Pillararene composites

Abstract

The purpose of the present invention is to provide a composite which has excellent heat resistance and / or hydrophobicity and into which a functional group is easily introduced. The composite according to the present invention contains a polymer and one or more cyclic compounds that include the polymer, the cyclic compound including a compound represented by formula (I), and either the polymer or the cyclic compound containing one or more elements selected from the group consisting of-CO-, a nitrogen atom, and a halogen atom. The other has a group containing a hydrogen atom capable of interacting with-CO-, a nitrogen atom, or a halogen atom. [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 1 describes a rotaxane comprising pillararene and polyethylene or polypropylene enclosed by the pillararene.

[0006] Prior art literature

[0007] Patent Literature

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

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

[0010] Non-patent literature

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

[0012] Technical problem to be solved by the invention

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

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

[0015] Technical solutions for solving technical problems

[0016] The present invention includes the following aspects.

[0017] [1] A complex comprising a polymer and one or more cyclic compounds encapsulating the polymer,

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

[0019]

[0020] [In formula (I),

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

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

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

[0024] One of the polymer and the cyclic compound contains one or more selected from -CO-, a nitrogen atom and a halogen atom, and the other has a group containing a hydrogen atom capable of interacting with -CO-, a nitrogen atom or a halogen atom.

[0025] [2] The complex according to [1], wherein the group containing a hydrogen atom capable of interacting with -CO-, a nitrogen atom or a halogen atom contains one or more selected from a proton donating group, an unsaturated group and a group containing a hydrogen atom having a charge density of 0.25 or more.

[0026] [3] The complex according to [1] or [2], wherein the cyclic compound comprises a compound represented by any one of the following formulae (1) to (3):

[0027]

[0028] [In formula (1),

[0029] R 1 represents independently at each occurrence a hydrogen atom or an organic group,

[0030] R 2represents independently at each occurrence a hydrogen atom or an organic group,

[0031] R 3 represents independently at each occurrence a hydrogen atom or an organic group,

[0032] R 4 represents independently at each occurrence a hydrogen atom or an organic group,

[0033] Among them, R 3 and R 4 At least one of them is a hydrogen atom,

[0034] n1 is an integer from 4 to 20.]

[0035]

[0036] [In formula (2),

[0037] R 5 represents independently at each occurrence a hydrogen atom or an organic group,

[0038] R 6 represents independently at each occurrence a hydrogen atom or an organic group,

[0039] n2 is an integer from 4 to 20.]

[0040]

[0041] [In formula (3),

[0042] R 7 represents independently at each occurrence a hydrogen atom or an organic group,

[0043] R 8 represents independently at each occurrence a hydrogen atom or an organic group,

[0044] R 9 represents independently at each occurrence a hydrogen atom or an organic group,

[0045] R 10 represents independently at each occurrence a hydrogen atom or an organic group,

[0046] R 11 represents independently at each occurrence a hydrogen atom or an organic group,

[0047] R 12 represents independently at each occurrence a hydrogen atom or an organic group,

[0048] n3 is an integer from 1 to 19,

[0049] n4 is an integer from 1 to 19,

[0050] The total of n3 and n4 is 4 to 20,

[0051] The order of existence of the units marked with n3 or n4 and enclosed in parentheses is arbitrary in formula (3). ].

[0052] [4] The complex according to [3], wherein in the above formula (1), R 1 ~R 4 One or more of them is a fluorine-containing organic group.

[0053] [5] The complex according to [3], wherein in the above formula (1), R 3 and R 4 One or more of them are hydrogen atoms.

[0054] [6] The complex according to any one of [1] to [5], wherein the cyclic compound is a compound represented by any one of the following formulas (1-A), (2-A) and (3-A),

[0055]

[0056] [In formula (1-A),

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

[0058] R 2a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0059] R 3a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0060] R 4a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0061] Among them, R 3a and R 4a At least one of them is a hydrogen atom,

[0062] n1 is an integer from 4 to 20.]

[0063]

[0064] [In formula (2-A),

[0065] R 5a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0066] R 6a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0067] n2 is an integer from 4 to 20.]

[0068]

[0069] [In formula (3-A),

[0070] R 7a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0071] R 8a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0072] R 9a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0073] R 10a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0074] R 11a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0075] R 12a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0076] n3 is an integer from 1 to 19,

[0077] n4 is an integer from 1 to 19,

[0078] The total of n3 and n4 is 4 to 20,

[0079] The order of existence of the units indicated by n3 or n4 and enclosed in parentheses is arbitrary in formula (3-A). ]

[0080] [7] The complex according to any one of [2] to [6], wherein the proton donating group contains a hydrogen atom having a charge density of 0.22 or more.

[0081] [8] The complex according to any one of [2] to [7], wherein the charge density of the hydrogen atom bonded to the carbon atom constituting the unsaturated group is 0.22 or more.

[0082] [9] The complex according to any one of [2] to [8], wherein the proton donating group is a group containing a hydrogen atom bonded to one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom.

[0083]

[10] The composite according to any one of [1] to [9], wherein the polymer is a linear polymer which may have a substituent.

[0084]

[11] The complex described in any one of [1] to

[10] , wherein the polymer is a polymer containing one or more selected from -CO-, a nitrogen atom and a halogen atom, and the cyclic compound contains a proton donating group.

[0085]

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

[11] , wherein the polymer is a polymer containing one or more selected from -CO-, a nitrogen atom and a halogen atom, and the cyclic compound is a compound represented by any one of the following formulas (1-B) and (3-B),

[0086]

[0087] [In formula (1-B),

[0088] R 1b Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0089] R 2b Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0090] R 3b Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0091] R 4bEach occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0092] Among them, R 3b and R 4b At least one of them is a hydrogen atom,

[0093] n1 is an integer from 4 to 20.]

[0094]

[0095] [In formula (3-B),

[0096] R 7b represents independently at each occurrence a hydrogen atom or an organic group,

[0097] R 8b represents independently at each occurrence a hydrogen atom or an organic group,

[0098] R 9b represents independently at each occurrence a hydrogen atom or an organic group,

[0099] R 10b represents independently at each occurrence a hydrogen atom or an organic group,

[0100] R 11b represents independently at each occurrence a hydrogen atom or an organic group,

[0101] R 12b represents independently at each occurrence a hydrogen atom or an organic group,

[0102] Among them, R 9b and R 10b At least one of them is a hydrogen atom,

[0103] n3 is an integer from 1 to 19,

[0104] n4 is an integer from 1 to 19,

[0105] The total of n3 and n4 is 4 to 20,

[0106] The order of existence of the units indicated by n3 or n4 and enclosed in parentheses is arbitrary in formula (3-B). ].

