Pillararene composites

Abstract

The purpose of the present invention is to provide a composite which has excellent heat resistance and / or hydrophobicity and into which a functional group is easily introduced. A complex according to the present invention contains a fluorine-containing polymer and one or more cyclic compounds including the fluorine-containing polymer, wherein the cyclic compounds include a compound represented by formula (I). [In formula (I), A each independently represents a divalent C4-50 organic group containing one or more elements selected from the group consisting of-OR and-CO-at each occurrence, R each independently represents a hydrogen atom or an organic group optionally containing one or more fluorine atoms at each occurrence, and n represents an integer from 4 to 20. ] # imgabs0 #

Description

Technical Field

[0001] The invention relates to a pillararene complex. Background Art

[0002] As complexes formed by a cyclic compound and a polymer, rotaxane and pseudorotaxane are known. Rotaxane is a structure having a cyclic compound, a polymer penetrating the ring of the cyclic compound, and a capping site (capping group) disposed at the end of the polymer. Pseudorotaxane is a structure having a cyclic compound and a polymer penetrating the ring of the cyclic compound without a capping site at the end of the polymer.

[0003] As such a complex, Patent Document 1 describes an inclusion compound in which a fluoropolyether molecule as a guest compound is included in cyclodextrin.

[0004] Patent Document 2 describes a polyrotaxane having polyethylene glycol, a pillararene that includes the polyethylene glycol in a string-like manner, and adamantyl groups disposed at both ends of the polyethylene glycol.

[0005] Non-Patent Document 3 describes a rotaxane comprising pillararene and polyethylene or polypropylene enclosed by the pillararene.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. 2007 / 058247

[0009] Patent Document 2: Japanese Patent Application Publication No. 2021-138635

[0010] Non-patent literature

[0011] Non-patent document 1: Tomoki Ogoshi et al., "Extension of polyethylene chains byformation of polypseudorotaxane structures with perpentylated piller[5]arenes", Polymer Journal (2014) 46, 77-81. Summary of the invention

[0012] Technical problem to be solved by the invention

[0013] The currently known composites cannot fully satisfy the requirements of heat resistance and hydrophobicity, and the functional groups that can be introduced into the cyclic compound are limited.

[0014] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composite material which has excellent heat resistance and / or hydrophobicity and into which a functional group can be easily introduced.

[0015] Technical solutions for solving technical problems

[0016] The present invention includes the following aspects.

[0017] [1] A composite comprising a fluorinated polymer and one or more cyclic compounds enclosing the fluorinated polymer,

[0018] The above-mentioned cyclic compound includes a compound represented by the following formula (I):

[0019]

[0020] [In formula (I),

[0021] A, when present, independently represents a divalent C containing one or more selected from -OR and -CO- 4－50 Organic groups,

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

[0023] n represents an integer of 4 to 20. ].

[0024] [2] The complex according to [1], wherein the cyclic compound comprises a compound represented by any one of the following formulae (1) to (3):

[0025]

[0026] [In formula (1),

[0027] R 1 represents independently at each occurrence a hydrogen atom or an organic group,

[0028] R 2 represents independently at each occurrence a hydrogen atom or an organic group,

[0029] R 3 represents independently at each occurrence a hydrogen atom or an organic group,

[0030] R 4 represents independently at each occurrence a hydrogen atom or an organic group,

[0031] n1 is an integer from 4 to 20.]

[0032]

[0033] [In formula (2),

[0034] R 5 represents independently at each occurrence a hydrogen atom or an organic group,

[0035] R 6 represents independently at each occurrence a hydrogen atom or an organic group,

[0036] n2 is an integer from 4 to 20.]

[0037]

[0038] [In formula (3),

[0039] R 7 represents independently at each occurrence a hydrogen atom or an organic group,

[0040] R 8 represents independently at each occurrence a hydrogen atom or an organic group,

[0041] R 9 represents independently at each occurrence a hydrogen atom or an organic group,

[0042] R 10 represents independently at each occurrence a hydrogen atom or an organic group,

[0043] R 11 represents independently at each occurrence a hydrogen atom or an organic group,

[0044] R 12 represents independently at each occurrence a hydrogen atom or an organic group,

[0045] n3 is an integer from 1 to 19,

[0046] n4 is an integer from 1 to 19,

[0047] The total of n3 and n4 is 4 to 20,

[0048] The order of existence of the units marked with n3 or n4 and enclosed in parentheses is arbitrary in formula (3). ].

[0049] [3] The complex according to [2], wherein in the above formula (1), R 1 ~R 4 One or more of them is a fluorine-containing organic group.

[0050] [4] The complex according to [2] or [3], wherein in the above formula (1), R 3 and R 4One or more of them are hydrogen atoms.

[0051] [5] The complex according to any one of [1] to [4], wherein the cyclic compound is a compound represented by any one of the following formulae (1-A), (2-A) and (3-A),

[0052]

[0053] [In formula (1-A),

[0054] R 1a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0055] R 2a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0056] R 3a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0057] R 4a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0058] n1 is an integer from 4 to 20.]

[0059]

[0060] [In formula (2-A),

[0061] R 5a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0062] R 6a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0063] n2 is an integer from 4 to 20.]

[0064]

[0065] [In formula (3-A),

[0066] R 7aEach occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0067] R 8a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0068] R 9a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0069] R 10a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0070] R 11a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0071] R 12a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0072] n3 is an integer from 1 to 19,

[0073] n4 is an integer from 1 to 19,

[0074] The total of n3 and n4 is 4 to 20,

[0075] However, the order of existence of the units indicated by n3 or n4 and enclosed in parentheses is arbitrary in formula (3-A). ]

[0076] [6] The composite according to any one of [1] to [5], wherein the fluorinated polymer is a linear fluorinated polymer which may have one or more substituents.

[0077] [7] The composite according to any one of [1] to [6], wherein the fluorinated polymer comprises a fluorinated olefin polymer.

[0078] [8] The composite material according to [7], wherein the fluorinated olefin polymer has a repeating unit composed of a fluorinated olefin compound represented by the following formula:

[0079] CR f20 R f21 =CR f22 R f23

[0080] [Wherein,

[0081] R f20 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups,

[0082] R f21 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups,

[0083] R f22 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups,

[0084] R f23 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups,

[0085] R f20 ~R f23 One or more of them are fluorine atoms. ].

[0086] [9] The composite according to [8], wherein the fluorine-containing olefin compound is one or more selected from tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, 1,2-difluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, vinyl fluoride, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether and perfluoropropyl vinyl ether.

[0087]

[10] A composite as described in any one of [7] to [9], wherein the above-mentioned fluorine-containing olefin polymer comprises one or more selected from chlorotrifluoroethylene / tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymers, ethylene / tetrafluoroethylene copolymers, ethylene / chlorotrifluoroethylene copolymers, polyvinylidene fluoride, vinylidene fluoride / tetrafluoroethylene copolymers, vinylidene fluoride / tetrafluoroethylene / chlorotrifluoroethylene copolymers, polychlorotrifluoroethylene, vinylidene fluoride / hexafluoropropylene copolymers, vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymers and poly(1,2-difluoroethylene).

[0088]

[11] The composite according to any one of [7] to

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

[0089]

[12] The composite according to any one of [1] to

[11] , wherein the fluorinated polymer comprises a fluorinated polyether.

[0090]

[13] The composite material according to

[12] , wherein the fluorinated polyether is represented by the following formula:

[0091] Y 1 -R f1 -R F -O q -R f2 -Y 2

[0092] [Where:

[0093] R F represents a divalent fluorinated polyether group,

[0094] Y 1 represents 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 1 of

[0095] Y 2 represents 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 1 of

[0096] 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,

[0097] R f3 Each occurrence independently represents a C which may have one or more substituents. 1－16 Alkyl or hydrogen atom,

[0098] R f4 Each occurrence independently represents a C which may have one or more substituents. 1－16 an alkyl group, a hydrogen atom or a halogen atom,

[0099] q is 0 or 1. ].

[0100]

[14] The complex as described in

[13] , wherein R F It is expressed by the following formula:

[0101] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f -

[0102] [Wherein,

[0103] R Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence,

[0104] 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 indicated by a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary. Fa When it is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more. ].

[0105]

[15] The complex according to

[13] or

[14] , wherein one or more R Fa A hydrogen atom.

[0106]

[16] The complex according to any one of

[13] to

[15] , wherein R F It is represented by the following formula (f7),

[0107] -(CF2CF2CH2O) d - (f7)

[0108] [In the formula, d represents an integer of 1 to 200. ]

[0109]

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

[16] , wherein the proportion of the cyclic compound in 100 parts by mass of the total of the fluorinated polymer and the cyclic compound is 0.01% by mass to 99% by mass.

[0110]

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

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

[0111]

[19] The composite material according to any one of [1] to

[18] , wherein the thermal decomposition temperature of the composite material is 170° C. or higher.

[0112]

[20] A method for producing a composite, which is the method for producing a composite according to any one of [1] to

[19] , comprising the step of contacting the fluorinated polymer with the cyclic compound represented by the formula (I) in the absence of a solvent to obtain the composite.

[0113]

[21] The production method according to

[20] , wherein the contact is performed at a temperature higher than at least one of the glass transition temperature and the melting point of the fluorinated polymer.

[0114]

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

[19] .

[0115]

[23] The composition according to

[22] , which is in powder form.

[0116]

[24] The composition according to

[22] , which is in liquid form.

[0117] Effects of the Invention

[0118] The composite of the present invention is excellent in heat resistance and / or hydrophobicity, and can be easily introduced with a functional group. BRIEF DESCRIPTION OF THE DRAWINGS

[0119] Figure 1 The NMR spectrum of the composite obtained in Example 1 is shown.

[0120] Figure 2 The NMR spectrum of the purified product obtained in Comparative Example 1 is shown.

[0121] Figure 3 The DSC spectra of each composite obtained in Example 2 are shown.

[0122] Figure 4 The DSC spectra of each composite obtained in Example 3 are shown.

[0123] Figure 5 The DSC spectra of each composite obtained in Example 4 are shown.

[0124] Figure 6 The X-ray diffraction spectrum of each composite obtained in Example 2 is shown.

[0125] Figure 7 The X-ray diffraction spectrum of each composite obtained in Example 3 is shown. DETAILED DESCRIPTION

[0126] <Compound>

[0127] The composite of the present invention comprises a fluorinated polymer and one or more cyclic compounds enclosing the fluorinated polymer.

[0128] The above-mentioned cyclic compound includes a compound represented by the following formula (I):

[0129]

[0130] [In formula (I),

[0131] A, when present, independently represents a divalent C containing one or more selected from -OR and -CO- 4－50 Organic groups,

[0132] R, at each occurrence, independently represents an organic group which may contain one or more fluorine atoms or a hydrogen atom,

[0133] n represents an integer of 4 to 20. ].

[0134] Since the composite of the present invention contains a fluoropolymer and the above-mentioned cyclic compound, it has good heat resistance and / or hydrophobicity, and is easy to introduce functional groups. It is expected that the composite of the present invention maintains the heat resistance and hydrophobicity of the fluoropolymer, and is also easy to mix with various resins that cannot be mixed in the fluoropolymer monomer, for example. In addition, in the composite of the present invention, since the cyclic compound is not fixed by the fluoropolymer, it is also movable when mixed with the resin, for example, and it is expected to be able to exert characteristics such as impact absorption.

