Pillararene composites

Abstract

The purpose of the present invention is to provide a composite which has excellent heat resistance, particularly excellent thermal decomposition resistance, and which is easy to introduce functional groups. The composite according to the present invention contains a polymer and one or more cyclic compounds including the polymer, the polymer having at least one selected from the group consisting of a glass transition temperature and a melting point at 130 DEG C or higher, and the cyclic compounds including 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 heat resistance, especially the resistance to thermal decomposition, 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, particularly resistance to thermal decomposition, 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 complex comprising a polymer and one or more cyclic compounds encapsulating the polymer,

[0018] The polymer has at least one selected from the group consisting of a glass transition temperature and a melting point at 130° C. or higher,

[0019] The above-mentioned cyclic compound includes a compound represented by the following formula (I):

[0020]

[0021] [In formula (I),

[0022] A, when present, independently represents a divalent C containing one or more selected from -OR and -CO- 4－50 Organic groups,

[0023] R, at each occurrence, independently represents an organic group which may contain one or more fluorine atoms or a hydrogen atom,

[0024] n represents an integer of 4 to 20. ].

[0025] [2] The complex according to [1], wherein the cyclic compound comprises a compound represented by any one of the following formulae (1) to (3):

[0026]

[0027] [In formula (1),

[0028] R 1 represents independently at each occurrence a hydrogen atom or an organic group,

[0029] R 2 represents independently at each occurrence a hydrogen atom or an organic group,

[0030] R 3 represents independently at each occurrence a hydrogen atom or an organic group,

[0031] R 4 represents independently at each occurrence a hydrogen atom or an organic group,

[0032] n1 is an integer from 4 to 20.]

[0033]

[0034] [In formula (2),

[0035] R 5 represents independently at each occurrence a hydrogen atom or an organic group,

[0036] R 6 represents independently at each occurrence a hydrogen atom or an organic group,

[0037] n2 is an integer from 4 to 20.]

[0038]

[0039] [In formula (3),

[0040] R 7 represents independently at each occurrence a hydrogen atom or an organic group,

[0041] R 8 represents independently at each occurrence a hydrogen atom or an organic group,

[0042] R 9 represents independently at each occurrence a hydrogen atom or an organic group,

[0043] R 10 represents independently at each occurrence a hydrogen atom or an organic group,

[0044] R 11 represents independently at each occurrence a hydrogen atom or an organic group,

[0045] R 12 represents independently at each occurrence a hydrogen atom or an organic group,

[0046] n3 is an integer from 1 to 19,

[0047] n4 is an integer from 1 to 19,

[0048] The total of n3 and n4 is 4 to 20,

[0049] The order of existence of the units marked with n3 or n4 and enclosed in parentheses is arbitrary in formula (3). ].

[0050] [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.

[0051] [4] The complex according to [2], wherein in the above formula (1), R 3 and R 4 One or more of them are hydrogen atoms.

[0052] [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),

[0053]

[0054] [In formula (1-A),

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

[0056] R 2a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0057] R 3a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0058] R 4a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0059] n1 is an integer from 4 to 20.]

[0060]

[0061] [In formula (2-A),

[0062] R 5a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0063] R 6a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0064] n2 is an integer from 4 to 20.]

[0065]

[0066] [In formula (3-A),

[0067] R 7a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0068] R 8a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0069] R 9a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0070] R 10a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0071] R 11a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0072] R 12a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0073] n3 is an integer from 1 to 19,

[0074] n4 is an integer from 1 to 19,

[0075] The total of n3 and n4 is 4 to 20,

[0076] However, the order of existence of the units indicated by n3 or n4 and enclosed in parentheses is arbitrary in formula (3-A). ]

[0077] [6] The composite according to any one of [1] to [5], wherein the thermal decomposition temperature of the cyclic compound is 250° C. or higher.

[0078] [7] The composite according to any one of [1] to [6], wherein the polymer has at least one selected from a glass transition temperature and a melting point at 140° C. or higher.

[0079] [8] The composite according to any one of [1] to [7], wherein the polymer is a linear polymer which may have a substituent.

[0080] [9] The composite material according to any one of [1] to [8], wherein the polymer is a linear polymer having one selected from the group consisting of a carbonyl group, an ester group, an amide group, an imide group and an ether group in a repeating structural unit.

[0081]

[10] The composite according to any one of [1] to [9], wherein the polymer is a linear polymer having an aromatic ring in a repeating structural unit.

[0082]

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

[10] , wherein the polymer comprises a polyester.

[0083]

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

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

[0084]

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

[12] , wherein the polymer comprises polyvinylidene fluoride.

[0085]

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

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

[0086]

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

[14] , wherein the thermal decomposition temperature of the composite material is t x , let the lower one of the thermal decomposition temperature of the polymer and the thermal decomposition temperature of the cyclic compound be t y When t x -t y Above 50°C.

[0087]

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

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

[0088]

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

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

[0089]

[18] The production method according to

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

[0090]

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

[16] .

[0091]

[20] The composition according to

[19] , which is in powder form.

[0092]

[21] The composition according to

[19] , which is in liquid form.

[0093] Effects of the Invention

[0094] The composite of the present invention is excellent in heat resistance, particularly resistance to thermal decomposition, and can easily be introduced with a functional group. BRIEF DESCRIPTION OF THE DRAWINGS

[0095] Figure 1 The NMR spectrum of the composite obtained in Example 1 is shown.

[0096] Figure 2 The NMR spectrum of the composite obtained in Example 2 is shown.

[0097] Figure 3 The NMR spectrum of the purified product obtained in Comparative Example 1 is shown.

[0098] Figure 4 The NMR spectrum of the purified product obtained in Comparative Example 2 is shown.

[0099] Figure 5 The DSC spectra of each composite obtained in Example 13 are shown.

[0100] Figure 6 The DSC spectra of each composite obtained in Example 14 are shown.

[0101] Figure 7 The DSC spectra of each composite obtained in Example 15 are shown.

[0102] Figure 8 The X-ray diffraction spectrum of each composite obtained in Example 13 is shown.

[0103] Fig. 9 The X-ray diffraction spectrum of each composite obtained in Example 14 is shown.

[0104] Fig.10 The FT-IR spectra of the complex and purified product obtained in Example 21 are shown. DETAILED DESCRIPTION

[0105] <Compound>

[0106] The complex of the present invention comprises a polymer and one or more cyclic compounds encapsulating the polymer.