[0107]

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

[12] , wherein the polymer contains an ester group in the main chain skeleton.

[0108]

[14] The complex according to any one of [3] to

[13] , wherein the polymer contains a proton donating group, and the cyclic compound contains a compound represented by any one of the formulas (2) or (3).

[0109]

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

[14] , wherein the polymer includes a polymer having an unsaturated bond.

[0110]

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

[15] , wherein the polymer comprises a diene polymer.

[0111]

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

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

[0112]

[18] A complex as described in any one of [1] to

[17] , wherein when the complex is mixed with a good solvent for the polymer, where the mass of the complex before mixing is w0 and the mass of the complex after mixing is w1, w1 / w0 is greater than 4 mass %.

[0113]

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

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

[0114]

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

[19] , 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.

[0115]

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

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

[0116] One of the polymer and the cyclic compound contains one or more selected from -CO-, a nitrogen atom and a halogen atom, and the other has a group containing a hydrogen atom capable of interacting with -CO-, a nitrogen atom or a halogen atom.

[0117]

[22] The production method according to

[21] , 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.

[0118]

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

[20] .

[0119]

[24] The composition according to

[23] , which is in powder form.

[0120]

[24] The composition according to

[23] , which is in liquid form.

[0121] Effects of the Invention

[0122] The composite of the present invention is excellent in heat resistance and / or hydrophobicity, and can be easily introduced with a functional group. BRIEF DESCRIPTION OF THE DRAWINGS

[0123] Figure 1 The NMR spectrum of the composite obtained in Example 1 is shown.

[0124] Figure 2 The IR spectrum of the composite obtained in Example 1 is shown.

[0125] Figure 3 The NMR spectrum of the composite obtained in Example 4 is shown.

[0126] Figure 4 The TGA curve of the composite obtained in Example 5 is shown.

[0127] Figure 5 The NMR spectrum of the complex obtained in Example 8 is shown.

[0128] Figure 6 The IR spectrum of the composite obtained in Example 8 is shown.

[0129] Figure 7 The NMR spectrum of the purified product obtained in Comparative Example 1 is shown.

[0130] Figure 8 The NMR spectrum of the purified product obtained in Comparative Example 2 is shown.

[0131] Fig. 9 The NMR spectrum of the composite obtained in Example 10 is shown.

[0132] Fig.10 The FT-IR spectra of the complex and purified product obtained in Example 28 are shown. DETAILED DESCRIPTION

[0133] <Compound>

[0134] The complex of the present invention comprises a polymer and one or more cyclic compounds encapsulating the polymer.

[0135] The above-mentioned cyclic compound includes a compound represented by the following formula (I):

[0136]

[0137] [In formula (I),

[0138] A, when present, independently represents a divalent C containing one or more selected from -OR and -CO- 4－50 Organic groups,

[0139] R, at each occurrence, independently represents an organic group which may contain one or more fluorine atoms or a hydrogen atom,

[0140] n represents an integer of 4 to 20. ].

[0141] One of the polymer and the cyclic compound contains one or more selected from -CO-, a nitrogen atom and a halogen atom, and the other has a group containing a hydrogen atom capable of interacting with -CO-, a nitrogen atom or a halogen atom.

[0142] In the above-mentioned group including a hydrogen atom capable of interacting with -CO-, a nitrogen atom or a halogen atom, the interaction between -CO-, a nitrogen atom or a halogen atom and the above-mentioned hydrogen atom may be a hydrogen bond interaction.

[0143] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and one or more selected from the group consisting of a fluorine atom and a chlorine atom are preferred.

[0144] Since the composite of the present invention contains a polymer and the above-mentioned cyclic compound, it has good heat resistance and / or hydrophobicity, and it is easy to introduce functional groups. Therefore, the composite of the present invention can also be easily mixed with various resins and the like. In addition, in the composite of the present invention, one of the polymer and the cyclic compound contains one or more selected from -CO-, nitrogen atoms and halogen atoms that can act as a proton acceptor, and the other has a group containing a hydrogen atom that can interact with -CO-, a nitrogen atom or a halogen atom, so that a hydrogen bond interaction can be generated between the above-mentioned proton acceptor and the above-mentioned group containing a hydrogen atom that can interact with -CO-, a nitrogen atom or a halogen atom, and the cyclic compound and the polymer in the composite can be in a properly fixed state while being movable. Therefore, it can be expected that the composite of the present invention, for example, when mixed with a resin, can exhibit characteristics such as impact absorption, and can also maintain mechanical strength.

[0145] In addition, in the present invention, one or more of the above-mentioned selected from -CO-, nitrogen atom and halogen atom and the group containing hydrogen atoms that can interact with -CO-, nitrogen atom or halogen atom are contained in the cyclic compound, and the other is contained in the polymer, and the polymer is enclosed by the cyclic compound. Therefore, it can be considered that -CO-, nitrogen atom and halogen atom exist close to the group containing hydrogen atoms that can interact with -CO-, nitrogen atom or halogen atom, and interact with each other in the restricted space inside the ring. Therefore, it is considered that in the present invention, in addition to the groups that are generally known as proton donating groups, even groups with lower proton donating properties than them can show hydrogen bond interactions. In addition, the above-mentioned group containing hydrogen atoms that can interact with -CO-, nitrogen atom or halogen atom and the above-mentioned proton acceptor do not necessarily form hydrogen bonds.

[0146] 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.

[0147] The form of the nitrogen atom that can be contained in one of the above-mentioned polymers and cyclic compounds is not particularly limited as long as it can function as a proton acceptor, and can be, for example, >N- (i.e., a nitrogen atom having three single bonds); -N= (i.e., a nitrogen atom having one single bond and one double bond), or N≡ (i.e., a nitrogen atom having one triple bond). Among them, the nitrogen atom bonded to the hydrogen atom can function as a proton donor, and therefore is not included in the above-mentioned nitrogen atom that can function as a proton acceptor.

[0148] The one or more selected from —CO—, a nitrogen atom and a halogen atom that may be contained in one of the polymer and the cyclic compound may be one or more selected from —CO— and a halogen atom in one preferred embodiment, and may be a nitrogen atom in another preferred embodiment.

[0149] The group containing a hydrogen atom capable of interacting with -CO-, a nitrogen atom or a halogen atom may be one or more selected from a proton donating group, an unsaturated group and a group containing a hydrogen atom having a charge density of 0.25 or more.