[0135] In the present invention, inclusion means that at least a portion of the fluoropolymer is present inside the ring of the cyclic compound. In one embodiment, the fluoropolymer may also penetrate the ring of the cyclic compound. In addition, the number of cyclic compounds that include one fluoropolymer may be one or more, preferably one in one embodiment, and preferably two or more in another embodiment. As an upper limit, each repeating unit of the polymer is 5 or less on average, or 3 or less, preferably 1 or less. 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 further preferably j or less.

[0136] In formula (I), A, at each occurrence, independently represents a divalent C 4－50 The organic group contains one or more selected from -OR and -CO-.

[0137] C 4－50 The organic group may preferably be C 4－20 An organic group, more preferably C4－10 Organic group.

[0138] In the present invention, a monovalent or divalent "organic group" means a monovalent or divalent group containing carbon. The monovalent or divalent organic group is not particularly limited and may be a hydrocarbon group or a derivative thereof. A derivative of a hydrocarbon group means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain. When referred to as an "organic group", it means a monovalent organic group.

[0139] In the present invention, a "hydrocarbon group" is a group containing carbon and hydrogen, and means a group in which one hydrogen atom is separated from a hydrocarbon. Such a hydrocarbon group is not particularly limited, and examples thereof include C 1－20 Hydrocarbon, such as C 1－20 Aliphatic hydrocarbon group, C 6－20 Aromatic hydrocarbon groups, etc. The above-mentioned "aliphatic hydrocarbon group" can be any of linear, branched or cyclic, and can also be any of saturated or unsaturated. In addition, the hydrocarbon group can also contain one or more ring structures. The hydrocarbon group can also have one or more substituents.

[0140] In the present invention, the substituent of the "hydrocarbon group" is not particularly limited, and examples thereof include: a halogen atom; a halogen atom selected from C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 Unsaturated cycloalkyl, 5-10 membered heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0141] The "divalent C" in the divalent organic group containing one or more divalent organic groups selected from -OR and -CO- represented by A is 4－50 The "organic group" may be preferably a divalent C 6－20 Aromatic hydrocarbon or divalent C 3－20 Alicyclic hydrocarbon group.

[0142] The above-mentioned 2-valent C 6－20 The aromatic hydrocarbon group may be preferably a divalent C 6－10 An aromatic hydrocarbon group, more preferably a divalent C 6－8 The aromatic hydrocarbon group is particularly preferably a phenylene group.

[0143] The above-mentioned 2-valent C 3－20 The alicyclic hydrocarbon group may be any of a saturated alicyclic hydrocarbon group and an unsaturated alicyclic hydrocarbon group. 3－20The alicyclic hydrocarbon group may preferably be a divalent C 6－10 An unsaturated alicyclic hydrocarbon group, more preferably a divalent C 6－8 The unsaturated hydrocarbon group is particularly preferably a cyclohexadienyl group.

[0144] The above-mentioned A contains one or more divalent C 4－50 The organic group may be independently selected from divalent C 6－20 Aromatic hydrocarbon group, C 3－20 A group in which a hydrogen atom bonded to a carbon atom constituting a ring in an alicyclic hydrocarbon group is substituted with -OR, and C 3－20 One of the groups in which -CH2- constituting the ring in the alicyclic hydrocarbon group is substituted with -CO- may more preferably be a divalent C 6－10 Aromatic hydrocarbon groups, and C 6－10 A group in which -CH2- constituting a ring in an alicyclic hydrocarbon group is replaced by -CO-.

[0145] The total number of -OR and -CO- contained in A is 1 to 4, and preferably 2.

[0146] R, at each occurrence, independently represents an organic group which may contain one or more fluorine atoms or a hydrogen atom.

[0147] Examples of the organic group represented by R include an alkyl group, an alkyloxy group, an alkyl ether group, a tosyl group, a trifluoromethanesulfonate group, and a phenyl group. These groups may have one or more substituents.

[0148] The substituents that the organic group represented by R may have are not particularly limited, and examples thereof include reactive functional groups such as hydroxyl, amino, carboxyl, thiol, isocyanate, nitrile, epoxy, and acetyl groups; aliphatic hydrocarbon groups such as alkyl, vinyl, and ethynyl groups; and halogen atoms. Examples of the halogen atoms include fluorine, chlorine, bromine, and iodine atoms, and preferably fluorine or chlorine atoms.

[0149] The alkyl group in R is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C 1－30 The alkyl group can be C 1－20 Alkyl, preferably C 1－10 Alkyl, more preferably C 1－30 In another embodiment, C 1－30 The alkyl group can be C 17－30 Alkyl, preferably C 18－30 Alkyl, more preferably C 26－30 alkyl.

[0150] As the substituent of the alkyl group in R, there can be mentioned: a halogen atom; a halogen atom which may be substituted with one or more halogen atoms and selected from C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 Unsaturated cycloalkyl, 5-10 membered heterocyclic group, C 6－10 One or more of 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 a fluorine atom or a chlorine atom is preferred.

[0151] The alkyloxy group in the above R is typically -O-R 21 (Where R 21 It is an alkyl group which may have one or more substituents.

[0152] R 21 The alkyl group in the above-mentioned group may be substituted by the above-mentioned substituent, preferably by a fluorine atom. The above-mentioned alkyl group is preferably a C 1－30 The alkyl group may be a straight chain or a branched chain. 1－30 The alkyl group can be C 1－20 Alkyl, preferably C 1－10 Alkyl, more preferably C 1－3 alkyl.

[0153] R 21 Preferably -R 22 -R 23 (Where R 22 For unsubstituted C 1－30 Alkylene, preferably C 1－20 Alkylene, more preferably C 1－10 Alkylene, R 23 C 1－10 Perfluoroalkyl, preferably C 1－6 Perfluoroalkyl. ) group.

[0154] The alkyl ether group in the above R is a compound having one or more etheric oxygen atoms in the molecular chain of the above alkyl group. The alkyl ether group is typically -R 26 -R 27 -(O-R 28 ) m -R 29 The group shown in the formula, R 26 is a single bond or an oxygen atom. 27 is a single bond or C 1－10 Alkylene. 28 C 1－10Alkylene. 29 A hydrogen atom or C 1－10 m represents an integer of 1 to 20, and is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0155] 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. In addition, the group may be substituted with other substituents.

[0156] 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 ethynyl group, a nitrile group, and an epoxy group.

[0157] In one embodiment, preferably R represents C which may have one or more substituents. 1－30 an alkyl group or a hydrogen atom.

[0158] n is 4 to 20, preferably 4 to 10, more preferably 4 to 7, and even more preferably 5 to 6. In one embodiment, n is 5. In another embodiment, n is 6.

[0159] The cyclic compound preferably includes a compound represented by any one of the following formulae (1) to (3):

[0160]

[0161] [In formula (1),

[0162] R 1 represents independently at each occurrence a hydrogen atom or an organic group,

[0163] R 2 represents independently at each occurrence a hydrogen atom or an organic group,

[0164] R 3 represents independently at each occurrence a hydrogen atom or an organic group,

[0165] R 4 represents independently at each occurrence a hydrogen atom or an organic group,

[0166] n1 is an integer from 4 to 20,

[0167] In a preferred embodiment, selected from R 1 ~R 4 One or more of the fluorine-containing organic groups are preferably fluorine-containing organic groups, more preferably C 2－6 A fluoroalkyl organic group,

[0168] In another preferred embodiment, selected from R 3 and R4 One or more of them may be hydrogen atoms, and more preferably R 3 and R 4 is a hydrogen atom.]

[0169]

[0170] [In formula (2),

[0171] R 5 represents independently at each occurrence a hydrogen atom or an organic group,

[0172] R 6 represents independently at each occurrence a hydrogen atom or an organic group,

[0173] n2 is an integer from 4 to 20.]

[0174]

[0175] [In formula (3),

[0176] R 7 represents independently at each occurrence a hydrogen atom or an organic group,

[0177] R 8 represents independently at each occurrence a hydrogen atom or an organic group,

[0178] R 9 represents independently at each occurrence a hydrogen atom or an organic group,

[0179] R 10 represents independently at each occurrence a hydrogen atom or an organic group,

[0180] R 11 represents independently at each occurrence a hydrogen atom or an organic group,

[0181] R 12 represents independently at each occurrence a hydrogen atom or an organic group,

[0182] n3 is an integer from 1 to 19,

[0183] n4 is an integer from 1 to 19,

[0184] The total of n3 and n4 is 4 to 20,

[0185] The order of existence of the units marked with n3 or n4 and enclosed in parentheses is arbitrary in formula (3). ].

[0186] When the cyclic compound is a compound represented by any one of the formulae (1) to (3), heat resistance and / or hydrophobicity are further improved, and it is easier to introduce a functional group, and the composite can be produced more efficiently.

[0187] In one embodiment, the cyclic compound preferably includes a compound represented by the following formula (1):

[0188]

[0189] [In formula (1),

[0190] R 1 represents independently at each occurrence a hydrogen atom or an organic group,

[0191] R 2 represents independently at each occurrence a hydrogen atom or an organic group,

[0192] R 3 represents independently at each occurrence a hydrogen atom or an organic group,

[0193] R 4 represents independently at each occurrence a hydrogen atom or an organic group,

[0194] n1 is an integer from 4 to 20. ].

[0195] In formula (1), R 1 Each occurrence independently represents a hydrogen atom or an organic group, R 2 Each occurrence independently represents a hydrogen atom or an organic group, R 3 Each occurrence independently represents a hydrogen atom or an organic group, R 4 Each occurrence independently represents a hydrogen atom or an organic group.

[0196] As R 1 , R 2 , R 3 or R 4 Examples of the organic group include an alkyl group, an alkyloxy group, an alkyl ether group, a tosyl group, a trifluoromethanesulfonate group, a phenyl group, and a fluorine-containing organic group. These groups may have one or more substituents.

[0197] As R 1 , R 2 , R 3 or R 4 The substituents that the organic groups shown may have are not particularly limited, and examples thereof include reactive functional groups such as hydroxyl, amino, carboxyl, thiol, isocyanate, nitrile, epoxy, and acetyl groups; and aliphatic hydrocarbon groups such as alkyl, vinyl, and ethynyl groups.

[0198] R 1 , R 2 , R 3 or R 4 The alkyl group in is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C 1－30 The alkyl group can be C 1－20 Alkyl, preferably C 1－10 Alkyl, more preferably C 1－30 In another embodiment, C 1－30 The alkyl group can be C 17－30 Alkyl, preferably C 18－30 Alkyl, more preferably C 26－30 alkyl.

[0199] As R 1 , R 2 , R 3 or R 4 The substituents of the alkyl group in the embodiment include: halogen atoms; alkyl groups selected from C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 Unsaturated cycloalkyl, 5-10 membered heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0200] The above R 1 , R 2 , R 3 or R 4 The alkyloxy group in the 21 (Where R 21 It is an alkyl group which may have one or more substituents.

[0201] R 21 The alkyl group in the above-mentioned group may be substituted by the above-mentioned substituent, preferably by a fluorine atom. The alkyl group is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C 1－30 The alkyl group can be C 1－20 Alkyl, preferably C 1－10 Alkyl, more preferably C 1－3 alkyl.

