -O-CH 2 It can be CH(CH 3 ) 2 , -O-CH(CH 3 ) 3 .
  • a divalent group containing a hydrogen group, a substituent that the C 6-10 aromatic hydrocarbon group represented by Ar 11 and the C 6-10 aromatic hydrocarbon group represented by Ar 12 may have; and , the C 1-16 hydroxyalkyl group as a substituent represented by R 10 may be linear or branched, preferably a linear or branched C 1-10 hydroxy
  • the C 6-20 aromatic hydrocarbon group as the substituent may be monocyclic or polycyclic. When the C 6-20 aromatic hydrocarbon group is polycyclic, two or more rings may or may not form a condensed ring.
  • Such a C 6-20 aromatic hydrocarbon group is preferably a C 6-10 aromatic hydrocarbon group, and more preferably a phenyl group, tolyl group, xylyl group, or naphthyl group.
  • the substituent represented is preferably one or more selected from a C 1-16 alkyl group; a C 1-16 fluoroalkyl group; a C 1-16 alkoxy group; and a fluorine atom, and a C 1-5 alkyl group; More preferably, one or more types selected from 1-5 fluoroalkyl group; and fluorine atom.
  • substituents that the hydrogen group may have include C 1-20 fluorine-containing organic group or C 2-20 fluorine-containing organic group; C 1-16 alkoxy group; C 1-16 hydroxyalkyl group; hydroxyl group; carboxyl
  • One or more selected from groups; glycidyl groups; and fluorine atoms are preferred.
  • the substituents that the C 1-16 alkylene group represented by R 1 and the divalent group containing the C 3-16 alicyclic hydrocarbon group represented by R 1 may have include 1 One or more selected from a C 6-20 aromatic hydrocarbon group which may have one or more substituents; a hydroxyl group; and a fluorine atom is preferred.
  • the substituent that the C 1-16 alkyl group represented by R 2 may have is preferably a fluorine atom.
  • k independently represents an integer of 0 to 4, preferably an integer of 0 to 1.
  • l independently represents an integer of 1 to 4, preferably an integer of 1 to 3.
  • m independently represents an integer of 0 to 4, preferably an integer of 0 to 3.
  • the fluorine-containing aromatic polymer represented by formula (I) has the following (i) and (ii): (i) k is 0 and formula (I) has one or more C 2-20 fluorine-containing organic groups; (ii) k is 1 or more and 4 or less, and formula (I) has one or more C 1-20 fluorine-containing organic groups.
  • the fluorine-containing aromatic polymer may have a C 1 fluorine-containing organic group, particularly -CF 3 .
  • the fluorine-containing aromatic polymer of the present disclosure has the above C 2-20 fluorine-containing organic group or C 1-20 fluorine-containing organic group, which is directly bonded to the aromatic ring, so that the fluorine-containing organic group Properties can be imparted to the aromatic polymer, such as flexibility, antifouling properties, frictional properties, antifouling properties, water and oil repellency, low adhesion, and antifouling properties, while further improving or maintaining the heat resistance of aromatic polymers at a high level. It is expected to have excellent properties such as high solvent solubility and high surface hardness.
  • the number of fluorine-containing organic groups contained in the units appended with n and enclosed in parentheses is preferably 1 or more, more preferably 1 to 6, per each unit, More preferably, the number may be 1 to 4.
  • the number of C 2-20 fluorine-containing organic groups contained in the units enclosed in parentheses with n is preferably 1 or more, and more preferably 1 to 2 per unit.
  • the number of C 1 fluorine-containing organic groups (especially -CF 3 ) contained in the units enclosed in parentheses with n is preferably 2 to 6, more preferably 2 to 4, and more preferably 2 to 6 per unit.
  • the number may be 3 to 4.
  • fluorine-containing organic groups can be introduced into aromatic polymers via hydrocarbon groups, oxygen atoms, etc., but bonds via hydrocarbon groups, oxygen atoms, etc. are sensitive to heat, light, acids, bases, etc.
  • the introduced fluorine-containing organic group can be easily removed.
  • the fluorine-containing aromatic polymer of the present disclosure since the fluorine-containing organic group is directly bonded to the aromatic ring, the fluorine-containing organic group is difficult to detach, and has high levels of heat resistance, flexibility, antifouling properties, and friction properties. It is thought that it is possible to achieve both water and oil repellency.
  • n represents an integer of 1 or more, preferably 3 or more and 2,000 or less, more preferably 5 or more and 1,000 or less, even more preferably 10 or more and 1,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2,000. It may be more than 200,000.
  • the number average molecular weight can be measured by gel permeation chromatography, and the number average molecular weight can be a converted value using polystyrene as a standard sample.
  • the above formula (I) is preferably the following formula (Ia): [In formula (I-a), A a independently at each occurrence represents an aliphatic or aromatic imido-diyl group; Ar a represents, at each occurrence independently, a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; na represents an integer of 1 or more, Formula (I-a) has one or more C 1-20 fluorine-containing organic groups. ] It is expressed as
  • the fluorine-containing aromatic polymer represented by formula (I-a) contains an imido-N-yl group in a repeating unit and can be polyimide, polyetherimide, or polyamideimide, and while maintaining the characteristics of these resins, Flexibility, adhesion (reactivity) and affinity with other materials, low dielectric properties, transparency, water and oil repellency, low adhesion, stain resistance, solvent solubility, high surface hardness, etc. It is expected to have excellent properties.
  • a a independently at each occurrence represents an aliphatic or aromatic imido-diyl group; such aliphatic or aromatic imido-diyl groups include the aliphatic or aromatic imido-diyl group represented by A; Groups similar to the group are mentioned.
  • A is preferably an aliphatic or aromatic imido-diyl group containing one or more imido rings and optionally having one or more substituents, and is represented by formula (A1).
  • the groups represented by formula (A2) are more preferred, the groups represented by formulas (A1-1) to (A1-19) are even more preferred.
  • Ar a independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; such a group includes: Examples include groups similar to the divalent group represented by Ar containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents.
  • Ar a is preferably a group represented by the formula (Ar1), such as a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,4'-diyl group, 1 selected from 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, diphenylsulfone-4,4'-diyl group or oxybisphenyl-4,4'-diyl group species are more preferred, and phenylene groups are even more preferred.
  • Ar1 a group represented by the formula (Ar1), such as a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,4
  • the above C 1-20 fluorine-containing organic group is an organic group containing a fluorine atom, and is preferably a group represented by one or more selected from the above formula (2A) and formula (2B), and is preferably a group represented by one or more of the above formulas (2A) and (2B).
  • a group represented by (2A) is preferable.
  • na represents an integer of 1 or more, preferably 3 or more and 2,000 or less, more preferably 5 or more and 1,000 or less, even more preferably 10 or more and 1,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-a) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, even more preferably 2 ,000 or more and 200,000 or less.
  • the above formula (I) is preferably the following formula (Ib): [In formula (I-b), Ar b each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; L b is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one type selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -, At each occurrence, R 1 is independently a C 1-16 alkylene group which may have a substituent, and a C 3-16 fatty acid which may have one or more substituents.
  • R 2 independently represents a C 1-16 alkyl group or a hydrogen atom which may have a substituent
  • nb represents an integer of 1 or more
  • Formula (I-b) has one or more C 2-20 fluorine-containing organic groups.
  • the fluorine-containing aromatic polymer represented by formula (I-b) can be, for example, polycarbonate, polyphenylene sulfide, polyphenylene ether, etc., and while maintaining the properties of these resins, it has flexibility and adhesiveness to other materials. It is expected to have excellent properties such as (reactivity) and affinity, low dielectric properties, transparency, water and oil repellency, low adhesion, antifouling properties, solvent solubility, and high surface hardness.
  • Each occurrence of Ar b independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; such groups include: Examples include groups similar to the divalent group represented by Ar containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents.
  • Ar b is preferably a group represented by formula (Ar1), such as a phenylene group, xylylene group, hydroxyphenylene group, hydroxyxylylene group, naphthylene group, 2,2-diphenylpropane-4,4'-diyl group, 1 selected from 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, diphenylsulfone-4,4'-diyl group or oxybisphenyl-4,4'-diyl group species are more preferred, and phenylene groups are even more preferred.
  • Ar1 a group represented by formula (Ar1), such as a phenylene group, xylylene group, hydroxyphenylene group, hydroxyxylylene group, naphthylene group, 2,2-diphenylpropane-4,4'-diyl group, 1 selected from 1,1-diphenylmethane-4
  • L b is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -.
  • R 1 and R 2 have the same meanings as above.
  • L b -O-CO-O-, -S-, and -O- are preferable.
  • the above C 2-20 fluorine-containing organic group is an organic group containing a fluorine atom, and is preferably a group represented by one or more selected from the above formula (1A) and the above formula (1B), and the above-mentioned More preferably, it is a group represented by formula (1A).
  • nb represents an integer of 1 or more, preferably 3 or more and 2,000 or less, more preferably 5 or more and 1,000 or less, even more preferably 10 or more and 1,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-b) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, even more preferably 2 ,000 or more and 200,000 or less.
  • the above formula (I-b) is preferably represented by the following formulas (I-b1), (I-b2), (I-b3), (I-b4), (I-b5), (I-b6) or (I-b7): [In formula (I-b1), (I-b2), (I-b3), (I-b4), (I-b5), (I-b6) or (I-b7), Ar b each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; nb represents an integer of 1 or more, In formula (I-b1), (I-b2), (I-b3), (I-b4), (I-b5), (I-b6) or (I-b7), each one or It has a C 2-20 fluorine-containing organic group. ] It is expressed as
  • the above C 2-20 fluorine-containing organic group is an organic group containing a fluorine atom, and is preferably a group represented by one or more selected from the above formula (1A) and formula (1B), and is preferably a group represented by one or more of the above formulas (1A) and (1B).
  • the formula represented by (1A) is more preferable.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-b1) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2,000 or more and 500,000 or less. ,000 or more and 200,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-b2) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2 ,000 or more and 200,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-b3) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2 ,000 or more and 200,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-b4) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, even more preferably 2 ,000 or more and 200,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-b5) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, even more preferably 2 ,000 or more and 200,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-b6) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2,000 or more and 500,000 or less. ,000 or more and 200,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-b7) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2,000 or more and 500,000 or less. ,000 or more and 200,000 or less.
  • the above formula (I) is preferably the following formula (I-c): [In formula (I-c), Ar c1 each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents; Ar c2 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; L c1 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -, L c2 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one
  • R 2 independently represents a C 1-16 alkyl group or a hydrogen atom which may have a substituent
  • nc represents an integer of 1 or more
  • Formula (Ic) has one or more C 2-20 fluorine-containing organic groups.
  • the fluorine-containing aromatic polymer represented by formula (I-c) can be, for example, polysulfone, polyamide, etc., and while maintaining the characteristics of these resins, it has flexibility and adhesion (reactivity) with other materials. It is expected to have excellent properties such as affinity, low dielectric properties, transparency, water and oil repellency, low tackiness, antifouling properties, high solvent solubility, and high surface hardness.
  • Ar c1 at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; such groups include: Examples include groups similar to the divalent group represented by Ar containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents.
  • Ar c1 is preferably a group represented by formula (Ar1), such as a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,4'-diyl group, 1 selected from 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, diphenylsulfone-4,4'-diyl group or oxybisphenyl-4,4'-diyl group species are more preferred, and phenylene groups are even more preferred.