[0150] In the present invention, the proton donating group can be a group that can become a proton donor (hydrogen donor) of a hydrogen bond, and representatively includes a hydrogen atom. From the viewpoint of being able to act as a proton donor, the proton donating group preferably contains a hydrogen atom with a charge density of more than 0.22. The charge density of the hydrogen atom is more preferably more than 0.25, more preferably more than 0.40, for example, it can be less than 1. In the present invention, the charge density can be understood as a value representing the charge of a certain atom or the strength of the bond it forms with other atoms. The charge density of the hydrogen atoms of the proton donating group can be understood as the charge density of the hydrogen atoms that can contribute to the formation of hydrogen bonds in the proton donating group. It is believed that the greater the charge density of the hydrogen atoms of the proton donating group, the higher the proton donating property (easy to form hydrogen bonds), and the smaller the charge density, the lower the proton donating property (not easy to form hydrogen bonds).

[0151] In this embodiment, in the cyclic compound, the hydrogen atom having a charge density of 0.22 or more of the proton donating group is preferably contained in the substituent (the front end of the ring of the cyclic compound) of A in the above formula (I). In addition, in the polymer, the hydrogen atom having a charge density of 0.22 or more of the proton donating group is preferably contained in the main chain of the polymer or the substituent (the atoms around the main chain of the polymer).

[0152] In a preferred embodiment, in the complex of the present invention, one of the polymer and the cyclic compound preferably contains a proton-donating group, and the other contains an atom with a charge density less than 0. It is believed that the proton-donating group contained in one of the polymer and the cyclic compound is easy to interact with the atom with a charge density less than 0 contained in the other by hydrogen bonding, and it is easy to form a complex more stably. The proton-donating group preferably contains a hydrogen atom with a charge density of 0.22 or more. The charge density of the hydrogen atom can be preferably 0.25 or more, more preferably 0.40 or more, for example, it can be 1 or less.

[0153] In this embodiment, the charge density of the atom having a charge density less than 0 may be preferably -0.1 or less, more preferably -0.20 or less, and may be, for example, -1 or more.

[0154] In this embodiment, the difference between the maximum charge density of hydrogen atoms contained in one of the polymer and the cyclic compound having a proton donating group and the minimum charge density contained in the other may be preferably 0.25 or more, more preferably 0.30 or more, for example, 1 or less.

[0155] In this embodiment, in the cyclic compound, the atom or protogenic group having a charge density of less than 0 is preferably contained in the substituent of A in the above formula (I) (the front end of the ring of the cyclic compound). In the polymer, the atom or protogenic group having a charge density of less than 0 is preferably contained in the main chain of the polymer or the substituent (the atoms around the main chain of the polymer).

[0156] In the present invention, the charge density can be calculated by electron density analysis (Gaussian) using the natural bond orbital (NBO) method. For example, first, using Gaussian 16 revision A.03 (Gaussian Company), using B3LYP as a functional, using 6-31G (d) as a basis function set, assuming the structural formula of the molecule to be calculated, and performing a structural optimization calculation, the optimized structure can be determined. Then, using the optimized structure, the electron density analysis using the natural bond orbital (NBO) method can be performed to calculate the charge density.

[0157] In addition, for polymers, a structure of three consecutive repeating structural units can be assumed, and the result of the central unit can be used. In addition, when calculating the atomic density of atoms contained in polymers and cyclic compounds, when there are two or more geometrically equivalent atoms of the same type, the charge density of the atom with the largest absolute value of the charge density among the two or more atoms of the same type can be used.

[0158] The above-mentioned proton donating group can be representatively a group containing a hydrogen atom bonded to an atom with high electron withdrawing property. Examples of the atom with high electron withdrawing property include: an oxygen atom; a nitrogen atom; a sulfur atom; and a carbon atom bonded to -CO-. In one embodiment, the above-mentioned proton donating group can be preferably a group containing a hydrogen atom bonded to one atom selected from an oxygen atom, a nitrogen atom and a sulfur atom, and more preferably one or more selected from -OH, -NH- and -SH.

[0159] In the present invention, the unsaturated group includes a group containing a carbon-carbon double bond (-CR=CR-, -CR=CR2, R represents a hydrogen atom or a C 1－4 Alkyl. ) and groups containing carbon-carbon triple bonds (-C≡CR, R represents a hydrogen atom or C 1－4 alkyl. ), preferably a group containing a carbon-carbon double bond, etc. As the polymer having such an unsaturated group, for example, a polymer having an unsaturated group in the polymer skeleton can be mentioned, and in particular, a diene polymer such as a polybutadiene polymer can be mentioned.

[0160] The charge density of the hydrogen atom bonded to the carbon atom constituting the unsaturated group may be preferably 0.22 or more, more preferably 0.25 or more, further preferably 0.40 or more, and may be, for example, 1 or less.

[0161] In the present invention, a group containing a hydrogen atom with a charge density of 0.25 or more does not reach the level of a proton donating group, but it is considered that it can interact with one or more of the above-mentioned -CO-, nitrogen atom and halogen atom that can act as a proton acceptor by hydrogen bonding. Therefore, the charge density of the hydrogen atom with a charge density of 0.25 or more is more preferably 0.27 or more, and further preferably 0.30 or more, and can be, for example, 1 or less.

[0162] In formula (I), A, at each occurrence, independently represents a divalent C 4－50 The organic group includes one or more selected from -OR and -CO-.

[0163] C 4－50 The organic group may preferably be C 4－20 An organic group, more preferably C 4－10 Organic group.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] 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 is preferably 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.

[0170] The above-mentioned A contains one or more divalent C 4－50 The organic group may be independently selected from divalent C 6－20 Aromatic hydrocarbon group, C 3－20 In an alicyclic hydrocarbon group, a hydrogen atom bonded to a carbon atom constituting the ring 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-, more preferably 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-.

[0171] The total number of -OR and -CO- contained in A is 1 to 4, and preferably 2.

[0172] R, at each occurrence, independently represents an organic group which may contain one or more fluorine atoms or a hydrogen atom.

[0173] 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.

[0174] The organic group represented by R may contain a fluorine atom, and the fluorine atom may be contained in the form of a substituent of the organic group. The substituent that the organic group represented by R may have is not particularly limited, and examples thereof include: reactive functional groups such as hydroxyl, amino, carboxyl, thiol, isocyanate, nitrile, epoxy, and acetyl; aliphatic hydrocarbon groups such as alkyl, vinyl, and ethynyl; and halogen atoms. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms, and preferably fluorine or chlorine atoms.