[0202] The above R 1 , R 2 , R 3 or R 4The alkyl ether group in is a compound having one or more etheric oxygen atoms in the molecular chain of the above-mentioned alkyl group. The alkyl ether group is typically -R 26 -R 27 -(O-R 28 ) m -R 29 The group shown in the formula, R 26 is a single bond or an oxygen atom. 27 is a single bond or C 1－10 Alkylene. 28 C 1－10 Alkylene. 29 A hydrogen atom or C 1－10 m represents an integer of 1 to 20, and is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0203] The above R 1 , R 2 , R 3 or R 4 The fluorine-containing organic group in the formula (a) may be preferably an organic group having a fluoroalkyl group with a carbon number of 2 or more, and more preferably a fluoroalkyl group or a fluoro(poly)ether group. The fluoroalkyl group is preferably C 1－10 Fluorinated alkyl, more preferably C 2－6 Fluorinated alkyl. The fluoroalkyl may be straight chain or branched chain, preferably straight chain. The fluoroalkyl is preferably a perfluoroalkyl. The fluoro(poly)ether group refers to a fluoroether group and / or a fluoropolyether group.

[0204] In one embodiment, the fluorine-containing organic group is a group represented by the following formula:

[0205] -(O p1 -R 20 q1 )-Rf a

[0206] [Where:

[0207] R 20 Each occurrence represents C independently 1－10 Alkylene.

[0208] R a Represents C 1－10 Fluorinated alkyl.

[0209] p1 is an integer from 0 to 2.

[0210] q1 is an integer from 0 to 3.

[0211] (O p1 -R 20 q1 ), O and R11a There is no restriction on the order in which they exist. ].

[0212] R 20 C 1－10 The alkylene group is preferably C 1－6 Alkylene, more preferably C 2－6 The alkylene group may be a straight chain or a branched chain, and is preferably a straight chain.

[0213] R a C 1－10 The fluoroalkyl group is preferably C 1－6 Fluorinated alkyl. The fluoroalkyl group may be straight chain or branched chain, preferably straight chain. The fluoroalkyl group is preferably a perfluoroalkyl group.

[0214] p1 is an integer of 0 to 2, and is preferably 1 or 2. In one embodiment, p1 is 1. In another embodiment, p1 is 2.

[0215] q1 is an integer of 0 to 3, preferably an integer of 1 to 3, and more preferably 1 or 2. In one embodiment, q1 is 1. In another embodiment, q1 is 2.

[0216] In a preferred embodiment, the fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a The groups shown.

[0217] [Where:

[0218] R 20 Each independently represents C 1－10 Alkylene.

[0219] R a Represents C 1－10 Fluorinated alkyl.

[0220] r1 is 0 or 1.]

[0221] In a more preferred embodiment, the fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a The groups shown.

[0222] [Where:

[0223] R 20 Each independently represents C 1－10 Alkylene.

[0224] R a Represents C 1－10 Perfluoroalkyl.

[0225] r1 is 0 or 1.]

[0226] n1 is an integer of 4 to 20, preferably an integer of 4 to 6, and more preferably 5 or 6.

[0227] In a particularly preferred embodiment,

[0228] R 13 and R 16 For-O-R 20 -(O-R 20 ) r1 -Rf a , R 14 and R 15 is a hydrogen atom, or

[0229] R 14 and R 15 For-O-R 20 -(O-R 20 ) r1 -Rf a , R 13 and R 16 is a hydrogen atom,

[0230] R 20 C 1－10 Alkylene, preferably C 1－6 Alkylene,

[0231] R a C 1－10 Perfluoroalkyl, preferably C 1－6 Perfluoroalkyl,

[0232] r1 is 0 or 1,

[0233] n1 is an integer of 4 to 6, and preferably 5 or 6.

[0234] 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. In addition, the group may be substituted with other substituents.

[0235] 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 ethynyl group, a nitrile group, and an epoxy group.

[0236] In one embodiment, preferably R 1 represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 2 represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R3 represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 4 represents a C which may have one or more substituents 1－30 an alkyl group or a hydrogen atom.

[0237] In a preferred embodiment, selected from R 1 ~R 4 One or more of the fluorine-containing organic groups are preferably fluorine-containing organic groups, more preferably C 2－6 An organic group of fluoroalkyl.

[0238] In other preferred embodiments, selected from R 3 and R 4 One or more of them may be hydrogen atoms, and more preferably R 3 and R 4 A hydrogen atom.

[0239] n1 is preferably 4 to 20, more preferably 4 to 10, further preferably 4 to 7, and still more preferably 5 to 6. In one embodiment, n1 is 5. In another embodiment, n1 is 6.

[0240] The above formula (1) is preferably represented by the following formula (1-A),

[0241]

[0242] [In formula (1-A),

[0243] R 1a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0244] R 2a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0245] R 3a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0246] R 4a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0247] n1 is an integer from 4 to 20. ].

[0248] In formula (1-A), R 1aEach occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 2a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 3a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 4a Each occurrence independently represents a C which may have one or more substituents. 1－30 an alkyl group or a hydrogen atom.

[0249] R 1a , R 2a , R 3a or R 4a The alkyl group shown is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C 1－30 The alkyl group can be C 1－20 Alkyl, preferably C 1－10 Alkyl, more preferably C 1－30 In another embodiment, C 1－30 The alkyl group can be C 17－30 Alkyl, preferably C 18－30 Alkyl, more preferably C 26－30 alkyl.

[0250] As R 1a , R 2a , R 3a or R 4a The substituents of the alkyl group shown in the figure include: halogen atoms; alkyl groups which may be substituted with one or more halogen atoms and selected from C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 Unsaturated cycloalkyl, 5-10 membered heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0251] In another embodiment, the above formula (1) can be represented by the following formula (1-A'):

[0252]

[0253] [In formula (1-A'),

[0254] R 13 represents independently at each occurrence a hydrogen atom or an organic group,

[0255] R 14 represents independently at each occurrence a hydrogen atom or an organic group,

[0256] R 15 represents independently at each occurrence a hydrogen atom or an organic group,

[0257] R 16 represents independently at each occurrence a hydrogen atom or an organic group,

[0258] n5 is an integer from 4 to 20,

[0259] Among them, R 13 , R 14 , R 15 and R 16 At least one of them is a fluorine-containing organic group,

[0260] R 14 and R 15 At least one of them is a hydrogen atom. ].

[0261] In the above formula (1-A'), R 13 Each occurrence is independently a hydrogen atom or an organic group, R 14 Each occurrence is independently a hydrogen atom or an organic group, R 15 Each occurrence is independently a hydrogen atom or an organic group, R 16 Each occurrence is independently a hydrogen atom or an organic group, R 13 , R 14 , R 15 and R 16 At least one of them is a fluorine-containing organic group.

[0262] As the above R 13 , R 14 , R 15 or R 16 Examples of the organic group include an alkyl group, an alkyloxy group, an alkyl ether group, a tosyl group, a trifluoromethanesulfonate group, and a phenyl group, which may be substituted with a substituent.

[0263] The substituent is not particularly limited, and examples thereof include: a halogen atom; a halogen atom selected from C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 unsaturated cycloalkyl, 5- to 10-membered heterocyclic group, 5- to 10-membered unsaturated heterocyclic group, C 6－10One or more of an aryl group, a 5- to 10-membered heteroaryl group, and a reactive functional group.

[0264] 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 ethynyl group, a nitrile group, and an epoxy group.

[0265] The above R 13 , R 14 , R 15 or R 16 The alkyl group in is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C 1－30 The alkyl group can be C 1－20 Alkyl, preferably C 1－10 Alkyl, more preferably C 1－30 In another embodiment, C 1－30 The alkyl group can be C 17－30 Alkyl, preferably C 18－30 Alkyl, more preferably C 26－30 alkyl.

[0266] As R 13 , R 14 , R 15 or R 16 The substituents of the alkyl group in the embodiment include: halogen atoms; alkyl groups selected from C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 Unsaturated cycloalkyl, 5-10 membered heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0267] The above R 13 , R 14 , R 15 or R 16 The alkyloxy group in the 21 (Where R 21 It is an alkyl group which may have one or more substituents.

[0268] R 21 The alkyl group in the above-mentioned group may be substituted by the above-mentioned substituent, preferably by a fluorine atom. The alkyl group is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C 1－30 The alkyl group can be C 1－20 Alkyl, preferably C1－10 Alkyl, more preferably C 1－3 alkyl.

[0269] R 21 Preferably -R 22 -R 23 (Where R 22 For unsubstituted C 1－30 Alkylene, preferably C 1－20 Alkylene, more preferably C 1－10 Alkylene, R 23 C 1－10 Perfluoroalkyl, preferably C 1－6 Perfluoroalkyl. ) group.

[0270] The alkyl ether group is a compound having one or more etheric oxygen atoms in the molecular chain of the alkyl group. The alkyl ether group is typically -R 26f -R 27f -(O-R 28f ) m1 -R 29f The group shown in the formula, R 26f is a single bond or an oxygen atom. 27f is a single bond or C 1－10 Alkylene. 28f C 1－10 Alkylene. 29f C can be substituted by fluorine atoms 1－10 An alkyl group or a hydrogen atom. m1 represents an integer of 1 to 20, and is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0271] 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. In addition, the group may be substituted with other substituents.

[0272] In one approach, R 13 and R 16 are independently an organic group, R 13 and R 16 At least one of them is a fluorine-containing organic group, or R 14 and R 15 are independently an organic group, R 14 and R 15 At least one of them is a fluorine-containing organic group.

[0273] R 14 and R 15 At least one of them is a hydrogen atom, and R 14 and R 15 is a hydrogen atom. 14 and R15 When at least one of the atoms is a hydrogen atom, the compound represented by formula (1-A') has -OH as a protogenic group. Therefore, it can be combined with a polymer containing one or more selected from -CO-, a nitrogen atom and a halogen atom.

[0274] In one approach, R 13 , R 14 , R 15 and R 16 At least two of them may be fluorinated organic groups, preferably R 13 , R 14 , R 15 and R 16 Two of them are fluorine-containing organic groups, and more preferably R 13 and R 16 It is a fluorine-containing organic group.

[0275] In one approach, R 14 and R 15 is a hydrogen atom, or R 13 and R 16 A hydrogen atom.

[0276] In a preferred embodiment, R 13 and R 16 are independently fluorinated organic groups, R 14 and R 15 A hydrogen atom.

[0277] The fluorinated organic group may be preferably an organic group having 2 or more carbon atoms and having a fluorinated alkyl group, and more preferably a fluorinated alkyl group or a fluorinated (poly)ether group. 1－10 Fluorinated alkyl, more preferably C 2－6 Fluorinated alkyl. The fluoroalkyl may be straight chain or branched chain, preferably straight chain. The fluoroalkyl is preferably a perfluoroalkyl. The fluoro(poly)ether group refers to a fluoroether group and / or a fluoropolyether group.

[0278] In one embodiment, the fluorine-containing organic group is a group represented by the following formula:

[0279] -(O p1 -R 20 q1 )-Rf a

[0280] [Where:

[0281] R 20 Each occurrence represents C independently 1－10 Alkylene.

[0282] R a Represents C1－10 Fluorinated alkyl.

[0283] p1 represents an integer from 0 to 2.

[0284] q1 represents an integer from 0 to 3.

[0285] (Op1-R 20 q1 ), O and R 11a There is no restriction on the order in which they exist. ].