[0107] The above-mentioned cyclic compound includes a compound represented by the following formula (I):

[0108]

[0109] [In formula (I),

[0110] A, when present, independently represents a divalent C containing one or more selected from -OR and -CO- 4－50 Organic groups,

[0111] R, at each occurrence, independently represents an organic group which may contain one or more fluorine atoms or a hydrogen atom,

[0112] n represents an integer of 4 to 20. ].

[0113] Since the composite of the present invention contains a polymer and the above-mentioned cyclic compound, it has good heat resistance, especially good resistance to thermal decomposition, and is easy to introduce functional groups. It is expected that the composite of the present invention maintains the heat resistance and hydrophobic properties of the polymer, and is also easy to mix with various resins, etc. In addition, in the composite of the present invention, the cyclic compound is not fixed by the polymer, so it is also movable when mixed with the resin, and it is expected to be able to exert characteristics such as impact absorption.

[0114] In the present invention, inclusion means that at least a portion of the polymer is present inside the ring of the cyclic compound. In one embodiment, the polymer may also penetrate the ring of the cyclic compound. In addition, the cyclic compound that includes one polymer may be one or more, in one embodiment, preferably one, and in another embodiment, preferably two or more. 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.

[0115] 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-.

[0116] C 4－50 The organic group may preferably be C 4－20 An organic group, more preferably C 4－10 Organic group.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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. 3－20 The 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.

[0123] 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 3－20A 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 hydrocarbons and C 6－10 A group in which -CH2- constituting a ring in an alicyclic hydrocarbon group is replaced by -CO-.

[0124] The total number of -OR and -CO- contained in A is 1 to 4, and preferably 2.

[0125] R, at each occurrence, independently represents an organic group which may contain one or more fluorine atoms or a hydrogen atom.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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 6－10One 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.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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 1－10 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.

[0134] 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.

[0135] 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.

[0136] In one embodiment, preferably R represents C which may have one or more substituents. 1－30 an alkyl group or a hydrogen atom.

[0137] 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.

[0138] The cyclic compound preferably includes a compound represented by any one of the following formulae (1) to (3).

[0139]

[0140] [In formula (1),

[0141] R 1 represents independently at each occurrence a hydrogen atom or an organic group,

[0142] R 2 represents independently at each occurrence a hydrogen atom or an organic group,

[0143] R 3 represents independently at each occurrence a hydrogen atom or an organic group,

[0144] R 4 represents independently at each occurrence a hydrogen atom or an organic group,

[0145] n1 is an integer from 4 to 20,

[0146] 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,

[0147] In another preferred embodiment, selected from R 3 and R 4 One or more of them may be hydrogen atoms, and more preferably R 3 and R 4 is a hydrogen atom.]

[0148]

[0149] [In formula (2),

[0150] R5 represents independently at each occurrence a hydrogen atom or an organic group,

[0151] R 6 represents independently at each occurrence a hydrogen atom or an organic group,

[0152] n2 is an integer from 4 to 20.]

[0153]

[0154] [In formula (3),

[0155] R 7 represents independently at each occurrence a hydrogen atom or an organic group,

[0156] R 8 represents independently at each occurrence a hydrogen atom or an organic group,

[0157] R 9 represents independently at each occurrence a hydrogen atom or an organic group,

[0158] R 10 represents independently at each occurrence a hydrogen atom or an organic group,

[0159] R 11 represents independently at each occurrence a hydrogen atom or an organic group,

[0160] R 12 represents independently at each occurrence a hydrogen atom or an organic group,

[0161] n3 is an integer from 1 to 19,

[0162] n4 is an integer from 1 to 19,

[0163] The total of n3 and n4 is 4 to 20,

[0164] The order of presence of the units marked with n3 or n4 and enclosed in parentheses is arbitrary in formula (3).]

[0165] When the cyclic compound includes a compound represented by any one of the formulae (1) to (3), heat resistance, especially resistance to thermal decomposition, becomes better, and it becomes easier to introduce a functional group, and the composite can be produced more efficiently.

[0166] In one embodiment, the cyclic compound preferably includes a compound represented by the following formula (1):

[0167]

[0168] [In formula (1),

[0169] R 1 represents independently at each occurrence a hydrogen atom or an organic group,

[0170] R 2 represents independently at each occurrence a hydrogen atom or an organic group,

[0171] R 3 represents independently at each occurrence a hydrogen atom or an organic group,

[0172] R 4 represents independently at each occurrence a hydrogen atom or an organic group,

[0173] n1 is an integer from 4 to 20. ].

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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, C1－30 The alkyl group can be C 17－30 Alkyl, preferably C 18－30 Alkyl, more preferably C 26－30 alkyl.

[0178] 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.

[0179] 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.

[0180] 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.

[0181] The above R 1 , R 2 , R 3 or R 4 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 1－10Alkylene. 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.

[0182] The above R 1 , R 2 , R 3 or R 4 The fluorinated organic group in the formula (a) may be preferably an organic group having 2 or more carbon atoms and having a fluoroalkyl group, more preferably a fluoroalkyl group or a fluoro(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.

[0183] In one embodiment, the fluorine-containing organic group is a group represented by the following formula:

[0184] -(O p1 -R 20 q1 )-Rf a

[0185] [Where:

[0186] R 20 Each occurrence represents C independently 1－10 Alkylene.

[0187] R a Represents C 1－10 Fluorinated alkyl.

[0188] p1 is an integer from 0 to 2.

[0189] q1 is an integer from 0 to 3.

[0190] (O p1 -R 20 q1 ), O and R 11a There is no restriction on the order in which they exist. ].

[0191] 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.

[0192] R a C 1－10 The fluoroalkyl group is preferably C1－6 Fluorinated alkyl. The fluoroalkyl group may be straight chain or branched chain, preferably straight chain. The fluoroalkyl group is preferably a perfluoroalkyl group.

[0193] 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.

[0194] 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.

[0195] In a preferred embodiment, the fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a The groups shown.

[0196] [Where:

[0197] R 20 Each independently represents C 1－10 Alkylene.

[0198] R a Represents C 1－10 Fluorinated alkyl.

[0199] r1 is 0 or 1. ].

[0200] In a more preferred embodiment, the fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a The groups shown.

[0201] [Where:

[0202] R 20 Each independently represents C 1－10 Alkylene.

[0203] R a Represents C 1－10 Perfluoroalkyl.

[0204] r1 is 0 or 1. ].

