Pillararene complex

Abstract

To provide a complex which is excellent in heat resistance and / or hydrophobicity, and into which a functional group is easily introduced.SOLUTION: A complex according to the present disclosure comprises a fluorine-containing polymer and one or more cyclic compounds that include the fluorine-containing polymer. The cyclic compounds include a compound represented by formula (I) in the figure (where each occurrence of A independently represents a divalent C4-50 organic group that comprises one or more selected from -OR and -CO-; each occurrence of R independently represents a hydrogen atom or an organic group which may comprise one or more fluorine atoms; and n represents an integer of 4 to 20). The number-average molecular weight of the fluorine-containing polymer is 3,000 or more.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present disclosure relates to pillararene conjugates. [Background technology]

[0002] Rotaxanes and pseudorotaxanes are known as complexes of cyclic compounds and polymers. A rotaxane is a structure having a cyclic compound, a polymer that penetrates the ring of the cyclic compound, and a blocking site arranged at the end of the polymer. A pseudorotaxane is a structure having a cyclic compound and a polymer that penetrates the ring of the cyclic compound, and does not have a blocking site at the end of the polymer.

[0003] As such a complex, Patent Document 1 describes an inclusion compound in which a fluoropolyether molecule is included as a guest compound in cyclodextrin. Patent Document 2 describes polyethylene glycol, a pillararene that includes the polyethylene glycol in a skewered shape, and a polyrotaxane in which adamantane groups are arranged at both ends of the polyethylene glycol. Non-Patent Document 3 describes a rotaxane containing a pillararene and polyethylene or polypropylene encapsulated in the pillararene. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2007 / 058247 [Patent Document 2] Patent Publication No. 2021-138635 [Non-patent literature]

[0005] [Non-Patent Document 1] Tomoki Ogoshi et al., "Extension of polyethylene chains by formation of polypseudorotaxane structures with perpentylated piller[5]arenes", Polymer Journal (2014) 46, 77-81.

Summary of the Invention

Problems to be Solved by the Invention

[0006] In the conventionally known composites, the heat resistance and hydrophobicity are not sufficiently satisfactory, and the functional groups that can be introduced into the cyclic compounds are limited.

[0007] In view of such circumstances, the present disclosure has been made, and an object thereof is to provide a composite excellent in heat resistance and / or hydrophobicity and easy to introduce functional groups.

Means for Solving the Problems

[0008] The present disclosure includes the following aspects. [1] A composite comprising a fluorine-containing polymer and one or more cyclic compounds that clathrate the fluorine-containing polymer, wherein the cyclic compound has the following formula (I):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[10] The fluorine-containing olefin polymer-containing composite according to any one of [7] to [9], wherein the fluorine-containing olefin polymer contains one or more selected from chlorotrifluoroethylene / tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer, ethylene / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer, polyvinylidene fluoride, vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene / chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer, and poly-1,2-difluoroethylene.

[11] The fluorine-containing olefin polymer-containing composite according to any one of [7] to

[10] , wherein the fluorine-containing olefin polymer contains polyvinylidene fluoride.

[12] The fluorine-containing polymer-containing composite according to any one of [1] to

[11] , wherein the fluorine-containing polymer contains a fluorine-containing polyether.

[13] The fluorine-containing polyether is represented by the following formula: The following formula: Y 1 -R f1 -R F -O q -R f2 -Y 2 [In the formula: R F represents a divalent fluoropolyether group, Y 1is a halogen atom, a hydrogen atom, -COOR f3 , -OR f3 , -NR f3 2, -NR f3 -CO-R f3 , -CO-NR f3 2, -NO2, -CN, -COR f4 , -SO3R f4 and -O-COR f4 represents one selected from them, Y 2 is a halogen atom, a hydrogen atom, -COOR f3 , -OR f3 , -NR f3 2, -NR f3 -CO-R f3 , -CO-NR f3 2, -NO2, -CN, -COR f4 , -SO3R f4 and -O-COR f4 represents one selected from them, R f1 represents a divalent hydrocarbon group or a single bond which may have one or more substituents, R f2 represents a divalent hydrocarbon group or a single bond which may have one or more substituents, R f3 each occurrence independently represents a C 1-16 alkyl group which may have one or more substituents or a hydrogen atom, R f4 each occurrence independently represents a C 1-16 alkyl group, a hydrogen atom or a halogen atom which may have one or more substituents, q is 0 or 1.] The complex according to

[12] , represented by

[14] R F is the following formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6)d -(OC2F4) e -(OCF2) f - [wherein, R Fa is, in each occurrence, independently a hydrogen atom, a fluorine atom or a chlorine atom, a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula. However, when all R Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more.] The complex according to

[13] , represented by

[15] The complex according to

[13] or

[14] , wherein one or more R Fa are hydrogen atoms.

[16] R F is the following formula (f7): -(CF2CF2CH2O) d - (f7) [wherein d represents an integer of 1 to 200.] The complex according to any one of

[13] to

[15] , represented by

[17] The complex according to any one of [1] to

[16] , wherein the proportion of the cyclic compound is 0.01% by mass or more and 99% by mass or less in 100 parts by mass in total of the fluorine-containing polymer and the cyclic compound.

[18] The complex according to any one of [1] to

[17] , wherein the fluorine-containing polymer has at least one selected from a glass transition temperature and a melting point at 50 °C or higher.

[19] The complex according to any one of [1] to

[18] , having a thermal decomposition temperature of 170 °C or higher

[20] A method for producing the complex according to any one of [1] to

[19] , comprising A production method comprising bringing the fluorine-containing polymer into contact with the cyclic compound represented by the formula (I) in the absence of a solvent to obtain the complex.

[21] The production method according to

[20] , wherein the contact is carried out at a temperature higher than at least one of the glass transition temperature and the melting point of the fluorine-containing polymer.

[22] A composition comprising the complex according to any one of [1] to

[19] .

[23] The composition according to

[22] , which is in powder form.

[24] The composition according to

[22] , which is in liquid form. [Effect of the Invention]

[0009] The complex of the present disclosure is excellent in heat resistance and / or hydrophobicity, and the introduction of functional groups is easy. [Brief Description of the Drawings]

[0010]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

[0011] [Complex] The complex of the present disclosure is It contains a fluorine-containing polymer and one or more cyclic compounds that clathrate the fluorine-containing polymer. The cyclic compound is represented by the following formula (I):

[0012] [Chemical formula] [In formula (I), A, in each occurrence, is independently a divalent C organic group containing one or more selected from -OR and -CO- 4-50 and represents an organic group, R, in each occurrence, independently represents an organic group that may contain one or more fluorine atoms or a hydrogen atom, and n represents an integer from 4 to 20.] It contains a compound represented by the formula.

[0013] Since the composite of the present disclosure contains a fluorine-containing polymer and the above cyclic compound, it has good heat resistance and / or hydrophobicity, and it is easy to introduce functional groups. The composite of the present disclosure is expected to be easily mixed with various resins that cannot be mixed with the fluorine-containing polymer alone while maintaining the heat resistance and hydrophobic properties of the fluorine-containing polymer. Furthermore, in the composite of the present disclosure, since the cyclic compound is not fixed to the fluorine-containing polymer, it is expected to be movable even when mixed with a resin and can exhibit properties such as shock absorbency.

[0014] In the present disclosure, inclusion means that at least a part of the fluorine-containing polymer is present inside the ring of the cyclic compound. In one aspect, the fluorine-containing polymer may penetrate the ring of the cyclic compound. Further, the cyclic compound that includes one fluorine-containing polymer may be one or more, and in one aspect, preferably one, and in another aspect, preferably two or more. The upper limit is, on average, 5 or less, or 3 or less, preferably 1 or less per repeating unit of the polymer. For example, when the number of repeating units of the polymer is j, the number of cyclic compounds contained in one complex is preferably 5×j or less, more preferably 3×j or less, and still more preferably j or less.

[0015] In formula (I), A, in each occurrence, is independently a divalent C 4-50 organic group, and includes one or more selected from -OR and -CO-. The above C 4-50 organic group is preferably a C 4-20 organic group, more preferably a C 4-10 organic group.

[0016] In the present disclosure, the monovalent or divalent "organic group" means a monovalent or divalent group containing carbon. The monovalent or divalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. The derivative of the hydrocarbon group means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the terminal or in the molecular chain of the hydrocarbon group. Note that when simply referred to as "organic group", it means a monovalent organic group.

[0017] Further, in the present disclosure, the "hydrocarbon group" is a group containing carbon and hydrogen, and means a group obtained by removing one hydrogen atom from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but is a C 1-20 hydrocarbon group, for example, a C 1-20 aliphatic hydrocarbon group, a C 6-20Examples include aromatic hydrocarbon groups and the like. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Further, the hydrocarbon group may contain one or more ring structures. Further, the hydrocarbon group may have one or more substituents.

[0018] In the present disclosure, the substituents of the "hydrocarbon group" are not particularly limited, but for example, a halogen atom; a C that may be substituted by one or two or more halogen atoms 1-6 alkyl group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5- to 10-membered heterocyclyl group, C 6-10 One or more groups selected from an aryl group and a 5- to 10-membered heteroaryl group are exemplified.

[0019] In the divalent organic group containing one or more selected from -OR and -CO- represented by A above, the "divalent C 4-50 organic group" is preferably a divalent C 6-20 aromatic hydrocarbon group or a divalent C 3-20 alicyclic hydrocarbon group. The above-mentioned divalent C 6-20 aromatic hydrocarbon group is preferably a divalent C 6-10 aromatic hydrocarbon group, more preferably a divalent C 6-8 aromatic hydrocarbon group, particularly preferably a phenylene group. The above-mentioned divalent C 3-20 alicyclic hydrocarbon group may be either a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group. The above-mentioned divalent C 3-20 alicyclic hydrocarbon group is preferably a divalent C 6-10 unsaturated alicyclic hydrocarbon group, more preferably a divalent C 6-8 unsaturated hydrocarbon group, particularly preferably a cyclohexadienyl group.

[0020] A divalent C containing one or more selected from -OR and -CO represented by the above A 4-50 The organic group is, in each occurrence, independently preferably a divalent C having -OR as a substituent 6-20 An aromatic hydrocarbon group, C 3-20 In an alicyclic hydrocarbon group, a group in which a hydrogen atom bonded to a carbon atom constituting the ring is substituted with -OR, and C 3-20 In an alicyclic hydrocarbon group, it may be one selected from a group in which -CH2- constituting the ring is replaced with -CO-, more preferably a divalent C having -OR as a substituent 6-10 An aromatic hydrocarbon group, and C 6-10 In an alicyclic hydrocarbon group, it may be one selected from a group in which -CH2- constituting the ring is replaced with -CO-.

[0021] The total number of -OR and -CO contained in A is 1 or more and 4 or less, preferably 2.

[0022] R represents, in each occurrence, independently an organic group which may contain one or more fluorine atoms or a hydrogen atom.

[0023] Examples of the organic group represented by R include an alkyl group, an alkyloxy group, an alkyl ether group, a tosyl group, a triflate group, a phenyl group, etc., and these groups may have one or more substituents.

[0024] The substituents that the organic group represented by R may have are not particularly limited, but for example, reactive functional groups such as a hydroxyl group, an amino group, a carboxy group, a thiol group, an isocyanate group, a nitrile group, an epoxy group, an acetyl group; aliphatic hydrocarbon groups such as an alkyl group, a vinyl group, an ethynyl group; a halogen atom. Such halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and may preferably be a fluorine atom or a chlorine atom.

[0025] The alkyl group in R is preferably C 1-30is an alkyl group. Such alkyl groups may be linear or branched. In one embodiment, C 1-30 The alkyl group is C 1-20 Alkyl groups, preferably C 1-10 Alkyl groups, more preferably C 1-30 In another embodiment, C 1-30 The alkyl group is C 17-30 Alkyl groups, preferably C 18-30 Alkyl groups, more preferably C 26-30 It may be an alkyl group.

[0026] The substituents of the alkyl group in R include a halogen atom; 1-6 Alkyl group, C 2-6 Alkenyl group, C 2-6 Alkynyl group, C 3-10 Cycloalkyl groups, C 3-10 Unsaturated cycloalkyl groups, 5-10 membered heterocyclyl groups, C 6-10 Examples of the halogen atom include one or more groups selected from an aryl group and a 5- to 10-membered heteroaryl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a fluorine atom or a chlorine atom.

[0027] The alkyloxy group in R is typically -OR 21 (In the formula, R 21 is an alkyl group which may have one or more substituents.

[0028] R 21 The alkyl group in may be substituted with the above-mentioned substituents, and preferably may be substituted with a fluorine atom. The alkyl group in may be substituted with a fluorine atom. 1-30 The alkyl group may be linear or branched. 1-30 The alkyl group is C 1-20 Alkyl groups, preferably C 1-10An alkyl group, more preferably a C 1-3 alkyl group, may be used.