[0286] R 20 C 1－10 The alkylene group is preferably C 1－6 Alkylene, more preferably C 2－6 The alkylene group may be a straight chain or a branched chain, and is preferably a straight chain.

[0287] R a C 1－10 The fluoroalkyl group is preferably C 1－6 Fluorinated alkyl. The fluoroalkyl group may be straight chain or branched chain, preferably straight chain. The fluoroalkyl group is preferably a perfluoroalkyl group.

[0288] p1 is an integer of 0 to 2, and is preferably 1 or 2. In one embodiment, p1 is 1. In another embodiment, p1 is 2.

[0289] q1 is an integer of 0 to 3, preferably an integer of 1 to 3, and more preferably 1 or 2. In one embodiment, q1 is 1. In another embodiment, q1 is 2.

[0290] In a preferred embodiment, the fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a The groups shown.

[0291] [Where:

[0292] R 20 Each independently represents C 1－10 Alkylene.

[0293] R a Represents C 1－10 Fluorinated alkyl.

[0294] r1 is 0 or 1.]

[0295] In a more preferred embodiment, the fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a The groups shown.

[0296] [Where:

[0297] R 20 Each independently represents C 1－10 Alkylene.

[0298] R a Represents C 1－10 Perfluoroalkyl.

[0299] r1 is 0 or 1.]

[0300] n1 is an integer of 4 to 20, preferably an integer of 4 to 6, and more preferably 5 or 6.

[0301] In a particularly preferred embodiment,

[0302] R 13 and R 16 For-O-R 20 -(O-R 20 ) r1 -Rf a , R 14 and R 15 is a hydrogen atom, or

[0303] R 14 and R 15 For-O-R 20 -(O-R 20 ) r1 -Rf a , R 13 and R 16 is a hydrogen atom,

[0304] R 20 C 1－10 Alkylene, preferably C 1－6 Alkylene,

[0305] R a C 1－10 Perfluoroalkyl, preferably C 1－6 Perfluoroalkyl,

[0306] r1 is 0 or 1,

[0307] n1 is an integer of 4 to 6, and preferably 5 or 6.

[0308] 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, a hydroxyl group is introduced into a predetermined position of pillar[n]arene and the hydroxyl group is reacted with a tosylate, a halide, or the like of an organic group having 2 or more carbon atoms and a fluoroalkyl group, thereby obtaining the compound represented by formula (1-A').

[0309] In one embodiment, preferably R 1a and R 2a is a hydrogen atom, R 3a and R 4a A hydrogen atom or a methyl group.

[0310] In another embodiment, the cyclic compound preferably includes a compound represented by the following formula (2):

[0311]

[0312] [In formula (2),

[0313] R 5 represents independently at each occurrence a hydrogen atom or an organic group,

[0314] R 6 represents independently at each occurrence a hydrogen atom or an organic group,

[0315] n2 is an integer from 4 to 20. ].

[0316] In formula (2), R 5 Each occurrence independently represents a hydrogen atom or an organic group, R 6 Each occurrence independently represents a hydrogen atom or an organic group.

[0317] As R 5 or R 6 Examples of the organic group include an alkyl group, an alkyloxy group, an alkyl ether group, a tosyl group, a trifluoromethanesulfonate group, and a phenyl group. These groups may have one or more substituents.

[0318] As R 5 or R 6 The substituents that the organic groups shown may have are not particularly limited, and examples thereof include reactive functional groups such as hydroxyl, amino, carboxyl, thiol, isocyanate, nitrile, epoxy, and acetyl groups; and aliphatic hydrocarbon groups such as alkyl, vinyl, and ethynyl groups.

[0319] R 5 or R 6 The alkyl group in is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C 1－30 The alkyl group can be C 1－20 Alkyl, preferably C 1－10 Alkyl, more preferably C 1－30 In another embodiment, C 1－30 The alkyl group can be C 17－30 Alkyl, preferably C 18－30 Alkyl, more preferably C26－30 alkyl.

[0320] As R 5 or R 6 The substituents of the alkyl group in the embodiment include: halogen atoms; alkyl groups selected from C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 Unsaturated cycloalkyl, 5-10 membered heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0321] The above R 5 or R 6 The alkyloxy group in the 21 (Where R 21 It is an alkyl group which may have one or more substituents.

[0322] R 21 The alkyl group in the above-mentioned group may be substituted by the above-mentioned substituent, preferably by a fluorine atom. The alkyl group is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C 1－30 The alkyl group can be C 1－20 Alkyl, preferably C 1－10 Alkyl, more preferably C 1－3 alkyl.

[0323] The above R 5 or R 6 The alkyl ether group in is a compound having one or more etheric oxygen atoms in the molecular chain of the above-mentioned alkyl group. The alkyl ether group is typically -R 26 -R 27 -(O-R 28 ) m -R 29 The group shown in the formula, R 26 is a single bond or an oxygen atom. 27 is a single bond or C 1－10 Alkylene. 28 C 1－10 Alkylene. 29 A hydrogen atom or C 1－10 m represents an integer of 1 to 20, and is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0324] 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. In addition, the group may be substituted with other substituents.

[0325] 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 ethynyl group, a nitrile group, and an epoxy group.

[0326] In one embodiment, preferably R 5 represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 6 represents a C which may have one or more substituents 1－30 an alkyl group or a hydrogen atom.

[0327] n2 is preferably 4 to 20, more preferably 4 to 10, further preferably 4 to 7, and still more preferably 5 to 6. In one embodiment, n2 is 5. In another embodiment, n2 is 6.

[0328] The above formula (2) is preferably represented by the following formula (2-A),

[0329]

[0330] [In formula (2-A),

[0331] R 5a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0332] R 6a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0333] n2 represents an integer from 4 to 20. ].

[0334] In formula (2-A), R 5a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 6a Each occurrence independently represents a C which may have one or more substituents. 1－30 an alkyl group or a hydrogen atom.

[0335] R 5a or R 6a The alkyl group shown is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C 1－30The alkyl group can be C 1－20 Alkyl, preferably C 1－10 Alkyl, more preferably C 1－30 In another embodiment, C 1－30 The alkyl group can be C 17－30 Alkyl, preferably C 18－30 Alkyl, more preferably C 26－30 alkyl.

[0336] As R 5a or R 6a The substituents in the alkyl group shown in the figure include: halogen atoms; alkyl groups which may be substituted with one or more halogen atoms and selected from C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 Unsaturated cycloalkyl, 5-10 membered heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0337] In one embodiment, preferably R 5a and R 6a A hydrogen atom.

[0338] In another embodiment, the cyclic compound preferably includes a compound represented by the following formula (3):

[0339]

[0340] [In formula (3),

[0341] R 7 represents independently at each occurrence a hydrogen atom or an organic group,

[0342] R 8 represents independently at each occurrence a hydrogen atom or an organic group,

[0343] R 9 represents independently at each occurrence a hydrogen atom or an organic group,

[0344] R 10 represents independently at each occurrence a hydrogen atom or an organic group,

[0345] R 11 represents independently at each occurrence a hydrogen atom or an organic group,

[0346] R 12 represents independently at each occurrence a hydrogen atom or an organic group,

[0347] n3 is an integer from 1 to 19,

[0348] n4 is an integer from 1 to 19,

[0349] The total of n3 and n4 is 4 to 20,

[0350] The order of existence of the units marked with n3 or n4 and enclosed in parentheses is arbitrary in formula (3). ].

[0351] In formula (3), R 7 Each occurrence independently represents a hydrogen atom or an organic group, R 8 Each occurrence independently represents a hydrogen atom or an organic group, R 9 Each occurrence independently represents a hydrogen atom or an organic group, R 10 Each occurrence independently represents a hydrogen atom or an organic group, R 11 Each occurrence independently represents a hydrogen atom or an organic group, R 12 Each occurrence independently represents a hydrogen atom or an organic group.

[0352] As R 7 , R 8 , R 9 , R 10 , R 11 or R 12 Examples of the organic group include an alkyl group, an alkyloxy group, an alkyl ether group, a tosyl group, a trifluoromethanesulfonate group, and a phenyl group. These groups may have one or more substituents.

[0353] As R 7 , R 8 , R 9 , R 10 , R 11 or R 12 The substituents that the organic groups shown may have are not particularly limited, and examples thereof include reactive functional groups such as hydroxyl, amino, carboxyl, thiol, isocyanate, nitrile, epoxy, and acetyl groups; and aliphatic hydrocarbon groups such as alkyl, vinyl, and ethynyl groups.

[0354] R 7 , R 8 , R 9 , R 10 , R 11 or R 12 The alkyl group in is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C 1－30 The alkyl group can be C 1－20 Alkyl, preferably C 1－10 Alkyl, more preferably C 1－30In another embodiment, C 1－30 The alkyl group can be C 17－30 Alkyl, preferably C 18－30 Alkyl, more preferably C 26－30 alkyl.

[0355] As R 7 , R 8 , R 9 , R 10 , R 11 or R 12 The substituents of the alkyl group in the embodiment include: halogen atoms; alkyl groups selected from C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 Unsaturated cycloalkyl, 5-10 membered heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0356] The above R 7 , R 8 , R 9 , R 10 , R 11 or R 12 The alkyloxy group in the 21 (Where R 21 It is an alkyl group which may have one or more substituents.

[0357] R 21 The alkyl group in the above-mentioned group may be substituted by the above-mentioned substituent, preferably by a fluorine atom. The alkyl group is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C 1－30 The alkyl group can be C 1－20 Alkyl, preferably C 1－10 Alkyl, more preferably C 1－3 alkyl.

[0358] The above R 7 , R 8 , R 9 , R 10 , R 11 or R 12 The alkyl ether group in is a compound having one or more etheric oxygen atoms in the molecular chain of the above-mentioned alkyl group. The alkyl ether group is typically -R 26 -R 27 -(O-R 28 ) m -R29 The group shown in the formula, R 26 is a single bond or an oxygen atom. 27 is a single bond or C 1－10 Alkylene. 28 C 1－10 Alkylene. 29 A hydrogen atom or C 1－10 m represents an integer of 1 to 20, and is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0359] In one embodiment, the above R 7 , R 8 , R 9 , R 10 , R 11 or R 12 The organic group shown may be an alkyl group, an alkyloxy group or an alkyl ether group substituted with a reactive functional group at the end. In addition, the group may also be substituted with other substituents.

[0360] 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 ethynyl group, a nitrile group, and an epoxy group.

[0361] In one embodiment, preferably R 7 represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 8 represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 9 represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 10 represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 11 represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 12 represents a C which may have one or more substituents 1－30 an alkyl group or a hydrogen atom.

[0362] n3 is preferably 1 to 19, more preferably 1 to 9, further preferably 1 to 6, and further preferably 1 to 5. n4 is preferably 1 to 19, more preferably 1 to 9, further preferably 1 to 6, and further preferably 1 to 5. n3+n4 is preferably 4 to 20, more preferably 4 to 10, further preferably 4 to 7, and further preferably 5 to 6.