[0205] n1 is an integer of 4 to 20, preferably an integer of 4 to 6, and more preferably 5 or 6.

[0206] In a particularly preferred embodiment,

[0207] 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

[0208] R 14 and R 15 For-O-R 20 -(O-R 20 ) r1 -Rf a , R 13 and R 16 is a hydrogen atom,

[0209] R 20 C 1－10 Alkylene, preferably C 1－6 Alkylene,

[0210] R a C 1－10 Perfluoroalkyl, preferably C 1－6 Perfluoroalkyl,

[0211] r1 is 0 or 1,

[0212] n1 is an integer of 4 to 6, and preferably 5 or 6.

[0213] 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.

[0214] 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.

[0215] 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, R 3 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.

[0216] 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.

[0217] In another preferred embodiment, 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.

[0218] 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.

[0219] The above formula (1) is preferably represented by the following formula (1-A),

[0220]

[0221] [In formula (1-A),

[0222] R 1a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0223] R 2a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0224] R 3a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0225] R 4a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0226] n1 is an integer from 4 to 20. ].

[0227] 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 an alkyl group or a hydrogen atom.

[0228] 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.

[0229] 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.

[0230] In another embodiment, the above formula (1) can be represented by the following formula (1-A'):

[0231]

[0232] [In formula (1-A'),

[0233] R 13 represents independently at each occurrence a hydrogen atom or an organic group,

[0234] R 14 represents independently at each occurrence a hydrogen atom or an organic group,

[0235] R 15 represents independently at each occurrence a hydrogen atom or an organic group,

[0236] R 16 represents independently at each occurrence a hydrogen atom or an organic group,

[0237] n5 is an integer from 4 to 20,

[0238] Among them, R 13 , R 14 , R 15 and R 16 At least one of them is a fluorine-containing organic group,

[0239] R 14 and R 15 At least one of them is a hydrogen atom. ].

[0240] 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.

[0241] 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.

[0242] 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 6－10 One or more of an aryl group, a 5- to 10-membered heteroaryl group, and a reactive functional group.

[0243] 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.

[0244] The above R 13 , R 14 , R 15 or R 16 The alkyl group in is preferably C 1－30The 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.

[0245] 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.

[0246] 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.

[0247] 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.

[0248] 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 1－10Perfluoroalkyl, preferably C 1－6 Perfluoroalkyl. ) group.

[0249] 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.

[0250] 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.

[0251] 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.

[0252] 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 R 15 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.

[0253] 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.

[0254] In one approach, R 14 and R 15 is a hydrogen atom, or R 13 and R 16 A hydrogen atom.

[0255] In a preferred embodiment, R 13 and R 16 are independently fluorinated organic groups, R 14 and R 15 A hydrogen atom.

[0256] The fluorinated organic group is 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.

[0257] In one embodiment, the fluorine-containing organic group is a group represented by the following formula:

[0258] -(O p1 -R 20 q1 )-Rf a

[0259] [Where:

[0260] R 20 Each occurrence represents C independently 1－10 Alkylene.

[0261] R a Represents C 1－10 Fluorinated alkyl.

[0262] p1 is an integer from 0 to 2.

[0263] q1 is an integer from 0 to 3.

[0264] (O p1 -R 20 q1 ), O and R 11a There is no restriction on the order in which they exist. ].

[0265] R 20 C1－10 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.

[0266] 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.

[0267] 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.

[0268] 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.

[0269] In a preferred embodiment, the fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a The groups shown.

[0270] [Where:

[0271] R 20 Each independently represents C 1－10 Alkylene.

[0272] R a Represents C 1－10 Fluorinated alkyl.

[0273] r1 is 0 or 1. ].

[0274] In a more preferred embodiment, the fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a The groups shown.

[0275] [Where:

[0276] R 20 Each independently represents C 1－10 Alkylene.

[0277] R a Represents C 1－10 Perfluoroalkyl.

[0278] r1 is 0 or 1. ].

[0279] n1 is an integer of 4 to 20, preferably an integer of 4 to 6, and more preferably 5 or 6.

[0280] In a particularly preferred embodiment,

[0281] 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

[0282] R 14 and R 15 For-O-R 20 -(O-R 20 ) r1 -Rf a , R 13 and R 16 is a hydrogen atom,

[0283] R 20 C 1－10 Alkylene, preferably C 1－6 Alkylene,

[0284] R a C 1－10 Perfluoroalkyl, preferably C 1－6 Perfluoroalkyl,

[0285] r1 is 0 or 1,

[0286] n1 is an integer of 4 to 6, and preferably 5 or 6.

[0287] 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').

[0288] 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.

[0289] In another embodiment, the cyclic compound preferably includes a compound represented by the following formula (2):

[0290]

[0291] [In formula (2),

[0292] R 5 represents independently at each occurrence a hydrogen atom or an organic group,

[0293] R 6 represents independently at each occurrence a hydrogen atom or an organic group,

[0294] n2 is an integer from 4 to 20. ].

[0295] 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.

[0296] 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.

[0297] 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.

[0298] 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 C 26－30 alkyl.

[0299] 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, C6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0300] 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.

[0301] 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.

[0302] 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.

[0303] 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.

[0304] 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.

[0305] In one embodiment, preferably R 5 represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 6represents a C which may have one or more substituents 1－30 an alkyl group or a hydrogen atom.

[0306] 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.

[0307] The above formula (2) is preferably represented by the following formula (2-A),

[0308]

[0309] [In formula (2-A),

[0310] R 5a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0311] R 6a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0312] n2 represents an integer from 4 to 20. ].

[0313] 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.

[0314] 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 1－30 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.

[0315] 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 C1－6 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.

[0316] In one embodiment, preferably R 5a and R 6a A hydrogen atom.

[0317] In another embodiment, the cyclic compound preferably includes a compound represented by the following formula (3):

[0318]

[0319] [In formula (3),

[0320] R 7 represents independently at each occurrence a hydrogen atom or an organic group,

[0321] R 8 represents independently at each occurrence a hydrogen atom or an organic group,

[0322] R 9 represents independently at each occurrence a hydrogen atom or an organic group,

[0323] R 10 represents independently at each occurrence a hydrogen atom or an organic group,

[0324] R 11 represents independently at each occurrence a hydrogen atom or an organic group,

[0325] R 12 represents independently at each occurrence a hydrogen atom or an organic group,

[0326] n3 is an integer from 1 to 19,

[0327] n4 is an integer from 1 to 19,

[0328] The total of n3 and n4 is 4 to 20,

[0329] The order of existence of the units marked with n3 or n4 and enclosed in parentheses is arbitrary in formula (3). ].