[0029] R 21 is preferably -R 22 -R 23 (In the formula, R 22 is an unsubstituted C 1-30 alkylene group, preferably a C 1-20 alkylene group, more preferably a C 1-10 alkylene group, and R 23 is a C 1-10 perfluoroalkyl group, preferably a C 1-6 perfluoroalkyl group.) It is a group represented by

[0030] The alkyl ether group in the above R is a compound having one or more ether oxygen atoms in the molecular chain of the above alkyl group. Such an alkyl ether group is typically -R 26 -R 27 -(O-R 28 ) m -R 29 represented by the formula. In the formula, R 26 is a single bond or an oxygen atom. R 27 is a single bond or a C 1-10 alkylene group. R 28 is a C 1-10 alkylene group. R 29 is a hydrogen atom or a C 1-10 alkyl group. m represents an integer of 1 to 20, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0031] In one embodiment, the organic group may be an alkyl group, an alkyloxy group, or an alkyl ether group whose terminal is substituted with a reactive functional group. Note that such a group may be further substituted with another substituent.

[0032] The reactive functional group is not particularly limited, and examples thereof include a hydroxyl group, an amino group, a carboxyl group, a thiol group, an isocyanate group, a vinyl group, an acetylene group, a nitrile group, an epoxy group, and the like.

[0033] In one embodiment, preferably, R represents a C alkyl group which may have one or more substituents or a hydrogen atom. 1-30

[0034] n is from 4 to 20, preferably from 4 to 10, more preferably from 4 to 7, and even more preferably from 5 to 6. In one embodiment, n is 5. In another embodiment, n is 6.

[0035] The cyclic compound is preferably the following formulas (1) to (3):

[0036] [Chemical formula]

[0037] [In formula (1), R 1 in each occurrence independently represents a hydrogen atom or an organic group, R 2 in each occurrence independently represents a hydrogen atom or an organic group, R 3 in each occurrence independently represents a hydrogen atom or an organic group, R 4 in each occurrence independently represents a hydrogen atom or an organic group, n1 is an integer from 4 to 20, In a preferred embodiment, one or more selected from R 1 ~R 4 are preferably fluoro-containing organic groups, and more preferably are organic groups containing a C fluoroalkyl group, 2-6 In another preferred embodiment, one or more selected from R 3 and R 4 are hydrogen atoms, and more preferably R 3 and R 4 can be hydrogen atoms.

[0038] ​​ [Chemical formula]

[0039] [In formula (2), R 5 independently represents a hydrogen atom or an organic group at each occurrence, R 6 independently represents a hydrogen atom or an organic group at each occurrence, n2 is an integer from 4 to 20.]

[0040] [Chemical formula]

[0041] [In formula (3), R 7 independently represents a hydrogen atom or an organic group at each occurrence, R 8 independently represents a hydrogen atom or an organic group at each occurrence, R 9 independently represents a hydrogen atom or an organic group at each occurrence, R 10 independently represents a hydrogen atom or an organic group at each occurrence, R 11 independently represents a hydrogen atom or an organic group at each occurrence, R 12 independently represents a hydrogen atom or an organic group at each occurrence, n3 is an integer from 1 to 19, n4 is an integer from 1 to 19, the sum of n3 and n4 is from 4 to 20, the order of the units enclosed in parentheses with n3 or n4 is arbitrary in formula (3).] It is preferable to contain a compound represented by any of the following.

[0042] When the cyclic compound is a compound represented by any of the above formulas (1) to (3), the heat resistance and / or hydrophobicity is better, and the introduction of functional groups is easier, and the complex can be produced more efficiently.

[0043] In one embodiment, the cyclic compound is the following formula (1):

[0044] [Chemical formula]

[0045] [In formula (1), R 1 each independently represents a hydrogen atom or an organic group at each occurrence, R 2 each independently represents a hydrogen atom or an organic group at each occurrence, R 3 each independently represents a hydrogen atom or an organic group at each occurrence, R 4 each independently represents a hydrogen atom or an organic group at each occurrence, n1 is an integer from 4 to 20.] Preferably, it contains a compound represented by

[0046] In formula (1), R 1 each independently represents a hydrogen atom or an organic group at each occurrence, R 2 each independently represents a hydrogen atom or an organic group at each occurrence, R 3 each independently represents a hydrogen atom or an organic group at each occurrence, R 4 each independently represents a hydrogen atom or an organic group at each occurrence.

[0047] R 1 , R 2 , R 3 or R 4Examples of the organic group represented by include an alkyl group, an alkyloxy group, an alkyl ether group, a tosyl group, a triflate group, a phenyl group, a fluorine-containing organic group, etc., and these groups may have one or more substituents.

[0048] R 1 、R 2 、R 3 Or R 4 The substituents that the organic group represented by may have are not particularly limited, and examples thereof include reactive functional groups such as a hydroxyl group, an amino group, a carboxy group, a thiol group, an isocyanate group, a nitrile group, an epoxy group, and an acetyl group; aliphatic hydrocarbon groups such as an alkyl group, a vinyl group, and an ethynyl group.

[0049] R 1 、R 2 、R 3 Or R 4 The alkyl group in is preferably a C 1-30 alkyl group. Such an alkyl group may be linear or branched. In one embodiment, the C 1-30 alkyl group may be a C 1-20 alkyl group, preferably a C 1-10 alkyl group, more preferably a C 1-30 alkyl group. In another embodiment, the C 1-30 alkyl group may be a C 17-30 alkyl group, preferably a C 18-30 alkyl group, more preferably a C 26-30 alkyl group.

[0050] R 1 、R 2 、R 3 Or R 4 The substituents of the alkyl group in include a halogen atom; a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 3-10 cycloalkyl group, an unsaturated cycloalkyl group, a 5- to 10-membered heterocyclyl group, which may be substituted by one or two or more halogen atoms; 3-10 ​6-10 Examples of one or more groups selected from an aryl group and a 5- to 10-membered heteroaryl group include.

[0051] The above R 1 , R 2 , R 3 or R 4 The alkyloxy group in is typically a group represented by -O-R 21 (wherein R 21 is an alkyl group which may have one or more substituents).

[0052] R 21 The alkyl group in may be substituted by the above-described substituents, preferably may be substituted by a fluorine atom. Such an alkyl group is preferably a C 1-30 alkyl group. Such an alkyl group may be linear or branched. In one embodiment, the C 1-30 alkyl group may be a C 1-20 alkyl group, preferably a C 1-10 alkyl group, more preferably a C 1-3 alkyl group.

[0053] The above R 1 , R 2 , R 3 or R 4 The alkyl ether group in is a compound having one or more ether oxygen atoms in the molecular chain of the above alkyl group. Such an alkyl ether group is typically a group represented by -R 26 -R 27 -(O-R 28 ) m -R 29 In the formula, R 26 is a single bond or an oxygen atom. R 27 is a single bond or a C 1-10 alkylene group. R 28 is a C 1-10 alkylene group. R 29 is a hydrogen atom or a C 1-10It is an alkyl group. m represents an integer from 1 to 20, preferably from 1 to 10, more preferably from 1 to 5, and even more preferably from 1 to 3.

[0054] The above R 1 , R 2 , R 3 Or R 4 The fluorine-containing organic group in is preferably an organic group having 2 or more carbon atoms with a fluoroalkyl group, and more preferably may be a fluoroalkyl group or a fluoro(poly)ether group. The above fluoroalkyl group is preferably a C 1-10 fluoroalkyl group, more preferably a C 2-6 fluoroalkyl group. Such a fluoroalkyl group may be linear or branched, preferably linear. Such a fluoroalkyl group is preferably a perfluoroalkyl group. The above fluoro(poly)ether group represents a fluoroether group and / or a fluoropolyether group.

[0055] In one embodiment, the fluorine-containing organic group has the following formula: -(O p1 -R 20 q1 )-Rf a [Wherein: R 20 Each occurrence independently represents a C 1-10 alkylene group. Rf a Represents a C 1-10 fluoroalkyl group. p1 is an integer from 0 to 2. q1 is an integer from 0 to 3. (O p1 -R 20 q1 ) In, the order of existence of O and R 11a is not limited.] It is a group represented by.

[0056] R 20 The C 1-10 alkylene group in is preferably a C 1-6An alkylene group, more preferably a C 2-6 is an alkylene group. Such an alkylene group may be linear or branched, preferably linear.

[0057] Rf a The C in 1-10 fluoroalkyl group is preferably a C 1-6 fluoroalkyl group. Such a fluoroalkyl group may be linear or branched, preferably linear. Such a fluoroalkyl group is preferably a perfluoroalkyl group.

[0058] p1 is an integer from 0 to 2, preferably 1 or 2. In one embodiment, p1 is 1. In another embodiment, p1 is 2.

[0059] q1 is an integer from 0 to 3, preferably an integer from 1 to 3, more preferably 1 or 2. In one embodiment, q1 is 1. In another embodiment, q1 is 2.

[0060] In a preferred embodiment, the above fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a [Wherein: R 20 each independently represents a C 1-10 alkylene group. Rf a represents a C 1-10 fluoroalkyl group. r1 is 0 or 1.] is a group represented by

[0061] In a more preferred embodiment, the above fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a [Wherein: R20 each independently represents a C 1-10 alkylene group. Rf a represents a C 1-10 perfluoroalkyl group. r1 is 0 or 1. is a group represented by

[0062] n1 is an integer from 4 to 20, preferably an integer from 4 to 6, more preferably 5 or 6.

[0063] In a particularly preferred embodiment, R 13 and R 16 are -O-R 20 -(O-R 20 ) r1 -Rf a wherein R 14 and R 15 are a hydrogen atom, or R 14 and R 15 are -O-R 20 -(O-R 20 ) r1 -Rf a wherein R 13 and R 16 are a hydrogen atom, R 20 each independently represents a C 1-10 alkylene group, preferably a C 1-6 alkylene group, Rf a represents a C 1-10 perfluoroalkyl group, preferably a C 1-6 perfluoroalkyl group, r1 is 0 or 1, n1 is an integer from 4 to 6, preferably 5 or 6.

[0064] In one embodiment, the organic group can be an alkyl group, an alkyloxy group, or an alkyl ether group having a terminal substituted by a reactive functional group. Such a group may be further substituted by another substituent.

[0065] The reactive functional group is not particularly limited, and examples thereof include a hydroxyl group, an amino group, a carboxyl group, a thiol group, an isocyanate group, a vinyl group, an acetylene group, a nitrile group, an epoxy group and the like.

[0066] In one embodiment, preferably, R 1 represents a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, and R 2 represents a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, and R 3 represents a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, and R 4 represents a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom.

[0067] In a preferred embodiment, one or more selected from R 1 to R 4 are preferably fluorine-containing organic groups, and more preferably organic groups containing a C 2-6 fluoroalkyl group.

[0068] In another preferred embodiment, one or more selected from R 3 and R 4 are hydrogen atoms, and more preferably R 3 and R 4 can be hydrogen atoms.

[0069] n1 is preferably 4 to 20, more preferably 4 to 10, still more preferably 4 to 7, and even more preferably 5 to 6. In one embodiment, n1 is 5. In another embodiment, n1 is 6.

[0070] The above formula (1) is preferably the following formula (1-A):

[0071] [Chemical formula]

[0072] [In formula (1-A), R 1a represents, in each occurrence independently, a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, R 2a represents, in each occurrence independently, a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, R 3a represents, in each occurrence independently, a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, R 4a represents, in each occurrence independently, a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, n1 is an integer from 4 to 20.] is represented by

[0073] In formula (1-A), R 1a represents, in each occurrence independently, a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, R 2a represents, in each occurrence independently, a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, R 3a represents, in each occurrence independently, a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, R 4a represents, in each occurrence independently, a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom.

[0074] R 1a , R 2a , R 3a or R4a The alkyl group represented by is preferably C 1-30 alkyl group. Such an alkyl group may be linear or branched. In one embodiment, C 1-30 alkyl group is C 1-20 alkyl group, preferably C 1-10 alkyl group, more preferably C 1-30 alkyl group. In another embodiment, C 1-30 alkyl group is C 17-30 alkyl group, preferably C 18-30 alkyl group, more preferably C 26-30 alkyl group.

[0075] R 1a 、R 2a 、R 3a or R 4a The substituents of the alkyl group represented by include a halogen atom; a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 3-10 cycloalkyl group, a C 3-10 unsaturated cycloalkyl group, a 5- to 10-membered heterocyclyl group, a C 6-10 aryl group, and one or more groups selected from 5- to 10-membered heteroaryl groups.