[0175] 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.

[0176] As the substituent of the alkyl group in R, there can be mentioned: a halogen atom; a halogen atom which may be substituted with one or more halogen atoms and selected from C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 Unsaturated cycloalkyl, 5-10 membered heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or a chlorine atom is preferred.

[0177] 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.

[0178] 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.

[0179] R 21 Preferably -R22 -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.

[0180] 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.

[0181] 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.

[0182] 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.

[0183] In one embodiment, preferably R represents C which may have one or more substituents. 1－30 an alkyl group or a hydrogen atom.

[0184] 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.

[0185] In one embodiment, the cyclic compound preferably contains one or more selected from -CO-, a nitrogen atom, and a halogen atom; more preferably contains one or more selected from -CO- and a halogen atom.

[0186] Examples of the cyclic compound containing one or more selected from -CO-, a nitrogen atom and a halogen atom include: In the above formula (I), A is a divalent C containing -CO- 4－50 In the above formula (I), A is a divalent C containing -OR- 4－50 An organic group, and a cyclic compound in which R contains one or more selected from an isocyanate group, a nitrile group and a fluorine atom as a substituent.

[0187] In another embodiment, the cyclic compound preferably contains a proton donating group.

[0188] Examples of the cyclic compound containing a proton donating group include: 4－50 An organic group and a compound in which R is a hydrogen atom, etc.

[0189] The cyclic compound preferably includes a compound represented by any one of the following formulae (1) to (3).

[0190]

[0191] [In formula (1),

[0192] R 1 represents independently at each occurrence a hydrogen atom or an organic group,

[0193] R 2 represents independently at each occurrence a hydrogen atom or an organic group,

[0194] R 3 represents independently at each occurrence a hydrogen atom or an organic group,

[0195] R 4 represents independently at each occurrence a hydrogen atom or an organic group,

[0196] Among them, R 3 and R 4 At least one of them is a hydrogen atom,

[0197] n1 is an integer from 4 to 20,

[0198] 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,

[0199] In another preferred embodiment, R 3 and R 4One or more of them are hydrogen atoms, and more preferably R 3 and R 4 is a hydrogen atom.]

[0200]

[0201] [In formula (2),

[0202] R 5 represents independently at each occurrence a hydrogen atom or an organic group,

[0203] R 6 represents independently at each occurrence a hydrogen atom or an organic group,

[0204] n2 is an integer from 4 to 20.]

[0205]

[0206] [In formula (3),

[0207] R 7 represents independently at each occurrence a hydrogen atom or an organic group,

[0208] R 8 represents independently at each occurrence a hydrogen atom or an organic group,

[0209] R 9 represents independently at each occurrence a hydrogen atom or an organic group,

[0210] R 10 represents independently at each occurrence a hydrogen atom or an organic group,

[0211] R 11 represents independently at each occurrence a hydrogen atom or an organic group,

[0212] R 12 represents independently at each occurrence a hydrogen atom or an organic group,

[0213] n3 is an integer from 1 to 19,

[0214] n4 is an integer from 1 to 19,

[0215] The total of n3 and n4 is 4 to 20,

[0216] The order of presence of the units marked with n3 or n4 and enclosed in parentheses is arbitrary in formula (3).]

[0217] When the cyclic compound is a compound represented by any one of the formulae (1) to (3), heat resistance and / or hydrophobicity are further improved, and it is easier to introduce a functional group, and the composite can be produced more efficiently.

[0218] In one embodiment, the cyclic compound preferably includes a compound represented by the following formula (1).

[0219]

[0220] [In formula (1),

[0221] R 1 represents independently at each occurrence a hydrogen atom or an organic group,

[0222] R 2 represents independently at each occurrence a hydrogen atom or an organic group,

[0223] R 3 represents independently at each occurrence a hydrogen atom or an organic group,

[0224] R 4 represents independently at each occurrence a hydrogen atom or an organic group,

[0225] Among them, R 3 and R 4 At least one of them is a hydrogen atom,

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

[0227] 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.

[0228] 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.

[0229] 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.

[0230] R 1 , R 2 , R 3 or R 4 The alkyl group in is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C 1－30 The alkyl group can be C 1－20 Alkyl, preferably C 1－10 Alkyl, more preferably C 1－30 In another embodiment, C 1－30 The alkyl group can be C 17－30 Alkyl, preferably C 18－30 Alkyl, more preferably C 26－30 alkyl.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] The above R 1 , R 2 , R 3 or R 4The alkyl ether group in is a compound having one or more etheric oxygen atoms in the molecular chain of the above-mentioned alkyl group. The alkyl ether group is typically -R 26 -R 27 -(O-R 28 ) m -R 29 The group shown. In the formula, R 26 is a single bond or an oxygen atom. 27 is a single bond or C 1－10 Alkylene. 28 C 1－10 Alkylene. 29 A hydrogen atom or C 1－10 m represents an integer of 1 to 20, and is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0235] 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.

[0236] In one embodiment, the fluorine-containing organic group is a group represented by the following formula:

[0237] -(O p1 -R 20 q1 )-Rf a

[0238] [Where:

[0239] R 20 In each occurrence, C is represented independently 1－10 Alkylene.

[0240] R a Represents C 1－10 Fluorinated alkyl.

[0241] p1 is an integer from 0 to 2.

[0242] q1 is an integer from 0 to 3.

[0243] (O p1 -R 20 q1 ), O and R11a There is no restriction on the order in which they exist. ].

[0244] 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.

[0245] 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.

[0246] 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.

[0247] 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.

[0248] In a preferred embodiment, the fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a The groups shown.

[0249] [Where:

[0250] R 20 Each independently represents C 1－10 Alkylene.

[0251] R a Represents C 1－10 Fluorinated alkyl.

[0252] r1 is 0 or 1.]

[0253] In a more preferred embodiment, the fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a The groups shown.

[0254] [Where:

[0255] R 20 Each independently represents C 1－10 Alkylene.

[0256] R a Represents C 1－10 Perfluoroalkyl.

[0257] r1 is 0 or 1.]

[0258] n1 is an integer of 4 to 20, preferably an integer of 4 to 6, and more preferably 5 or 6.