[0330] 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, R9 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.

[0331] 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.

[0332] 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.

[0333] 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 1－30 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.

[0334] As R 7 , R 8 , R 9 , R 10 , R 11 or R 12The 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.

[0335] 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.

[0336] 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.

[0337] 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 -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.

[0338] 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.

[0339] 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.

[0340] 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.

[0341] 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.

[0342] The above formula (3) is preferably represented by the following formula (3-A),

[0343]

[0344] [In formula (3-A),

[0345] R 7a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0346] R 8aEach occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0347] R 9a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0348] R 10a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0349] R 11a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0350] R 12a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0351] The meanings of n3 and n4 are the same as above.

[0352] However, the order of existence of the units indicated by n3 or n4 and enclosed in parentheses is arbitrary in formula (3-A). ]

[0353] 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 an alkyl group or a hydrogen atom.

[0354] R 7a , R 8a , R9a , 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.

[0355] As R 7a , R 8a , R 9a , R 10a , R 11a or R 12a 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.

[0356] In one approach, R 7a , R 8a , R 9a , R 10a , R 11a and R 12a Preferred is a hydrogen atom.

[0357] The cyclic compound is preferably a compound represented by one or more selected from formulae (1), (2) and (3), and more preferably a compound represented by one or more selected from formulae (1-A), (2-A) and (3-A).

[0358] The thermal decomposition temperature of the cyclic compound itself (cyclic compound alone) is preferably 250°C or more, more preferably 260°C or more, and further preferably 270°C or more. When the heat resistance of the cyclic compound itself is high, when the composite is prepared by the melting method, even if the melting point of the polymer side is 250°C or more, thermal decomposition will not occur, and melt mixing can be performed. In addition, for example, even if the polymer has a low melting point, the melt viscosity of the polymer itself usually decreases when the temperature rises, so it can be expected that by increasing the contact opportunity between the cyclic compound and the polymer terminal, inclusion can be performed in a short time.

[0359] When the complex contains two or more cyclic compounds, the two or more cyclic compounds may be the same or different.

[0360] In the total of 100 parts by mass of the polymer and the cyclic compound described later, the ratio of the cyclic compound is 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 ratio of the cyclic compound is within the above range, the heat resistance, especially the thermal decomposition resistance of the composite is good.

[0361] The polymer has at least one of a glass transition temperature and a melting point at 130°C or above. In other words, it is preferred that the glass transition temperature of the polymer is 130°C or above, or the melting point of the polymer is 130°C or above. Specifically, when the 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 may be 130°C or above. When the 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 may be 130°C or above. When the polymer has at least one of a glass transition temperature and a melting point at 130°C or above, the heat resistance, especially the heat decomposition resistance, of the obtained composite is good. It is preferred that the polymer has at least one of a glass transition temperature and a melting point at 150°C or above, may have at least one of a glass transition temperature and a melting point at 300°C or below, and may have at least one of a glass transition temperature and a melting point at 250°C or below.

[0362] 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.

[0363] In the present invention, the polymer may have one or more substituents. Examples of the substituents that the polymer may have include -COOR f13 ,-OR f13 , -NRf13 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 One or more of an alkyl group and a halogen atom.

[0364] Among the substituents which the polymer may have, the total number of C, N, O and S may be 1 or more, preferably 5 or less, more preferably 3 or less, and further preferably 2 or less.

[0365] 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.

[0366] R f13 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.

[0367] 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.

[0368] 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, more preferably C 1－4 Perfluoroalkyl.

[0369] 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-.

[0370] R f14Each 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.

[0371] 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.

[0372] 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.

[0373] In one embodiment, the above R f14 The C shown 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.

[0374] 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.

[0375] The above 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.

[0376] 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 C1－5 Alkyl, preferably C 1－4 Perfluoroalkyl.

[0377] 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-.

[0378] 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.

[0379] The above-mentioned polymer preferably includes one or more selected from: a linear polymer having one selected from hydroxyl group, carbonyl group, ester group, amide group, imide group and ether group in a repeating structural unit; a linear polymer having an aromatic ring in a repeating structural unit; and a fluorine-containing polymer.

[0380] Examples of the linear polymer having one selected from a hydroxyl group, a carbonyl group, an ester group, an amide group, an imide group and an ether group include polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polyacetals, polyamides, polycarbonates, polyphenylene ethers, polyesters, polyarylates, polysulfones, polyether ketones and polyether ether ketones, among which polyesters are preferred.

[0381] Examples of the linear polymer having one selected from a hydroxyl group, a carbonyl group, an ester group, an amide group, an imide group and an ether group in the repeating structural unit include polymers having one or more repeating structural units selected from the following formulae (B1) to (B8):

[0382] -[O-R b1 ]- (B1)

[0383] -[O-CO-O-R b2 ]- (B2)

[0384] -[O-CO-R b2 -CO-O-R b2 ]- (B3)

[0385] -[NH-CO-R b2 -CO-NH-R b2 ]- (B4)

[0386] -[O-R b2 -SO2-R b2 -O-R b2 ]- (B5)

[0387] -[O-R b2 -CO-Rb2 ]- (B6)

[0388] -[O-R b2 -O-R b2 -CO-R b2 ]- (B7)

[0389] -[-CH2-CH(OH)]- (B8)

[0390] [In formulas (B1) to (B8),

[0391] R b1 It means that it contains C which may have one or more substituents. 6－20 Aromatic hydrocarbon divalent group or -CH2-;

[0392] R b2 Each occurrence independently represents a C 6－20 A divalent aromatic hydrocarbon group, or a C 1－16 Alkylene. ].

[0393] The polymer may have a repeating structural unit other than the repeating structural units represented by the above formulae (B1) to (B8). As such a repeating structural unit, the following formula (B9):

[0394] -[CR b3 2-CR b3 2]-(B9)

[0395] [In formula (B9),

[0396] R b3 represents a C which may have one or more substituents 1－16 Alkyl group or hydrogen atom. ].

[0397] When the polymer contains two or more types of repeating structural units, the polymer may be a block copolymer or a random copolymer.

[0398] When the polymer includes a polymer having the above-mentioned repeating structural unit, the heat resistance, especially the resistance to thermal decomposition, of the obtained composite is good.