[0076] In another embodiment, the above formula (1) is the following formula (1-A’):

[0077]

Chemical formula

[0078] [In formula (1-A’), R 13 each occurrence independently represents a hydrogen atom or an organic group, R 14 each occurrence independently represents a hydrogen atom or an organic group, R 15represents, independently at each occurrence, a hydrogen atom or an organic group, R 16 represents, independently at each occurrence, a hydrogen atom or an organic group, n5 is an integer from 4 to 20, provided that at least one of R 13 R 14 R 15 and R 16 is a fluorine-containing organic group, R 14 and R 15 at least one of which is a hydrogen atom.] can be represented by.

[0079] In the above formula (1-A’), R 13 represents, independently at each occurrence, a hydrogen atom or an organic group, and R 14 represents, independently at each occurrence, a hydrogen atom or an organic group, and R 15 represents, independently at each occurrence, a hydrogen atom or an organic group, and R 16 represents, independently at each occurrence, a hydrogen atom or an organic group, and R 13 R 14 R 15 and R 16 at least one of which is a fluorine-containing organic group.

[0080] Examples of the organic group represented by the above R 13 R 14 R 15 or R 16 include an alkyl group, an alkyloxy group, an alkyl ether group, a tosyl group, a triflate group, a phenyl group, etc., which may be substituted by a substituent.

[0081] The substituent is not particularly limited. For example, a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 3-10 cycloalkyl group, a C3-10 An unsaturated cycloalkyl group, a 5- to 10-membered heterocyclyl group, a 5- to 10-membered unsaturated heterocyclyl group, C 6-10 An aryl group, and one or more groups selected from a 5- to 10-membered heteroaryl group, and a reactive functional group are mentioned.

[0082] The above reactive functional group is not particularly limited, and examples thereof include a hydroxyl group, an amino group, a carboxyl group, a thiol group, an isocyanate group, a vinyl group, an acetylene group, a nitrile group, an epoxy group, and the like.

[0083] The above R 13 , R 14 , R 15 Or R 16 The alkyl group in 1-30 is preferably a C 1-30 alkyl group. Such an alkyl group may be linear or branched. In one embodiment, the C 1-20 alkyl group is a C 1-10 alkyl group, preferably a C 1-30 alkyl group, more preferably a C 1-30 alkyl group may be. In another embodiment, the C 17-30 alkyl group is a C 18-30 alkyl group, preferably a C 26-30 alkyl group may be.

[0084] R 13 , R 14 , R 15 Or R 16 The substituents of the alkyl group in 1-6 include a halogen atom; a C 2-6 alkyl group, a C 2-6 alkenyl group, a C 3-10 alkynyl group, a C 3-10 cycloalkyl group, a C 6-10 unsaturated cycloalkyl group, a 5- to 10-membered heterocyclyl group, a C

[0085] The above R 13 , R 14 , R 15 or R 16 The alkyloxy group in is typically -O-R 21 (wherein R 21 is an alkyl group which may have one or more substituents.).

[0086] R 21 The alkyl group in may be substituted by the above-mentioned substituents, preferably may be substituted by a fluorine atom. Such an alkyl group is preferably a C 1-30 alkyl group. Such an alkyl group may be linear or branched. In one embodiment, the C 1-30 alkyl group may be a C 1-20 alkyl group, preferably a C 1-10 alkyl group, more preferably a C 1-3 alkyl group.

[0087] R 21 is preferably -R 22 -R 23 (wherein R 22 is an unsubstituted C 1-30 alkylene group, preferably a C 1-20 alkylene group, more preferably a C 1-10 alkylene group, and R 23 is a C 1-10 perfluoroalkyl group, preferably a C 1-6 perfluoroalkyl group.).

[0088] The above alkyl ether group is a compound having one or more ether oxygen atoms in the molecular chain of the above alkyl group. Such an alkyl ether group is typically -R 26f -R 27f -(O-R 28f ) m1 -R 29f represented by the formula. In the formula, R 26f is a single bond or an oxygen atom. R27f is a single bond or a C 1-10 alkylene group. R 28f is a C 1-10 alkylene group. R 29f may be a C 1-10 alkyl group substituted by a fluorine atom or a hydrogen atom. m1 represents an integer from 1 to 20, preferably from 1 to 10, more preferably from 1 to 5, and even more preferably from 1 to 3.

[0089] In one embodiment, the organic group may be an alkyl group, an alkyloxy group, or an alkyl ether group whose terminal is substituted by a reactive functional group. Note that such a group may be further substituted by another substituent.

[0090] In one embodiment, R 13 and R 16 are each independently an organic group, and at least one of R 13 and R 16 is a fluorine-containing organic group, or R 14 and R 15 are each independently an organic group, and at least one of R 14 and R 15 is a fluorine-containing organic group.

[0091] R 14 and R 15 at least one of which is a hydrogen atom, preferably, R 14 and R 15 can be a hydrogen atom. When at least one of R 14 and R 15 is a hydrogen atom, the compound represented by the formula (1-A') has -OH as a proton-donating group. Therefore, it can be combined with a polymer containing one or more selected from -CO-, a nitrogen atom, and a halogen atom.

[0092] In one embodiment, R 13 , R 14 , R 15 and R 16At least two of them are fluorine-containing organic groups, preferably R 13 , R 14 , R 15 and R 16 Two of them are fluorine-containing organic groups, more preferably, R 13 and R 16 may be fluorine-containing organic groups.

[0093] In one embodiment, R 14 and R 15 are hydrogen atoms, or R 13 and R16 are hydrogen atoms.

[0094] In a preferred embodiment, R 13 and R 16 are each independently a fluorine-containing organic group, and R 14 and R 15 are hydrogen atoms.

[0095] The above fluorine-containing organic group is preferably an organic group having 2 or more carbon atoms having a fluoroalkyl group, and more preferably may be a fluoroalkyl group or a fluoro(poly)ether group. The above fluoroalkyl group is preferably a C 1-10 fluoroalkyl group, more preferably a C 2-6 fluoroalkyl group. Such a fluoroalkyl group may be linear or branched, preferably linear. Such a fluoroalkyl group is preferably a perfluoroalkyl group. The above fluoro(poly)ether group represents a fluoroether group and / or a fluoropolyether group.

[0096] In one embodiment, the above fluorine-containing organic group has the following formula: -(O p1 -R 20 q1 )-Rf a [Wherein: R 20 represents, in each occurrence, independently of each other, a C 1-10 alkylene group. Rfa represents C 1-10 a fluoroalkyl group. p1 is an integer from 0 to 2. q1 is an integer from 0 to 3. (O p1 -R 20 q1 In (O 11a and R, the order of their presence is not limited. is a group represented by

[0097] R 20 the C 1-10 alkylene group in is preferably a C 1-6 alkylene group, more preferably a C 2-6 alkylene group. Such an alkylene group may be linear or branched, preferably linear.

[0098] Rf a the C 1-10 fluoroalkyl group in is preferably a C 1-6 fluoroalkyl group. Such a fluoroalkyl group may be linear or branched, preferably linear. Such a fluoroalkyl group is preferably a perfluoroalkyl group.

[0099] p1 is an integer from 0 to 2, preferably 1 or 2. In one embodiment, p1 is 1. In another embodiment, p1 is 2.

[0100] q1 is an integer from 0 to 3, preferably an integer from 1 to 3, more preferably 1 or 2. In one embodiment, q1 is 1. In another embodiment, q1 is 2.

[0101] In a preferred embodiment, the above fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a [wherein: R 20 each independently represents C 1-10represents an alkylene group. Rf a is a 1-10 fluoroalkyl group. r1 is 0 or 1. It is a group represented by

[0102] In a more preferred embodiment, the above fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a [wherein: R 20 each independently represents a 1-10 alkylene group. Rf a is a 1-10 perfluoroalkyl group. r1 is 0 or 1. It is a group represented by

[0103] n1 is an integer from 4 to 20, preferably an integer from 4 to 6, more preferably 5 or 6.

[0104] In a particularly preferred embodiment, R 13 and R 16 are -O-R 20 -(O-R 20 ) r1 -Rf a and R 14 and R 15 are a hydrogen atom, or R 14 and R 15 are -O-R 20 -(O-R 20 ) r1 -Rf a and R 13 and R 16 are a hydrogen atom, R 20 each independently represents a 1-10 alkylene group, preferably a 1-6 alkylene group. Rf a is a C 1-10 perfluoroalkyl group, preferably a C 1-6 perfluoroalkyl group, and r1 is 0 or 1, and n1 is an integer from 4 to 6, preferably 5 or 6.

[0105] The compound represented by formula (1-A’) can be obtained by converting the substituent of pillar[n]arene into a fluorine-containing organic group. Typically, the compound represented by formula (1-A’) can be obtained by introducing a hydroxyl group at a predetermined position of pillar[n]arene and reacting the hydroxyl group with a tosylate, halide, or the like of an organic group having 2 or more carbon atoms and a fluoroalkyl group.

[0106] In one aspect, preferably, R 1a and R 2a are hydrogen atoms, and R 3a and R 4a are hydrogen atoms or methyl groups.

[0107] In another aspect, the cyclic compound is represented by the following formula (2):

[0108]

Chemical formula

[0109] In formula (2), R 5 each occurrence independently represents a hydrogen atom or an organic group, and R 6 each occurrence independently represents a hydrogen atom or an organic group.

[0110] R 5 or R 6 Examples of the organic group represented by R or R include an alkyl group, an alkyloxy group, an alkyl ether group, a tosyl group, a triflate group, a phenyl group, etc., and these groups may have one or more substituents.

[0111] R 5 or R 6 The substituents that the organic group represented by R or R may have are not particularly limited, and examples include reactive functional groups such as a hydroxyl group, an amino group, a carboxy group, a thiol group, an isocyanate group, a nitrile group, an epoxy group, an acetyl group; aliphatic hydrocarbon groups such as an alkyl group, a vinyl group, an ethynyl group.

[0112] R 5 or R 6 The alkyl group in R or R is preferably a C 1-30 alkyl group. Such an alkyl group may be linear or branched. In one embodiment, the C 1-30 alkyl group may be a C 1-20 alkyl group, preferably a C 1-10 alkyl group, more preferably a C 1-30 alkyl group. In another embodiment, the C 1-30 alkyl group may be a C 17-30 alkyl group, preferably a C 18-30 alkyl group, more preferably a C 26-30 alkyl group.

[0113] R 5 or R 6 Examples of the substituent of the alkyl group in R or R include a halogen atom; a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 3-10 cycloalkyl group, an unsaturated cycloalkyl group, a 5- to 10-membered heterocyclyl group, a C 3-10 which may be substituted by one or two or more halogen atoms. 6-10Examples thereof include one or more groups selected from an aryl group and a 5- to 10-membered heteroaryl group.

[0114] The above R 5 or R 6 The alkyloxy group in is typically -O-R 21 (wherein R 21 is an alkyl group which may have one or more substituents).

[0115] The alkyl group in R 21 may be substituted by the above-described substituents, preferably may be substituted by a fluorine atom. Such an alkyl group is preferably a C 1-30 alkyl group. Such an alkyl group may be linear or branched. In one embodiment, the C 1-30 alkyl group is a C 1-20 alkyl group, preferably a C 1-10 alkyl group, more preferably a C 1-3 alkyl group.

[0116] The above R 5 or R 6 The alkyl ether group in is a compound having one or more ether oxygen atoms in the molecular chain of the above alkyl group. Such an alkyl ether group is typically -R 26 -R 27 -(O-R 28 ) m -R 29 represented by the formula. In the formula, R 26 is a single bond or an oxygen atom. R 27 is a single bond or a C 1-10 alkylene group. R 28 is a C 1-10 alkylene group. R 29 is a hydrogen atom or a C 1-10 alkyl group. m represents an integer of 1 to 20, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0117] In one embodiment, the organic group can be an alkyl group, an alkyloxy group, or an alkyl ether group having a terminal substituted by a reactive functional group. Such a group may be further substituted by another substituent.

[0118] The reactive functional group is not particularly limited, and examples thereof include a hydroxyl group, an amino group, a carboxyl group, a thiol group, an isocyanate group, a vinyl group, an acetylene group, a nitrile group, an epoxy group, and the like.

[0119] In one embodiment, preferably, R 5 represents a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, and R 6 represents a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom.

[0120] n2 is preferably from 4 to 20, more preferably from 4 to 10, still more preferably from 4 to 7, and even more preferably from 5 to 6. In one embodiment, n2 is 5. In another embodiment, n2 is 6.

[0121] The above formula (2) is preferably the following formula (2-A):

[0122]

Chemical formula

[0123] [In formula (2-A), R 5a represents, in each occurrence, independently of one another, a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, R 6a represents, in each occurrence, independently of one another, a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, and n2 represents an integer from 4 to 20.] It is represented by

[0124] In formula (2-A), R 5a each independently in each occurrence may have one or more substituents and represents a C 1-30 alkyl group or a hydrogen atom, and R 6a each independently in each occurrence may have one or more substituents and represents a C 1-30 alkyl group or a hydrogen atom.