[0259] In a particularly preferred embodiment,

[0260] 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

[0261] R 14 and R 15 For-O-R 20 -(O-R 20 ) r1 -Rf a , R 13 and R 16 is a hydrogen atom,

[0262] R 20 C 1－10 Alkylene, preferably C 1－6 Alkylene,

[0263] R a C 1－10 Perfluoroalkyl, preferably C 1－6 Perfluoroalkyl,

[0264] r1 is 0 or 1,

[0265] n1 is an integer of 4 to 6, and preferably 5 or 6.

[0266] 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.

[0267] 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.

[0268] In one embodiment, preferably R 1 represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 2 represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R3 represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 4 represents a C which may have one or more substituents 1－30 an alkyl group or a hydrogen atom.

[0269] 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.

[0270] 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. 3 and R 4 When at least one of the atoms is a hydrogen atom, the compound represented by formula (1) 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.

[0271] 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.

[0272] In a preferred embodiment, the above formula (1) can be represented by the following formula (1-A).

[0273]

[0274] [In formula (1-A),

[0275] R 1a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0276] R 2a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0277] R 3a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0278] R 4aEach occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0279] Among them, R 3a and R 4a At least one of represents a hydrogen atom,

[0280] n1 is an integer from 4 to 20.]

[0281] 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.

[0282] 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.

[0283] 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 6－10One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0284] R 3a and R 4a At least one of them is a hydrogen atom, and R 3a and R 4a is a hydrogen atom. 3a and R 4a When at least one of the atoms is a hydrogen atom, the compound represented by formula (1) 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.

[0285] 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.

[0286] In another embodiment, the above formula (1) can be represented by the following formula (1-A').

[0287]

[0288] [In formula (1-A'),

[0289] R 13 represents independently at each occurrence a hydrogen atom or an organic group,

[0290] R 14 represents independently at each occurrence a hydrogen atom or an organic group,

[0291] R 15 represents independently at each occurrence a hydrogen atom or an organic group,

[0292] R 16 represents independently at each occurrence a hydrogen atom or an organic group,

[0293] n5 is an integer from 4 to 20,

[0294] Among them, R 13 , R 14 , R 15 and R 16 At least one of them is a fluorine-containing organic group,

[0295] R 14 and R 15 At least one of them is a hydrogen atom.]

[0296] In the above formula (1-A'), R 13 Each occurrence is independently a hydrogen atom or an organic group, R14 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.

[0297] 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.

[0298] 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.

[0299] 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.

[0300] The above R 13 , R 14 , R 15 or R 16 The alkyl group in is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C 1－30 The alkyl group can be C 1－20 Alkyl, preferably C 1－10 Alkyl, more preferably C 1－30 In another embodiment, C 1－30 The alkyl group can be C 17－30 Alkyl, preferably C 18－30 Alkyl, more preferably C 26－30 alkyl.

[0301] As R 13 , R 14 , R 15or 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.

[0302] 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.

[0303] 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.

[0304] 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.

[0305] 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 C1－10 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.

[0306] 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.

[0307] 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.

[0308] 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.

[0309] In one approach, R 13 , R 14 , R 15 and R 16 At least two of them are fluorine-containing organic groups, preferably R 13 , R 14 , R 15 and R 16 Two of them are fluorine-containing organic groups, and more preferably R 13 and R 16 It is a fluorine-containing organic group.

[0310] In one approach, R 14 and R 15 is a hydrogen atom, or R 13 and R 16 A hydrogen atom.

[0311] In a preferred embodiment, R 13 and R 16 are independently fluorinated organic groups, R14 and R 15 A hydrogen atom.

[0312] 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.

[0313] In one embodiment, the fluorine-containing organic group is of the following formula: p1 -R 20 q1 )-Rf a The groups shown.

[0314] [Where:

[0315] R 20 In each occurrence, C is represented independently 1－10 Alkylene.

[0316] R a Represents C 1－10 Fluorinated alkyl.

[0317] p1 is an integer from 0 to 2.

[0318] q1 is an integer from 0 to 3.

[0319] (O p1 -R 20 q1 ), O and R 11a There is no restriction on the order in which they exist.]

[0320] 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.

[0321] 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.

[0322] 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.

[0323] 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.

[0324] In a preferred embodiment, the fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a The groups shown.

[0325] [Where:

[0326] R 20 Each independently represents C 1－10 Alkylene.

[0327] R a Represents C 1－10 Fluorinated alkyl.

[0328] r1 is 0 or 1.]

[0329] In a more preferred embodiment, the fluoro(poly)ether group is -O-R 20 -(O-R 20 ) r1 -Rf a The groups shown.

[0330] [Where:

[0331] R 20 Each independently represents C 1－10 Alkylene.

[0332] R a Represents C 1－10 Perfluoroalkyl.

[0333] r1 is 0 or 1.]

[0334] n1 is an integer of 4 to 20, preferably an integer of 4 to 6, and more preferably 5 or 6.

[0335] In a particularly preferred embodiment,

[0336] 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

[0337] R 14 and R 15 For-O-R 20 -(O-R20 ) r1 -Rf a , R 13 and R 16 is a hydrogen atom,

[0338] R 20 C 1－10 Alkylene, preferably C 1－6 Alkylene,

[0339] R a C 1－10 Perfluoroalkyl, preferably C 1－6 Perfluoroalkyl,

[0340] r1 is 0 or 1,

[0341] n1 is an integer of 4 to 6, and preferably 5 or 6.

[0342] 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').

[0343] In another more preferred embodiment, the above formula (1) can be represented by the following formula (1-B).

[0344]

[0345] [In formula (1-B),

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

[0347] R 2b Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0348] R 3b Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0349] R 4b Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0350] Among them, R3b and R 4b At least one of them is a hydrogen atom,

[0351] n1 is an integer from 4 to 20.]

[0352] In formula (1-B), R 1b Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 2b Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 3b Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 4b Each occurrence independently represents a C which may have one or more substituents. 1－30 an alkyl group or a hydrogen atom.

[0353] R 1b , R 2b , R 3b or R 4b 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.

[0354] As R 1b , R 2b , R 3b or R 4b 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.

[0355] R 1b , R 2b , R 3b and R4b At least one of them is a hydrogen atom, and can be preferably selected from R 1b , R 2b , R 3b and R 4b One or two of them are hydrogen atoms.

[0356] In one embodiment, preferably R 1b and R 2b is a hydrogen atom, R 3b and R 4b is a hydrogen atom or a methyl group. 3b and R 4b When at least one of the atoms is a hydrogen atom, the compound represented by formula (1-B) 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.

[0357] In another embodiment, the cyclic compound preferably includes a compound represented by the following formula (2).