[0399] R b1 It means that it contains C which may have one or more substituents. 6－20 Aromatic hydrocarbon divalent group or -CH2-, R b2 It means that it contains C which may have one or more substituents. 6－20 A divalent aromatic hydrocarbon group, or a C1－16 Alkylene. b3 represents a C which may have one or more substituents 1－16 an alkyl group or a hydrogen atom.

[0400] R b1 or R b2 The C 6－20 The "C 6－20 The "aromatic hydrocarbon group" may be a monocyclic ring or a polycyclic ring. In the case of a polycyclic ring, two or more rings may form a condensed ring or may not form a condensed ring. In addition, in the case of a C 6－20 In the divalent group of the aromatic hydrocarbon group, the number of the aromatic hydrocarbon groups may be 1 or more, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and further preferably 1 or 2. The aromatic hydrocarbon group may be preferably C 6－10 The aromatic hydrocarbon group is more preferably a phenylene group, a benzylene group, a xylylene group or a naphthylene group, and still more preferably a phenylene group, a benzylene group or a xylylene group.

[0401] In the C 6－20 In the divalent group of the aromatic hydrocarbon group, two or more aromatic hydrocarbon groups may be bonded via a single bond or a divalent organic group. Examples of the organic group include linear or branched C 1－4 alkyl.

[0402] R b1 or R b2 The C 6－20 The divalent group of the aromatic hydrocarbon group is preferably represented by the following formula,

[0403] *-Ar 1 -(X 1 -Ar 1 ) n10 -*

[0404] [Wherein,

[0405] Ar 1 Each occurrence independently represents a divalent C 6－10 Aromatic hydrocarbon groups,

[0406] X 1 Indicates a single bond, -O-, -CO-, -SO2- or C 1－4 Alkylene,

[0407] n10 represents an integer greater than or equal to 0 and less than or equal to 3,

[0408] * indicates a valence bond,

[0409] The total number of carbon atoms in the formula is 6 or more and 20 or less. ].

[0410] Ar 1 represents a divalent C which may have one or more substituents 6－10 Aromatic hydrocarbon group.

[0411] The above-mentioned divalent C optionally having one or more substituents 6－20 The "divalent C 6－20 The "aromatic hydrocarbon group" may be a monocyclic ring or a polycyclic ring. In the case of a polycyclic ring, two or more rings may or may not form a condensed ring. A divalent C 6－20 The "divalent C 6－20 The "aromatic hydrocarbon group" is preferably a divalent C 6－15 Aromatic hydrocarbon group, more preferably a divalent C6

[0412] －10 The aromatic hydrocarbon group is more preferably a phenylene group, a benzylene group, a xylylene group or a naphthylene group, and still more preferably a phenylene group, a benzylene group or a xylylene group.

[0413] As Ar 1 The divalent C 6－10 The substituent that the aromatic hydrocarbon 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.

[0414] The above-mentioned 2-valent C 6－10 The substituent that the aromatic 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.

[0415] X 1Indicates a single bond, -O-, -CO-, -SO2- or C 1－4 Alkylene. 1－4 The alkylene group may be a straight chain or a branched chain, and is preferably a straight chain or a branched chain C 1－3 The alkylene group may specifically be -CH2- or -C(CH3)2-.

[0416] As R b1 or R b2 The included C 6－20 The substituent that the divalent aromatic hydrocarbon group may have includes a substituent 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.

[0417] The above contains divalent C 6－10 The substituent that the divalent aromatic hydrocarbon group may have may preferably be selected from the group consisting of -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.

[0418] R b1 or R b2 The C 6－20 The divalent group of the aromatic hydrocarbon group is preferably a phenylene group, a benzylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a biphenylene group, a 3,3'-dimethylbiphenylene group, a 3,3',5,5'-tetramethylbiphenylene group, a 2,2-diphenylpropane-4,4'-diyl group, a 1,1-diphenylmethane-4,4'-diyl group, a benzophenone-4,4'-diyl group, a diphenylsulfone-4,4'-diyl group, or an oxybisphenyl-4,4'-diyl group, and more preferably a phenylene group, a xylylene group, a hydroxyphenylene group, a hydroxyxylylene group, a naphthylene group, a 2,2-diphenylpropane-4,4'-diyl group, a 1,1-diphenylmethane-4,4'-diyl group, a benzophenone-4,4'-diyl group, a diphenylsulfone-4,4'-diyl group, or an oxybisphenyl-4,4'-diyl group.

[0419] R b2 The C shown may have one or more substituents. 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 The alkylene group may specifically be -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, -C(CH3)2-, -CH2CH2CH2CH2-, -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-, -C(CH3)2CH2-, -CH2CH2CH2CH2-, -CH(CH3)CH2CH2-, -C(CH3)2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)CH2CH2CH2-, -CH2CH(CH 3)CH2CH2-, -C(CH3)2CH2CH2-, -CH2C(CH3)2CH2-, -CH2CH2CH2CH2CH2CH2-, CH(CH3)CH2CH2CH2CH2- , -CH2CH(CH3)CH2CH2CH2-, -CH2CH2CH(CH3)CH2CH2-, -C(CH3)2CH2CH2CH2- or -CH2C(CH3)2CH2CH2-.

[0420] As R b2 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.

[0421] The above R b2 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.

[0422] Rb3 The C shown 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 1－10 Alkyl, more preferably a linear or branched C 1－6 Alkyl group, specifically -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)CH3, -C(CH3)2CH3, -CH2CH2CH2CH2CH3, -CH(CH3)CH2CH2CH3, -CH2CH(CH3 )CH2CH3, -C(CH3)2CH2CH3, -CH2C(CH3)2CH3, -CH2CH2CH2CH2CH2CH3, CH(CH3)CH2CH2CH2CH3, -CH2CH(CH3)CH2CH2CH3, -CH2CH2CH(CH3)CH2CH3, -C(CH3)2CH2CH2CH3 or -CH2C(CH3)2CH2CH3.

[0423] As R b3 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-NRf 13 2. -NO2, -CN, -COR 14 ,-SO3R f14 , -O-COR f14 and halogen atoms. f13 and R f14 The meaning is the same as above.

[0424] The above R b3 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.

[0425] The number average molecular weight of the linear polymer having one selected from a hydroxyl group, a carbonyl group, an ester group, an amide group, an imide group and an ether group in a repeating structural unit is, for example, 500 to 1,000,000, preferably 1,000 to 500,000, more preferably 1,500 to 300,000, further preferably 2,000 to 300,000, and can be, for example, 3,000 to 300,000.