[0125] R 5a or R 6a The alkyl group represented by is preferably a C 1-30 alkyl group. Such an alkyl group may be linear or branched. In one embodiment, the C 1-30 alkyl group is a C 1-20 alkyl group, preferably a C 1-10 alkyl group, more preferably a C 1-30 alkyl group. In another embodiment, the C 1-30 alkyl group is a C 17-30 alkyl group, preferably a C 18-30 alkyl group, more preferably a C 26-30 alkyl group.

[0126] R 5a or R 6a Examples of the substituent in the alkyl group represented by include a halogen atom; a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 3-10 cycloalkyl group, a C 3-10 unsaturated cycloalkyl group, a 5- to 10-membered heterocyclyl group, a C 6-10 aryl group, and one or more groups selected from 5- to 10-membered heteroaryl groups.

[0127] In one embodiment, preferably, R 5a and R 6a are hydrogen atoms.

[0128] In still another aspect, the cyclic compound is represented by the following formula (3):

[0129] [Chemical formula] [In formula (3), R 7 represents, in each occurrence, independently of one another, a hydrogen atom or an organic group, R 8 represents, in each occurrence, independently of one another, a hydrogen atom or an organic group, R 9 represents, in each occurrence, independently of one another, a hydrogen atom or an organic group, R 10 represents, in each occurrence, independently of one another, a hydrogen atom or an organic group, R 11 represents, in each occurrence, independently of one another, a hydrogen atom or an organic group, R 12 represents, in each occurrence, independently of one another, a hydrogen atom or an organic group, n3 is an integer from 1 to 19, n4 is an integer from 1 to 19, the sum of n3 and n4 is from 4 to 20, the order of presence of the units enclosed in parentheses with n3 or n4 is arbitrary in formula (3).] Preferably, it contains a compound represented by the following formula (3).

[0130] In formula (3), R 7 represents, in each occurrence, independently of one another, a hydrogen atom or an organic group, R 8 represents, in each occurrence, independently of one another, a hydrogen atom or an organic group, R 9 represents, in each occurrence, independently of one another, a hydrogen atom or an organic group, R 10 represents, in each occurrence, independently of one another, a hydrogen atom or an organic group, R 11 represents, in each occurrence, independently of one another, a hydrogen atom or an organic group, R 12Each occurrence independently represents a hydrogen atom or an organic group.

[0131] R 7 、R 8 、R 9 、R 10 、R 11 またはR 12 Examples of the organic group represented by R 7 , R 8 , R 9 , R 10 , R 11 or R 12 include an alkyl group, an alkyloxy group, an alkyl ether group, a tosyl group, a triflate group, a phenyl group, etc. These groups may have one or more substituents.

[0132] R 7 、R 8 、R 9 、R 10 、R 11 またはR 12 Examples of the substituent that the organic group represented by R 7 , R 8 , R 9 , R 10 , R 11 or R 12 may have are not particularly limited. For example, reactive functional groups such as a hydroxyl group, an amino group, a carboxy group, a thiol group, an isocyanate group, a nitrile group, an epoxy group, an acetyl group; aliphatic hydrocarbon groups such as an alkyl group, a vinyl group, an ethynyl group, etc.

[0133] R 7 、R 8 、R 9 、R 10 、R 11 またはR 12 The alkyl group in R 7 , R 8 , R 9 , R 10 , R 11 or R 12 is preferably a C 1-30 alkyl group. Such an alkyl group may be linear or branched. In one embodiment, the C 1-30 alkyl group can be a C 1-20 alkyl group, preferably a C 1-10 alkyl group, more preferably a C 1-30 alkyl group. In another embodiment, the C 1-30 alkyl group can be a C 17-30 alkyl group, preferably a C 18-30 alkyl group, more preferably a C 26-30 alkyl group.

[0134] R 7 、R 8 、R​​​​​​​​​​​​​​​​​​9 , R 10 , R 11 or R 12 Examples of the substituent of the alkyl group in or R include a halogen atom; a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 3-10 cycloalkyl group, a C 3-10 unsaturated cycloalkyl group, a 5- to 10-membered heterocyclyl group, a C 6-10 aryl group, and one or more groups selected from 5- to 10-membered heteroaryl groups.

[0135] The above R 7 , R 8 , R 9 , R 10 , R 11 or R 12 The alkyloxy group in or R is typically a group represented by -O-R 21 (wherein R 21 is an alkyl group which may have one or more substituents).

[0136] The alkyl group in R 21 may be substituted with the above-described substituents, preferably may be substituted with a fluorine atom. Such an alkyl group is preferably a C 1-30 alkyl group. Such an alkyl group may be linear or branched. In one embodiment, the C 1-30 alkyl group may be a C 1-20 alkyl group, preferably a C 1-10 alkyl group, more preferably a C 1-3 alkyl group.

[0137] The above R 7 , R 8 , R 9 , R 10 , R 11 or R 12The alkyl ether group in [description] is a compound having one or more ether oxygen atoms in the molecular chain of the above alkyl group. Such an alkyl ether group is typically -R 26 -R 27 -(O-R 28 ) m -R 29 represented by the group. In the formula, R 26 is a single bond or an oxygen atom. R 27 is a single bond or a C 1-10 alkylene group. R 28 is a C 1-10 alkylene group. R 29 is a hydrogen atom or a C 1-10 alkyl group. m represents an integer from 1 to 20, preferably from 1 to 10, more preferably from 1 to 5, and even more preferably from 1 to 3.

[0138] In one embodiment, the organic group represented by the above R 7 , R 8 , R 9 , R 10 , R 11 or R 12 can be an alkyl group, an alkyloxy group, or an alkyl ether group whose terminal is substituted by a reactive functional group. Note that such a group may be further substituted by another substituent.

[0139] The reactive functional group is not particularly limited, and examples thereof include a hydroxyl group, an amino group, a carboxyl group, a thiol group, an isocyanate group, a vinyl group, an acetylene group, a nitrile group, an epoxy group, and the like.

[0140] In one embodiment, preferably, R 7 represents a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, R 8 represents a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, R 9 represents a C 1-30 alkyl group which may have one or more substituents or a hydrogen atom, R10 represents a C alkyl group or a hydrogen atom which may have one or more substituents, and R 1-30 represents a C alkyl group or a hydrogen atom which may have one or more substituents, and R 11 represents a C alkyl group or a hydrogen atom which may have one or more substituents, and R 1-30 represents a C alkyl group or a hydrogen atom which may have one or more substituents, and R 12 represents a C alkyl group or a hydrogen atom which may have one or more substituents, and R 1-30 represents a C alkyl group or a hydrogen atom which may have one or more substituents.

[0141] n3 is preferably from 1 to 19, more preferably from 1 to 9, still more preferably from 1 to 6, and even more preferably from 1 to 5. n4 is preferably from 1 to 19, more preferably from 1 to 9, still more preferably from 1 to 6, and even more preferably from 1 to 5. n3 + n4 is preferably from 4 to 20, more preferably from 4 to 10, still more preferably from 4 to 7, and even more preferably from 5 to 6.

[0142] The above formula (3) is preferably the following formula (3-A):

[0143]

Chemical formula

[0144] [In formula (3-A), R 7a each occurrence independently represents a C alkyl group or a hydrogen atom which may have one or more substituents, and 1-30 R each occurrence independently represents a C alkyl group or a hydrogen atom which may have one or more substituents, and 8a R 1-30 each occurrence independently represents a C alkyl group or a hydrogen atom which may have one or more substituents, and R 9a each occurrence independently represents a C alkyl group or a hydrogen atom which may have one or more substituents, and 1-30 R each occurrence independently represents a C alkyl group or a hydrogen atom which may have one or more substituents, and 10a R 1-30represents an alkyl group or a hydrogen atom, R 11a in each occurrence, independently represents a C 1-30 alkyl group which may have one or more substituents, or a hydrogen atom, R 12a in each occurrence, independently represents a C 1-30 alkyl group which may have one or more substituents, or a hydrogen atom, n3 is an integer from 1 to 19, n4 is an integer from 1 to 19, the sum of n3 and n4 is from 4 to 20, provided that the order of the units enclosed in parentheses with n3 or n4 is arbitrary in formula (3-A).] is represented by

[0145] In formula (3-A), R 7a in each occurrence, independently represents a C 1-30 alkyl group which may have one or more substituents, or a hydrogen atom, R 8a in each occurrence, independently represents a C 1-30 alkyl group which may have one or more substituents, or a hydrogen atom, R 9a in each occurrence, independently represents a C 1-30 alkyl group which may have one or more substituents, or a hydrogen atom, R 10a in each occurrence, independently represents a C 1-30 alkyl group which may have one or more substituents, or a hydrogen atom, R 11a in each occurrence, independently represents a C 1-30 alkyl group which may have one or more substituents, or a hydrogen atom, R 12a in each occurrence, independently represents a C 1-30 alkyl group which may have one or more substituents, or a hydrogen atom.

[0146] R 7a 、R 8a 、R9a , R 10a , R 11a or R 12a The alkyl group represented by is preferably a C 1-30 alkyl group. Such an alkyl group may be linear or branched. In one embodiment, the C 1-30 alkyl group is a C 1-20 alkyl group, preferably a C 1-10 alkyl group, more preferably a C 1-30 alkyl group. In another embodiment, the C 1-30 alkyl group is a C 17-30 alkyl group, preferably a C 18-30 alkyl group, more preferably a C 26-30 alkyl group.

[0147] R 7a , R 8a , R 9a , R 10a , R 11a or R 12a Examples of the substituent in the alkyl group represented by include a halogen atom; a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 3-10 cycloalkyl group, a C 3-10 unsaturated cycloalkyl group, a 5- to 10-membered heterocyclyl group, a C 6-10 aryl group, and one or more groups selected from 5- to 10-membered heteroaryl groups.

[0148] In one embodiment, R 7a , R 8a , R 9a , R 10a , R 11a and R 12a are preferably hydrogen atoms.

[0149] The above cyclic compound is preferably a compound represented by one or more selected from the formulas (1), (2), and (3), and more preferably may be a compound represented by one or more selected from the formulas (1-A), (2-A), and (3-A).

[0150] When two or more cyclic compounds are included in the above complex, the two or more cyclic compounds may be the same or different from each other.

[0151] The proportion of the above cyclic compound is preferably 0.01% by mass or more and 99% by mass or less, more preferably 0.1% by mass or more and 95% by mass or less, and even more preferably 1% by mass or more and 90% by mass or less in a total of 100 parts by mass of the fluorine-containing polymer and the cyclic compound described later. When the proportion of the cyclic compound is within the above range, the heat resistance and / or hydrophobicity of the complex is good.

[0152] The above fluorine-containing polymer may be any polymer containing a fluorine atom and may have one or more substituents. The above fluorine-containing polymer may preferably be a linear fluorine-containing polymer that may have one or more substituents. When the above fluorine-containing polymer is linear, it becomes easier for the fluorine-containing polymer to penetrate into the inside of the ring of the cyclic compound, and the formation of the complex may be facilitated.

[0153] The above polymer may preferably be a linear polymer. When the above polymer is linear, it becomes easier for the polymer to penetrate into the inside of the ring of the cyclic compound, and the formation of the complex may be facilitated.

[0154] In the present disclosure, the above polymer may have one or more substituents. Examples of the substituents that may be included in the above fluorine-containing polymer include -COOR f13 , -OR f13 , -NR f13 2, -NR f13 -CO-R f13 , -CO-NR f13 2, -NO2, -CN, -COR 14 , -SO2R f14, -O-COR f14 , C optionally substituted by one or more halogen atoms 1-5 One or more selected from an alkyl group and a halogen atom may be mentioned. The number of carbon atoms of such a substituent may preferably be 1 or more and 5 or less, more preferably 1 or more and 3 or less.

[0155] R f13 In each occurrence, each independently represents a C alkyl group optionally substituted by one or more halogen atoms or a hydrogen atom. 1-4 R f13 The "C alkyl group" in the C alkyl group optionally substituted by one or more halogen atoms represented by may be linear or branched, preferably a linear or branched C alkyl group, more preferably a linear C alkyl group. 1-4 alkyl group 1-4 alkyl group 1-3 alkyl group 1-3

[0156] The above R f13 The halogen atoms that may substitute the C alkyl group represented by include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferred. 1-4

[0157] In one aspect, the C alkyl group optionally substituted by one or more halogen atoms represented by R f13 is preferably a C alkyl group substituted by one or more halogen atoms, more preferably a C alkyl group substituted by one or more fluorine atoms, still more preferably a C 1-4 alkyl group 1-4 alkyl group 1-4 alkyl group 1-4 perfluoroalkyl group

[0158] The above R f13 In the C 1-4 ​​​The perfluoroalkyl group may be linear or branched, preferably linear or branched C 1-3 is a perfluoroalkyl group, more preferably linear C 1-3 perfluoroalkyl group, specifically CF3-, CF3CF2- or CF3CF2CF2-.