  • Ar1 a group represented by formula (Ar1), such as a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,4'
  • Ar c2 at each occurrence independently represents a divalent group comprising a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; such groups include: Examples include groups similar to the divalent group represented by Ar containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents.
  • Ar c2 is preferably a group represented by formula (Ar1), such as a phenylene group, xylylene group, hydroxyphenylene group, hydroxyxylylene group, naphthylene group, 2,2-diphenylpropane-4,4'-diyl group, 1 selected from 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, diphenylsulfone-4,4'-diyl group or oxybisphenyl-4,4'-diyl group species are more preferred, and phenylene groups are even more preferred.
  • Ar1 a group represented by formula (Ar1), such as a phenylene group, xylylene group, hydroxyphenylene group, hydroxyxylylene group, naphthylene group, 2,2-diphenylpropane-4,4'-diyl group, 1 selected from 1,1-diphenylmethane
  • L c1 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -.
  • R 1 and R 2 have the same meanings as above.
  • L c1 -SO 2 - and -NR 2 -CO- are preferable.
  • L c2 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -.
  • R 1 and R 2 have the same meanings as above.
  • L c2 -O- and -CO-NR 2 - are preferable.
  • the above C 2-20 fluorine-containing organic group is an organic group containing a fluorine atom, and is preferably a group represented by one or more selected from the above formula (1A) and formula (1B), and is preferably a group represented by one or more of the above formulas (1A) and (1B).
  • a group represented by (1A) is more preferable.
  • one group in at least one of the combinations of Ar c1 and Ar c2 and the combination of L c1 and L c2 , one group is a different group from the other group, preferably, In the combination of L c1 and L c2 , one group is a different group from the other group.
  • nc represents an integer of 1 or more, preferably 3 or more and 2,000 or less, more preferably 5 or more and 1,000 or less, even more preferably 10 or more and 1,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-c) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2 ,000 or more and 200,000 or less.
  • the above formula (I-c) is preferably the following formula (I-c1), (I-c2) or (I-c3): [In formula (I-c1), (I-c2) or (I-c3), Ar c1 each independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents; Ar c2 represents each occurrence each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents, nc independently represents an integer of 1 or more in each occurrence, Formula (I-c1), (I-c2) or (I-c3) each has one or more C 2-20 fluorine-containing organic groups. ] It is expressed as
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-c1) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2,000 or more and 500,000 or less. ,000 or more and 200,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-c2) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2,000 or more and 500,000 or less. ,000 or more and 200,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-c3) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, even more preferably 2 ,000 or more and 200,000 or less.
  • the above (I) preferably has the following formula (I-d): [In formula (I-d), Ar d1 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; Ar d2 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; Ar d3 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; L d1 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -, L d2 is independently at each occurrence -R 1 -, -O-, -
  • R 2 independently represents a C 1-16 alkyl group or a hydrogen atom which may have a substituent
  • nd represents an integer of 1 or more
  • Formula (I-d) has one or more C 2-20 fluorine-containing organic groups.
  • the fluorine-containing aromatic polymer represented by formula (I-d) may be, for example, polyetheretherketone, polyethersulfone, etc., and while maintaining the properties of these resins, it has flexibility and adhesion to other materials. It is expected to have excellent properties such as reactivity and affinity, low dielectric properties, transparency, water and oil repellency, low adhesion, antifouling properties, solvent solubility, and high surface hardness. .
  • Ar d1 at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; such groups include: Examples include groups similar to the divalent group represented by Ar containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents.
  • Ar d1 is preferably a group represented by the formula (Ar1), such as a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,4'-diyl group, 1 selected from 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, diphenylsulfone-4,4'-diyl group or oxybisphenyl-4,4'-diyl group species are more preferred, and phenylene groups are even more preferred.
  • Ar1 a group represented by the formula (Ar1), such as a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,
  • Ar d2 at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; such groups include: Examples include groups similar to the divalent group represented by Ar containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents.
  • Ar d2 is preferably a group represented by formula (Ar1), such as a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,4'-diyl group, 1 selected from 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, diphenylsulfone-4,4'-diyl group or oxybisphenyl-4,4'-diyl group species are more preferred, and phenylene groups are even more preferred.
  • Ar1 a group represented by formula (Ar1), such as a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,4'
  • Ar d3 at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; such groups include: Examples include groups similar to the divalent group represented by Ar containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents.
  • Ar d3 is preferably a group represented by formula (Ar1), such as a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,4'-diyl group, 1 selected from 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, diphenylsulfone-4,4'-diyl group or oxybisphenyl-4,4'-diyl group Seeds are more preferred.
  • Ar1 a group represented by formula (Ar1), such as a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,4'-diyl group, 1 selected from
  • L d1 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -.
  • R 1 and R 2 have the same meanings as above.
  • L d1 is preferably one selected from the group consisting of -CO- and -SO 2 -.
  • L d2 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -.
  • R 1 and R 2 have the same meanings as above.
  • L d2 -O- is preferable.
  • L d3 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -.
  • R 1 and R 2 have the same meanings as above.
  • L d3 -O- is preferable.
  • the above C 2-20 fluorine-containing organic group is an organic group containing a fluorine atom, and is preferably a group represented by one or more selected from the above formula (1A) and formula (1B), and is preferably a group represented by one or more of the above formulas (1A) and (1B).
  • a group represented by (1A) is more preferable.
  • one group in at least one combination of Ar d1 , Ar d2 and Ar d3 and the combination of L d1 , L d2 and L d3 , one group is at least one of the other two groups.
  • one group is different from at least one of the other two groups.
  • nd represents an integer of 1 or more, preferably 3 or more and 2,000 or less, more preferably 5 or more and 1,000 or less, even more preferably 10 or more and 1,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-d) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2,000 or more and 500,000 or less. ,000 or more and 200,000 or less.
  • the above formula (I-d) is preferably the following formula (I-d1) or (I-d2): [In formula (I-d1) or (I-d2), Ar d1 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; Ar d2 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; Ar d3 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; nd independently represents an integer of 1 or more in each occurrence, Formulas (I-d1) and (I-d2) each have one or more C 2-20 fluorine-containing organic groups. ] It is expressed as
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-d1) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, even more preferably 2 ,000 or more and 200,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-d2) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2,000 or more and 1,000,000 or less. ,000 or more and 200,000 or less.
  • the above (I) preferably has the following formula (Ie): [In formula (Ie), Ar e1 each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; L e1 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -, L e2 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -, L e3
  • R 2 independently represents a C 1-16 alkyl group or a hydrogen atom which may have a substituent
  • ne represents an integer of 1 or more
  • Formula (Ie) has one or more C 2-20 fluorine-containing organic groups.
  • the fluorine-containing aromatic polymer represented by formula (I-e) may be polyether, polyester, or polyamide, and while maintaining the properties of these resins, it has flexibility, adhesion (reactivity) with other materials, and It is expected to have excellent properties such as affinity, low dielectric properties, transparency, water and oil repellency, low adhesion, antifouling properties, solvent solubility, and high surface hardness.
  • Ar e1 at each occurrence independently represents a divalent group comprising a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; such groups include: Examples include groups similar to the divalent group represented by Ar containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents.
  • Ar e1 is preferably a group represented by formula (Ar1), such as a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,4'-diyl group, 1 selected from 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, diphenylsulfone-4,4'-diyl group or oxybisphenyl-4,4'-diyl group species are more preferred, and phenylene groups are even more preferred.
  • Ar1 a group represented by formula (Ar1), such as a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,4'
  • L e1 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -.
  • R 1 and R 2 have the same meanings as above.
  • L e1 is preferably one selected from the group consisting of -CO-O-, -O- and CO-NH-.
  • L e2 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -.
  • R 1 and R 2 have the same meanings as above.
  • L e2 -R 1 - is preferable.
  • L e3 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -.
  • R 1 and R 2 have the same meanings as above.
  • L e3 is preferably one selected from the group consisting of -O-CO-, -O- and NH-CO-.
  • the above C 2-20 fluorine-containing organic group is an organic group containing a fluorine atom, and is preferably a group represented by one or more selected from the above formula (1A) and formula (1B), and is preferably a group represented by one or more of the above formulas (1A) and (1B).
  • a group represented by (1A) is more preferable.
  • ne represents an integer of 1 or more, preferably 3 or more and 2,000 or less, more preferably 5 or more and 1,000 or less, even more preferably 10 or more and 1,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-e) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2 ,000 or more and 200,000 or less.
  • the above formula (I-e) is preferably the following formula (I-e1), (I-e2) or (I-e3): [In formula (I-e1), (I-e2) or (I-e3), Ar e1 each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; R 7 is a C 1-16 alkylene group which may have one or more substituents, and a C 3-16 alicyclic group which may have one or more substituents Represents one type selected from divalent groups containing hydrocarbon groups, ne independently represents an integer of 1 or more in each occurrence, Formula (I-e1), (I-e2) or (I-e3) each has one or more C 2-20 fluorine-containing organic groups. ] It is expressed as
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-e1) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2,000 or more and 500,000 or less. ,000 or more and 200,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-e2) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, even more preferably 2 ,000 or more and 200,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-e3) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2,000 or more and 500,000 or less. ,000 or more and 200,000 or less.
  • the formula (I) preferably has the following formula (Ig): [In formula (Ig), Ar g each independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; mg independently represents an integer from 1 to 4 in each occurrence, ng1 represents an integer of 1 or more, ng2 represents an integer of 1 or more, Formula (Ig) has one or more C 2-20 fluorine-containing organic groups. ] It is expressed as
  • the fluorine-containing aromatic polymer represented by formula (Ig) can be a copolymer of an aromatic polymer and a polymer containing an aliphatic or alicyclic group, and has flexibility while maintaining the properties of these resins.
  • Various properties such as adhesiveness (reactivity) and affinity with other materials, low dielectric properties, transparency, water and oil repellency, low adhesion, antifouling properties, solvent solubility, and high surface hardness. expected to excel in
  • Each occurrence of Ar g independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; such groups include: Examples include groups similar to the divalent group represented by Ar containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents.
  • Arg is preferably a group represented by formula (Ar1), such as a phenylene group, xylylene group, hydroxyphenylene group, hydroxyxylylene group, naphthylene group, 2,2-diphenylpropane-4,4'-diyl group, 1 selected from 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, diphenylsulfone-4,4'-diyl group or oxybisphenyl-4,4'-diyl group species are more preferred, and phenylene groups are even more preferred.
  • formula (Ar1) such as a phenylene group, xylylene group, hydroxyphenylene group, hydroxyxylylene group, naphthylene group, 2,2-diphenylpropane-4,4'-diyl group, 1 selected from 1,1-diphenylmethane-4,4'-diyl group
  • L g1 is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -.
  • R 1 and R 2 have the same meanings as above.
  • L g1 is preferably -R 1 -, more preferably a divalent group containing a C 3-16 alicyclic hydrocarbon group which may have one or more substituents, More preferably, it is a C 3-16 alicyclic hydrocarbon group which may have one or more substituents.
  • mg represents an integer of 1 or more and 4 or less, and preferably may be 1.
  • the above C 2-20 fluorine-containing organic group is an organic group containing a fluorine atom, and is preferably a group represented by one or more selected from the above formula (1A) and formula (1B), and is preferably a group represented by one or more of the above formulas (1A) and (1B).
  • a group represented by (1A) is more preferable.