[0363] The above formula (3) is preferably represented by the following formula (3-A),

[0364]

[0365] [In formula (3-A),

[0366] R 7a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0367] R 8a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0368] R 9a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0369] R 10a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0370] R 11a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0371] R 12a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0372] n3 is an integer from 1 to 19,

[0373] n4 is an integer from 1 to 19,

[0374] The total of n3 and n4 is 4 to 20,

[0375] However, the order of existence of the units indicated by n3 or n4 and enclosed in parentheses is arbitrary in formula (3-A). ]

[0376] In formula (3-A), R 7a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 8a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 9a Each occurrence independently represents a C which may have one or more substituents. 1－30Alkyl or hydrogen atom, R 10a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 11a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 12a Each occurrence independently represents a C which may have one or more substituents. 1－30 an alkyl group or a hydrogen atom.

[0377] R 7a , R 8a , R 9a , R 10a , R 11a or R 12a The alkyl group shown is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C 1－30 The alkyl group can be C 1－20 Alkyl, preferably C 1－10 Alkyl, more preferably C 1－30 In another embodiment, C 1－30 The alkyl group can be C 17－30 Alkyl, preferably C 18－30 Alkyl, more preferably C 26－30 alkyl.

[0378] As R 7a , R 8a , R 9a , R 10a , R 11a or R 12a The substituents in the alkyl group shown in the figure include: halogen atoms; alkyl groups which may be substituted with one or more halogen atoms and selected from C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 Unsaturated cycloalkyl, 5-10 membered heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0379] In one approach, R 7a , R 8a , R 9a , R 10a , R 11a and R 12a Preferred is a hydrogen atom.

[0380] The cyclic compound may preferably be one or more compounds selected from the group consisting of formulae (1), (2) and (3), and more preferably one or more compounds selected from the group consisting of formulae (1-A), (2-A) and (3-A).

[0381] When the complex contains two or more cyclic compounds, the two or more cyclic compounds may be the same or different.

[0382] In the total of 100 parts by mass of the fluorinated polymer and the cyclic compound described later, the proportion of the cyclic compound may be preferably 0.01% by mass to 99% by mass, more preferably 0.1% by mass to 95% by mass, and further preferably 1% by mass to 90% by mass. When the proportion of the cyclic compound is within the above range, the heat resistance and / or hydrophobicity of the composite are good.

[0383] The fluorinated polymer may be a polymer containing fluorine atoms and may have one or more substituents. The fluorinated polymer is preferably a linear fluorinated polymer having one or more substituents. Since the fluorinated polymer is linear, the fluorinated polymer easily penetrates the inside of the ring of the cyclic compound and can easily form a complex.

[0384] The polymer may be preferably a linear polymer. When the polymer is linear, the polymer easily penetrates the inside of the ring of the cyclic compound and can easily form a complex.

[0385] In the present invention, the polymer may have one or more substituents. Examples of the substituents that the fluorine-containing polymer 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 , C may be substituted by one or more halogen atoms 1－5 The substituent may preferably have 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.

[0386] R f13 Each occurrence independently represents a C which may be substituted with one or more halogen atoms. 1－4 an alkyl group or a hydrogen atom.

[0387] R f13The C shown may be substituted with one or more halogen atoms 1－4 The "C" in the alkyl 1－4 The "alkyl" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－3 Alkyl, more preferably a straight chain C 1－3 alkyl.

[0388] As can be seen in the above R f13 C shown 1－4 Examples of the halogen atom substituted on 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 preferred.

[0389] In one approach, R f13 The above-mentioned C may be substituted with one or more halogen atoms. 1－4 The alkyl group is preferably a C 1－4 Alkyl, more preferably C 1－4 Alkyl, preferably C 1－4 Perfluoroalkyl.

[0390] The above R f13 C 1－4 The perfluoroalkyl group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－3 Perfluoroalkyl, more preferably linear C 1－3 Perfluoroalkyl group, specifically CF3-, CF3CF2- or CF3CF2CF2-.

[0391] R f14 Each occurrence independently represents a C which may be substituted with one or more fluorine atoms. 1－4 an alkyl group, a hydrogen atom or a halogen atom.

[0392] R f14 The C shown may be substituted with one or more halogen atoms 1－4 The "C" in the alkyl 1－4 The "alkyl" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－3 Alkyl, more preferably a straight chain C 1－3 alkyl.

[0393] As can be seen in the above R f14 C shown 1－4 Examples of the halogen atom substituted on 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 preferred.

[0394] In one embodiment, the above R f14 The C shown may be substituted with one or more halogen atoms 1－4The alkyl group is preferably a C 1－4 Alkyl, preferably C 1－4 Alkyl, preferably C 1－4 Perfluoroalkyl.

[0395] The above R f14 C 1－4 The perfluoroalkyl group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－3 Perfluoroalkyl, more preferably linear C 1－3 Perfluoroalkyl group, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0396] C may be substituted with one or more halogen atoms as substituents 1－5 The "C" in the alkyl 1－5 The "alkyl" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－3 Alkyl, more preferably a straight chain C 1－3 alkyl.

[0397] As the above substituent, C 1－5 The halogen atom of the alkyl group may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a fluorine atom or a chlorine atom. 1－5 The alkyl group is preferably a C 1－5 Alkyl, more preferably C 1－5 Alkyl, preferably C 1－4 Perfluoroalkyl.

[0398] C 1－4 The perfluoroalkyl group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－3 Perfluoroalkyl, more preferably linear C 1－3 Perfluoroalkyl group, specifically CF3-, CF3CF2- or CF3CF2CF2-.

[0399] Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, an iodine atom and a bromine atom, and a fluorine atom or a chlorine atom is preferred.

[0400] Examples of the fluorine-containing polymer include fluorine-containing olefin polymers, fluorinated polyethers, and fluorinated acrylic polymers. The fluorine-containing polymer may preferably contain one or more selected from fluorine-containing olefin polymers and fluorinated polyethers.

[0401] The fluorine-containing olefin polymer may be a polymer of a fluorine-containing olefin compound, and may have one or two or more repeating units formed from the fluorine-containing olefin compound.

[0402] The fluorine-containing olefin compound is preferably represented by the following formula:

[0403] CR f20 R f21 =CR f22 R f23

[0404] [Wherein,

[0405] R f20 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups,

[0406] R f21 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups,

[0407] R f22 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups,

[0408] R f23 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups,

[0409] R f20 ~R f23 One or more of them are fluorine atoms. ].

[0410] In the above formula, R f20 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups, R f21 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups, R f22 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups, R f23 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5A type of perfluoroalkoxy group.

[0411] R f20 , R f21 , R f22 or R f23 C shown 1－5 The fluoroalkyl group may be a straight chain or a branched chain, and may preferably be a straight chain or a branched chain C 1－5 Fluorinated alkyl groups, especially C 1－3 Fluorinated alkyl, more preferably linear C 1－3 In one embodiment, R f20 , R f21 , R f22 or R f23 C shown 1－5 The fluoroalkyl group is preferably C 1－5 Perfluoroalkyl. 1－5 The perfluoroalkyl group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－5 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl, more preferably linear C 1－3 Perfluoroalkyl. f20 , R f21 , R f22 or R f23 C shown 1－5 Specific examples of the fluoroalkyl group include -CF3, -CF2CF3 and -CF2CF2CF3.

[0412] R f20 , R f21 , R f22 or R f23 C shown 1－5 The perfluoroalkoxy group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－5 Perfluoroalkoxy, especially C 1－3 The perfluoroalkoxy group is more preferably a linear perfluoroalkoxy group, specifically -O-CF3, -O-CF2CF3 or -O-CF2CF2CF3.

[0413] In one embodiment, 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 fluorine atom or a hydrogen atom. In another embodiment, 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 C 1－5 Perfluoroalkyl or C1－5 Perfluoroalkoxy.

[0414] The fluorine-containing olefin compound preferably includes one or more selected from tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, 1,2-difluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, vinyl fluoride, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether and perfluoropropyl vinyl ether.

[0415] In one embodiment, the fluorine-containing olefin compound may preferably be vinylidene fluoride.

[0416] As the fluorine-containing olefin polymer, the fluorine-containing olefin polymer may be 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 polyvinylidene fluoride. In one embodiment, the fluorine-containing olefin polymer includes 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 polyvinylidene fluoride.

[0417] The number average molecular weight of the fluorinated olefin polymer may preferably be from 1,000 to 1,000,000, more preferably from 2,000 to 500,000, and still more preferably from 3,000 to 300,000.

[0418] In the present invention, the number average molecular weight of the fluorinated olefin polymer can be measured by gel permeation chromatography, and can be measured as a value converted using polystyrene as a standard sample.

[0419] The fluoropolyether may be a polymer having an oxyfluoroalkylene unit. The fluoropolyether is preferably represented by the following formula:

[0420] Y 1 -R f1 -R F -O q -R f2 -Y 2

[0421] [Where:

[0422] R F represents a divalent fluorinated polyether group,

[0423] Y 1represents 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 1 of

[0424] Y 2 represents 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 1 of

[0425] 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,

[0426] R f3 Each occurrence independently represents a C which may have one or more substituents. 1－16 Alkyl or hydrogen atom,

[0427] R f4 Each occurrence independently represents a C which may have one or more substituents. 1－16 an alkyl group, a hydrogen atom or a halogen atom,

[0428] q is 0 or 1. ].

[0429] R F The preferred formula is: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - the group shown.

[0430] [Where:

[0431] R Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence,

[0432] 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 indicated by a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary. Fa When it is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more. ].

[0433] R Fa Preferably, it is a hydrogen atom or a fluorine atom, and more preferably, it is a fluorine atom. Fa When it is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more.

[0434] It is preferred that a, b, c, d, e and f are each independently an integer of 0 to 100.

[0435] The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, 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, further preferably 60 or less, for example, 50 or less or 30 or less.

[0436] These repeating units can be straight chain, branched chain, or contain ring structures. 12 )- can be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10)- may be any of -(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 The -(OCF2CF2CF2)- may be any of -(OCF(CF3)CF2)-, -(OCF2CF(CF3))-, and -(OCF2CF(CF3))-. The -(OC2F4)- may be any of -(OCF2CF2)-, and -(OCF(CF3))-.

[0437] The ring structure may be a three-membered ring, a four-membered ring, a five-membered ring or a six-membered ring.

[0438]

[0439] [Wherein, * represents the bonding position.]

[0440] The above ring structure may preferably be a four-membered ring, a five-membered ring or a six-membered ring, and more preferably a four-membered ring or a six-membered ring.

[0441] The repeating unit having a ring structure may preferably be the following units.

[0442]

[0443] [Wherein, * represents the bonding position.]

[0444] In one embodiment, the repeating unit is linear. By making the repeating unit linear, the surface smoothness and wear durability of the surface treatment layer can be improved.

[0445] In one embodiment, the repeating unit is branched. By making the repeating unit branched, the dynamic friction coefficient of the surface treatment layer can be increased.

[0446] In one approach, R F Each occurrence is independently a group represented by any one of the following formulae (f1) to (f7), preferably a group represented by the following formula (f7).