[0159] R f14 each occurrence independently represents a C 1-4 alkyl group, hydrogen atom or halogen atom which may be substituted by one or more fluorine atoms.

[0160] R f14 represents a C 1-4 alkyl group which may be substituted by one or more halogen atoms represented by 1-4 The "C 1-3 alkyl group" in the alkyl group may be linear or branched, preferably linear or branched C 1-3 alkyl group, more preferably linear C

[0161] The above R f14 represents a C 1-4 Examples of the halogen atom which may substitute the alkyl group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or a chlorine atom is preferable. In one embodiment, the C f14 alkyl group which may be substituted by one or more halogen atoms represented by the above R 1-4 is preferably a C 1-4 alkyl group substituted by one or more halogen atoms, more preferably a C 1-4 alkyl group substituted by one or more fluorine atoms, still more preferably C 1-4 perfluoroalkyl group.

[0162] The above R f14 in the C 1-4The perfluoroalkyl group may be linear or branched, preferably a linear or branched C 1-3 perfluoroalkyl group, more preferably a linear C 1-3 perfluoroalkyl group, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0163] The C which may be substituted by one or more halogen atoms as the above substituent 1-5 In the alkyl group, "C 1-5 alkyl group" may be linear or branched, preferably a linear or branched C 1-3 alkyl group, more preferably a linear C 1-3 alkyl group.

[0164] The C as the above substituent 1-5 Examples of the halogen atom which may substitute the alkyl group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or a chlorine atom is preferable. In one aspect, the C which may be substituted by one or more halogen atoms 1-5 alkyl group is preferably a C which is substituted by one or more halogen atoms 1-5 alkyl group, more preferably a C which is substituted by one or more fluorine atoms 1-5 alkyl group, still more preferably a C 1-4 perfluoroalkyl group.

[0165] The above C 1-4 perfluoroalkyl group may be linear or branched, preferably a linear or branched C 1-3 perfluoroalkyl group, more preferably a linear C 1-3 perfluoroalkyl group, specifically CF3-, CF3CF2- or CF3CF2CF2-.

[0166] Examples of the halogen atom as the above-mentioned substituent include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and a fluorine atom or a chlorine atom is preferable.

[0167] Examples of the fluorine-containing polymer include a fluorine-containing olefin-based polymer, a fluoropolyether, and a fluorine-containing acrylic polymer. The fluorine-containing polymer preferably contains one or more selected from a fluorine-containing olefin-based polymer and a fluoropolyether.

[0168] The fluorine-containing olefin-based polymer can be a polymer of a fluorine-containing olefin compound and has one or more repeating units formed from the fluorine-containing olefin compound.

[0169] The fluorine-containing olefin compound preferably has the following formula: CR f20 R f21 =CR f22 R f23 [wherein, R f20 represents one selected from a hydrogen atom, a fluorine atom, a chlorine atom, a C 1-5 fluoroalkyl group, and a C 1-5 perfluoroalkoxy group, R f21 represents one selected from a hydrogen atom, a fluorine atom, a chlorine atom, a C 1-5 fluoroalkyl group, and a C 1-5 perfluoroalkoxy group, R f22 represents one selected from a hydrogen atom, a fluorine atom, a chlorine atom, a C 1-5 fluoroalkyl group, and a C 1-5 perfluoroalkoxy group, R f23 represents one selected from a hydrogen atom, a fluorine atom, a chlorine atom, a C 1-5 fluoroalkyl group, and a C 1-5 perfluoroalkoxy group, R f20 ~R f23One or more of them are fluorine atoms. is represented by

[0170] In the above formula, R f20 represents one selected from a hydrogen atom, a fluorine atom, a chlorine atom, C 1-5 fluoroalkyl group and C 1-5 perfluoroalkoxy group, R f21 represents one selected from a hydrogen atom, a fluorine atom, a chlorine atom, C 1-5 fluoroalkyl group and C 1-5 perfluoroalkoxy group, R f22 represents one selected from a hydrogen atom, a fluorine atom, a chlorine atom, C 1-5 fluoroalkyl group and C 1-5 perfluoroalkoxy group, R f23 represents one selected from a hydrogen atom, a fluorine atom, a chlorine atom, C 1-5 fluoroalkyl group and C 1-5 perfluoroalkoxy group.

[0171] R f20 , R f21 , R f22 or R f23 The C 1-5 fluoroalkyl group represented by may be linear or branched, preferably a linear or branched C 1-5 fluoroalkyl group, particularly a C 1-3 fluoroalkyl group, more preferably a linear C 1-3 fluoroalkyl group. In one embodiment, R f20 , R f21 , R f22 or R f23 The C 1-5 fluoroalkyl group represented by is preferably a C 1-5 perfluoroalkyl group. The above C 1-5 perfluoroalkyl group may be linear or branched, preferably a linear or branched C 1-5 perfluoroalkyl group, particularly a C 1-3 perfluoroalkyl group, more preferably a linear C 1-3It may be a perfluoroalkyl group. R f20 、R f21 、R f22 or R f23 The C 1-5 fluoroalkyl group represented by is specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0172] R f20 、R f21 、R f22 or R f23 The C 1-5 perfluoroalkoxy group represented by may be linear or branched, preferably a linear or branched C 1-5 perfluoroalkoxy group, particularly a C 1-3 perfluoroalkoxy group, more preferably a linear perfluoroalkoxy group, specifically -O-CF3, -O-CF2CF3 or -O-CF2CF2CF3.

[0173] In one embodiment, preferably, R f20 is a fluorine atom or a hydrogen atom, R f21 is a fluorine atom or a hydrogen atom, R f22 is a fluorine atom or a hydrogen atom, R f23 can be a fluorine atom or a hydrogen atom. In another embodiment, preferably, R f20 is a fluorine atom or a hydrogen atom, R f21 is a fluorine atom or a hydrogen atom, R f22 is a fluorine atom or a hydrogen atom, R f23 is a C 1-5 perfluoroalkyl group or a C 1-5 perfluoroalkoxy group.

[0174] The above fluorine-containing olefin compound preferably contains one or more selected from tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, 1,2-difluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropene, vinyl fluoride, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, and perfluoropropyl vinyl ether.

[0175] In one aspect, the above fluorine-containing olefin compound can preferably be vinylidene fluoride.

[0176] Examples of the above fluorine-containing olefin polymer include one or more selected from chlorotrifluoroethylene / tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer, ethylene / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer, polyvinylidene fluoride, vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene / chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer, and poly-1,2-difluoroethylene. In one aspect, the above fluorine-containing olefin polymer contains one or more selected from polyvinylidene fluoride, vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene / chlorotrifluoroethylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer, and poly-1,2-difluoroethylene.

[0177] The number average molecular weight of the above fluorine-containing olefin polymer can preferably be 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 3,000 or more and 300,000 or less. In the present disclosure, the number average molecular weight of the fluorine-containing olefin polymer can be measured by gel permeation chromatography and can be measured as a conversion value using polystyrene as a standard sample.

[0178] The above fluoropolyether can be a polymer having oxyfluoroalkylene units. The above fluoropolyether preferably has the following formula: Y 1 -R f1 -R F -O q -R f2 -Y 2 [wherein: R F represents a divalent fluoropolyether group, Y 1 represents one selected from a halogen atom, a hydrogen atom, -COOR f3 -OR f3 -NR f3 2, -NR f3 -CO-R f3 -CO-NR f3 2, -NO2, -CN, -COR f4 -SO2R f4 and -O-COR f4 and represents one selected from the group consisting of, Y 2 represents one selected from a halogen atom, a hydrogen atom, -COOR f3 -OR f3 -NR f3 2, -NR f3 -CO-R f3 -CO-NR f3 2, -NO2, -CN, -COR f4 -SO2R f4 and -O-COR f4 and represents one selected from the group consisting of, R f1 represents a divalent hydrocarbon group which may have one or more substituents or a single bond, R f2 represents a divalent hydrocarbon group which may have one or more substituents or a single bond, R f3represents, independently at each occurrence, a C alkyl group which may have one or more substituents or a hydrogen atom, 1-16 and, R f4 represents, independently at each occurrence, a C alkyl group which may have one or more substituents, a hydrogen atom or a halogen atom, 1-16 and q is 0 or 1.] It is represented by

[0179] R F is preferably a group of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [wherein: R Fa represents, independently at each occurrence, a hydrogen atom, a fluorine atom or a chlorine atom, a, b, c, d, e and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of presence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula. However, when all R Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more.] is a group represented by

[0180] 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 a, b, c, e and f is 1 or more.

[0181] a, b, c, d, e and f are preferably each independently an integer from 0 to 100.

[0182] The sum of a, b, 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 a, b, 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.

[0183] These repeating units may be linear, branched, or may contain a ring structure. For example, -(OC6F 12 )- may be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10 )- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)- (i.e., in the above formula, R Fa is a fluorine atom) may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- may be any of -(OCF2CF2)- and -(OCF(CF3))-.

[0184] The above ring structure can be a three-membered ring, four-membered ring, five-membered ring, or six-membered ring below.

[0185]

Chem.

[0186] The above ring structure may preferably be a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.

[0187] The repeating unit having a ring structure may preferably be the following unit.

[0188]

Chem.

[0189] In one aspect, the above repeating unit is linear. By making the above repeating unit linear, the surface slipperiness, wear durability, etc. of the surface treatment layer can be improved.

[0190] In one aspect, the above repeating unit is branched. By making the above repeating unit branched, the coefficient of kinetic friction of the surface treatment layer can be increased.

[0191] In one aspect, R F is, in each occurrence, independently a group represented by any of the following formulas (f1) to (f7), and is preferably a group represented by the following formula (f7).

[0192] -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer from 1 to 200, and e is 0 or 1.];

[0193] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [wherein, c and d are each independently an integer of 0 or more and 30 or less, e and f are each independently an integer of 1 or more and 200 or less, the sum of c, d, e and f is 2 or more, the order of presence of each repeating unit enclosed in parentheses with subscript c, d, e or f is arbitrary in the formula.];

[0194] -(R 36 -R 37 ) g - (f3) [wherein, R 36 is OCF2 or OC2F4, R 37 is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, g is an integer of 2 to 100.];

[0195] -(R 36 -R 37 ) g -R r -(R 37’ -R 36’ ) g’ - (f4) [wherein, R 36 is OCF2 or OC2F4, R 37 is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, R 36’ is OCF2 or OC2F4, R 37’ is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100, g’ is an integer from 2 to 100, R r is

[0196] [Chemical formula] (wherein, * indicates the bonding position.) is;

[0197] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) [wherein, e is an integer from 1 to 200, and a, b, c, d, and f are each independently integers from 0 to 200, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.]

[0198] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f6) [wherein, f is an integer from 1 to 200, and a, b, c, d, and e are each independently integers from 0 to 200, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.];

[0199] -(CF2CF2CH2O) d - (f7) [wherein, d represents an integer from 1 to 200.]

[0200] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, still more preferably 15 to 50, for example, 25 to 35. OC3F6 in the above formula (f1) is preferably (OCF2CF2CF2), (OCF(CF3)CF2) or (OCF2CF(CF3)), more preferably (OCF2CF2CF2). (OC2F4) in the above formula (f1) is preferably (OCF2CF2) or (OCF(CF3)), more preferably (OCF2CF2). In one embodiment, e is 0. In another embodiment, e is 1.

[0201] In the above formula (f2), e and f are each independently preferably an integer of 5 to 200, more preferably 10 to 200. Also, 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. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f a group represented by -. In another embodiment, the formula (f2) may be a group represented by -(OC2F4) e -(OCF2) f -.

[0202] In the above formula (f3), R 36 is preferably OC2F4. In the above (f3), R 37is preferably a group selected from OC2F4, OC3F6 and OC4F8, or a combination of two or three groups independently selected from these groups, more preferably a group selected from OC3F6 and OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8 is not particularly limited, and examples thereof include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-, and -OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 may be either linear or branched, preferably linear. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g - or -(OC2F4-OC4F8) g -.

[0203] In the above formula (f4), R 36 , R 37 and g have the same meanings as described in the above formula (f3) and have the same embodiments. R 36’ , R 37’ and g' each have the same meanings as R 36 , R 37 and g described in the above formula (f3) and have the same embodiments. R r is preferably

[0204]

Chemical formula

[0205] [Chemical formula] [In the formula, * indicates the bonding position.] is.

[0206] In the above formula (f5), e is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0207] In the above formula (f6), f is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0208] In the above formula (f7), d is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less, still more preferably 10 or more and 100 or less.