[0426] In the present invention, the number average molecular weight can be measured by gel permeation chromatography, and can be measured as a converted value using polystyrene as a standard sample.

[0427] Examples of the linear polymer having an aromatic ring in the repeating structural unit include those having R in the above formulae (B1) to (B7): b1 and R b2 A polymer containing one or more repeating structural units containing an aromatic ring.

[0428] The number average molecular weight of the linear polymer having an aromatic ring in the repeating structural unit is, for example, 500 to 1,000,000, preferably 1,000 to 500,000, more preferably 1,500 to 300,000, further preferably 2,000 to 300,000, and may be, for example, 3,000 to 250,000.

[0429] Examples of the fluorine-containing polymer include fluorine-containing olefin polymers, fluorine-containing acrylic polymers, etc. The polymer may preferably contain one or more selected from fluorine-containing olefin polymers.

[0430] 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.

[0431] The fluorine-containing olefin compound is preferably represented by the following formula:

[0432] CR f20 R f21 =CR f22 R f23

[0433] [Wherein,

[0434] 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,

[0435] R f21 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C 1－5One of the perfluoroalkoxy groups,

[0436] 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,

[0437] 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,

[0438] R f20 ~R f23 One or more of them are fluorine atoms. ].

[0439] 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 1－5 A type of perfluoroalkoxy group.

[0440] 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, and may preferably be a straight chain or a branched chain C 1－5 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl, more preferably linear C1－3 Perfluoroalkyl. f20 , R f21 , R f22 or R f23 C shown 1－5 Specific examples of the fluoroalkyl group include -CF3, -CF2CF3 and -CF2CF2CF3.

[0441] 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.

[0442] 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, preferably R f20 is a fluorine atom or a hydrogen atom, R f21 is a fluorine atom or a hydrogen atom, R f22 is a fluorine atom or a hydrogen atom, R f23 C 1－5 Perfluoroalkyl or C 1－5 Perfluoroalkoxy.

[0443] 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.

[0444] In one embodiment, the fluorine-containing olefin compound may preferably be vinylidene fluoride.

[0445] As the above-mentioned fluorine-containing olefin polymer, the fluorine-containing olefin polymer can be 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 above-mentioned fluorine-containing olefin polymer includes polyvinylidene fluoride.

[0446] The number average molecular weight of the fluorinated olefin polymer may be preferably from 1,000 to 1,000,000, more preferably from 2,000 to 500,000, further preferably from 3,000 to 300,000.

[0447] 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.

[0448] The polymer may or may not have a capping site at the end. The capping site may be a C 6－30 An aromatic hydrocarbon group, or a C 6－30 Alicyclic hydrocarbon group. Examples of the above-mentioned end-capping sites include: dinitrophenyl; cyclodextrin; adamantyl; trityl; fluorescein; pyrene; phenyl having one or more selected from alkyl, alkoxy, hydroxyl, halogen, cyano, sulfonyl, carboxyl, amino and phenyl as substituents; 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 polymer may be 1 or more and 2 or less.

[0449] The number average molecular weight of the 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, and for example, may be 3,000 to 300,000.

[0450] In one embodiment, it is preferred that the cyclic compound includes a compound represented by formula (1), and the polymer includes a fluorinated olefin polymer or a polyester.

[0451] The thermal decomposition temperature of the composite is preferably 170° C. or higher, more preferably 200° C. or higher, for example, 400° C. or lower. The composite of the present invention has excellent heat resistance, especially resistance to thermal decomposition, and can be suitably used in applications requiring high heat resistance.

[0452] 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.

[0453] 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.

[0454] 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.

[0455] <Method for producing composite material>

[0456] The composite can be produced by a production method comprising the step of bringing a polymer into contact with the cyclic compound represented by the above formula (I) in the absence of a solvent to obtain the composite.

[0457] The manufacturing method of the present invention is contacted under the condition of no solvent, so no matter how the degree of compounding is, it is easy to carry out the inclusion of the cyclic compound to the polymer. When the contact is carried out under a solvent, when the polymer is included by the cyclic compound, there may be a situation where the solubility in the solvent changes and the compounding cannot be carried out. In the manufacturing method of the present invention, since no solvent is used, it is not affected by the change of solubility as the compounding proceeds, and it is easy to obtain the desired complex.

[0458] 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.

[0459] The contact is preferably performed at a temperature higher than at least one of the glass transition temperature and the melting point of the polymer. This allows the polymer to be easily deformed freely, and the composite can be produced more efficiently.

[0460] 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 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 polymer may be, for example, 50° C. or lower, or 30° C. or lower.

[0461] In the production method of the present invention, the 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.

[0462] 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.

[0463] <Composition>

[0464] A composition containing the above-mentioned complex is also included in the technical scope of the present invention.

[0465] The composition may contain, in addition to the above-mentioned complex, one or more selected from a resin, a solvent and other additives.

[0466] In the composition, the content of the complex is 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.

[0467] 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.

[0468] 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.

[0469] 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.

[0470] 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.

[0471] Example

[0472] 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.

[0473] The structures of the cyclic compounds used in Examples are shown.

[0474]

[0475] The polymers used in Examples and Comparative Examples are shown.

[0476] 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.

[0477]

[0478] 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)

[0479] PVDF2: PVDF Kyner HSV900 manufactured by Arkema, melting point 162°C, MFR 230°C 10kgf: 0.2g / 10min

[0480] PLA: As polylactic acid, a commercially available product having a weight average molecular weight of 10,000 to 18,000, a melting point of 140° C., and a glass transition temperature of 51° C. was used. The structural formula is shown below.

[0481]

[0482] High melting point PLA (PLLA): A commercially available product having a melting point of 180° C. and having an optical isomer ratio of 99% or more of the L form is used. The structural formula is shown below.

[0483]

[0484] The measuring methods used in the examples are shown.

[0485] (1) NMR

[0486] The measurement was performed using an NMR measuring apparatus manufactured by JEOL Ltd. (JNM-ECZ500R or JEOL JNM-ECS400).

[0487] 1 H-NMR measurement conditions: 500 MHz or 400 MHz (tetramethylsilane = 0 ppm)

[0488] (2) IR analysis

[0489] The measurement was performed at room temperature using a Fourier transform infrared spectrophotometer (IRPrestige-21) manufactured by Shimadzu Corporation.