[0447] -(OC3F6) d -(OC2F4) e - (f1)

[0448] [Wherein, d is an integer from 1 to 200, and e is 0 or 1. ];

[0449] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2)

[0450] [wherein, c and d are each independently an integer from 0 to 30, e and f are each independently an integer from 1 to 200,

[0451] The sum of c, d, e and f is greater than 2,

[0452] The order of presence of the repeating units marked with the subscript c, d, e or f and enclosed in brackets in the formula is arbitrary. ];

[0453] -(R 36 -R 37 ) g - (f3)

[0454] [Where R 36 For OCF2 or OC2F4,

[0455] R 37 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0456] g is an integer from 2 to 100. ];

[0457] -(R 36 -R 37 ) g -R r -(R 37’ -R 36’ ) g’ - (f4)

[0458] [Where R 36 For OCF2 or OC2F4,

[0459] R 37 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12or a combination of 2 or 3 groups independently selected from these groups,

[0460] R 36’ For OCF2 or OC2F4,

[0461] R 37’ is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0462] g is an integer from 2 to 100,

[0463] g' is an integer from 2 to 100,

[0464] R r for

[0465]

[0466] (Where * represents the bonding position.) ];

[0467] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5)

[0468] [In the formula, e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[0469] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f6)

[0470] [In the formula, f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula. ];

[0471] -(CF2CF2CH2O) d - (f7)

[0472] [In the formula, d represents an integer of 1 to 200.]

[0473] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, further 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.

[0474] In the above formula (f2), e and f are each independently preferably an integer of 5 to 200, more preferably an integer of 10 to 200. In addition, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, 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 In another embodiment, formula (f2) may be -(OC2F4) e -(OCF2) f - the group shown.

[0475] In the above formula (f3), R 36 Preferably, it is OC2F4. In the above (f3), R 37It is preferably a group selected from OC2F4, OC3F6 and OC4F8, or a combination of two or three groups independently selected from these groups, and 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-, -OC2F 4OC2F4OC3F6-, -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 an integer of 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 It may be a straight chain or a branched chain, preferably a straight chain. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g - or - (OC2F4 - OC4F8) g -

[0476] In the above formula (f4), R 36 , R 37 and g have the same meanings as those in the above formula (f3) and have the same aspects. 36’ , R 37’ and g' respectively have the same meanings as R described in the above formula (f3). 36 , R 37 Same as g, in the same way. r Preferably

[0477]

[0478] [Wherein, * represents the bonding position.],

[0479] More preferably

[0480]

[0481] [Wherein, * represents the bonding position. ].

[0482] In the above formula (f5), e is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 to 100.

[0483] In the above formula (f6), f is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 to 100.

[0484] In the above formula (f7), d is preferably an integer of 1 to 100, more preferably 5 to 100, and even more preferably 10 to 100.

[0485] In one embodiment, the above R F It is a group represented by the above formula (f1).

[0486] In one embodiment, the above R F It is a group represented by the above formula (f2).

[0487] In one embodiment, the above R F It is a group represented by the above formula (f3).

[0488] In one embodiment, the above R F It is a group represented by the above formula (f4).

[0489] In one embodiment, the above R F It is a group represented by the above formula (f5).

[0490] In one embodiment, the above R F It is a group represented by the above formula (f6).

[0491] In one embodiment, the above R F It is a group represented by the above formula (f7).

[0492] In the above R F In the embodiment of the present invention, 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, further preferably 0.2 to 1.5, and further more preferably 0.2 to 0.85. By making the e / f ratio less than 10, the smoothness, wear durability and chemical resistance (for example, durability to artificial sweat) of the surface treatment layer obtained from the compound are further improved. The smaller the e / f ratio, the more the smoothness and wear durability of the surface treatment layer are improved. On the other hand, by making the e / f ratio greater than 0.1, the stability of the compound can be further improved. The larger the e / f ratio, the more the stability of the compound is improved.

[0493] The above RF The number average molecular weight of the moiety shown is not particularly limited, and is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. F The number average molecular weight of the parts shown is calculated using 19 The value measured by F-NMR.

[0494] In another way, R F The number average molecular weight of the moiety shown is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, further preferably 2,000 to 10,000, and for example, may be 3,000 to 6,000.

[0495] In another embodiment, R F The number average molecular weight of the moiety shown may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0496] R f1 Each occurrence independently represents a divalent hydrocarbon group which may have one or more substituents or a single bond.

[0497] The "hydrocarbon group" in the above-mentioned hydrocarbon group which may have one or more substituents may be preferably a divalent C 1－20 A hydrocarbon group, more preferably a divalent C 1－20 Aliphatic hydrocarbon group, more preferably C 1－16 Alkylene.

[0498] The hydrocarbon group which may have one or more substituents is preferably a C 1－16 Alkylene. C may be substituted with one or more fluorine atoms 1－16 The "C" in the alkylene 1－16 The "alkylene" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－10 Alkylene, more preferably a linear or branched C 1－6 Alkylene, more preferably a linear or branched C 1－3 Alkylene, more preferably a straight chain C 1－6 Alkylene, especially straight chain C 1－3 Alkylene.

[0499] Examples of the substituent that the hydrocarbon group may have include: -COOR f13 ,-OR f13 , -NR f13 2. -NR f13 -CO-Rf13 , -CO-NR f13 2. -NO2, -CN, -COR 14 ,-SO3R f14 , -O-COR f14 and halogen atoms. f13 and R f14 The meaning is the same as above.

[0500] The substituent that the above hydrocarbon group may have may be preferably selected from -COOH, -OH, -NH2, -CONR f13 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f14 and halogen atoms, more preferably a halogen atom, and still more preferably a fluorine atom or a chlorine atom.

[0501] In one embodiment, the above R f1 The hydrocarbon group which may have one or more substituents is preferably a C 1－16 Alkylene.

[0502] The above C may be substituted with one or more fluorine atoms 1－16 The "C" in the alkylene 1－16 The "alkylene" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Alkylene, especially C 1－3 Alkylene, more preferably a straight chain C 1－6 Alkylene, especially C 1－3 Alkylene.

[0503] The above R f1 Preferably, C is substituted with one or more fluorine atoms. 1－16 Alkylene, more preferably C 1－16 Perfluoroalkylene.

[0504] C 1－16 The perfluoroalkylene group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Perfluoroalkylene, especially C 1－3 Perfluoroalkylene, more preferably linear C 1－6 Perfluoroalkylene, especially C 1－3 Perfluoroalkylene is specifically -CF2-, -CF2CF2- or -CF2CF2CF2-.

[0505] In the above formula, R f2 It represents a divalent hydrocarbon group which may have one or more substituents or a single bond.

[0506] The "hydrocarbon group" in the above-mentioned hydrocarbon group which may have one or more substituents may preferably be C 1－20 Hydrocarbyl, more preferably C 1－20 Aliphatic hydrocarbon group, more preferably C 1－16 alkyl.

[0507] The hydrocarbon group which may have one or more substituents is preferably a C 1－16 Alkyl. C may be substituted with one or more fluorine atoms 1－16 The "C" in the alkyl 1－16 The "alkyl" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－10 Alkyl, more preferably a linear or branched C 1－6 Alkyl, more preferably a linear or branched C 1－3 Alkyl, more preferably a straight chain C 1－6 Alkyl groups, especially straight-chain C 1－3 alkyl.

[0508] Examples of the substituent that 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 halogen atoms. f13 and R f14 The meaning is the same as above.

[0509] The substituent that the above hydrocarbon group may have may be preferably selected from -COOH, -OH, -NH2, -CONR f13 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f14 and halogen atoms, more preferably a halogen atom, and still more preferably a fluorine atom or a chlorine atom.

[0510] In one approach, R f2 The hydrocarbon group which may have one or more substituents is preferably a C 1－16 alkyl.

[0511] The above C may be substituted with one or more fluorine atoms 1－16 The "C" in the alkyl 1－16The "alkyl" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Alkyl groups, especially C 1－3 Alkyl, more preferably a straight chain C 1－6 Alkyl groups, especially C 1－3 alkyl.

[0512] The above R f2 Preferably, C is substituted with one or more fluorine atoms. 1－16 Alkyl, more preferably C 1－16 Perfluoroalkyl.

[0513] C 1－16 The perfluoroalkyl group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl, more preferably linear C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl group, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0514] In the above formula, Y 1 represents 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 1 of them.

[0515] In addition, in the above formula, Y 2 represents 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 1 of them.

[0516] R f3 Each occurrence independently represents a C which may have one or more substituents. 1－16 an alkyl group or a hydrogen atom.

[0517] The above C may be substituted with one or more fluorine atoms 1－16 The "C" in the alkylene 1－16 The "alkylene" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Alkylene, especially C 1－3 Alkylene, more preferably a straight chain C 1－6 Alkylene, especially C 1－3 Alkylene.

[0518] As the above R f3 C shown 1－16 The substituent that the alkylene group may have is selected from -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 halogen atoms. f13 and R f14 The meaning is the same as above.

[0519] The above R f3 C shown 1－16 The substituent that the alkylene group may have may be preferably selected from -COOH, -OH, -NH2, -CONR f13 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f14 and halogen atoms, more preferably a halogen atom, and still more preferably a fluorine atom or a chlorine atom.

[0520] In one embodiment, the above R f3 The C shown may have one or more substituents. 1－16 The alkylene group is preferably a C 1－16 Alkylene.

[0521] The above R f3 The C shown may be substituted with one or more fluorine atoms 1－16 The alkylene group is preferably a C 1－16 Alkylene, more preferably C 1－16 Perfluoroalkylene.

[0522] The above R f3 C 1－16The perfluoroalkylene group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Perfluoroalkylene, especially C 1－3 Perfluoroalkylene, more preferably linear C 1－6 Perfluoroalkylene, especially C 1－3 Perfluoroalkylene is specifically -CF2-, -CF2CF2- or -CF2CF2CF2-.

[0523] R f4 Each occurrence independently represents a C which may have one or more substituents. 1－16 an alkyl group, a hydrogen atom or a halogen atom.

[0524] The above C which may have one or more substituents 1－16 The "C" in the alkyl 1－16 The "alkyl" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－5 Alkyl groups, especially C 1－3 Alkyl, more preferably a straight chain C 1－6 Alkyl groups, especially C 1－3 alkyl.

[0525] As the above R f4 C shown 1－16 The substituent that the alkyl group may have is selected from -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 halogen atoms. f13 and R f14 The meaning is the same as above.

[0526] The above R f4 C shown 1－16 The substituent that the alkyl group may have may be preferably selected from -COOH, -OH, -NH2, -CONR f13 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f14 and halogen atoms, more preferably a halogen atom, and still more preferably a fluorine atom or a chlorine atom.

[0527] In one embodiment, the above R f4 The C shown may have one or more substituents.1－16 The alkyl group may be preferably a C 1－16 alkyl.

[0528] The above R f4 The C shown may be substituted with one or more fluorine atoms 1－16 The alkyl group is preferably a C 1－16 Alkyl, more preferably C 1－16 Perfluoroalkyl.

[0529] The above R f4 C 1－16 The perfluoroalkyl group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl, more preferably linear C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl group, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0530] As the above Y 1 or Y 2 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or a chlorine atom is preferred.

[0531] Y 1 It may be preferably selected from -COOH, -OH, -NH2, -CONR f3 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f4 and halogen atoms.

[0532] Y 2 It may be preferably selected from -COOH, -OH, -NH2, -CONR f3 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f4 and halogen atoms.

[0533] In the above formula, q is 0 or 1. In one embodiment, q is 0, and in another embodiment, q is 1.

[0534] The number average molecular weight of the fluoropolyether is not particularly limited, and is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. 19 The measurement was performed by F-NMR.

[0535] In another embodiment, the number average molecular weight of the fluoropolyether is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, further preferably 2,000 to 10,000, and for example, may be 3,000 to 6,000.