[0358]

[0359] [In formula (2),

[0360] R 5 represents independently at each occurrence a hydrogen atom or an organic group,

[0361] R 6 represents independently at each occurrence a hydrogen atom or an organic group,

[0362] n2 is an integer from 4 to 20.]

[0363] The compound represented by formula (2) contains -CO- which can function as a proton acceptor, and therefore can be combined with a polymer having a group containing a hydrogen atom that can interact with -CO-, a nitrogen atom or a halogen atom.

[0364] 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.

[0365] 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.

[0366] As R 5 or R 6The 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.

[0367] 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.

[0368] As R 5 or R 6 The substituents of the alkyl group in the embodiment include: halogen atoms; alkyl groups selected from C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 Unsaturated cycloalkyl, 5-10 membered heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0369] 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.

[0370] 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.

[0371] The above R 5 or R 6The 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.

[0372] 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.

[0373] 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.

[0374] In one embodiment, preferably R 5 represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 6 represents a C which may have one or more substituents 1－30 an alkyl group or a hydrogen atom.

[0375] 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.

[0376] In a preferred embodiment, the above formula (2) can be represented by the following formula (2-A).

[0377]

[0378] [In formula (2-A),

[0379] R 5a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0380] R 6a Each occurrence independently represents a C which may have one or more substituents. 1－30Alkyl or hydrogen atom,

[0381] n2 represents an integer from 4 to 20. ]

[0382] The compound represented by formula (2-A) contains —CO— that can function as a proton acceptor, and therefore can be combined with a polymer having a group containing a hydrogen atom that can interact with —CO—, a nitrogen atom, or a halogen atom.

[0383] 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.

[0384] 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.

[0385] As R 5a or R 6a 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.

[0386] In one embodiment, preferably R 5a and R 6a A hydrogen atom.

[0387] In another embodiment, the cyclic compound preferably includes a compound represented by the following formula (3).

[0388]

[0389] [In formula (3),

[0390] R 7 represents independently at each occurrence a hydrogen atom or an organic group,

[0391] R 8 represents independently at each occurrence a hydrogen atom or an organic group,

[0392] R 9 represents independently at each occurrence a hydrogen atom or an organic group,

[0393] R 10 represents independently at each occurrence a hydrogen atom or an organic group,

[0394] R 11 represents independently at each occurrence a hydrogen atom or an organic group,

[0395] R 12 represents independently at each occurrence a hydrogen atom or an organic group,

[0396] n3 is an integer from 1 to 19,

[0397] n4 is an integer from 1 to 19,

[0398] The total of n3 and n4 is 4 to 20,

[0399] The order of presence of the units marked with n3 or n4 and enclosed in parentheses is arbitrary in formula (3).]

[0400] The compound represented by formula (3) contains -CO- which can function as a proton acceptor, and therefore can be combined with a polymer having a group containing a hydrogen atom that can interact with -CO-, a nitrogen atom or a halogen atom.

[0401] In formula (3), R 7 Each occurrence independently represents a hydrogen atom or an organic group, R 8 Each occurrence independently represents a hydrogen atom or an organic group, R 9 Each occurrence independently represents a hydrogen atom or an organic group, R 10 Each occurrence independently represents a hydrogen atom or an organic group, R 11 Each occurrence independently represents a hydrogen atom or an organic group, R 12 Each occurrence independently represents a hydrogen atom or an organic group.

[0402] As R 7 , R 8 , R 9 , R 10 , R 11or 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.

[0403] 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.

[0404] 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.

[0405] As R 7 , R 8 , R 9 , R 10 , R 11 or R 12 The substituents of the alkyl group in the embodiment include: halogen atoms; alkyl groups selected from C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 Unsaturated cycloalkyl, 5-10 membered heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0406] The above R 7 , R 8 , R 9 , R 10 , R 11 or R12 The alkyloxy group in the 21 (Where R 21 It is an alkyl group which may have one or more substituents.

[0407] 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.

[0408] 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.

[0409] 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.

[0410] 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.

[0411] In one embodiment, preferably R7 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.

[0412] 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.

[0413] In a preferred embodiment, the above formula (3) can be represented by the following formula (3-A).

[0414]

[0415] [In formula (3-A),

[0416] R 7a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0417] R 8a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0418] R 9a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0419] R 10a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0420] R 11aEach occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0421] R 12a Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom,

[0422] n3 is an integer from 1 to 19,

[0423] n4 is an integer from 1 to 19,

[0424] The total of n3 and n4 is 4 to 20,

[0425] The order of existence of the units marked with n3 or n4 and enclosed in parentheses is arbitrary in formula (3-A).

[0426] The compound represented by formula (3-A) contains -CO- which can function as a proton acceptor, and therefore can be combined with a polymer having a group containing a hydrogen atom that can interact with -CO-, a nitrogen atom, or a halogen atom.

[0427] 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.

[0428] R 7a , R 8a , R 9a , R 10a , R 11a or R 12a The alkyl group shown is preferably C 1－30 The alkyl group may be a straight chain or a branched chain. In one embodiment, C1－30 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.

[0429] 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.

[0430] In one approach, R 7a , R 8a , R 11a and R 12a It may be preferably a hydrogen atom, R 9a and R 10a Preferred is methyl.

[0431] In another preferred embodiment, the above formula (3) can be represented by the following formula (3-B).

[0432]

[0433] [In formula (3-B),

[0434] R 7b represents independently at each occurrence a hydrogen atom or an organic group,

[0435] R 8b represents independently at each occurrence a hydrogen atom or an organic group,

[0436] R 9b represents independently at each occurrence a hydrogen atom or an organic group,

[0437] R 10b represents independently at each occurrence a hydrogen atom or an organic group,

[0438] R11b represents independently at each occurrence a hydrogen atom or an organic group,

[0439] R 12b represents independently at each occurrence a hydrogen atom or an organic group,

[0440] Among them, R 9b and R 10b At least one of them is a hydrogen atom,

[0441] n3 is an integer from 1 to 19,

[0442] n4 is an integer from 1 to 19,

[0443] The total of n3 and n4 is 4 to 20,

[0444] The order of existence of the units indicated by n3 or n4 and enclosed in parentheses is arbitrary in formula (3-B).]

[0445] The compound represented by formula (3-B) contains -CO- which can function as a proton acceptor, and therefore can be combined with a polymer having a group containing a hydrogen atom that can interact with -CO-, a nitrogen atom, or a halogen atom.