[0209] In one aspect, the above R F is a group represented by the above formula (f1).

[0210] In one aspect, the above R F is a group represented by the above formula (f2).

[0211] In one aspect, the above R F is a group represented by the above formula (f3).

[0212] In one aspect, the above R F is a group represented by the above formula (f4).

[0213] In one aspect, the above R Fis a group represented by the above formula (f5).

[0214] In one aspect, the above R F is a group represented by the above formula (f6).

[0215] In one aspect, the above R F is a group represented by the above formula (f7).

[0216] In the above R F the ratio of e to f (hereinafter referred to as "e / f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By setting the e / f ratio to 10 or less, the slipperiness, wear durability, and chemical resistance (for example, durability against artificial sweat) of the surface treatment layer obtained from this compound are further improved. The smaller the e / f ratio, the more improved the slipperiness and wear durability of the surface treatment layer. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further enhanced. The larger the e / f ratio, the more improved the stability of the compound.

[0217] In the above R F The number average molecular weight of the part represented is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000. In this specification, the number average molecular weight of the part represented by R F is 19 the value measured by F-NMR.

[0218] In another aspect, the number average molecular weight of the part represented by R F is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 2,000 to 10,000, and can be, for example, 3,000 to 6,000.

[0219] In still another aspect, R FThe number average molecular weight of the moiety represented by can be from 4,000 to 30,000, preferably from 5,000 to 10,000, more preferably from 6,000 to 10,000.

[0220] R f1 In each occurrence, independently represents a divalent hydrocarbon group which may have one or more substituents or a single bond.

[0221] In the hydrocarbon group which may have one or more substituents, the "hydrocarbon group" is preferably a divalent C 1-20 hydrocarbon group, more preferably a divalent C 1-20 aliphatic hydrocarbon group, still more preferably a C 1-16 alkylene group.

[0222] The hydrocarbon group which may have one or more substituents is preferably a C 1-16 alkylene group which may have one or more substituents. A C 1-16 alkylene group which may be substituted by one or more fluorine atoms, in the "C 1-16 alkylene group", may be linear or branched, preferably a linear or branched C 1-10 alkylene group, more preferably a linear or branched C 1-6 alkylene group, still more preferably a linear or branched C 1-3 alkylene group, even more preferably a linear C 1-6 alkylene group, particularly a linear C 1-3 alkylene group.

[0223] Examples of the substituent which the hydrocarbon group may have include -COOR f13 、-OR f13 、-NR f13 2、-NR f13 -CO-R f13 、-CO-NR f13 2、-NO2、-CN、-COR 14 、-SO3R f14 、-O-COR f14and one or more selected from halogen atoms. R f13 and R f14 have the same meanings as defined above.

[0224] The substituent that the hydrocarbon group may have is preferably one or more selected from -COOH, -OH, -NH2, -CONR f13 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f14 and one or more selected from halogen atoms, more preferably a halogen atom, and still more preferably a fluorine atom or a chlorine atom.

[0225] In one embodiment, the hydrocarbon group which may have one or more substituents represented by the above R f1 is preferably a C 1-16 alkylene group which may be substituted by one or more fluorine atoms.

[0226] In the C 1-16 alkylene group which may be substituted by one or more fluorine atoms, the "C 1-16 alkylene group" may be linear or branched, preferably a linear or branched C 1-6 alkylene group, particularly a C 1-3 alkylene group, and more preferably a linear C 1-6 alkylene group, particularly a C 1-3 alkylene group.

[0227] The above R f1 is preferably a C 1-16 alkylene group substituted by one or more fluorine atoms, and more preferably a C 1-16 perfluoroalkylene group.

[0228] The above C 1-16 perfluoroalkylene group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkylene group, particularly a C 1-3It is a perfluoroalkylene group, more preferably a linear C 1-6 perfluoroalkylene group, especially C 1-3 perfluoroalkylene group, specifically -CF2-, -CF2CF2- or -CF2CF2CF2-.

[0229] In the above formula, R f2 represents a divalent hydrocarbon group or a single bond which may have one or more substituents.

[0230] In the hydrocarbon group which may have one or more substituents, the "hydrocarbon group" is preferably C 1-20 hydrocarbon group, more preferably C 1-20 aliphatic hydrocarbon group, still more preferably C 1-16 alkyl group.

[0231] The hydrocarbon group which may have one or more substituents is preferably a C 1-16 alkyl group which may have one or more substituents. A C 1-16 alkyl group which may be substituted by one or more fluorine atoms, the "C 1-16 alkyl group" may be linear or branched, preferably a linear or branched C 1-10 alkyl group, more preferably a linear or branched C 1-6 alkyl group, still more preferably a linear or branched C 1-3 alkyl group, even more preferably a linear C 1-6 alkyl group, especially a linear C 1-3 alkyl group.

[0232] Examples of the substituent which the hydrocarbon group may have include -COOR f13 , -OR f13 , -NR f13 2, -NR f13 -CO-R f13 , -CO-NR f13 2, -NO2, -CN, -COR 14 , -SO2R f14, -O-COR f14 and one or more selected from a halogen atom are included. R f13 and R f14 have the same meaning as described above.

[0233] The substituent that the hydrocarbon group may have is preferably -COOH, -OH, -NH2, -CONR f13 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f14 and one or more selected from a halogen atom, more preferably a halogen atom, and even more preferably a fluorine atom or a chlorine atom.

[0234] In one embodiment, the hydrocarbon group which may have one or more substituents represented by R f2 is preferably a C 1-16 alkyl group which may be substituted by one or more fluorine atoms.

[0235] In the C 1-16 alkyl group which may be substituted by one or more fluorine atoms, the "C 1-16 alkyl group" may be linear or branched, preferably a linear or branched C 1-6 alkyl group, particularly a C 1-3 alkyl group, more preferably a linear C 1-6 alkyl group, particularly a C 1-3 alkyl group.

[0236] The above R f2 is preferably a C 1-16 alkyl group substituted by one or more fluorine atoms, more preferably a C 1-16 perfluoroalkyl group.

[0237] The above C 1-16 perfluoroalkyl group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkyl group, particularly a C 1-3is a perfluoroalkyl group, more preferably a linear C 1-6 perfluoroalkyl group, especially C 1-3 perfluoroalkyl group, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0238] In the above formula, Y 1 represents one selected from a halogen atom, a hydrogen atom, -COOR f3 , -OR f3 , -NR f3 2, -NR f3 -CO-R f3 , -CO-NR f3 2, -NO2, -CN, -COR f4 , -SO2R f4 and -O-COR f4 represents one selected from the group consisting of. Also, in the above formula, Y 2 represents one selected from a halogen atom, a hydrogen atom, -COOR f3 , -OR f3 , -NR f3 2, -NR f3 -CO-R f3 , -CO-NR f3 2, -NO2, -CN, -COR f4 , -SO2R f4 and -O-COR f4 represents one selected from the group consisting of.

[0239] R f3 represents, in each occurrence, independently of one another, a C 1-16 alkyl group which may have one or more substituents or a hydrogen atom.

[0240] The "C 1-16 alkylene group" in the above-mentioned C 1-16 alkylene group which may be substituted by one or more fluorine atoms may be linear or branched, preferably a linear or branched C 1-6 alkylene group, especially C 1-3 alkylene group, more preferably a linear C 1-6 alkylene group, especially C 1-3 alkylene group.

[0241] The above R f3 The C represented by 1-16 Examples of the substituent that the alkylene group may have include -COOR f13 , -OR f13 , -NR f13 2, -NR f13 -CO-R f13 , -CO-NR f13 2, -NO2, -CN, -COR 14 , -SO3R f14 , -O-COR f14 and one or more selected from halogen atoms. R f13 and R f14 have the same meanings as described above.

[0242] The above R f3 The substituent that the C represented by 1-16 the alkylene group may have is preferably one or more selected from -COOH, -OH, -NH2, -CONR f13 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f14 and one or more selected from halogen atoms, more preferably a halogen atom, and even more preferably a fluorine atom or a chlorine atom.

[0243] In one aspect, the C f3 alkylene group which may have one or more substituents represented by the above R 1-16 may preferably be a C 1-16 alkylene group which may be substituted by one or more fluorine atoms.

[0244] The above R f3 alkylene group which may be substituted by one or more fluorine atoms represented by the above R 1-16 may preferably be a C 1-16 alkylene group which is substituted by one or more fluorine atoms, and more preferably a C 1-16 perfluoroalkylene group.

[0245] The above Rf3 C in 1-16 The perfluoroalkylene group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkylene group, especially C 1-3 is a perfluoroalkylene group, more preferably a linear C 1-6 perfluoroalkylene group, especially C 1-3 The perfluoroalkylene group is specifically -CF2-, -CF2CF2- or -CF2CF2CF2-.

[0246] R f4 In each occurrence, independently represents a C 1-16 alkyl group, hydrogen atom or halogen atom which may have one or more substituents.

[0247] The C 1-16 alkyl group which may have the above one or more substituents, the "C 1-16 alkyl group" may be linear or branched, preferably a linear or branched C 1-5 alkyl group, especially C 1-3 is an alkyl group, more preferably a linear C 1-6 alkyl group, especially C 1-3 is an alkyl group.

[0248] The above R f4 The substituents which the C 1-16 alkyl group represented by may have include -COOR f13 、-OR f13 、-NR f13 2、-NR f13 -CO-R f13 、-CO-NR f13 2、-NO2、-CN、-COR 14 、-SO2R f14 、-O-COR f14 and one or more selected from halogen atoms. R f13 and R f14 have the same meanings as above.

[0249] The above Rf4 C represented by 1-16 The substituent that the alkyl group may have is preferably -COOH, -OH, -NH2, -CONR f13 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f14 and one or more selected from halogen atoms, more preferably a halogen atom, and still more preferably a fluorine atom or a chlorine atom.

[0250] In one embodiment, the above R f4 C which may have one or more substituents represented by 1-16 The alkyl group may preferably be a C 1-16 alkyl group which may be substituted by one or more fluorine atoms.

[0251] The above R f4 C which may be substituted by one or more fluorine atoms represented by 1-16 The alkyl group is preferably a C 1-16 alkyl group substituted by one or more fluorine atoms, and more preferably a C 1-16 perfluoroalkyl group.

[0252] The above R f4 The C 1-16 perfluoroalkyl group in may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkyl group, particularly a C 1-3 perfluoroalkyl group, and more preferably a linear C 1-6 perfluoroalkyl group, particularly a C 1-3 perfluoroalkyl group, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0253] The halogen atom represented by the above Y 1 or Y 2 includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferred.

[0254] Y 1 is preferably one selected from -COOH, -OH, -NH2, -CONR f3 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f4 and a halogen atom. Y 2 is preferably one selected from -COOH, -OH, -NH2, -CONR f3 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f4 and a halogen atom.

[0255] In the above formula, q is 0 or 1. In one embodiment, q is 0, and in another embodiment, q is 1.

[0256] The number average molecular weight of the above fluoropolyether is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000. In the present specification, the number average molecular weight of the fluoropolyether is 19 measurable by 19F-NMR.

[0257] In another embodiment, the number average molecular weight of the fluoropolyether may be 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 2,000 to 10,000, for example 3,000 to 6,000.

[0258] In yet another embodiment, the number average molecular weight of the fluoropolyether may be 4,000 to 30,000, preferably 5,000 to 10,000, more preferably 6,000 to 10,000.

[0259] The above fluorine-containing polymer may be crystalline or amorphous. In one embodiment, in the differential scanning calorimetry of the fluorine-containing polymer, if a crystallization temperature is observed, it may be determined as a crystalline polymer, and if no crystallization temperature is observed, it may be determined as an amorphous polymer. In one embodiment, the above fluorine-containing polymer is crystalline. In another embodiment, the above fluorine-containing polymer is amorphous.

[0260] The above fluorine-containing polymer preferably has at least one of a glass transition temperature and a melting point at 50°C or higher. In other words, it is preferable that the glass transition temperature of the above fluorine-containing polymer is 50°C or higher, or the melting point of the above fluorine-containing polymer is 50°C or higher. Specifically, when the above fluorine-containing polymer is a crystalline polymer, since it has both a glass transition temperature and a melting point, it is sufficient that at least one of the glass transition temperature and the melting point is 50°C or higher. When the above fluorine-containing polymer is an amorphous polymer, since it has only a glass transition temperature, it is sufficient that the glass transition temperature is 50°C or higher. When the above fluorine-containing polymer has at least one of a glass transition temperature and a melting point at 50°C or higher, the resulting composite has good heat resistance. The above fluorine-containing polymer may, for example, have at least one of a glass transition temperature and a melting point at 70°C or higher and 400°C or lower, and further may have at least one of a glass transition temperature and a melting point at 150°C or higher and 300°C or lower.