[0536] In another embodiment, the number average molecular weight of the fluoropolyether may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0537] The fluorinated polymer may be crystalline or non-crystalline. In one embodiment, in differential scanning calorimetry of the fluorinated polymer, when a crystallization temperature is observed, the polymer may be determined to be a crystalline polymer, and when a crystallization temperature is not observed, the polymer may be determined to be a non-crystalline polymer. In one embodiment, the fluorinated polymer is crystalline. In another embodiment, the fluorinated polymer is non-crystalline.

[0538] The fluorinated polymer preferably has at least one of a glass transition temperature and a melting point above 50°C. In other words, it is preferred that the glass transition temperature of the fluorinated polymer is above 50°C, or the melting point of the fluorinated polymer is above 50°C. In detail, when the fluorinated polymer is a crystalline polymer, since it has both a glass transition temperature and a melting point, at least one of the glass transition temperature and the melting point can be above 50°C. When the fluorinated polymer is a non-crystalline polymer, since it only has a glass transition temperature, at least one of the glass transition temperature and the melting point can be above 50°C. Since the fluorinated polymer has at least one of a glass transition temperature and a melting point above 50°C, the heat resistance of the obtained composite is good. For example, the fluorinated polymer may have at least one of a glass transition temperature and a melting point above 70°C and below 400°C, and may also have at least one of a glass transition temperature and a melting point above 150°C and below 300°C.

[0539] The fluorinated polymer may or may not have a capping site at the end. The capping site may be a C 6－30 Aromatic hydrocarbon group, or C optionally having one or more substituents 6－30Alicyclic hydrocarbon group. Examples of the above-mentioned end-capping site include: dinitrophenyl; cyclodextrin; adamantyl; trityl; fluorescein; pyrene; phenyl having one or more selected from alkyl, alkoxy, hydroxyl, halogen atom, cyano, sulfonyl, carboxyl, amino and phenyl as a substituent; steroids, etc., preferably one or more selected from dinitrophenyl, cyclodextrin, adamantyl, trityl, fluorescein and pyrene, more preferably one or more selected from adamantyl and trityl. The number of end-capping sites contained in the above-mentioned fluorine-containing polymer may be 1 or more and 2 or less.

[0540] 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, further preferably 2,000 to 300,000, for example, 3,000 to 300,000.

[0541] In one embodiment, it is preferred that the cyclic compound includes a compound represented by formula (1), and the fluorinated polymer includes a fluorinated olefin polymer.

[0542] The thermal decomposition temperature of the composite is preferably 170° C. or higher, more preferably 200° C. or higher, and for example, may be 400° C. or lower. The composite of the present invention has excellent heat resistance and can be suitably used in applications requiring high heat resistance.

[0543] In the present invention, the thermal decomposition temperature is the temperature at which the mass of the sample to be measured decreases by 5% by mass compared with the mass of the sample before the start of the measurement when thermogravimetric measurement is performed on about 10 mg of the sample in a nitrogen atmosphere at a nitrogen flow rate of 200 mL / min.

[0544] Assume that the thermal decomposition temperature of the above-mentioned complex is t x t is the lower of the thermal decomposition temperature of the cyclic compound before forming the composite and the thermal decomposition temperature of the fluorinated polymer before forming the composite. y When t x -t y The temperature is preferably 50°C or higher, may be 50°C or higher and 300°C or lower, and may be 55°C or higher and 250°C or lower.

[0545] In the composite of the present invention, the reason is not clear, but the thermal decomposition temperature is greatly increased by compounding the polymer with a very small amount of the cyclic compound relative to the polymer. For example, when the amount of the cyclic compound is less than 10 parts by mass relative 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 is preferably 30°C or more, more preferably 50°C or more.

[0546] <Method for producing composite material>

[0547] The composite can be produced by a production method comprising the step of bringing the fluorinated polymer and the cyclic compound represented by the formula (I) into contact in the absence of a solvent to obtain the composite.

[0548] The manufacturing method of the present invention is used for contacting in the absence of a solvent, so that regardless of the degree of compounding, the inclusion of the cyclic compound to the fluorinated polymer is easy. When the contact is carried out in a solvent, when the fluorinated polymer is included by the cyclic compound, there may be a situation where the solubility in the solvent changes and compounding cannot be carried out. In the case of the manufacturing method of the present invention, since no solvent is used, it is not affected by the change in solubility as the compounding proceeds, and the desired composite is easily obtained.

[0549] The contact method is not particularly limited, and examples thereof include methods using a ball mill, a rotation / revolution mixer, a homogenizer, and ultrasonic dispersion.

[0550] 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 fluorinated polymer. This allows the fluorinated polymer to deform freely and more efficiently produce the composite.

[0551] 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 fluorinated polymer by preferably 5° C. or higher, more preferably 10° C. or higher. 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 fluorinated polymer may be, for example, 50° C. or lower, or 30° C. or lower.

[0552] In the production method of the present invention, the fluorinated polymer and the cyclic compound are contacted in the absence of a solvent, but the present invention is not limited thereto and the contact may be carried out in the presence of a solvent. 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.

[0553] The composite of the present invention can be produced by the above-mentioned production method, but is not limited to the production by the above-mentioned production method. In addition, although the above-mentioned production method can produce the composite of the present invention, it is not limited to the mode of producing the composite of the present invention.

[0554] <Composition>

[0555] A composition containing the above-mentioned complex is also included in the technical scope of the present invention.

[0556] The composition may contain, in addition to the above-mentioned complex, one or more selected from a resin, a solvent and other additives.

[0557] In the composition, the content of the complex may be preferably 0.1 mass % or more and less than 100 mass %, more preferably 1 mass % or more and 99 mass % or less, based on 100 mass % of the solid content of the composition.

[0558] Examples of the resin include acrylic resins, polyurethane resins, polyolefin resins, polyester resins, polyamide resins, vinyl chloride resins, styrene resins, vinyl ether resins, polyvinyl alcohol resins, polycarbonate resins, and polysulfone resins.

[0559] 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, ethylene glycol, and mixtures thereof.

[0560] Examples of the additives include emulsifiers, defoamers, surfactants, leveling agents, thickeners, viscoelasticity regulators, defoamers, wetting agents, dispersants, preservatives, plasticizers, penetrants, fragrances, bactericides, miticides, mildewicides, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments, and the like.

[0561] The composition may be in powder form or in liquid form. In one embodiment, the composition is in powder form; in another embodiment, the composition is in liquid form.

[0562] Example

[0563] The present invention will be described in more detail below with reference to the following examples, but the present invention is not limited to these examples.

[0564] (Synthesis example 1)

[0565] In a 2 L single-necked round-bottom flask, 25.0 g of the compound represented by formula (1-2) and 350 mL of MeCN were added, and a solution prepared by dissolving 122.9 g of potassium monopersulfate complex salt (OXONE) (2KHSO5·KHSO4·K2SO4) in 350 mL of water was added.

[0566]

[0567] Next, 7.5 mL of iodobenzene was added and the mixture was vigorously stirred at room temperature for 48 hours. The reaction solution was then poured into water and filtered by suction. The resulting yellow precipitate was washed with a large amount of water and methanol and then dried.

[0568] First, 18.264 g of the washed and dried precipitate was 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 allowed to stand at 6 to 10°C for 8 hours. The precipitated fine crystals were suction filtered, washed three times with a small amount of 1,1,2,2-tetrachloroethane, and then washed three times with a small amount of methanol, and then dried to obtain the compound represented by formula (3-2).

[0569]

[0570] pass 1 H NMR, 13 C NMR, time-of-flight mass spectrometry (ESI-TOF-MS), melting point measurement and IR measurement confirmed that the compound represented by formula (3-2) was obtained.

[0571] 1 H NMR (500.13MHz, TFA-d, ppm): δ = 6.93 (s, 10H, CH), 3.61 (s, 10H, CH2).

[0572] 13 C NMR (125.72MHz, TFA-d, ppm): δ = 190.5 (s, C = O), 146.8 (s, C-CH2), 138.1 (CH), 28.0 (CH2).

[0573] HRMS(ESI-TOF-MS):

[0574] m / z[M+Na]+(calculated for)C 35 H 21 O 10 Theoretical calculated value: 601.1129; measured value (found): 601.1132

[0575] m / z[M+Na]+C 35 H 20 O 10 Na theoretical calculated value: 623.0949; measured value: 623.0930

[0576] Melting point: No melting point is shown. It decomposes at temperatures above 250°C.

[0577] IR (paraffin paste (Nujol mull), cm -1 ):1654,1610,1461,1377,1286,1250,1125,921,722

[0578] The structures of the cyclic compounds used in Examples are shown.

[0579]

[0580] The polymers used in Examples and Comparative Examples are shown.

[0581] PBR: As polybutadiene, a commercially available product having a weight average molecular weight of 5,000, 80% of cis- and trans-1,4-bis-butylene and 20% of vinyl group was used. A representative structural formula is shown below.

[0582]

[0583] PVDF1: PVDF VP-832 manufactured by Daikin Industries, Ltd., melting point 178°C, MFR 230°C 10kgf: 3.15g / 10min, molecular weight Mw 200,000 (GPC)

[0584] PVDF2: PVDF Kyner HSV900 manufactured by Arkema, melting point 162°C, MFR 230°C 10kgf: 0.2g / 10min

[0585] FPE: A fluorine-containing polyether having a number average molecular weight of 4,400 to 5,000 and a melting point of 70° C. represented by the following formula was used.

[0586] H-(CF2CF2CH2O) n -COOH

[0587] The measuring methods used in the examples are shown.

[0588] (1) NMR

[0589] The measurement was performed using an NMR measuring apparatus manufactured by JEOL Ltd. (JEOL JNM-ECS400).

[0590] 1 H-NMR measurement conditions: 400 MHz (tetramethylsilane = 0 ppm)

[0591] (2)DSC

[0592] Using DSC (Differential Scanning Calorimeter: Hitachi High-tech Solutions, DSC7020), the temperature was increased (first run) - decreased - increased (second run) in the temperature range of 30° C. to 200° C. at 10° C. / min.

[0593] (3) X-ray diffraction

[0594] The measurement was performed under the following conditions using a fully automatic multifunctional X-ray diffractometer (SmartLab: manufactured by Rigaku Corporation).

[0595] ·Measurement angle: 10~30°(light source: Cu / Kα, wavelength: )

[0596] (4) Thermal decomposition temperature

[0597] The measurement was performed using a TG / DTA analyzer (thermogravimetric differential thermal analyzer) (STA7200) manufactured by Hitachi High-tech Solutions, Inc., for 10 mg of a sample in a nitrogen atmosphere at a nitrogen flow rate of 200 mL / min, in a temperature range of 23°C to 600°C and a temperature increase rate of 10°C / min. The thermal decomposition temperature is the temperature at which the mass of the object to be measured decreases by 5% compared to the mass of the object to be measured before the start of the measurement.

[0598] Example 1 (complex of FPE and P5Q)

[0599] After adding 0.65 g (5 mmol) of FPE to a 5 mL glass tube, the temperature was raised to 80°C to completely melt the FPE. 0.06 g (0.1 mmol) of P5Q as a cyclic compound was added thereto, and the mixture was left standing at 80°C for 15 hours, and then returned to room temperature to obtain a solid composite. The obtained composite was washed 5 times in total with 30 mL of diethyl ether as a good solvent for FPE for purification.