  • the order in which the units attached with ng1 and enclosed in parentheses and the units attached with ng2 and enclosed in parentheses are present is not particularly limited.
  • the fluorine-containing aromatic polymer represented by the formula (I-g) is a random copolymer in which units labeled ng1 and enclosed in parentheses and units labeled ng2 and enclosed in parentheses are randomly arranged.
  • it may be a block copolymer containing a block consisting of units attached with ng1 and enclosed in parentheses, and a block consisting of units attached with ng2 enclosed in parentheses.
  • the above (I) preferably has the following formula (Ih): [In formula (Ih), A h independently at each occurrence represents an aliphatic or aromatic imido-diyl group; Ar h at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; L h is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -, At each occurrence, R 1 is independently a C 1-16 alkylene group which may have a substituent, and a C 3-16 fatty acid which may have one or more substituents.
  • the fluorine-containing aromatic polymer represented by formula (Ih) may be a polyamide-imide containing an imido-N-yl group as a repeating unit, and while maintaining the characteristics of these resins, it has flexibility and compatibility with other materials. It is expected to have excellent properties such as adhesion (reactivity) and affinity, low dielectric properties, transparency, water and oil repellency, low tackiness, antifouling properties, solvent solubility, and high surface hardness. Ru.
  • a h at each occurrence independently represents an aliphatic or aromatic imido-diyl group; such aliphatic or aromatic imido-diyl groups include the aliphatic or aromatic imido-diyl group represented by A; Groups similar to the group are mentioned.
  • a h is preferably an aliphatic or aromatic imido-diyl group containing one or more imido rings and optionally having one or more substituents, and is represented by formula (A1-II).
  • the group represented by the formula (A2-II) is more preferable, and the group represented by the formula (A2-II) is even more preferable.
  • Each occurrence of Ar h independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; such groups include: Examples include groups similar to the divalent group represented by Ar containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents.
  • Ar h is preferably a group represented by formula (Ar1), such as a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,4'-diyl group, 1 selected from 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, diphenylsulfone-4,4'-diyl group or oxybisphenyl-4,4'-diyl group species are more preferred, and phenylene groups are even more preferred.
  • Ar1 a group represented by formula (Ar1), such as a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,4'-
  • L h is independently at each occurrence -R 1 -, -O-, -S-, -NR 2 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 2 -CO- and CO-NR 2 -.
  • R 1 and R 2 have the same meanings as above.
  • L h -NH-CO- is preferable.
  • the above C 1-20 fluorine-containing organic group is an organic group containing a fluorine atom, and is preferably a group represented by one or more selected from the above formula (2A) and formula (2B), and the above-mentioned A group represented by formula (2A) is more preferred.
  • nh represents an integer of 1 or more, preferably 3 or more and 2,000 or less, more preferably 5 or more and 1,000 or less, even more preferably 10 or more and 1,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (Ih) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, even more preferably 2 ,000 or more and 200,000 or less.
  • the above formula (Ih) is preferably the following formula (Ih1): [In formula (I-h1), A h independently at each occurrence represents an aliphatic or aromatic imido-diyl group; Ar h at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; nh represents an integer of 1 or more independently in each occurrence, In formula (I-h1), each has one or more C 1-20 fluorine-containing organic groups. ] It is expressed as
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-h1) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, even more preferably 2 ,000 or more and 200,000 or less.
  • the fluorine-containing aromatic polymer of the present disclosure can be produced by a production method including obtaining a fluorine-containing aromatic polymer by introducing a fluorine-containing organic group into an aromatic polymer (Production method 1). Further, the fluorine-containing aromatic polymer of the present disclosure can be obtained by introducing a fluorine-containing group into an aromatic monomer to obtain a fluorine-containing aromatic monomer, and by using the above-mentioned fluorine-containing aromatic monomer as a monomer. It can be manufactured by a manufacturing method including obtaining a polymer (manufacturing method 2).
  • a compound represented by formula (II) described below is used as a compound for introducing a fluorine-containing organic group, and various fluorine-containing organic groups can be introduced. Further, in the production method of the present disclosure, by using the compound represented by the formula (II), a fluorine-containing organic group can be introduced into both the monomer and the polymer, and the fluorine-containing organic group in the fluorine-containing aromatic polymer can be introduced. The distribution of organic groups can also be controlled.
  • the present disclosure includes the following formula (I-1): [In formula (I-1), A 1 each independently represents a divalent organic group containing one or more imide rings and optionally having one or more substituents; Ar 1 at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; L 1 is independently at each occurrence -R 11 -, -O-, -S-, -NR 12 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one type selected from the group consisting of -O-, -SO 2 -, -NR 12 -CO- and CO-NR 12 -, Each occurrence of R 11 is independently a C 1-16 alkylene group which may have a substituent, and a C 3-16 fatty acid which may have one or more substituents.
  • R 12 at each occurrence independently represents a C 1-16 alkyl group optionally having a substituent, a C 6-20 aromatic carbonized group optionally having one or more substituents
  • R 12 represents a hydrogen group or hydrogen atom
  • k1 represents an integer from 0 to 4 independently in each occurrence
  • l1 independently represents an integer from 1 to 4 in each occurrence
  • m1 represents an integer from 0 to 4 independently in each occurrence
  • n1 represents an integer of 1 or more
  • Formula (I-1) has one or more C 1-20 fluorine-containing organic groups.
  • R 2 independently represents a C 1-16 alkyl group or a hydrogen atom which may have a substituent
  • k2 represents an integer from 0 to 4 independently in each occurrence
  • l2 independently represents an integer of 1 to 4 in each occurrence
  • m2 represents an integer from 0 to 4 independently in each occurrence
  • n2 represents an integer of 1 or more
  • the order of appearance of the units suffixed with k2, l2, and m2 and enclosed in parentheses is arbitrary.
  • the fluorine-containing organic group is introduced after producing the aromatic polymer, so the structure and number average molecular weight of the polymer can be easily selected from a wide range. Furthermore, for the same reason, it is possible to utilize widely distributed and easily available aromatic polymers as raw materials, and it is possible to easily produce fluorine-containing aromatic polymers. Further, the raw aromatic polymer is not limited to non-molded bodies such as powder or pellets, and easily available molded articles such as plates, films, and various parts can also be used. In this case, it is possible to introduce the fluorine-containing organic group only into the surface of the molded product without changing its shape.
  • fluorine-containing organic groups tend to be introduced at multiple positions on the aromatic ring, and formally a polymer having a composition similar to a random copolymer can be produced.
  • a random copolymer-like polymer is an effective molecular design for exhibiting flexibility represented by low Tg and high thermal expansion (CTE) due to its low orderliness.
  • CTE thermal expansion
  • a substituent effect is observed in the introduction of such a fluorine-containing organic group into an aromatic ring, and an electron-withdrawing substituent inactivates the aromatic ring.
  • a fluorine-containing organic group can be effectively introduced even into an inert aromatic ring having an electron-withdrawing substituent.
  • a 1 at each occurrence independently represents an aliphatic or aromatic imido-diyl group; such aliphatic or aromatic imido-diyl groups include the aliphatic or aromatic imido-diyl group represented by A; Groups similar to the group are mentioned.
  • a 1 is preferably an aliphatic or aromatic imido-diyl group containing one or more imido rings and optionally having one or more substituents, and is represented by formula (A1).
  • the groups represented by formula (A2) are more preferred, the groups represented by formulas (A1-1) to (A1-19) are even more preferred.
  • the aliphatic or aromatic imido-diyl group represented by A 1 may have a substituent.
  • substituents include one or more selected from a C 1-20 fluorine-containing organic group; a C 1-16 alkyl group; a C 1-16 alkoxy group ; and a fluorine atom; One or more selected from 1-16 alkoxy groups; and fluorine atoms are preferred.
  • the above C 1-20 fluorine-containing organic group is an organic group containing a fluorine atom, and is preferably a group represented by one or more selected from the above formula (2A) and formula (2B), and is preferably a group represented by one or more of the above formulas (2A) and (2B).
  • the C 1-20 fluorine-containing organic group is an organic group containing a fluorine atom, and is preferably a group represented by the above formula (2A), the above formula (2-a), the formula A group represented by (2-b) or formula (2-c) is more preferable.
  • a 2 at each occurrence independently represents an aliphatic or aromatic imido-diyl group; such aliphatic or aromatic imido-diyl groups include the aliphatic or aromatic imido-diyl group represented by A; Groups similar to the group are mentioned.
  • a 2 is preferably an aliphatic or aromatic imido-diyl group containing one or more imido rings and optionally having one or more substituents, and is represented by formula (A1).
  • the groups represented by formula (A2) are more preferred, the groups represented by formulas (A1-1) to (A1-19) are even more preferred.
  • the aliphatic or aromatic imido-diyl group represented by A 2 may have a substituent.
  • substituents include one or more selected from C 1-16 alkyl groups; C 1-16 alkoxy groups; and fluorine atoms.
  • Ar 1 at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; such groups include: Examples include groups similar to the divalent group represented by Ar containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents.
  • Ar 1 is preferably a group represented by the formula (Ar1), such as a phenylene group, a xylylene group, a 2,2-diphenylpropane-4,4'-diyl group, or a 1,1-diphenylmethane-4,4'-diyl group.
  • a phenylene group such as a phenylene group, a xylylene group, a 2,2-diphenylpropane-4,4'-diyl group, or a 1,1-diphenylmethane-4,4'-diyl group.
  • a benzophenone-4,4'-diyl group a diphenylsulfone-4,4'-diyl group, or an oxybisphenyl-4,4'-diyl group is more preferable, and a phenylene group is even more preferable.
  • the divalent group containing a C 6-20 aromatic hydrocarbon group represented by Ar 1 may have a substituent.
  • substituents include the same substituents as the substituent that may be possessed by a divalent group containing a C 6-20 aromatic hydrocarbon group represented by Ar, and C 1-20 fluorine-containing organic group; C 1-16 alkyl group; C 1-16 alkoxy group; and one or more selected from fluorine atom; C 1-20 fluorine-containing organic group; C 1-16 alkoxy group; and fluorine atom are preferred.
  • two or more substituents that the C 6-20 aromatic hydrocarbon group may have are bonded to each other and together with the C 6-20 aromatic hydrocarbon group form a ring. You may do so.
  • Ar 2 at each occurrence independently represents a divalent group comprising a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; such groups include: Examples include groups similar to the divalent group represented by Ar containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents.
  • Ar 2 is preferably a group represented by formula (Ar1), such as a phenylene group, a xylylene group, a 2,2-diphenylpropane-4,4'-diyl group, or a 1,1-diphenylmethane-4,4'-diyl group.
  • a phenylene group such as a phenylene group, a xylylene group, a 2,2-diphenylpropane-4,4'-diyl group, or a 1,1-diphenylmethane-4,4'-diyl group.
  • a benzophenone-4,4'-diyl group a diphenylsulfone-4,4'-diyl group, or an oxybisphenyl-4,4'-diyl group is more preferable, and a phenylene group is even more preferable.
  • the divalent group containing a C 6-20 aromatic hydrocarbon group represented by Ar 2 may have a substituent.
  • substituents include groups similar to the substituents that a divalent group containing a C 6-20 aromatic hydrocarbon group represented by Ar may have, such as a C 1-16 alkyl group; One or more types selected from a C 1-16 alkoxy group; and a fluorine atom can be mentioned, with a C 1-16 alkoxy group and a fluorine atom being preferred.