[0446] In formula (3-B), R 7b Each occurrence independently represents a hydrogen atom or an organic group, R 8b Each occurrence independently represents a hydrogen atom or an organic group, R 9b Each occurrence independently represents a hydrogen atom or an organic group, R 10b Each occurrence independently represents a hydrogen atom or an organic group, R 11b Each occurrence independently represents a hydrogen atom or an organic group, R 12b Each occurrence independently represents a hydrogen atom or an organic group.

[0447] As R 7b , R 8b , R 9b , R 10b , R 11b or R 12b 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.

[0448] As R 7b , R 8b , R 9b , R 10b , R 11b or R 12bThe 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.

[0449] R 7b , R 8b , R 9b , R 10b , R 11b or R 12b 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.

[0450] As R 7b , R 8b , R 9b , R 10b , R 11b or R 12b 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.

[0451] The above R 7b , R 8b , R 9b , R 10b , R 11b or R 12b The alkyloxy group in the 21 (Where R 21 It is an alkyl group which may have one or more substituents.

[0452] 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 1－30The 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 1－3 alkyl.

[0453] The above R 7b , R 8b , R 9b , R 10b , R 11b or R 12b 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.

[0454] In one embodiment, the above R 7b , R 8b , R 9b , R 10b , R 11b or R 12b 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.

[0455] 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.

[0456] In one embodiment, preferably R 7b represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 8b represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 9b represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 10brepresents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 11b represents a C which may have one or more substituents 1－30 Alkyl or hydrogen atom, R 12b represents a C which may have one or more substituents 1－30 an alkyl group or a hydrogen atom.

[0457] R 9b and R 10b At least one of them is a hydrogen atom, and R 9b and R 10b is a hydrogen atom. 9b and R 10b When at least one of the atoms is a hydrogen atom, the compound represented by formula (3-B) 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.

[0458] The cyclic compound may preferably be one or more compounds selected from the group consisting of formulae (1), (2) and (3), and more preferably one or more compounds selected from the group consisting of formulae (1-A), (2-A) and (3-A).

[0459] When the complex contains two or more cyclic compounds, the two or more cyclic compounds may be the same or different.

[0460] In the total of 100 parts by mass of the polymer and the cyclic compound described later, the ratio of the cyclic compound can be preferably 0.01% by mass to 99% by mass, more preferably 0.1% by mass to 95% by mass, and further preferably 1% by mass to 90% by mass. When the ratio of the cyclic compound is within the above range, the heat resistance and / or hydrophobicity of the composite are good.

[0461] In the composite of the present invention, the polymer is encapsulated by the cyclic compound, one of the polymer and the cyclic compound contains one or more selected from -CO-, a nitrogen atom and a halogen atom, and the other has a group containing a hydrogen atom capable of interacting with -CO-, a nitrogen atom or a halogen atom.

[0462] In one embodiment, the polymer preferably contains one or more selected from -CO-, nitrogen atoms and halogen atoms. The positions of -CO- and nitrogen atoms in the polymer are not particularly limited, and they may exist as the ends of the polymer or as part of the polymer molecule. Examples of polymers containing -CO- include: polymers containing amide groups in the main chain skeleton such as polyamides; polymers containing ester groups in the main chain skeleton such as polycarbonates, polyesters, and polyarylates; polymers containing carbonyl groups in the main chain skeleton such as polyether ketones and polyetheretherketones (excluding polymers containing amide groups or ester groups in the main chain skeleton). Examples of polymers containing nitrogen atoms include polyamides. Examples of polymers containing halogen atoms include fluorine-containing polymers, chlorine-containing polymers, and the like.

[0463] In another embodiment, the polymer preferably has a group containing a hydrogen atom that can interact with -CO-, a nitrogen atom or a halogen atom. As the polymer containing a protogenic group, a polymer containing an OH group can be cited, and a polymer containing a vinyl alcohol unit is preferably cited. As the polymer having an unsaturated bond, a diene polymer is preferably cited.

[0464] In another embodiment, the polymer preferably contains an OH group. Examples of the polymer containing an OH group include polymers containing vinyl alcohol units.

[0465] 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.

[0466] In the present invention, the polymer may have one or more substituents. Examples of the substituents that may be contained in the polymer include -COOR f13 ,-OR f13 , -NR f13 2. -NR f13 -CO-R f13 , -CO-NR f13 2. -NO2, -CN, -COR 14 , -SO2R f14 , -O-COR f14 , C may be substituted by one or more halogen atoms 1－5 One or more of an alkyl group and a halogen atom.

[0467] 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.

[0468] R f13Each occurrence independently represents a C which may be substituted with one or more halogen atoms. 1－4 an alkyl group or a hydrogen atom.

[0469] 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.

[0470] 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.

[0471] In one approach, R f13 The above-mentioned C may be substituted with one or more halogen atoms. 1－4 The alkyl group is preferably a C 1－4 Alkyl, more preferably C 1－4 Alkyl, preferably C 1－4 Perfluoroalkyl.

[0472] 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-.

[0473] R f14 Each occurrence independently represents a C which may be substituted with one or more fluorine atoms. 1－4 an alkyl group, a hydrogen atom or a halogen atom.

[0474] 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.

[0475] As a substitute for the above R f14 C shown 1－4Examples of the halogen atom of 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.

[0476] 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.

[0477] 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.

[0478] 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.

[0479] As the above substituent, C 1－5 The halogen atom of the alkyl group may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a fluorine atom or a chlorine atom. 1－5 The alkyl group is preferably a C 1－5 Alkyl, more preferably C 1－5 Alkyl, more preferably C 1－4 Perfluoroalkyl.

[0480] 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-.

[0481] 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.

[0482] Preferred examples of the polymer containing one or more selected from -CO- and a nitrogen atom include polymers having one or more repeating structural units selected from the following formulae (B1) to (B6).

[0483] -[NH-CO-R b2 -CO-NH-R b2 ]- (B1)

[0484] -[NH-CO-R b2 ]- (B2)

[0485] -[O-CO-O-R b2 ]- (B3)

[0486] -[O-CO-R b2 ]- (B4)

[0487] -[O-CO-R b2 -CO-O-R b2 ]- (B5)

[0488] -[O-R b2 -O-R b2 -CO-R b2 ]- (B6)

[0489] [In formulas (B1) to (B6),

[0490] R b2 Each occurrence independently represents a C 6－20 A divalent aromatic hydrocarbon group, or a C 1－16 Alkylene.

[0491] R b3 Each occurrence independently represents a C which may have one or more substituents. 1－16 Alkyl group or hydrogen atom.]