[0600] The purified complex was dissolved in acetone d6 and assayed 1 After H-NMR, peaks derived from FPE and P5Q were observed. The results are shown in Figure 1 For comparison, the results of FPE alone are also shown.

[0601] In addition, the ratio of the P5Q unit to the repeating unit of FPE was obtained from the integral ratio of NMR, which was P5Q:FPE=1:2 (molar ratio). This ratio was calculated from the ratio of the integral value of hydrogen a of FPE with a chemical shift of about 4.8 ppm (equivalent to H, 2) to the integral value of hydrogen b of P5Q with a chemical shift of about 6.8 ppm (equivalent to H, 10).

[0602] Comparative Example 1 (composite of PBR and C2P5A)

[0603] After adding 0.27 g (5 mmol) of PBR (liquid polymer) to a 5 mL glass tube, the mixture was kept at room temperature, and 0.089 g (0.1 mmol) of C2P5A as a cyclic compound was added. After standing at room temperature for 15 hours, a liquid complex was obtained. The obtained complex was washed 4 times with 30 mL of hexane, a good solvent for PBR, to obtain a purified product.

[0604] The purified product was dissolved in chloroform d and measured 1 After H-NMR, no peak derived from PBR was observed, and no composite was obtained. The results are shown in Figure 2 For comparison, the results for PBR alone are also shown.

[0605] Example 2

[0606] 10 mg of PVDF1 as a polymer was weighed in a 5 mL sample bottle and heated to 200°C. PVDF was molten, and the amount of C2P5A as a cyclic compound described in Table 1 was added, and the temperature was kept constant at 200°C, and a spatula was used to make it fully contacted, and it was kept at 150°C for 2 hours, and returned to room temperature to obtain each composite. The table summarizing the mixing ratio and type is shown below.

[0607] In addition, the thermal decomposition temperature of each composite was measured. As a result, the thermal decomposition temperature of all composites was 170° C. or higher.

[0608] [Table 1]

[0609]

[0610] Example 3

[0611] Each composite 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.

[0612] The thermal decomposition temperature of each composite was measured. As a result, the thermal decomposition temperature of all composites was 170° C. or higher.

[0613] [Table 2]

[0614]

[0615] Example 4

[0616] Each composite was obtained in the same manner as in Example 2 except that the cyclic compound was changed to C5P5A.

[0617] [Table 3]

[0618]

[0619] Example 5

[0620] The results of DSC measurement of each composite obtained in Example 2 and the results of DSC measurement of C2P5A and PVDF1 alone as comparative data are shown in FIG. Figure 3 .

[0621] The results show that the melting point of PVDF1 (VP832) gradually disappears as the amount of C2P5A added increases. This is thought to be because the inclusion of C2P5A inhibits the crystallization of PVDF itself.

[0622] It can also be seen that when the amount of PVDF1 increases, the crystallization temperature of C2P5A also shifts to a higher temperature, and the melting point peak gradually disappears. This is considered to be because the inclusion of C2P5A increases the temperature required for crystallization, and ultimately crystallization fails.

[0623] Example 6

[0624] The results of DSC measurement of each composite obtained in Example 3 and the results of DSC measurement of C2P5A and PVDF2 alone as comparative data are shown in FIG. Figure 4 In Example 3, although the polymer was changed from PVDF1 (VP832) to low melting point PVDF2 (HSV900) compared to Example 2, the results were the same as in Example 2, and the melting points of PVDF2 and C2P5A disappeared, indicating that an inclusion complex was generated.

[0625] Example 7

[0626] The results of DSC measurement of each composite obtained in Example 4 are shown in Figure 5 In Example 4, although the cyclic compound was changed from C2P5A to C5P5A compared with Example 2, the results were the same, and the melting points of PVDF1 and C5P5A disappeared, indicating that an inclusion complex was generated.

[0627] Example 8

[0628] The results of X-ray diffraction measurement of each composite obtained in Example 2 and the results of X-ray diffraction measurement of C2P5A and PVDF1 alone as comparative data are shown in FIG. Figure 6 .

[0629] Similar to the DSC results, the diffraction peak indicating the crystallinity of PVDF1 disappeared as C2P5A was gradually added from the use of PVDF1 (VP832) alone.

[0630] In addition, by adding C2P5A, a new long-period structure can be reconfirmed near 2θ = 8°. If it is assumed that the interplanar spacing of C2P5A contained in PVDF1 is analyzed, it can be said that one C2P5A is inserted for about four repeating structural units (monomer units) of PVDF1.

[0631] Example 9

[0632] The results of X-ray diffraction measurement of each composite obtained in Example 3 and the results of X-ray diffraction measurement of C2P5A and PCDF2 alone as comparative data are shown in FIG. Figure 7 .

[0633] Similar to DSC, although the type of polymer was changed from PVDF1 (VP832) to PVDF2 (HSV900), the diffraction peak representing the crystallinity of PVDF disappeared as C2P5A was gradually added from using PVDF2 (HSV900) alone.

[0634] In addition, by adding C2P5A, a new long-period structure can be reconfirmed near 2θ = 8°. If it is assumed that the interplanar spacing of C2P5A contained in PVDF2 is analyzed, it can be said that one C2P5A is inserted for about four repeating structural units (monomer units) of PVDF2.

Claims

1. A composite, characterized in that: Containing a fluorine-containing polymer and one or more cyclic compounds enclosing the fluorine-containing polymer, The cyclic compound includes a compound represented by the following formula (I): In formula (I), A, when present, independently represents a divalent C containing one or more selected from -OR and -CO- 4－50 Organic groups, R, at each occurrence, independently represents an organic group which may contain one or more fluorine atoms or a hydrogen atom, n represents an integer of 4 to 20.

2. The composite according to claim 1, characterized in that: The cyclic compound includes a compound represented by any one of the following formulae (1) to (3), In formula (1), R 1 represents independently at each occurrence a hydrogen atom or an organic group, R 2 represents independently at each occurrence a hydrogen atom or an organic group, R 3 represents independently at each occurrence a hydrogen atom or an organic group, R 4 represents independently at each occurrence a hydrogen atom or an organic group, n1 is an integer from 4 to 20; In formula (2), R 5 represents independently at each occurrence a hydrogen atom or an organic group, R 6 represents independently at each occurrence a hydrogen atom or an organic group, n2 is an integer from 4 to 20; In formula (3), R 7 represents independently at each occurrence a hydrogen atom or an organic group, R 8 represents independently at each occurrence a hydrogen atom or an organic group, R 9 represents independently at each occurrence a hydrogen atom or an organic group, R 10 represents independently at each occurrence a hydrogen atom or an organic group, R 11 represents independently at each occurrence a hydrogen atom or an organic group, R 12 represents independently at 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 total of n3 and n4 is 4 to 20, The order of existence of the units indicated by n3 or n4 and enclosed in parentheses is arbitrary in formula (3).

3. The composite according to claim 2, characterized in that: In the formula (1), R 1 ~R 4 One or more of them is a fluorine-containing organic group.

4. The composite according to claim 2 or 3, characterized in that: In the formula (1), R 3 and R 4 One or more of them are hydrogen atoms.

5. The composite according to any one of claims 1 to 4, characterized in that: The cyclic compound is a compound represented by any one of the following formulas (1-A), (2-A) and (3-A), In formula (1-A), R 1a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 2a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 3a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 4a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, n1 is an integer from 4 to 20; In formula (2-A), R 5a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 6a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, n2 is an integer from 4 to 20; In formula (3-A), R 7a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 8a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 9a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 10a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 11a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 12a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, n3 is an integer from 1 to 19, n4 is an integer from 1 to 19, The total of n3 and n4 is 4 to 20, However, the order of existence of the units indicated by n3 or n4 and enclosed in parentheses is arbitrary in formula (3-A).

6. The composite according to any one of claims 1 to 5, characterized in that: The fluorine-containing polymer is a linear fluorine-containing polymer which may have one or more substituents.

7. The composite according to any one of claims 1 to 6, characterized in that: The fluorine-containing polymer includes a fluorine-containing olefin-based polymer.

8. The composite according to claim 7, characterized in that: The fluorinated olefin polymer has a repeating unit composed of a fluorinated olefin compound represented by the following formula: CR f20 R f21 =CR f22 R f23 In the formula, R f20 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups, R f21 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups, R f22 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups, R f23 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5 One of the perfluoroalkoxy groups, R f20 ~R f23 One or more of them are fluorine atoms.

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

10. The composite according to any one of claims 7 to 9, characterized in that: The fluorine-containing olefin polymer comprises one or more selected from chlorotrifluoroethylene / tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymers, ethylene / tetrafluoroethylene copolymers, ethylene / chlorotrifluoroethylene copolymers, polyvinylidene fluoride, vinylidene fluoride / tetrafluoroethylene copolymers, vinylidene fluoride / tetrafluoroethylene / chlorotrifluoroethylene copolymers, polychlorotrifluoroethylene, vinylidene fluoride / hexafluoropropylene copolymers, vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymers and poly(1,2-difluoroethylene).

11. The composite according to any one of claims 7 to 10, characterized in that: The fluorine-containing olefin polymer includes polyvinylidene fluoride.

12. The composite according to any one of claims 1 to 11, characterized in that: The fluorine-containing polymer comprises a fluorine-containing polyether.

13. The composite according to claim 12, characterized in that: The fluorinated polyether is represented by the following formula, Y 1 -R f1 -R F -O q -R f2 -Y 2 Where: R F represents a divalent fluorinated polyether group, Y 1 represents 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 1 of Y 2 represents 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 1 of 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 which may have one or more substituents. 1－16 Alkyl or hydrogen atom, R f4 Each occurrence independently represents a C which may have one or more substituents. 1－16 an alkyl group, a hydrogen atom or a halogen atom, q is 0 or 1.

14. The composite according to claim 13, characterized in that: R F It is expressed by the following formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - In the formula, R Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence, a, b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f is 1 or more, the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary, wherein in all R Fa When it is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more.

15. The composite according to claim 13 or 14, characterized in that: 1 or more R Fa A hydrogen atom.

16. The composite according to any one of claims 13 to 15, characterized in that: R F It is represented by the following formula (f7), -(CF2CF2CH2O) d -(f7) In the formula, d represents an integer of 1 to 200.

17. The composite according to any one of claims 1 to 16, characterized in that: The ratio of the cyclic compound in 100 parts by mass of the total of the fluorinated polymer and the cyclic compound is 0.01% by mass or more and 99% by mass or less.

18. The composite according to any one of claims 1 to 17, characterized in that: 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 composite according to any one of claims 1 to 18, characterized in that: The thermal decomposition temperature of the composite is above 170°C.

20. A method for producing a composite, which is the method for producing a composite according to any one of claims 1 to 19, wherein: The method comprises the step of contacting the fluorine-containing polymer with the cyclic compound represented by the formula (I) in the absence of a solvent to obtain the composite.

21. The manufacturing method according to claim 20, characterized in that: The contacting is performed at a temperature above at least one of a glass transition temperature and a melting point of the fluoropolymer.

22. A composition, characterized in that: A composite comprising the composite according to any one of claims 1 to 19.

23. The composition of claim 22, wherein: It is in powder form.

24. The composition of claim 22, wherein: It is in liquid form.

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