  • two or more substituents that the divalent group containing the above C 6-20 aromatic hydrocarbon group may have are bonded to each other and combined with the above C 6-20 aromatic hydrocarbon group. and may form a ring.
  • L 1 is independently at each occurrence -R 11 -, -O-, -S-, -NR 12 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 12 -CO- and CO-NR 12 -.
  • Each occurrence of R 11 is independently a C 1-16 alkylene group which may have a substituent, and a C 3-16 fatty acid which may have one or more substituents. Represents one type selected from divalent groups containing cyclic hydrocarbon groups.
  • C 1-16 alkylene group in the above-mentioned C 1-16 alkylene group which may have one or more substituents may be linear or branched, and is preferably is a straight-chain or branched C 1-10 alkylene group, more preferably a straight-chain or branched C 1-5 alkylene group, and in one embodiment, a straight-chain or branched C 1-10 alkylene group; It is a 1-3 alkylene group, and specifically can be -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -.
  • the above R 11 may be a C 1-16 alkylene group having no substituent. In another embodiment, the above R 11 may be a C 1-16 alkylene group having a substituent.
  • R 11 is preferably a C 1-16 fluoroalkylene group substituted with one or more fluorine atoms, more preferably a C 1-16 perfluoroalkylene group, More preferred is a C 1-6 perfluoroalkylene group, and even more preferred is a C 1-3 perfluoroalkylene group.
  • the above C 1-16 perfluoroalkylene group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkylene group, more preferably , a linear or branched C 1-3 perfluoroalkylene group, specifically -CF 2 -, -CF 2 CF 2 -, CF 2 CF 2 CF 2 -, CF 2 CF (CF 3 ) - It is.
  • the C 1-16 alkylene group represented by R 11 may have include a C 1-20 fluorine-containing organic group.
  • the C 1-20 fluorine-containing organic group is an organic group containing a fluorine atom, and is preferably a group represented by one or more selected from formula (2A) and formula (2B), and is preferably a group represented by one or more selected from formula (2A) and formula (2B). ) is more preferable.
  • the “C 3-16 alicyclic hydrocarbon group” in the above divalent group containing a C 3-16 alicyclic hydrocarbon group which may have one or more substituents is a monocyclic group. In the case of a polycyclic ring, two or more rings may form a bridged ring or may not form a bridged ring.
  • the number of alicyclic hydrocarbon groups is 1 or more, preferably may be 1 or more and 4 or less, more preferably 1 or more and 3 or less, even more preferably 1 or 2.
  • a divalent group containing such an alicyclic hydrocarbon group preferably a divalent C 3-16 alicyclic hydrocarbon group, more preferably a divalent C 6-12 alicyclic hydrocarbon group More preferably, it may be a cyclohexanediyl group, a decahydronaphthyl group, an isobornyl group, a tricyclo[5.2.1.0 2,6 ]decanediyl group, or an adamantyl group.
  • two or more alicyclic hydrocarbon groups are a single bond or a divalent group. may be bonded via an organic group.
  • organic groups include linear or branched C 1-4 alkyl groups.
  • the divalent alicyclic hydrocarbon group represented by R 11 is a divalent alicyclic hydrocarbon group having a substituent, and in another embodiment, it is a divalent alicyclic hydrocarbon group having no substituent. is a valent alicyclic hydrocarbon group.
  • substituents that the divalent group containing a C 3-16 alicyclic hydrocarbon group represented by R 11 may include a C 1-20 fluorine-containing organic group and a fluorine atom; Atoms are preferred.
  • the above C 1-20 fluorine-containing organic group is an organic group containing a fluorine atom, and is preferably a group represented by one or more selected from formula (2A) and formula (2B), and is preferably a group represented by one or more selected from formula (2A) and formula (2B). ) is more preferable.
  • the divalent C 3-16 alicyclic hydrocarbon group represented by R 11 is preferably a divalent C 3-16 alicyclic hydrocarbon group having no substituent, more preferably may be a divalent C 6-12 alicyclic hydrocarbon group having no substituents.
  • the above R 11 may be a C 1-16 alkylene group having no substituent. In another embodiment, the above R 11 may be a C 1-16 alkylene group having a substituent. In yet another embodiment, R 11 may be a divalent C 1-16 alicyclic hydrocarbon group having no substituents.
  • R 12 at each occurrence independently represents a C 1-16 alkyl group optionally having one or more substituents, a C 1-16 alkyl group optionally having one or more substituents; 6-20 represents an aromatic hydrocarbon group or a hydrogen atom.
  • C 1-16 alkyl group in the above-mentioned C 1-16 alkyl group which may have one or more substituents may be linear or branched, preferably A straight-chain or branched C 1-10 alkyl group, more preferably a straight-chain or branched C 1-5 alkyl group, and in one embodiment, a straight-chain or branched C 1-5 alkyl group .
  • -4 alkyl group specifically -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH(CH 3 ) 2 , -CH(CH 3 ) 3 .
  • R 12 may be a C 1-16 alkyl group without a substituent. In another embodiment, the above R 12 may be a C 1-16 alkyl group having a substituent.
  • R 12 is preferably a C 1-16 fluoroalkyl group substituted with one or more fluorine atoms, more preferably a C 1-16 perfluoroalkyl group, More preferably a C 1-6 perfluoroalkyl group, even more preferably a C 1-4 perfluoroalkyl group, specifically -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF( CF3 ) 2 , -CF2CF2CF2CF3 , -CF2CF ( CF3 ) 2 , -CF( CF3 ) 3 .
  • the "C 6-20 aromatic hydrocarbon group" in the above C 6-20 aromatic hydrocarbon group which may have one or more substituents may be monocyclic or polycyclic. In the case of a polycyclic ring, two or more rings may not form a condensed ring or may form a condensed ring.
  • the above C 6-20 aromatic hydrocarbon group which may have one or more substituents is preferably a C 6-10 aromatic hydrocarbon group, more preferably a phenylene group, a tolylene group, It can be a xylylene group or a naphthylene group, more preferably a phenylene group, a tolylene group or a xylylene group in one embodiment, and even more preferably a naphthylene group in another embodiment.
  • Examples of the substituent that the C 6-20 aromatic hydrocarbon group may have include a hydroxyl group.
  • L 1 is preferably 1 selected from the group consisting of -O-, -S-, -CO-, -O-CO-O-, -SO 2 -, -NR 12 -CO- and CO-NR 12 - It is a seed.
  • L 2 is independently at each occurrence -R 21 -, -O-, -S-, -NR 22 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one selected from the group consisting of -O-, -SO 2 -, -NR 22 -CO- and CO-NR 22 -.
  • R 21 is independently a C 1-16 alkylene group which may have a substituent, and a C 3-16 fatty acid which may have one or more substituents. Represents one type selected from divalent groups containing cyclic hydrocarbon groups.
  • C 1-16 alkylene group in the above-mentioned C 1-16 alkylene group which may have one or more substituents may be linear or branched, and is preferably is a straight-chain or branched C 1-10 alkylene group, more preferably a straight-chain or branched C 1-5 alkylene group, and in one embodiment, a straight-chain or branched C 1-10 alkylene group; It is a 1-3 alkylene group, and specifically can be -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -.
  • the alkylene group represented by R 21 above may be a C 1-16 alkylene group having no substituent. In another embodiment, the alkylene group represented by R 21 above may be a C 1-16 alkylene group having a substituent.
  • R 11 is preferably a C 1-16 fluoroalkylene group substituted with one or more fluorine atoms, more preferably a C 1-16 perfluoroalkylene group, More preferred is a C 1-6 perfluoroalkylene group, and even more preferred is a C 1-3 perfluoroalkylene group.
  • the above C 1-16 perfluoroalkylene group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkylene group, more preferably , a linear or branched C 1-3 perfluoroalkylene group, specifically -CF 2 -, -CF 2 CF 2 -, CF 2 CF 2 CF 2 -, CF 2 CF (CF 3 ) - It is.
  • the C 1-16 alkylene group represented by R 21 may have include a C 1-20 fluorine-containing organic group.
  • the C 1-20 fluorine-containing organic group is an organic group containing a fluorine atom, and is preferably a group represented by one or more selected from formula (2A) and formula (2B), and is preferably a group represented by one or more selected from formula (2A) and formula (2B). ) is more preferable.
  • the “C 3-16 alicyclic hydrocarbon group” in the above divalent group containing a C 3-16 alicyclic hydrocarbon group which may have one or more substituents is a monocyclic group. In the case of a polycyclic ring, two or more rings may form a bridged ring or may not form a bridged ring.
  • the number of alicyclic hydrocarbon groups is 1 or more, preferably may be 1 or more and 4 or less, more preferably 1 or more and 3 or less, even more preferably 1 or 2.
  • a divalent group containing such an alicyclic hydrocarbon group preferably a divalent C 3-16 alicyclic hydrocarbon group, more preferably a divalent C 6-12 alicyclic hydrocarbon group More preferably, it may be a cyclohexanediyl group, a decahydronaphthyl group, an isobornyl group, a tricyclo[5.2.1.0 2,6 ]decanediyl group, or an adamantyl group.
  • two or more alicyclic hydrocarbon groups are a single bond or a divalent group. may be bonded via an organic group.
  • organic groups include linear or branched C 1-4 alkyl groups.
  • the divalent alicyclic hydrocarbon group represented by R 21 is a divalent alicyclic hydrocarbon group having a substituent, and in another embodiment, it is a divalent alicyclic hydrocarbon group having no substituent. is a valent alicyclic hydrocarbon group.
  • substituents that the divalent group containing a C 3-16 alicyclic hydrocarbon group represented by R 11 may include a C 1-20 fluorine-containing organic group and a fluorine atom; Atoms are preferred.
  • the above C 1-20 fluorine-containing organic group is an organic group containing a fluorine atom, and is preferably a group represented by one or more selected from formula (2A) and formula (2B), and is preferably a group represented by one or more selected from formula (2A) and formula (2B). ) is more preferable.
  • the divalent C 3-16 alicyclic hydrocarbon group represented by R 21 is preferably a divalent C 3-16 alicyclic hydrocarbon group having no substituent, more preferably may be a divalent C 6-12 alicyclic hydrocarbon group having no substituents.
  • R 21 may be a C 1-16 alkylene group without a substituent. In another embodiment, the above R 21 may be a C 1-16 alkylene group having a substituent. In yet another embodiment, R 21 may be a divalent C 1-16 alicyclic hydrocarbon group having no substituent.
  • R 22 at each occurrence independently represents a C 1-16 alkyl group optionally having one or more substituents, a C 1-16 alkyl group optionally having one or more substituents; 6-20 represents an aromatic hydrocarbon group or a hydrogen atom.
  • C 1-16 alkyl group in the above-mentioned C 1-16 alkyl group which may have one or more substituents may be linear or branched, preferably A straight-chain or branched C 1-10 alkyl group, more preferably a straight-chain or branched C 1-5 alkyl group, and in one embodiment, a straight-chain or branched C 1-5 alkyl group .
  • -4 alkyl group specifically -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH(CH 3 ) 2 , -CH(CH 3 ) 3 .
  • R 22 may be a C 1-16 alkyl group without a substituent. In another embodiment, the above R 22 may be a C 1-16 alkyl group having a substituent.