[0490] (3) Thermal decomposition temperature

[0491] The measurement was performed using a TG / DTA analyzer (thermogravimetric differential thermal analyzer) (STA7200) manufactured by Hitachi High-tech Solutions, with a nitrogen flow rate of 200 mL / min for a sample of about 10 mg, in a nitrogen atmosphere, at 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.

[0492] (4)DSC

[0493] 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.

[0494] (5) X-ray diffraction

[0495] The measurement was performed under the following conditions using a fully automatic multifunctional X-ray diffractometer (SmartLab: manufactured by Rigaku Corporation).

[0496] ·Measurement angle: 10~30°(light source: Cu / Kα, wavelength: )

[0497] Example 1 (Melt compounding of PLA and P5OH)

[0498] After adding 0.36g (5mmol) of PLA to a 5mL glass tube, the temperature was raised to 150°C to completely melt the PLA. 0.061g (0.1mmol) of P5OH as a cyclic compound was added thereto, and after standing at 150°C for 15 hours, 24 hours, and 65 hours, it was returned to room temperature to obtain a solid complex. After washing the obtained complex with 90mL of chloroform, which is a good solvent for PLA, an undissolved complex was observed. It is considered that this is because P5OH is encapsulated by PLA and its solubility has changed. By using the cleaning treatment with the good solvent, the unencapsulated PLA is washed away, so that only the encapsulated complex can be purified.

[0499] The purified complex was dissolved in acetone d6 and assayed 1 After H-NMR, peaks derived from PLA and P5OH were observed for all samples. The results are shown in Figure 1 For comparison, the results of PLA alone and the positions of the chemical shifts of the hydrogen atoms of P5OH are also shown.

[0500] From the above results, it was confirmed that the inclusion complex was obtained by treating at 150° C. for at least 15 hours.

[0501] In addition, an attempt was made to double the washing amount of chloroform to 180 mL, and a solid was obtained in the same manner. Peaks derived from PLA and P5OH were also observed by NMR.

[0502] In addition, the ratio of the P5OH unit to the repeating unit of PLA was calculated based on the integral ratio of NMR, which was P5OH:PLA=1:0.7 (molar ratio). This ratio was calculated based on the integral value of hydrogen of b1 of PLA with a chemical shift of about 5.2 ppm (equivalent to H, 1) and the integral value of hydrogen of a3 of P5OH with a chemical shift of about 3.6 ppm (equivalent to H, 10).

[0503] Example 2 (complex of high melting point PLA and P5OH)

[0504] A solution of 0.36 g (5 mmol) of high melting point PLA (PLLA) (melting point 180°C) dissolved in 1 mL of acetone and a solution of 0.061 g (0.1 mmol) of P5OH as a cyclic compound dissolved in 1 mL of acetone were added to a 5 mL glass tube, and the acetone was removed by vacuum drying, and the mixture was heated to 180°C to completely melt. After standing at 180°C for 15 hours, the mixture was returned to room temperature to obtain a solid composite. The composite was washed with 300 mL of trichloroethylene, a good solvent for PLLA, and purified.

[0505] The purified complex was dissolved in acetone d6 and assayed 1 After H-NMR, peaks derived from PLLA and P5OH were observed. The results are shown in Figure 2 For comparison, the results of PLA alone and P5OH alone are also shown.

[0506] Comparative Example 1 (composite of PBR and P5OH)

[0507] After adding 0.27 g (5 mmol) of PBR (liquid polymer) to a 5 mL glass tube, 0.061 g (0.1 mmol) of P5OH as a cyclic compound was added while maintaining room temperature, and the mixture was allowed to stand at room temperature for 15 hours to obtain a liquid mixture. The obtained mixture was washed with 30 mL of chloroform as a good solvent for PBR for a total of 4 times to obtain a purified product.

[0508] The purified product was dissolved in acetone d6 and measured 1 After H-NMR, no peak derived from PBR was observed, and no composite was obtained. The results are shown in Figure 3 For comparison, the results of P5OH alone and PBR alone are also shown.

[0509] Comparative Example 2 (composite of PBR and C2P5A)

[0510] After adding 0.27 g (5 mmol) of PBR (liquid polymer) to a 5 mL glass tube, 0.089 g (0.1 mmol) of C2P5A as a cyclic compound was added while maintaining room temperature, and the mixture was allowed to stand at room temperature for 15 hours to obtain a liquid mixture. The obtained mixture was washed 4 times in total with 30 mL of hexane as a good solvent for PBR to obtain a purified product.

[0511] 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 4 For comparison, the results for PBR alone are also shown.

[0512] Example 3 (PLA and P5OH complex solution method)

[0513] 0.118 g (1.6 mmol) of PLA and 0.01 g (0.016 mmol) of P5OH were added to a 5 mL sample tube, and 2 g of dichloromethane was added as a solvent, and the mixture was uniformly dissolved using an ultrasonic cleaner. The mixture was concentrated using a rotary evaporator at 40°C and then vacuum dried at 50°C to obtain a composite.

[0514] Example 4 (PLA and P5OH complex solution method)

[0515] A composite was obtained by the same operation as in Example 3 while changing the amount of P5OH as shown in the following table.

[0516] [Table 1]

[0517]

[0518] Examples 5 to 7 (PeC and P5Q complex solution method)

[0519] PeC was used instead of PLA, and P5Q was used instead of P5OH. The quantitative ratios were as shown in the table below. The same operation as in Example 3 was performed to obtain a composite.

[0520] [Table 2]

[0521]

[0522] Examples 8 to 11 (PeC and P5OH complex solution method)

[0523] A composite was obtained by the same operation as in Example 3 except that PeC was used instead of PLA in the amount ratio shown in the table below.

[0524] [Table 3]

[0525]

[0526] Example 12 Comparison of thermal decomposition temperatures using TGA

[0527] The thermal decomposition temperatures of the composites obtained in Examples 3 to 11 were determined by TGA. As described above, the temperature at which the mass decreased by 5% was defined as the thermal decomposition temperature.

[0528] For comparison, the thermal decomposition temperatures of PeC alone and PLA alone and the differences between the thermal decomposition temperatures are shown in the table.

[0529] [Table 4]

[0530]

[0531] [Table 5]

[0532]

[0533] [Table 6]

[0534]

[0535] Reference Example 1

[0536] The thermal decomposition temperatures of P5Q alone and C2P5A alone as cyclic compounds were determined by TGA method.

[0537] The results are shown in the following table.