[0261] The above fluorine-containing polymer may have a blocking site at the end, or may not have a blocking site. The blocking site may be a C 6-30 aromatic hydrocarbon group, or a C 6-30It may be an alicyclic hydrocarbon group. Examples of the blocking site include, for example, a dinitrophenyl group; cyclodextrin; an adamantyl group; a trityl group; fluorescein; pyrene; a phenyl group having one or more selected from an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, a cyano group, a sulfonyl group, a carboxy group, an amino group, and a phenyl group as substituents; steroids, etc. One or more selected from a dinitrophenyl group, cyclodextrin, an adamantyl group, a trityl group, fluorescein, and pyrene are preferred, and one or more selected from an adamantyl group and a trityl group are more preferred. The number of blocking sites contained in the fluorine-containing polymer may be 1 or more and 2 or less.

[0262] The number average molecular weight of the fluorine-containing polymer is, for example, 500 to 1,000,000, preferably 1,000 to 700,000, more preferably 2,000 to 500,000, even more preferably 2,000 to 300,000, and may be, for example, 3,000 to 300,000.

[0263] In one aspect, it is preferable that the cyclic compound contains a compound represented by the formula (1) and the fluorine-containing polymer contains a fluorine-containing olefin polymer.

[0264] The thermal decomposition temperature of the composite is preferably 170 °C or higher, more preferably 200 °C or higher, and may be, for example, 400 °C or lower. The composite of the present disclosure has good heat resistance and can be suitably used for applications requiring high heat resistance. In the present disclosure, the thermal decomposition temperature is the temperature at which the mass of the measurement object decreases by 5% by mass compared to the mass of the measurement object before the start of the measurement when thermogravimetric measurement is performed on a sample of about 10 mg in a nitrogen atmosphere with a nitrogen flow rate of 200 mL / min.

[0265] Let the thermal decomposition temperature of the composite be t x and the lower of the thermal decomposition temperature of the cyclic compound before forming the composite and the thermal decomposition temperature of the fluorine-containing polymer before forming the composite be t y When it is set as, tx -t y is preferably 50 °C or higher, may be 50 °C or higher and 300 °C or lower, and may further be 55 °C or higher and 250 °C or lower.

[0266] In the composite of the present disclosure, for some reason, the thermal decomposition temperature is greatly improved by complexing the polymer with a very small amount of the cyclic compound. For example, when the amount of the cyclic compound is 10 parts by mass or less with respect to 100 parts by mass of the polymer, the difference between the thermal decomposition temperature of the obtained composite and the thermal decomposition temperature of the polymer may preferably be 30 °C or higher, more preferably 50 °C or higher.

[0267] <Method for producing composite> The above composite can be produced by a production method including bringing a fluorine-containing polymer and the cyclic compound represented by the above formula (I) into contact with each other in the absence of a solvent to obtain a composite.

[0268] According to the production method of the present disclosure, since the contact is carried out in the absence of a solvent, it is easy to promote the inclusion of the fluorine-containing polymer by the cyclic compound regardless of the degree of progress of the complexation. When the contact is carried out in a solvent, when the fluorine-containing polymer is included in the cyclic compound, the solubility in the solvent changes there, and the complexation may not proceed. In the production method of the present disclosure, since no solvent is used, it is easy to obtain a desired composite without being affected by the change in solubility accompanying the progress of the complexation.

[0269] The contact method is not particularly limited, and examples thereof include methods using a ball mill, a rotating and revolving mixer, a homogenizer, ultrasonic dispersion, and the like.

[0270] The contact is preferably carried out at a temperature higher than at least one of the glass transition temperature and the melting point of the fluorine-containing polymer. Thereby, the fluorine-containing polymer is more easily deformed freely, and the composite can be produced more efficiently.

[0271] Preferably, the contact is carried out at a temperature preferably 5 °C or more, more preferably 10 °C or more higher than at least one of the glass transition temperature and the melting point of the fluorine-containing polymer. The difference between the temperature at which the contact is carried out and at least one of the glass transition temperature and the melting point of the fluorine-containing polymer can be, for example, 50 °C or less, more preferably 30 °C or less.

[0272] In the production method of the present disclosure, the fluorine-containing polymer and the cyclic compound are in contact with each other without a solvent, but the present disclosure is not limited thereto, and the contact may be carried out in the presence of a solvent. Examples of such a solvent include water, ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethyl sulfoxide, water, hydrogen peroxide, methylamine, sodium hydroxide solution, N-methylpyrrolidone ether, acetonitrile, benzyl chloride, triethylamine, or ethylene glycol, or a mixture thereof.

[0273] The composite of the present disclosure can be produced by the above production method, but is not limited to those produced by the above production method. Further, the above production method can produce the composite of the present disclosure, but is not limited to only the mode of producing the composite of the present disclosure.

[0274] <Composition> A composition containing the above composite is also included in the technical scope of the present disclosure. Such a composition may further contain one or more selected from resins, solvents, and other additives in addition to the above composite.

[0275] In such a composition, the content of the above composite can be preferably 0.1% by mass or more and less than 100% by mass, more preferably 1% by mass or more and 99% by mass or less in 100% by mass of the solid content of the composition.

[0276] Examples of the resin include acrylic resin, polyurethane resin, polyolefin resin, polyester resin, polyamide resin, vinyl chloride resin, styrene resin, vinyl ether resin, polyvinyl alcohol resin, polycarbonate resin, polysulfone resin, and the like.

[0277] Examples of the solvent include water, ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethyl sulfoxide, water, hydrogen peroxide, methylamine, sodium hydroxide solution, N-methylpyrrolidone ether, acetonitrile, benzyl chloride, triethylamine, or ethylene glycol, or a mixture thereof.

[0278] Examples of the additive include emulsifier, defoamer, surfactant, leveling agent, thickener, viscoelasticity modifier, defoamer, wetting agent, dispersant, preservative, plasticizer, penetrant, fragrance, bactericide, acaricide, fungicide, ultraviolet absorber, antioxidant, antistatic agent, flame retardant, dye, pigment, and the like.

[0279] The composition may be in powder form or liquid form. In one embodiment, the composition is in powder form, and in another embodiment, the composition is in liquid form.

Examples

[0280] The present invention will be described more specifically by the following examples, but the present invention is not limited thereto.

[0281] (Synthesis Example 1) Into a 2 L one-neck round-bottom flask, 25.0 g of the compound represented by the formula (1-2) and 350 mL of MeCN were placed, and a solution prepared by dissolving 122.9 g of oxone (2KHSO5·KHSO4·K2SO4) in 350 mL of water was added.

[0282]

Chemical formula

[0283] Next, 7.5 mL of iodobenzene was added, and the mixture was stirred vigorously at room temperature for 48 hours. Thereafter, the reaction solution was poured into water and filtered by suction. The obtained yellow precipitate was washed with a large amount of water and methanol and dried.

[0284] The 18.264 g of the washed and dried precipitate was first dissolved in 350 mL of boiling 1,1,2,2-tetrachloroethane, and the insoluble matter was removed by suction filtration. The obtained red transparent filtrate was allowed to stand at room temperature for 6 hours and then at 6 - 10 °C for 8 hours. The precipitated fine crystals were filtered by suction, washed three times with a small amount of 1,1,2,2-tetrachloroethane, further washed three times with a small amount of methanol, and dried to obtain the compound represented by formula (3-2).

[0285]

Chemical formula

[0286] The fact that the compound represented by formula (3-2) was obtained was 1 confirmed by 13 1H NMR, 1 13C NMR, time-of-flight mass spectrometer (ESI-TOF-MS), melting point measurement and IR measurement. 13 1H NMR (500.13 MHz, TFA-d, ppm): δ = 6.93 (s, 10H, CH), 3.61 (s, 10H, CH2). 13C NMR (125.72 MHz, TFA-d, ppm): δ = 190.5 (s, C=O), 146.8 (s, C-CH2), 138.1 (CH), 28.0 (CH2). HRMS (ESI-TOF-MS): 35 H 21 O 10 : 601.1129; found: 601.1132 m / z [M + Na]+ calcd for C 35 H 20 O 10Na: 623.0949; found: 623.0930 Melting point: Does not show a melting point and decomposes above 250 °C IR (Nujol mull, cm -1 ): 1654, 1610, 1461, 1377, 1286, 1250, 1125, 921, 722

[0287] Shows the structure of the cyclic compound used in the examples.

[0288]

Chem.

[0289] Shows the polymers used in the examples and comparative examples. PBR: As polybutadiene, a commercially available one with a weight-average molecular weight of 5,000, 80% cis- and trans-1,4, and 20% vinyl groups was used. A representative structural formula is shown below.

[0290]

Chem.

[0291] PVDF1: PVDF VP-832 manufactured by Daikin Industries, Ltd., melting point 178 °C, MFR at 230 °C under 10 kgf: 3.15 g / 10 min, molecular weight Mw 200,000 (GPC) PVDF2: PVDF Kyner HSV900 manufactured by Arkema, melting point 162 °C, MFR at 230 °C under 10 kgf: 0.2 g / 10 min

[0292] FPE: A fluorine-containing polyether represented by the following formula, with a number-average molecular weight of 4,400 to 5,000 and a melting point of 70 °C, was used. H-(CF2CF2CH2O) n -COOH

[0293] Shows the measurement methods used in the examples.

[0294] (1) NMR Measurements were carried out using an NMR measuring device (JEOL JNM-ECS400) manufactured by JEOL Ltd., Japan. 1 1H-NMR measurement conditions: 400 MHz (tetramethylsilane = 0 ppm)

[0295] (2) DSC Using a DSC (differential scanning calorimeter: Hitachi High-Tech Solutions Corporation, DSC7020), the temperature range from 30 °C to 200 °C was heated (first run) - cooled - heated (second run) at a rate of 10 °C / min.

[0296] (3) X-ray diffraction Measurements were carried out using a fully automatic multi-purpose X-ray diffractometer (SmartLab: manufactured by Rigaku Corporation) under the following conditions. · Measurement angle: 10 - 30° (light source: Cu / Kα, wavelength: 1.5418 Å) (4) Thermal decomposition temperature Using a TG / DTA analyzer (thermogravimetric differential thermal analyzer) (STA7200) manufactured by Hitachi High-Tech Solutions Corporation, for a 10 mg sample, measurements were carried out under measurement conditions consisting of a nitrogen gas atmosphere with a nitrogen flow rate of 200 mL / min, a temperature range from 23 °C to 600 °C, and a heating rate of 10 °C / min. The thermal decomposition temperature was defined as the temperature at which the mass of the measurement object decreased by 5% compared to the mass of the measurement object before the start of the measurement.

[0297] Example 1 (Complex of FPE and P5Q) After putting 0.65 g (5 mmol) of FPE into a 5 mL glass tube and heating it to 80 °C to completely melt the FPE. Then 0.06 g (0.1 mmol) of P5Q as a cyclic compound was added, and after standing at 80 °C for 15 hours, it was returned to room temperature to obtain a solid complex. The obtained complex was purified by washing a total of 5 times with 30 mL of diethyl ether, which is a good solvent for FPE. The purified complex was dissolved in acetone-d6 1 1H-NMR was measured, and peaks based on FPE and P5Q were observed. The results are shown in Figure 1. The results of FPE alone are also shown for comparison.

[0298] Also, when the ratio of the P5Q unit to the repeating unit unit of FPE was determined from the integration ratio of NMR, it was found that P5Q:FPE = 1:2 (molar ratio). This ratio was calculated from the ratio of the integrated value of the a hydrogen of FPE with a chemical shift of about 4.8 ppm (equivalent to 2 H) to the integrated value of the b hydrogen of P5Q with a chemical shift of about 6.8 ppm (equivalent to 10 H).

[0299] Comparative Example 1 (Complex of PBR and C2P5A) After putting 0.27 g (5 mmol) of PBR (liquid polymer) into a 5 mL glass tube, 0.089 g (0.1 mmol) of C2P5A as a cyclic compound was added at room temperature, and after allowing to stand at room temperature for 15 hours, a liquid mixture was obtained. The obtained mixture was washed 4 times in total with 30 mL of hexane, which is a good solvent for PBR, to obtain a purified product. The purified product was dissolved in chloroform-d 1 When 1H-NMR was measured, no peak based on PBR was observed, and no complex was obtained. The results are shown in Figure 2. For comparison, the results of PBR alone are also shown.

[0300] Example 2 10 mg of PVDF1 as a polymer was weighed into a 5 mL sample bottle and heated to 200 °C. When PVDF was in a molten state, C2P5A as a cyclic compound was added in the amounts shown in Table 1, and they were sufficiently contacted using a spatula at 200 °C, held at 150 °C for 2 hours, and then returned to room temperature to obtain each complex. A table summarizing the blending ratios and types is shown below. Also, when the thermal decomposition temperature of each complex was measured, the thermal decomposition temperature of all complexes was 170 °C or higher.