  • R 22 is preferably a C 1-16 fluoroalkyl group substituted with one or more fluorine atoms, more preferably a C 1-16 perfluoroalkyl group, More preferably a C 1-6 perfluoroalkyl group, even more preferably a C 1-4 perfluoroalkyl group, specifically -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF( CF3 ) 2 , -CF2CF2CF2CF3 , -CF2CF ( CF3 ) 2 , -CF( CF3 )3 .
  • the "C 6-20 aromatic hydrocarbon group" in the above C 6-20 aromatic hydrocarbon group which may have one or more substituents may be monocyclic or polycyclic. In the case of a polycyclic ring, two or more rings may not form a condensed ring or may form a condensed ring.
  • the above C 6-20 aromatic hydrocarbon group which may have one or more substituents is preferably a C 6-10 aromatic hydrocarbon group, more preferably a phenylene group, a tolylene group, It can be a xylylene group or a naphthylene group, more preferably a phenylene group, a tolylene group or a xylylene group in one embodiment, and even more preferably a naphthylene group in another embodiment.
  • Examples of the substituent that the C 6-20 aromatic hydrocarbon group may have include a hydroxyl group.
  • L 2 is preferably 1 selected from the group consisting of -O-, -S-, -CO-, -O-CO-O-, -SO 2 -, -NR 22 -CO- and CO-NR 22 - It is a seed.
  • k1 independently represents an integer from 0 to 4 in each occurrence, preferably an integer from 0 to 1.
  • l1 each independently represents an integer of 1 to 4, preferably an integer of 1 to 3.
  • m1 independently represents an integer of 0 to 4, preferably an integer of 0 to 3.
  • k2 represents an integer of 0 to 4, preferably an integer of 0 to 1, independently in each occurrence.
  • l2 each independently represents an integer of 1 or more and 4 or less, preferably 1 or more and 3 or less, in each occurrence.
  • m2 independently represents an integer of 0 to 4, preferably an integer of 0 to 3.
  • n1 represents an integer of 1 or more, preferably 5 or more and 2,000 or less, more preferably 10 or more and 1,000 or less.
  • n2 represents an integer of 1 or more, preferably 5 or more and 2,000 or less, more preferably 10 or more and 1,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-1) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and even more preferably 2,000 or more and 500,000 or less. ,000 or more and 200,000 or less.
  • the number average molecular weight of the fluorine-containing aromatic polymer represented by formula (I-2) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, even more preferably 2 ,000 or more and 200,000 or less.
  • R f1 represents a C 1-20 fluorine-containing organic group.
  • a C 1-20 fluorine-containing organic group is a C 1-20 organic group containing a fluorine atom, preferably a group represented by one or more selected from formula (2A) and formula (2B), More preferred are groups represented by formula (2-a), formula (2-b), formula (2-c) and formula (2B).
  • the C 1-20 fluorine-containing organic group is a C 1-20 organic group containing a fluorine atom, preferably a group represented by formula (2A), more preferably a group represented by formula (2- a), formula (2-b) and formula (2-c).
  • Ratio between the amount of the compound represented by formula (II) above and the amount of all aromatic rings contained in the aromatic polymer (the amount of compound represented by formula (II) is expressed as the amount of all aromatic rings contained in the aromatic polymer) (divided value) is preferably 0.01 or more, more preferably 0.02 or more and 10 or less, still more preferably 0.05 or more and 5 or less, and even more preferably 0.05 or more and 3 or less.
  • reaction method 1 Reaction of introducing fluorine-containing organic group into aromatic polymer
  • the above reaction may be carried out under light irradiation.
  • light irradiation is preferably ultraviolet irradiation, and can be performed by irradiating light with a wavelength of 300 to 400 nm, for example, 350 to 380 nm.
  • the light source used for such light irradiation includes, but is not particularly limited to, an LED, a mercury lamp, a xenon lamp, a UV lamp, a halogen lamp, a fluorescent lamp, sunlight, indoor light, etc., and preferably an LED is used.
  • the above reaction can preferably be carried out using a basic compound, a catalyst, a one-electron reducing agent, or a radical generator.
  • Examples of the basic compound include inorganic bases such as Cs 2 CO 3 , K 2 CO 3 , Na 2 CO 3 , Li 2 CO 3 , CsF, CsHCO 3 , KHCO 3 , NaHCO 3 , LiHCO 3 , triethylamine, and triethylamine.
  • inorganic bases such as Cs 2 CO 3 , K 2 CO 3 , Na 2 CO 3 , Li 2 CO 3 , CsF, CsHCO 3 , KHCO 3 , NaHCO 3 , LiHCO 3 , triethylamine, and triethylamine.
  • Amine compounds such as butylamine, diisopropylethylamine, N,N,N',N'-tetramethylenediamine, N,N,N',N'-tetraethylenediamine, pyrrolidine, pyridine, collidine, ammonia, dimethylamine, DBU, tributyl Examples include phosphine, triphenylphosphine, triarylphosphines, disubstituted phosphines, and preferably Cs 2 CO 3 is used.
  • Examples of the above-mentioned catalysts include transition metal complexes, organic dye compounds, and enamine compounds.
  • Examples of the central metal species of the transition metal complex include cobalt, ruthenium, rhodium, rhenium, iridium, zinc, nickel, palladium, osmium, and platinum.
  • organic pigment compounds examples include rose bengal, erythrosin, eosin (eg, eosin B, eosin Y), acriflavin, lipoflavin, thionin, phenoxazine, and phenothiazine.
  • the above enamine compounds are The structure is represented by aldehydes.
  • R 51 is a phenyl group or a benzyl group
  • R 52 is a hydrogen atom, a methyl group, or a phenyl group.
  • pyrrolidines In the formula, R 53 is a hydrogen atom or a bis(3,4-dimethoxyphenyl)methoxymethyl group.
  • aldehydes examples include 3-phenyl-2-methylpropanal, 2-phenylpropanal, diphenylacetaldehyde, and phenylacetaldehyde.
  • Examples of the above pyrrolidines include pyrrolidine, (S)-2-[3,4-bis(dimethoxyphenyl)methoxymethyl]pyrrolidine, and the like.
  • Examples of the one-electron reducing agent include sodium thiosulfate, lithium dithionite, sodium dithionite, potassium dithionite, cesium dithionite, copper(I) iodide, copper(I) bromide, and copper chloride.
  • (I) triethylamine, tributylamine, tetrabutylammonium iodide, tetrabutylphosphonium iodide, ascorbic acid, ascorbate, zinc powder, indium powder, magnesium powder, etc., preferably sodium thiosulfate, dithionite Sodium, copper(I) iodide, or copper(I) bromide, particularly preferably sodium thiosulfate or sodium dithionite.
  • radical generator examples include organic peroxides, inorganic peroxides, organic azo compounds, etc., and organic peroxides are preferably used.
  • organic peroxides include benzoyl peroxide, potassium persulfite as inorganic peroxides, and azobisisobutyronitrile (AIBN) as organic azo compounds, but are not limited to the following. It will be done.
  • solvents are not particularly limited, but include, for example, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, dichloropentafluoropropane (HCFC-225), and perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane). , perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g. bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g.
  • C 6 F 13 CH 2 CH 3 (for example, Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeolora (manufactured by Nippon Zeon Co., Ltd.) (registered trademark) H); Hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether (C 3 F 7 OCH 3 ) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Ltd.), perfluorobutyl methyl ether ( C 4 F 9 OCH 3 ) (for example, Novec (trademark) 7100 manufactured by Sumitomo 3M Ltd.), perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ) (for example, Novec (trademark) manufactured by Sumitomo 3M Ltd.
  • alkyl perfluoroalkyl ethers perfluoroalkyl groups and alkyl groups may be straight-chain or branched
  • aromatic hydrocarbons CF 3 CH 2 OCF 2 CHF 2 (for example, Asahiklin® AE-3000 manufactured by Asahi Glass Co., Ltd.)
  • Sulfonic solvents for example, dimethylsulfone, sulfolane
  • Ether solvents for example, tetrahydrofuran, 1,4-dioxane, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, monoglyme, diglyme, triglyme, tetraglyme); acetonitrile; nitromethane; amide solvents (N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N
  • the reaction temperature in the above reaction is preferably 0 to 60°C, more preferably 10 to 40°C, for example room temperature.
  • the reaction time in the above reaction can be, for example, 1 to 72 hours, preferably 12 to 48 hours.
  • the aromatic polymer represented by the above formula (I-2) can be produced by polymerizing aromatic monomers, and commercially available products may be used.
  • aromatic monomer examples include compounds containing an aromatic ring and having two or more groups having active hydrogen atoms, preferably the following formula (III): R 4 -Ar 3 -R 4 (III)
  • Ar 3 independently at each occurrence represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents;
  • Each occurrence of R 4 independently represents -OH, -NH 2 , a fluorine atom or a chlorine atom.
  • Ar 3 at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents.
  • the “C 6-20 aromatic hydrocarbon group” in the above divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents is a monocyclic group; may also be polycyclic, and in the case of polycyclic, two or more rings may or may not form a condensed ring.
  • the number of aromatic hydrocarbon groups contained in the divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents is 1 or more, preferably It may be 1 or more and 4 or less, more preferably 1 or more and 3 or less, still more preferably 1 or 2.
  • a divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents
  • two or more rings are connected via a single bond or a divalent organic group.
  • Two or more substituents that the divalent group containing the above C 6-20 aromatic hydrocarbon group may have are bonded to each other and combined with the above C 6-20 aromatic hydrocarbon group. , may form a ring.
  • Ar 3 is preferably a group represented by the above formula (Ar1), more preferably a phenylene group, xylylene group, naphthylene group, biphenylene group, 3,3'-dimethylbiphenylene group, 2,2'- Dimethylbiphenylene group, 2,2'-dimethoxybiphenylene group, 3,3',5,5'-tetramethylbiphenylene group, 3,3',5,5'-tetraethylbiphenylene group, 2,2-diphenylpropane-4 , 4'-diyl group, 2,2-diphenylpropane-4,4'-diyl group, 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, diphenylsulfone-4 ,4'-diyl group or oxybisphenyl-4,4'-diyl group, more preferably phenylene group
  • R 4 at each occurrence independently represents -OH, -NH 2 , a fluorine atom or a chlorine atom, and may preferably be -OH or NH 2 .
  • the two R 4 may be different from each other, for example, one R 4 may be -OH and one R 4 may be a fluorine atom.
  • two R 4 can be the same group.
  • the aromatic polymer represented by the above formula (I-2) may be produced by reacting an aromatic monomer and a second monomer.
  • Examples of the second monomer include monomers that can react with the aromatic monomer represented by formula (III), and monomers that have two or more groups that can react with an amino group or a hydroxyl group in one molecule are preferred.
  • Such monomers include, for example, the following formula (IV): R 5 -L 10 -R 5 (IV) [In formula (IV), R 5 independently represents the following formulas (r-1) to (r-18) at each occurrence: [In formulas (r-1) to (r-18), * represents a bond.
  • L 10 is the following formula (l-1) to (l-11): [In formulas (l-1) to (l-11), R 6 is a C 1-16 alkylene group optionally substituted with one or more fluorine atoms, or one or more substituted represents a divalent group containing a C 6-20 aromatic hydrocarbon group which may have a group, * represents a bond. ] Represents one type selected from.