[0538] [Table 7]

[0539] Cyclic compounds Thermal decomposition temperature Q5 263℃ C2P5A 370℃

[0540] Example 13

[0541] Weigh 10 mg of PVDF1 as a polymer into a 5 mL sample bottle and heat it to 200°C. PVDF1 is in a molten state, and the amount of C2P5A as a cyclic compound described in Table 2 is added, and the temperature is kept constant at 200°C, and a spatula is used to make it fully contacted, and it is kept at 150°C for 2 hours, and returned to room temperature to obtain each composite. The DSC and X-ray diffraction of the obtained composite are measured. The table summarizing the proportions and types is shown below.

[0542] [Table 8]

[0543]

[0544] Embodiment 14

[0545] Each composite was obtained in the same manner as in Example 13 except that the polymer was changed to PVDF2 (HSV900) and the amount of the cyclic compound was changed as described in the following table. The DSC and X-ray diffraction of the obtained composite were measured.

[0546] [Table 9]

[0547]

[0548] Embodiment 15

[0549] Each composite was obtained in the same manner as in Example 13 except that the cyclic compound was changed to C5P5A. DSC and X-ray diffraction of the obtained composite were measured.

[0550] [Table 10]

[0551]

[0552] Example 16

[0553] The results of DSC measurement of each composite obtained in Example 13 and the results of DSC measurement of C2P5A and PVDF1 alone as comparative data are shown in FIG. Figure 5 .

[0554] 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.

[0555] 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.

[0556] Embodiment 17

[0557] The results of DSC measurement of each composite obtained in Example 14 and the results of DSC measurement of C2P5A and PVDF2 alone as comparative data are shown in FIG. Figure 6 In Example 7, although the polymer was changed from PVDF1 (VP832) to low melting point PVDF2 (HSV900) compared to Example 6, 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.

[0558] Embodiment 18

[0559] The results of DSC measurement of each composite obtained in Example 15 are shown in FIG. Figure 7 In Example 8, although the cyclic compound was changed from C2P5A to C5P5A compared with Example 6, the results were the same, and the melting points of PVDF1 and C5P5A disappeared, indicating that an inclusion complex was generated.

[0560] Embodiment 19

[0561] The results of X-ray diffraction measurement of each composite obtained in Example 13 and the results of X-ray diffraction measurement of C2P5A and PVDF1 alone as comparative data are shown in FIG. Figure 8 .

[0562] Similar to the DSC results, the diffraction peak indicating the crystallinity of PVDF1 disappeared when PVDF1 (VP832) was used alone and C2P5A was gradually added.

[0563] 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.

[0564] Embodiment 20

[0565] The results of X-ray diffraction measurement of each composite obtained in Example 14 and the results of X-ray diffraction measurement of C2P5A and PCDF2 alone as comparative data are shown in FIG. Fig. 9 .

[0566] Similar to DSC, although the type of polymer was changed from PVDF1 (VP832) to PVDF2 (HSV900), the results were the same as those of DSC, in that the diffraction peak indicating the crystallinity of PVDF disappeared when PVDF2 (HSV900) was used alone and C2P5A was gradually added.

[0567] 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.

[0568] Embodiment 21

[0569] Research on PA11 / P5Q

[0570] Study on polyamide 11 (purchased from Sigma-Ardrich as a reagent) (PA11) and P5Q

[0571]

[0572] (Mixing Research)

[0573] Using a circulating twin-screw extruder (Xplore MC15HT: manufactured by Xplore Instruments), the mixing of 10.30 g of PA11 and 0.21 g of P5Q was studied. The materials were pre-dry blended, then fed from a hopper and mixed at 240°C, 3 min, and 200 rpm. After mixing, samples were collected in the form of strands. The melting point of the PA11 used was 189.7°C.

[0574] (Evaluation of Thermal Decomposition Temperature)

[0575] The temperature (Td5) at which the weight of the strand decreased by 5% was evaluated by the TGA method.

[0576] [Table 11]

[0577] sample Td5(℃) PA11 Single 382 PA11 / P5Q 379 P5Q alone 263

[0578] (FT-IR measurement)

[0579] according to Fig.10Compared with PA11, the 1540cm -1 : The amide C-N-H bending vibration shifted to the low wave number side. This confirmed that the amide of PA11 and the C=O of P5Q interacted with each other.

Claims

1. A composite, characterized in that: Containing a polymer and one or more cyclic compounds encapsulating the polymer, The polymer has at least one selected from a glass transition temperature and a melting point at 130° C. or above, 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 thermal decomposition temperature of the cyclic compound is 250° C. or higher.

7. The composite according to any one of claims 1 to 6, characterized in that: The polymer has at least one selected from a glass transition temperature and a melting point at 140° C. or higher.

8. The composite according to any one of claims 1 to 7, characterized in that: The polymer is a linear polymer which may have a substituent.

9. The composite according to any one of claims 1 to 8, characterized in that: The polymer is a linear polymer having one selected from the group consisting of a carbonyl group, an ester group, an amide group, an imide group and an ether group in a repeating structural unit.

10. The composite according to any one of claims 1 to 9, characterized in that: The polymer is a linear polymer having an aromatic ring in a repeating structural unit.

11. The composite according to any one of claims 1 to 10, characterized in that: The polymer comprises a polyester.

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

13. The composite according to any one of claims 1 to 12, characterized in that: The polymer comprises polyvinylidene fluoride.

14. The composite according to any one of claims 1 to 13, characterized in that: The thermal decomposition temperature of the composite is above 170°C.

15. The composite according to any one of claims 1 to 14, characterized in that: Assume that the thermal decomposition temperature of the composite is t x , let the lower one of the thermal decomposition temperature of the polymer and the thermal decomposition temperature of the cyclic compound be t y When t x -t y Above 50°C.

16. The composite according to any one of claims 1 to 15, characterized in that: The ratio of the cyclic compound in 100 parts by mass of the total of the polymer and the cyclic compound is 0.01% by mass or more and 99% by mass or less.

17. A method for producing a composite, which is the method for producing a composite according to any one of claims 1 to 16, wherein: The method comprises the step of contacting the polymer with the cyclic compound represented by the formula (I) in the absence of a solvent to obtain the composite.

18. The manufacturing method according to claim 17, characterized in that: The contacting is performed at a temperature higher than at least one of a glass transition temperature and a melting point of the polymer.

19. A composition, characterized in that: A composite comprising the composite according to any one of claims 1 to 16.

20. The composition of claim 19, wherein: It is in powder form.

21. The composition of claim 19, wherein: It is in liquid form.

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