[0301]

Table 1

[0302] Example 3 Each complex was obtained in the same manner as in Example 2, except that the polymer was changed to PVDF2 (HSV900) and the amount of the cyclic compound was changed as described in Table 2. When the thermal decomposition temperature of each complex was measured, the thermal decomposition temperature of all complexes was 170 °C or higher.

[0303]

Table 2

[0304] Example 4 Each complex was obtained in the same manner as in Example 2, except that the cyclic compound was changed to C5P5A.

[0305]

Table 3

[0306] Example 5 The results of DSC measurements for each complex obtained in Example 2, and as comparative data, the results of DSC measurements for C2P5A and PVDF1 alone are shown in Figure 3. From these results, it can be seen that as the addition amount of C2P5A increases, the melting point of PVDF1 (VP832) disappears. This is considered to be because the crystallization of PVDF itself is inhibited by the inclusion of C2P5A. Also, it can be seen that the crystallization temperature of C2P5A also shifts to a higher temperature as the amount of PVDF1 increases, and the melting point peak also disappears. This is considered to be because the temperature required for crystallization becomes higher due to the inclusion of C2P5A, and finally crystallization cannot occur.

[0307] Example 6 For each of the complexes obtained in Example 3, the results of DSC measurements, and as comparative data, the results of DSC measurements for C2P5A and PVDF2 alone are shown in Fig. 4. In Example 3, compared with Example 2, the polymer was changed from PVDF1 (VP832) to the low melting point type PVDF2 (HSV900), but the results were the same as in Example 2. The melting point disappearance of PVDF2 and the melting point disappearance of C2P5A were observed, suggesting the formation of an inclusion complex.

[0308] Example 7 The results of DSC measurements for each of the complexes obtained in Example 4 are shown in Fig. 5. In Example 4, compared with Example 2, the cyclic compound was changed from C2P5A to C5P5A, but the results were the same. The melting point disappearance of PVDF1 and the melting point disappearance of C5P5A were observed, suggesting the formation of an inclusion complex.

[0309] Example 8 The results of X-ray diffraction measurements for each of the complexes obtained in Example 2, and as comparative data, the results of X-ray diffraction measurements for C2P5A and PVDF1 alone are shown in Fig. 6. Similar to the DSC results, when C2P5A was added to PVDF1 (VP832) alone, the diffraction peak indicating the crystallinity of PVDF1 disappeared. In addition, a new long-period structure was confirmed around 2θ = 8° with the addition of C2P5A. Assuming this is the interplanar spacing of C2P5A included in PVDF1 and analyzing it, it can be said that one C2P5A is inserted for about four repeating structural units (monomer units) of PVDF1.

[0310] Example 9 The results of X-ray diffraction measurements for each of the complexes obtained in Example 3, and as comparative data, the results of X-ray diffraction measurements for C2P5A and PCDF2 alone are shown in Fig. 7. Similar to DSC, the type of polymer was changed from PVDF1 (VP832) to PVDF2 (HSV900), but similar to the DSC results, when C2P5A was added to PVDF2 (HSV900) alone, the diffraction peak indicating the crystallinity of PVDF disappeared. In addition, a new long-period structure was newly confirmed near 2θ = 8° by the addition of C2P5A. When analyzed assuming that this is the interplanar spacing of C2P5A incorporated in PVDF2, it can be said that one C2P5A is inserted for about four repeating structural units (monomer units) of PVDF2.

Claims

1. A composite comprising a fluorine-containing polymer and one or more cyclic compounds that inclusion-complex the fluorine-containing polymer, wherein the cyclic compound is represented by the following formula (I): 【Chemical 1】 [In formula (I), A, in each occurrence, is independently a divalent C containing one or more selected from among -OR and -CO each time, ４－５０ represents an organic group, R independently represents, in each occurrence, an organic group that may contain one or more fluorine atoms or a hydrogen atom, n represents an integer from 4 to 20. ] and contains a compound represented by the formula, wherein the number average molecular weight of the fluorine-containing polymer is 4,400 or more, and the thermal decomposition temperature is 170 ° C or higher.

2. The cyclic compound is represented by the following formulas (1) to (3): 【Chemical 2】 [In formula (1), R １ which, in each occurrence, independently represents a hydrogen atom or an organic group, R ２ each independently at each occurrence represents a hydrogen atom or an organic group, R ３ each occurrence independently represents a hydrogen atom or an organic group, R ４ represents, in each occurrence independently, a hydrogen atom or an organic group, n1 is an integer from 4 to 20. ] 【Chemical Formula 3】 [In formula (2), R ５ which, in each occurrence, independently represents a hydrogen atom or an organic group, R ６ each independently represents, in each occurrence, a hydrogen atom or an organic group, n2 is an integer from 4 to 20. ] 【Chemical 4】 [In formula (3), R ７ which, in each occurrence, independently represents a hydrogen atom or an organic group, R ８ represents, in each occurrence, independently of one another, a hydrogen atom or an organic group, R ９ which, in each occurrence, independently represents a hydrogen atom or an organic group, R １０ represents, independently at each occurrence, a hydrogen atom or an organic group, R １１ each independently at each occurrence represents a hydrogen atom or an organic group, R １２ each independently represents, in each occurrence, a hydrogen atom or an organic group, n3 is an integer from 1 to 19, n4 is an integer from 1 to 19, the sum of n3 and n4 is from 4 to 20, and the order of presence of the units enclosed in parentheses with n3 or n4 is arbitrary in formula (3). ] The composite according to claim 1, comprising a compound represented by any of the above.

3. In the formula (1), R １ ~R ４ One or more selected from are fluorine-containing organic groups, and the complex according to claim 2.

4. In the formula (1), R ３ and R ４ One or more selected from are hydrogen atoms, and the complex according to claim 2.

5. The cyclic compound is represented by the following formulas (1-A), (2-A) and (3-A): 【Chemical Formula 5】 [In formula (1-A), R １ａ represents, independently at each occurrence, a C １－３０ alkyl group which may have one or more substituents, or a hydrogen atom, R ２ａ represents, in each occurrence independently, a C １－３０ alkyl group which may have one or more substituents or a hydrogen atom, R ３ａ represents, independently at each occurrence, a C １－３０ alkyl group which may have one or more substituents or a hydrogen atom, R ４ａ represents, independently at each occurrence, a C １－３０ alkyl group which may have one or more substituents or a hydrogen atom, n1 is an integer from 4 to 20. ] 【Chemical Formula 6】 [In formula (2-A), R ５ａ represents, independently at each occurrence, a C １－３０ alkyl group which may have one or more substituents, or a hydrogen atom, R ６ａ represents, independently at each occurrence, a C １－３０ alkyl group which may have one or more substituents or a hydrogen atom, n2 is an integer from 4 to 20. ] 【Chemical Formula 7】 [In formula (3-A), R ７ａ represents, in each occurrence independently, an optionally substituted C １－３０ alkyl group or a hydrogen atom, R ８ａ represents, independently at each occurrence, a C １－３０ alkyl group which may have one or more substituents or a hydrogen atom, R ９ａ represents, in each occurrence independently, a C １－３０ alkyl group which may have one or more substituents or a hydrogen atom, R １０ａ represents, in each occurrence independently, a C １－３０ alkyl group which may have one or more substituents or a hydrogen atom, R １１ａ represents, in each occurrence independently, a C １－３０ alkyl group which may have one or more substituents or a hydrogen atom, R １２ａ represents, in each occurrence independently, a C １－３０ alkyl group which may have one or more substituents, or a hydrogen atom, n3 is an integer from 1 to 19, n4 is an integer from 1 to 19, the sum of n3 and n4 is from 4 to 20, provided that the order of presence of the units enclosed in parentheses with n3 or n4 is arbitrary in formula (3-A). ] The composite according to claim 1, which is a compound represented by any of the above.

6. The composite according to claim 1, wherein the fluorine-containing polymer is a linear fluorine-containing polymer that may have one or more substituents.

7. The composite according to claim 1, wherein the fluorine-containing polymer includes a fluorine-containing olefin polymer.

8. The fluorine-containing olefin polymer is represented by the following formula: CR ｆ２０ R ｆ２１ =CR ｆ２２ R ｆ２３ [In the formula, R ｆ２０ represents one selected from a hydrogen atom, a fluorine atom, a chlorine atom, C １－５ a fluoroalkyl group and C １－５ a perfluoroalkoxy group, R ｆ２１ represents one selected from a hydrogen atom, a fluorine atom, a chlorine atom, C １－５ a fluoroalkyl group and C １－５ a perfluoroalkoxy group, R ｆ２２ represents one selected from a hydrogen atom, a fluorine atom, a chlorine atom, C １－５ fluoroalkyl group and C １－５ perfluoroalkoxy group, R ｆ２３ represents one selected from a hydrogen atom, a fluorine atom, a chlorine atom, C １－５ a fluoroalkyl group and C １－５ a perfluoroalkoxy group, R ｆ２０ to R ｆ２３ One or more of which is a fluorine atom.] The composite according to claim 7, which has a repeating unit formed from a fluorine-containing olefin compound represented by the formula.

9. The fluorine-containing olefin compound in the composite according to claim 8 is one or more selected from tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, 1,2-difluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropene, vinyl fluoride, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, and perfluoropropyl vinyl ether.

10. The fluorine-containing olefin polymer in the composite according to claim 7 contains one or more selected from chlorotrifluoroethylene / tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer, ethylene / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer, polyvinylidene fluoride, vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene / chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer, and poly-1,2-difluoroethylene.

11. The fluorine-containing olefin polymer in the composite according to claim 7 contains polyvinylidene fluoride.

12. The fluorine-containing polymer in the composite according to claim 1 contains a fluorine-containing polyether.

13. The fluorine-containing polyether is represented by the following formula: Y １ -R ｆ１ -R Ｆ -O ｑ -R ｆ２ -Y ２ [wherein: R Ｆ represents a divalent fluoropolyether group, Y １ represents one selected from a halogen atom, a hydrogen atom, -COOR ｆ３ , -OR ｆ３ , -NR ｆ３ ２ , -NR ｆ３ -CO-R ｆ３ , -CO-NR ｆ３ ２ , -NO ２ , -CN, -COR ｆ４ , -SO ３ R ｆ４ and -O-COR ｆ４ and represents one selected therefrom, Y ２ represents one selected from a halogen atom, a hydrogen atom, -COOR ｆ３ , -OR ｆ３ , -NR ｆ３ ２ , -NR ｆ３ -CO-R ｆ３ , -CO-NR ｆ３ ２ , -NO ２ , -CN, -COR ｆ４ , -SO ３ R ｆ４ and -O-COR ｆ４ and represents one selected therefrom, R ｆ１ represents a divalent hydrocarbon group or a single bond which may have one or more substituents, R ｆ２ represents a divalent hydrocarbon group or a single bond which may have one or more substituents, R ｆ３ represents, in each occurrence independently, a C １－１６ alkyl group which may have one or more substituents or a hydrogen atom, R ｆ４ represents, in each occurrence independently, a C １－１６ alkyl group which may have one or more substituents, a hydrogen atom or a halogen atom, q is 0 or 1.] in the composite according to claim 12.

14. R Ｆ is given by the following formula: -(OC ６ F １２ ) ａ -(OC ５ F １０ ) ｂ -(OC ４ F ８ ) ｃ -(OC ３ R Ｆａ ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - [wherein, R Ｆａ which, in each occurrence, is independently a hydrogen atom, a fluorine atom or a chlorine atom, a, b, c, d, e, and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more. The order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f attached is arbitrary in the formula. However, when all R Ｆａ is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f is 1 or more.] in the composite according to claim 13.

15. One or more Rs Ｆａ The complex according to claim 13, wherein Ｆａ is a hydrogen atom.

16. R Ｆ is represented by the following formula (f7): -(CF ２ CF ２ CH ２ O) ｄ -(f7) [wherein d represents an integer from 1 to 200.] in the composite according to claim 13.

17. The proportion of the cyclic compound is 0.01% by mass or more and 99% by mass or less in a total of 100 parts by mass of the fluorine-containing polymer and the cyclic compound in the composite according to claim 1.

18. The fluorine-containing polymer has at least one selected from the glass transition temperature and the melting point at 50°C or higher in the composite according to claim 1.

19. A method for producing the composite according to any one of claims 1 to 18, A production method comprising bringing the fluorine-containing polymer into contact with the cyclic compound represented by the formula (I) in the absence of a solvent to obtain the composite.

20. The production method according to claim 19, wherein the contact is carried out at a temperature higher than at least one of the glass transition temperature and the melting point of the fluorine-containing polymer.

21. A composition comprising the composite according to any one of claims 1 to 18.

22. The composition according to claim 21, which is in powder form.

23. The composition according to claim 21, which is in liquid form.

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