  • L 10 when R 5 is a divalent group, L 10 can be a tetravalent group, for example, the following formula: (*-) 2 R 60 (-*) 2 (1-12) (R 60 is a C 1-16 alkantetrayl group optionally substituted with one or more fluorine atoms, or has one or more substituents) represents a tetravalent C 6-20 aromatic hydrocarbon group which may be
  • R 6 is a C 1-16 alkylene group optionally substituted with one or more fluorine atoms, or a C 6-20 aromatic carbonized group optionally having one or more substituents Represents a divalent group containing a hydrogen group.
  • the "C 1-16 alkylene group" in the C 1-16 alkylene group optionally substituted with one or more fluorine atoms may be linear or branched, and is preferably is a straight-chain or branched C 1-10 alkylene group, more preferably a straight-chain or branched C 1-5 alkylene group, and in one embodiment, a straight-chain or branched C 1-10 alkylene group; It is a 1-3 alkylene group, and specifically can be -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -.
  • R 6 is preferably a C 1-16 fluoroalkylene group substituted with one or more fluorine atoms, more preferably a C 1-16 perfluoroalkylene group, More preferred is a C 1-6 perfluoroalkylene group, and even more preferred is a C 1-3 perfluoroalkylene group.
  • R 6 may be a C 1-16 alkylene group that is not substituted with a fluorine atom.
  • the above C 1-16 perfluoroalkylene group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkylene group, more preferably , linear or branched C 1-3 perfluoroalkylene groups, specifically -CF 2 -, -CF 2 CF 2 -, -CF 2 CF 2 CF 2 -, -CF 2 CF (CF 3 )-.
  • the “C 6-20 aromatic hydrocarbon group” in the above divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents is a monocyclic group; may also be polycyclic, and in the case of polycyclic, two or more rings may or may not form a condensed ring.
  • the number of aromatic hydrocarbon groups contained in the divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents is 1 or more, preferably may be 1 or more and 4 or less, more preferably 1 or more and 3 or less, still more preferably 1 or 2.
  • Such an aromatic hydrocarbon group is preferably a C 6-10 aromatic hydrocarbon group, more preferably a phenylene group, tolylene group, xylylene group or naphthylene group, even more preferably a phenylene group, tolylene group or xylylene group. It can be.
  • aromatic hydrocarbon groups are connected via a single bond or an organic group.
  • organic groups include linear or branched C 1-4 alkyl groups.
  • the divalent group containing an aromatic hydrocarbon group represented by R 6 above is preferably a group represented by the above formula (Ar1), more preferably a phenylene group, tolylene group, xylylene group, or naphthylene group. group, biphenylene group, 3,3'-dimethylbiphenylene group, 2,2'-dimethylbiphenylene group, 2,2'-dimethoxybiphenylene group, 3,3',5,5'-tetramethylbiphenylene group, 3,3 ',5,5'-tetraethylbiphenylene group, 2,2-diphenylpropane-4,4'-diyl group, 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, Diphenylsulfone-4,4'-diyl group or oxybisphenyl-4,4'-diyl group, more preferably pheny
  • R 5 is a group represented by any one of formulas (r-1), (r-2), and (r-9), and L 10 is A compound that is a group represented by formula (l-3); R 5 is a group represented by either formula (r-3) or (r-10), and L 10 is a group represented by formula (l-1); ), (l-4), (l-7), (l-8) and (l-9); R 5 is a group represented by formula (r-3), (r- 5), (r-6), (r-7), (r-8), (r-10), (r-11), (r-12), (r-13) and (r-14) is a group represented by any of the following, and L 10 is a group represented by formulas (l-1), (l-4) and (l-7), (l-8), (l-9) and (l-10) A compound where R 5 is a group represented by formula (r-4) and L 10 is a group represented by any of formulas (l-1) to (l-7); Compounds where R 5 is a group represented by formula (r-4) and L 10 is
  • the second monomer is preferably 0.1 mol or more and 10 mols or less, more preferably 0.2 mol or more and 5 mols or less, and even more preferably 0.5 mol or more and 2 mols or less, per 1 mol of the aromatic monomer. It can be:
  • the reaction using the aromatic monomer as a monomer and the reaction between the aromatic monomer and the second monomer can be carried out by a known method.
  • the present disclosure also includes the following formula (I-1): [In formula (I-1), A 1 each independently represents a divalent organic group containing one or more imide rings and optionally having one or more substituents; Ar 1 at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; L 1 is independently at each occurrence -R 11 -, -O-, -S-, -NR 12 -, -CO-, -CO-O-, -O-CO-, -O-CO Represents one type selected from the group consisting of -O-, -SO 2 -, -NR 12 -CO- and CO-NR 12 -, Each occurrence of R 11 is independently a C 1-16 alkylene group which may have a substituent, and a C 3-16 fatty acid which may have one or more substituents.
  • R 12 at each occurrence independently represents a C 1-16 alkyl group optionally having a substituent, a C 6-20 aromatic carbonized group optionally having one or more substituents
  • k1 represents an integer from 0 to 4 independently in each occurrence
  • l1 independently represents an integer from 1 to 4 in each occurrence
  • m1 represents an integer from 0 to 4 independently in each occurrence
  • n1 represents an integer of 1 or more
  • Formula (I-1) has one or more C 1-20 fluorine-containing organic groups]
  • the bonding position of the fluorine-containing organic group in the obtained fluorine-containing aromatic polymer is clear, resulting in a more ordered main chain structure. It is possible to design. This can be an effective manufacturing method for enhancing the properties of crystallinity, high Tg, and low CTE, for example. Furthermore, it may be easy to obtain a fluorine-containing aromatic polymer in which the distribution density of the fluorine-containing organic groups is high and the characteristics of the fluorine-containing organic groups are more reflected. On the other hand, it is also possible to reduce and/or control the distribution density of fluorine-containing organic groups to a desired range by copolymerizing a fluorine-free monomer as necessary.
  • a 1 , Ar 1 , L 1 , k1, l1, m1, R 11 , R 12 and R f1 have the same meanings as above.
  • aromatic monomer examples include compounds containing an aromatic ring and having two or more groups having an active hydrogen atom. More preferably, compounds containing an aromatic ring and having a hydroxyl group (-OH) and an amino group (-NH Examples include compounds having two or more of one type of group selected from 2 ), and more preferably aromatic monomers represented by the above formula (III).
  • the fluorine-containing aromatic monomer and a second monomer may be reacted.
  • the second monomer include monomers that can react with the aromatic monomer represented by formula (III), and monomers that have two or more groups that can react with an amino group or a hydroxyl group in one molecule are preferred.
  • Examples of such monomers include the compound represented by the above formula (IV).
  • the second monomer is preferably 0.1 mol or more and 10 mols or less, more preferably 0.2 mol or more and 5 mols or less, and even more preferably 0.5 mol or more, per 1 mol of the fluorine-containing aromatic monomer. It can be up to 2 moles.
  • the amount of the compound represented by formula (II) is preferably 0.01 mol or more, more preferably 0.01 mol or more per 1 mol of aromatic monomer.
  • the amount may be .02 mol or more and 10 mol or less, more preferably 0.05 mol or more and 5 mol or less.
  • the reaction between the aromatic monomer and the compound represented by formula (II) may be carried out under light irradiation.
  • light irradiation is preferably ultraviolet irradiation, and is carried out by irradiating light with a wavelength of 300 to 400 nm, for example, 350 to 380 nm.
  • the light source used for such light irradiation includes, but is not particularly limited to, an LED, a mercury lamp, a xenon lamp, a UV lamp, a halogen lamp, etc., and preferably an LED is used.
  • the above reaction can preferably be carried out using a basic compound, a catalyst, a one-electron reducing agent, or a radical generator.
  • a basic compound, catalyst, one-electron reducing agent, or radical generator any of the compounds described above in Production Method 1 can be used.
  • the above reaction is preferably carried out in a solvent.
  • a solvent any of the solvents described above in Manufacturing Method 1 can be used.
  • the reaction temperature in the above reaction is preferably 0 to 60°C, more preferably 10 to 40°C, for example room temperature.
  • the reaction time in the above reaction can be, for example, 1 to 72 hours, preferably 12 to 48 hours.
  • reaction using the fluorine-containing aromatic monomer as a monomer can be carried out by a method known as a method for carrying out a reaction using an aromatic monomer as a monomer. Further, the reaction between the fluorine-containing aromatic monomer and the second monomer can be carried out by a known method for reacting the aromatic monomer with the second monomer.
  • reaction solvent described in Production Method 1 can be used as the reaction solvent.
  • the type and amount of the solvent used may be determined as appropriate depending on the fluorine-containing aromatic monomer and second monomer used.
  • the present disclosure includes the following formula (III-1): R 41 -A 31 -R 41 (III-1) [In formula (III-1), Ar 31 at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents; R 41 each independently represents -OH, -NH 2 , a glycidyloxy group, a fluorine atom or a chlorine atom, Formula (III-1) has one or more C 1-20 fluorine-containing organic groups.
  • the C 1-20 fluorine-containing organic group has the following formula (2-1A) and formula (2B): R 33 -X 1 -(R F1 ) r -CF 2 -* (2-1A) *-X 1 -CF 2 -* (2B) [In formula (2-1A) and formula (2B), R F1 represents -(Rf) p -R F -(O) q -, Rf each independently represents a C 1-16 alkylene group optionally substituted with one or more fluorine atoms; R F represents a divalent fluoro(poly)ether group, X 1 represents a C 1-16 alkylene group or a single bond optionally substituted with one or more halogen atoms, R 33 is a C 6-20 aromatic hydrocarbon group which may have one or more substituents, a silsesquioxane residue which may have one or more substituents , -COOR f2 , -OR f2 , -SO 2 R
  • a fluorine-containing aromatic polymer can be produced using such a fluorine-containing aromatic monomer.
  • a fluorine-containing aromatic monomer By using such a fluorine-containing aromatic monomer, it is possible to clarify the bonding positions of the fluorine-containing organic groups in the resulting fluorine-containing aromatic polymer, and it is possible to design a more ordered main chain structure. This can be an effective manufacturing method for enhancing the properties of crystallinity, high Tg, and low CTE, for example.
  • X 1 , R F1 , R f2 , R f3 , p, q and r have the same meanings as above.
  • Ar 31 at each occurrence independently represents a divalent group containing a C 6-20 aromatic hydrocarbon group optionally having one or more substituents.
  • the “C 6-20 aromatic hydrocarbon group” in the above divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents is a monocyclic group; may also be polycyclic, and in the case of polycyclic, two or more rings may or may not form a condensed ring.
  • the number of aromatic hydrocarbon groups contained in the divalent group containing a C 6-20 aromatic hydrocarbon group which may have one or more substituents is 1 or more, preferably It may be 1 or more and 4 or less, more preferably 1 or more and 3 or less, still more preferably 1 or 2.
  • two or more rings are connected via a single bond or a divalent organic group. may be combined.
  • Ar 31 is preferably a group represented by the above formula (Ar1), more preferably a phenylene group, xylylene group, naphthylene group, biphenylene group, 2,2-diphenylpropane-4,4'-diyl group , 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, diphenylsulfone-4,4'-diyl group or oxybisphenyl-4,4'-diyl group, More preferably, phenylene group, xylylene group, 2,2-diphenylpropane-4,4'-diyl group, 1,1-diphenylmethane-4,4'-diyl group, benzophenone-4,4'-diyl group, diphenyl It is a sulfone-4,4'-diyl group or an oxybisphenyl-4,4'-diy
  • R 41 at each occurrence independently represents -OH, -NH 2 , a glycidyloxy group, a fluorine atom or a chlorine atom, and may preferably be -OH or NH 2 .
  • the two R 41s are different from each other, for example, one R 41 can be -OH and one R 41 can be a fluorine atom. In another embodiment, two R 41 can be the same group.
  • Substituents in the above C 6-20 aromatic hydrocarbon group which may have one or more substituents include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; C 1- 4 alkyl group; C 1-4 alkoxy group; R 20 -O-CO- (wherein R 20 represents a C 1-4 alkyl group), preferably a halogen atom, particularly preferably a fluorine atom It is.
  • R 20 may be a straight chain or branched chain, preferably a straight chain or branched C 1-3 alkyl group, and specifically, -CH 3 and -CH 2 CH 3 are preferred.
  • the C 6-20 aromatic hydrocarbon group represented by R 33 above is preferably a C 6-10 aromatic hydrocarbon group which may have one or more substituents, and more preferably is a C 6-10 aromatic hydrocarbon group which may have one or more substituents.
  • the C 6-20 aromatic hydrocarbon group represented by R 33 above preferably has a substituent, and in another embodiment, the C 6-20 aromatic hydrocarbon group represented by R 33 above It is preferable that the hydrogen group has no substituent.
  • the “silsesquioxane residue” in the silsesquioxane residue optionally having one or more substituents represented by R 33 above means that the substituent on Si in the silsesquioxane is It is a monovalent group from which one has been eliminated, and may have any of a cage-shaped structure, a ladder-shaped structure, and a random structure.
  • the substituent in the silsesquioxane residue which may have one or more substituents is preferably a C 1-10 alkyl group which may be substituted with one or more halogen atoms. ; a phenyl group, more preferably a C 1-6 alkyl group optionally substituted with one or more halogen atoms; a phenyl group.
  • the "C 1-10 alkyl group" in the C 1-10 alkyl group which may be substituted with one or more halogen atoms as a substituent of the above-mentioned silsesquioxane residue is a straight chain It may also be a branched chain, preferably a straight or branched C 1-8 alkyl group, more preferably a straight chain C 1-6 alkyl group.
  • halogen atom in the C 1-10 alkyl group which may be substituted with one or more halogen atoms as a substituent of the silsesquioxane residue include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • halogen atoms include atoms, preferably fluorine atoms and iodine atoms.
  • the C 1-10 alkyl group optionally substituted with one or more halogen atoms as a substituent of the silsesquioxane residue is preferably -CHI-CH 2 -CF 2 CF 2 CF 2 -I.
  • a phenyl group and an isobutyl group are preferable.
  • R 33 is an iodine atom, in the unit represented by formula (2-1A), R 33 is replaced with a bond, and X 1 bonded to R 33 is an aromatic atom of another fluorine-containing aromatic monomer. May be bonded to a group ring.
  • the iodine atom of the compound in which the iodine atom is bonded to the unit represented by formula (2-1A) is extracted and becomes a reaction point, and the aromatic monomer of the aromatic monomer It is believed that the fluorine-containing aromatic monomer represented by formula (III-1) can be obtained by bonding to the ring.
  • R 33 is an iodine atom, it is considered that the iodine atom corresponding to R 33 can be similarly extracted and bonded to another aromatic ring.
  • the substituent of the group represented by R 33 includes an I atom, and the group bonded to the I atom may be bonded to another aromatic ring.
  • the total number of carbon atoms in formula (2-1A) may be 1 or more and 20 or less, preferably 1 or more and 15 or less.
  • the total number of carbon atoms in formula (2B) may be 1 or more and 20 or less, preferably 1 or more and 15 or less.
  • the C 1-20 fluorine-containing organic group represented by the above formula (2-1A) and formula (2B) is a C 1-20 fluoroalkyl group, a C 1-20 fluorine-containing organic group having a functional group, or a C 1-20 fluorine-containing organic group having a functional group.
  • a 1-20 fluoro(poly)ether group is preferred.
  • formula (2-1A) and formula (2B) can be replaced by the following formula (2-1a), formula (2-1b), formula (2-1c), and formula (2B):
  • FX 1 -CF 2 -* (2-1a) R 33 -X 1 -CF 2 -* (2-1b)
  • R F1 represents -(Rf) p -R F -(O) q -
  • Rf each independently represents a C 1-16 alkylene group optionally substituted with one or more fluorine atoms
  • R F represents a divalent fluoro(poly)ether group
  • X 1 represents a C 1-16 alkylene group or a single bond optionally substituted with one or more halogen atoms
  • R 33 is a C 6-20 aromatic hydrocarbon group which may have one or more substitu
  • the number of fluorine-containing organic groups contained in the fluorine-containing aromatic monomer is 1 or more, preferably 1 to 8, more preferably 1 to 4, and even more preferably 1 to 3. It can be: Further, the number of fluorine-containing organic groups contained in the fluorine-containing aromatic monomer is preferably 1 or more and 4 or less, more preferably 1 or more per aromatic ring contained in the fluorine-containing aromatic monomer. There may be no more than two. In one embodiment, when the fluorine-containing organic group is a C 1 fluorine-containing organic group (especially -CF 3 ), the number of fluorine-containing organic groups is preferably 2 to 6, more preferably 2 to 4, and more preferably 2 to 6 per unit. Preferably, the number may be 3 to 4. Further, in such an aromatic ring, the substitution position of the fluorine-containing organic group is preferably an ortho position with respect to R 41 .
  • the surface treatment agent has the following formula (II-1A) and formula (II-1B): R 32 -X 1 -(R F1 ) r -CF 2 -I (II-1A) I-X 1 -CF 2 -I (II-1B) [In formula (II-1A) and formula (II-1B), R F1 represents -(Rf) p -R F -(O) q -, Rf each independently represents a C 1-16 alkylene group optionally substituted with one or more fluorine atoms; R F represents a divalent fluoro(poly)ether group, X 1 represents a C 1-16 alkylene group or a single bond optionally substituted with one or more halogen atoms, R 32 is a C 1-16 alkyl group optionally substituted with one or more halogen atoms
  • the article of the present disclosure has a fluorine-containing organic group added to the base material containing the aromatic polymer, the article further improves the heat resistance of the aromatic polymer while also improving flexibility, antifouling properties, frictional properties, and It is expected to further provide stain resistance, water and oil repellency.
  • the above-mentioned base material may contain an aromatic polymer.
  • aromatic polymers include polyimide resins, polyetherimide resins, polyamideimide resins, polysulfone resins, aromatic polyamide resins, polyetheretherketone resins, polyethersulfone resins, aromatic polyester resins, phenolic resins, cresol resins, and epoxy resins.
  • resins containing aromatic rings such as resins and polyamic acids.
  • the base material may be composed only of an aromatic polymer, or may be a combination of an aromatic polymer and other materials.
  • Such other materials include glass, other resins, metals (aluminum, copper, iron, etc. or alloys containing such metals), ceramics, semiconductors (silicon, germanium, etc.), fur, leather, wood, paper. , ceramic, stone, fabric, etc., may include any suitable material.
  • the base material may be in the form of powder, membrane, plate, film, pellet, molded body (various parts, etc.), fiber (thread, woven fabric, non-woven fabric), etc.
  • the surface area of the base material on which a layer is to be formed with the above-mentioned surface treatment agent may be determined as appropriate, as long as it is at least a part of the surface of the base material, depending on the intended use and specific specifications of the article to be manufactured. For example, it is possible to introduce a fluorine-containing organic group into only a portion of the surface of the molded product.
  • the surface treatment agent includes a compound represented by one or more of the above formulas (II-1A) and (II-1B), preferably a compound represented by the above formula (II-1A). including.
  • the surface treatment agent includes a basic compound, a catalyst, a one-electron reducing agent, in addition to a compound represented by one or more selected from the above formula (II-1A) and formula (II-1B). , a radical generator, a solvent, etc. may be further included.
  • the basic compound, catalyst, one-electron reducing agent, radical generator, and solvent the same compounds as those explained in Production Method 1 can be used.
  • the method for producing an article of the present disclosure includes forming a layer on the surface of the base material by reacting the base material with the surface treatment agent, the base material containing an aromatic polymer, and the surface treatment agent comprising: forming a layer on the surface of the base material;
  • the processing agent contains a compound represented by one or more selected from the above formula (II-1A) and formula (II-1B), and preferably contains a compound represented by the above formula (II-1A).
  • the above reaction may be carried out under light irradiation.
  • light irradiation is preferably ultraviolet irradiation, and can be performed by irradiating light with a wavelength of 300 to 400 nm, for example, 350 nm to 380 nm.
  • the light source described in manufacturing method 1 can be used.
  • the reaction temperature in the above reaction is preferably 0 to 60°C, more preferably 10 to 40°C, for example room temperature. Further, the reaction time in the above reaction may be, for example, 1 to 72 hours, preferably 12 to 48 hours.
  • the method for producing the article may further include, after forming the surface layer of the base material, removing unreacted surface treatment agents and/or byproducts. Removal of unreacted surface treatment agents and/or byproducts may be performed by one or more methods selected from washing and drying. Articles from which unreacted surface treatment agents and/or byproducts have been removed are also included within the technical scope of the articles of the present disclosure.
  • Example 1 To a dichloromethane solution of 3,3',5,5'-tetramethylbenzidine (1) (0.3 mmol), perfluorohexyl iodide (5 equivalents), 5 equivalents of sodium thiosulfate aqueous solution (2 mL of water), and cesium carbonate were added. 3 equivalents of were added and irradiated with light using a 365 nm LED for 48 hours. After completion of the reaction, a liquid separation operation was performed, and then purification by column chromatography was performed to obtain the target diamine compound (2) with an isolated yield of 32%.
  • Example 2 1 equivalent of 4,4'-oxydiphthalic anhydride (3) was added to a dimethylacetamide solution (0.23 mL) of diamine monomer (2) (58.9 mg, 0.11 mmol), and the mixture was stirred at room temperature for 1 hour. I did it. As a result, a viscous solution was obtained, and NMR and GPC measurements revealed that polyamic acid (4) with a number average molecular weight of 1.3 ⁇ 10 3 and a molecular weight distribution of 1.2 was obtained.
  • Example 3 To a dichloromethane solution (2.5 mL) of 3,3',5,5'-tetramethylbenzidine (1) (0.3 mmol), perfluoropropyl iodide (5 equivalents) and sodium thiosulfate aqueous solution were added in 5 equivalents (water 2 mL), 3 equivalents of cesium carbonate were added, and light irradiation with a 365 nm LED was performed for 48 hours. After the reaction was completed, a liquid separation operation was performed, and as a result of purification by column chromatography, the target diamine compound (5) was obtained with an isolated yield of 35%.
  • Example 4 To a dichloromethane solution (2.5 mL) of 3,3',5,5'-tetramethylbenzidine (1) (0.3 mmol), perfluoropropyl iodide (5 equivalents) and sodium thiosulfate aqueous solution were added in 5 equivalents (water 2 mL), 3 equivalents of cesium carbonate were added, and light irradiation with a 365 nm LED was performed for 48 hours. After the completion of the reaction, a separation operation was performed, and then purification by column chromatography was performed to obtain the desired diamine compound (6) and compound (7) in isolated yields of 39% and 7%, respectively.
  • Example 5 To a dichloromethane solution (2.5 mL) of 3,3',5,5'-tetramethylbenzidine (1) (0.3 mmol), 5 equivalents of 1,4-diiodoperfluorobutane and 5 equivalents of an aqueous sodium thiosulfate solution were added. An equivalent amount (2 mL of water) and 3 equivalents of cesium carbonate were added, and light irradiation with a 365 nm LED was performed for 48 hours. After the reaction was completed, a liquid separation operation was performed, and then purification by column chromatography was performed to obtain the target diamine compound (8) with an isolated yield of 13%.
  • Example 6 To a dichloromethane solution (2.5 mL) of 3,3',5,5'-tetramethylbenzidine (1) (0.3 mmol), 5 equivalents of 1,6-diiodoperfluorohexane and 5 equivalents of an aqueous sodium thiosulfate solution were added. An equivalent amount (2 mL of water) and 3 equivalents of cesium carbonate were added, and light irradiation with a 365 nm LED was performed for 48 hours. After the reaction was completed, a liquid separation operation was performed, and then purification by column chromatography was performed to obtain the target diamine compound (9) with an isolated yield of 14%.
  • Example 7 To a dichloromethane solution (2 mL) of 3,3'-tetramethylbenzidine (10), 1 equivalent of perfluorohexyl iodide, 5 equivalents of sodium thiosulfate aqueous solution (2 mL), and 3 equivalents of cesium carbonate were added, and the mixture was exposed to light using a 365 nm LED. Irradiation was carried out for 24 hours. As a result, the target diamine compound (11) was obtained with an isolated yield of 12%.
  • Example 8 To a mixed solution of 4,4' dihydroxybiphenyl (12) (0.2 mmol) in acetonitrile (5 mL)/water (1 mL), 6 equivalents of perfluorohexyl iodide, Phloxin B (20 mol%), and ascorbic acid (4 equivalents) were added. , cesium carbonate (3.5 equivalents) was added, and light irradiation with a white LED was performed for 24 hours under an argon atmosphere. As a result of NMR analysis, it was found that the desired dihydroxy monomer (13) was produced in a yield of 67% and (14) in a yield of 14%.
  • Example 9 To 4,4'-diaminodiphenylphenyl ether (15) (0.6 mmol), 5 equivalents of perfluorohexyl iodide, 5 equivalents (4 mL) of sodium thiosulfate aqueous solution, and 3 equivalents of cesium carbonate were added, and the temperature was measured at 365 nm. Light irradiation was performed for 24 hours. When the resulting reaction mixture was purified by column chromatography, 4% of the compound (16) with one perfluorohexyl group introduced, 30% of the compound (17) with two perfluorohexyl groups introduced, and 3% of the compound (17) with two perfluorohexyl groups introduced.
  • Example 11 To a mixed solution of 4,4'-dihydroxydiphenyl ether (20) in acetonitrile (5 mL)/water (1 mL), 1 equivalent of perfluorohexyl iodide, Phloxine B (20 mol%), ascorbic acid (4 equivalents), cesium carbonate ( 2.5 equivalents) was added thereto, and light irradiation was performed using a white LED for 24 hours under an argon atmosphere. As a result of NMR analysis, it was found that the target dihydroxy monomer (21) was synthesized with a yield of 21%.
  • Example 12 To a mixed solution of 4,4'-methylene diphenol (22) in acetonitrile (5 mL)/water (1 mL), 1 equivalent of perfluorohexyl iodide, Phloxin B (20 mol%), ascorbic acid (4 equivalents), and cesium carbonate. (2.5 equivalents) was added, and light irradiation was performed using a white LED for 24 hours under an argon atmosphere. As a result of NMR analysis, it was found that the target dihydroxy monomer (23) was synthesized with a yield of 12%.
  • Example 17 Water (0.5 mL) and perfluorohexyl iodide (0.5 mL) were added to a petri dish to form two liquid layers. Subsequently, a polycarbonate sheet (manufactured by As One: 63-508476, 2 cm square, 1 mm thick) was floated between these two layers, and a 365 nm LED was irradiated from above to perform a surface reaction for 30 minutes. After the photoreaction was completed, the film was taken out and washed with methanol. After washing, the water contact angle value of the film surface (the upper surface near the LED light source) was significantly improved from 44° to 102°. From this result, it was confirmed that a perfluorohexyl group was introduced and water repellency derived from the skeleton was imparted to the film surface.
  • a perfluorohexyl group was introduced and water repellency derived from the skeleton was imparted to the film surface.
  • Example 18 To a mixed solution of 4,4'-dihydroxybiphenyl (12) (0.2 mmol) in acetonitrile (5 mL)/water (1 mL), 6 equivalents of perfluoropropyl iodide, Phloxin B (20 mol%), and ascorbic acid (4 equivalents) were added. ), cesium carbonate (2.5 equivalents) was added, and light irradiation was performed using a white LED for 24 hours under an argon atmosphere. As a result of NMR analysis, it was found that the target dihydroxy monomer (31) was synthesized in a yield of 30% and the target dihydroxy monomer (32) in a yield of 3%.
  • Example 19 1 equivalent of 4,4'-oxydiphthalic anhydride (3) was added to a dimethylacetamide solution (20% by weight) of diamine monomer (2) (0.26 mmol), heated at 50°C for 50 hours, and then heated at 80°C. The temperature was raised to 110° C. for 14 hours, then the temperature was raised to 110° C. for 24 hours, and then the temperature was raised to 140° C. and stirring was performed for 24 hours.
  • polyimide (33) having a number average molecular weight of 5.5 ⁇ 10 3 and a molecular weight distribution of 1.7 was obtained with an isolated yield of 69%.
  • Example 20 To a mixed solution of 4-fluorophenol (34) (0.2 mmol) in acetonitrile (5 mL)/water (1 mL), 6 equivalents of perfluorohexyl iodide, Phloxin B (20 mol%), ascorbic acid (4 equivalents), and carbonic acid were added. Cesium (2.5 equivalents) was added, and light irradiation with a white LED was performed for 24 hours under an argon atmosphere. As a result of NMR analysis, it was found that the desired AB type monomer (35) was produced at a yield of 30% and (36) at a yield of 8%.
  • Example 21 Under an argon atmosphere, 2 equivalents of heptafluoropropyl iodide and eosin Y-2Na were added to a solution of 4,4'-oxydianiline (15, 0.3 mmol) in CH 3 CN/H 2 O (5 mL/1 mL). 10 mol%, 4 equivalents of ascorbic acid, and 2.5 equivalents of cesium carbonate were added, and after freezing and degassing, light irradiation with a white LED and stirring were performed at room temperature for 24 hours. The resulting reaction mixture was purified by column chromatography, and as a result, monosubstituted product (18) was obtained with an isolation yield of 32% and disubstituted product (19) with an isolated yield of 8%.
  • Example 22 Under an argon atmosphere, 6 equivalents of perfluorohexyl iodide and 10 mol of EY were added to a mixed solution of 4,4'-oxydianiline (15) (0.2 mmol) in CH 3 CN/H 2 O (5 mL/1 mL). %, 4 equivalents of ascorbic acid and 1.5 equivalents of cesium carbonate were added, and light irradiation with a white LED and stirring were performed for 24 hours. As a result of NMR analysis, it was confirmed that the monosubstituted product (37) was produced in a yield of 14% and the disubstituted product (38) in a yield of 10%.
  • Example 23 Under an argon atmosphere, 6 equivalents of perfluoropropyl iodide and 5 equivalents of Na 2 S 2 O 3 were added to a mixed solution of compound (39) (0.6 mmol) in CH 2 Cl 2 /H 2 O (5 mL/4 mL). , 3 equivalents of cesium carbonate were added, and light irradiation with a white LED and stirring were performed for 24 hours. As a result of NMR analysis, it was confirmed that compound (40) was produced at a yield of 44%.
  • Example 24 Under an argon atmosphere, 6 equivalents of perfluoropropyl iodide and 5 equivalents of Na 2 S 2 O 3 were added to a mixed solution of compound (41) (0.6 mmol) in CH 2 Cl 2 /H 2 O (5 mL/4 mL). , 3 equivalents of cesium carbonate were added, and light irradiation with a white LED and stirring were performed for 24 hours.
  • the reaction mixture was purified by recycle preparative size exclusion chromatography to obtain compound (42) in an isolated yield of 12% and compound (43) in an isolated yield of 5%.
  • Example 25 Under an argon atmosphere, 6 equivalents of perfluoropropyl iodide and 5 equivalents of Na 2 S 2 O 3 were added to a mixed solution of compound (44) (0.6 mmol) in CH 2 Cl 2 /H 2 O (5 mL/4 mL). , 3 equivalents of cesium carbonate were added, and light irradiation with a white LED and stirring were performed for 24 hours. As a result of NMR analysis, it was confirmed that compound (45) was produced at a yield of 7%.
  • Example 28 Under an argon atmosphere, 0.3 mmol of 1,4-diiodoperfluorobutane and Na 2 S 2 O 3 were added to a mixed solution of 5 equivalents of compound (15) in CH 2 Cl 2 /H 2 O (3 mL/2 mL). 5.0 equivalents and 1.5 equivalents of cesium carbonate were added, and light irradiation with a white LED and stirring were performed for 24 hours. As a result of purification by column chromatography, compound (52) was obtained with an isolated yield of 22%.
  • Example 29 A polyimide was synthesized using a monosubstituted 4,4'-oxydianiline (18). Under an argon atmosphere, 1 equivalent of 6FDA was added to a DMF (50 wt%) solution of monosubstituted 4,4'-oxydianiline (18, 0.5 mmol), and the mixture was stirred at 180°C for 2.5 hours. Ta. Thereafter, DMF was added to the reaction solution to dissolve the product, and reprecipitation was performed using water/methanol (50 mL/50 mL) as a poor solvent. The generated solid was collected by filtration, dried, and then subjected to NMR and GPC measurements (Scheme 8).
  • polyimide (53) having a number average molecular weight of 3900 and a molecular weight distribution of 2.83 was obtained with an isolated yield of 96%. Note that the obtained polyimide 53 was soluble in tetrahydrofuran, DMF, and chloroform.
  • the obtained polymer was evaluated for water and oil repellency, and the water contact angle was 101° and the oil contact angle (dodecane was used as oil) was 32°.
  • Example 40 Under air, to a dichloromethane solution (5 mL) of polyphenylene ether (75) (total amount of repeating units: 0.5 mmol), 1 equivalent of perfluoropropyl iodide, 3 equivalents (1 mL) of sodium thiosulfate aqueous solution, and 1.5 aqueous cesium carbonate solution were added. An equivalent amount (1 mL) was added and irradiated with light using a 365 nm LED at room temperature for 24 hours. The resulting reaction mixture was subjected to reprecipitation, and the solid content obtained by filtration was dissolved in a solvent and filtered again. After concentrating the obtained filtrate, purification by reprecipitation was performed again.
  • the raw material polymer (71) was poorly soluble in tetrahydrofuran
  • the produced polymer (76) was easily soluble in tetrahydrofuran, confirming that the introduction of the perfluoropropyl group improved its solvent solubility.
  • the order of existence of units enclosed in parentheses with X, Y and z is arbitrary.
  • polymer (82) was easily soluble in tetrahydrofuran and chloroform.

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JP2004143051A (ja) * 2002-10-22 2004-05-20 Chisso Corp ジアミン、それを用いた配向膜、および該配向膜を有する液晶表示素子
JP2007536394A (ja) * 2004-05-03 2007-12-13 インテグリス・インコーポレーテッド フッ素化芳香族重合体

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