[0492] When the polymer includes a polymer having the above-mentioned repeating structural unit, the heat resistance of the obtained composite is good.

[0493] The polymer containing the repeating structural unit represented by formula (B4) or formula (B5) is equivalent to polyester and is easily hydrolyzed in its chemical structure. For example, the improvement of hydrolysis resistance of polylactic acid, which is expected to be a biodegradable polymer, is considered a technical problem. Regarding the composite of the present invention, since the cyclic compound and the polymer containing the repeating structural unit represented by formula (B4) or (B5) can interact with each other, not only heat resistance but also improvement of hydrolysis resistance can be expected.

[0494] 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 benzal group, a xylylene group or a naphthylene group, and more preferably a phenylene group, a benzal group or a xylylene group.

[0495] 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.

[0496] R b2 The C 6－20 The divalent group of the aromatic hydrocarbon group can be preferably represented by the following formula.

[0497] *-Ar 1 -(X 1 -Ar 1 ) n10 -*

[0498] [Wherein,

[0499] Ar 1 Each occurrence independently represents a divalent C 6－10 Aromatic hydrocarbon groups,

[0500] X 1 Indicates a single bond, -O-, -CO-, -SO2- or C 1－4 Alkylene,

[0501] n10 represents an integer greater than or equal to 0 and less than or equal to 3,

[0502] * indicates a valence bond,

[0503] The total number of carbon atoms in the formula is 6 or more and 20 or less. ].

[0504] Ar 1represents a divalent C which may have one or more substituents 6－10 Aromatic hydrocarbon group.

[0505] 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

[0506] －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.

[0507] As Ar 1 The divalent C 6－10 The substituent that the 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.

[0508] The above-mentioned 2-valent C 6－10 The substituent that the aromatic hydrocarbon group may have is 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.

[0509] X 1 Indicates 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 1－3The alkylene group may specifically be -CH2- or -C(CH3)2-.

[0510] As 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.

[0511] The above contains divalent C 6－10 The substituent that the divalent 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.

[0512] 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.

[0513] 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 1－10Alkylene, 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-.

[0514] 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.

[0515] 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.

[0516] The number average molecular weight of the polymer containing one or more selected from -CO- and nitrogen atoms is, for example, 500 to 1,000,000, preferably 1,000 to 500,000, more preferably 2,000 to 300,000, further preferably 2,000 to 250,000, for example, 3,000 to 250,000.

[0517] 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.

[0518] Examples of the above-mentioned polymer containing halogen atoms (hereinafter also referred to as "halogen-containing polymer") include polymers containing one or more selected from fluorine atoms, chlorine atoms, bromine atoms and iodine atoms. Representatively, polymers containing one or more selected from fluorine atoms and chlorine atoms are preferred. In one embodiment, polymers containing fluorine atoms or chlorine atoms are preferred, and in another embodiment, polymers containing fluorine atoms and chlorine atoms are preferred. Examples of the above-mentioned polymer containing halogen atoms include polymers having repeating structural units containing fluorine atoms as substituents in the above-mentioned formulas (B1) to (B6); fluorine-containing olefin polymers; fluorinated polyethers; and fluorine-containing acrylic polymers; chlorine-containing polymers such as chlorine-containing olefin polymers, chlorine-containing acrylic polymers, and polymers having repeating structural units containing chlorine atoms as substituents in the above-mentioned formulas (B1) to (B6). The halogen-containing polymer may preferably include one or more selected from a polymer having a repeating structural unit containing a fluorine atom as a substituent in any of the above formulae (B1) to (B6); a fluorinated olefin polymer; a fluorinated polyether; and a chlorine-containing polymer.

[0519] In one embodiment, the fluorinated polymer preferably includes a polymer having a repeating structural unit containing a fluorine atom as a substituent in any one of the formulae (B1) to (B6).

[0520] 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.

[0521] The fluorine-containing olefin compound is preferably represented by the following formula.

[0522] CR f20 R f21 =CR f22 R f23

[0523] [Wherein,

[0524] R f20 represents a hydrogen atom, a fluorine atom, a chlorine atom, a C 1－5 Fluorinated alkyl and C1－5 One of the perfluoroalkoxy groups,

[0525] 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,

[0526] 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,

[0527] 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,

[0528] R f20 ~R f23 One or more of them are fluorine atoms.]

[0529] 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.

[0530] 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 C1－5 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 C 1－3 Perfluoroalkyl. f20 , R f21 , R f22 or R f23 C shown 1－5 Specific examples of the fluoroalkyl group include -CF3, -CF2CF3 and -CF2CF2CF3.

[0531] 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.

[0532] In one embodiment, R f20 is a fluorine atom or a hydrogen atom, R f21 is a fluorine atom or a hydrogen atom, R f22 is a fluorine atom or a hydrogen atom, R f23 is a fluorine atom or a hydrogen atom. In another embodiment, R f20 is a fluorine atom or a hydrogen atom, R f21 is a fluorine atom or a hydrogen atom, R f22 is a fluorine atom or a hydrogen atom, R f23 C 1－5 Perfluoroalkyl or C 1－5 Perfluoroalkoxy.

[0533] 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.

[0534] In one embodiment, the fluorine-containing olefin compound may preferably be vinylidene fluoride.

[0535] 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 / tetrafluoroethylene / hexafluoropropylene copolymer, vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer and polyvinylidene fluoride. In one embodiment, the above-mentioned fluorine-containing olefin polymer includes polyvinylidene fluoride.

[0536] The number average molecular weight of the fluorinated olefin polymer is preferably from 1,000 to 1,000,000, more preferably from 2,000 to 500,000, and still more preferably from 3,000 to 300,000.

[0537] 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.

[0538] The fluoropolyether may be a polymer having an oxyfluoroalkylene unit. The fluoropolyether is preferably represented by the following formula.

[0539] Y 1 -R f1 -R F -O q -R f2 -Y 2

[0540] [Where:

[0541] R F represents a divalent fluorinated polyether group,

[0542] Y 1 represents a halogen atom, a hydrogen atom, -COOR f3 ,-OR f3 , -NR f3 2. -NR f3 -CO-R f3 , -CO-NR f3 2. -NO2, -CN, -COR f4 , -SO2R f4 AND-O-COR f4 1 of

[0543] Y 2 represents a halogen atom, a hydrogen atom, -COOR f3 ,-OR f3 , -NR f3 2. -NR f3-CO-R f3 , -CO-NR f3 2. -NO2, -CN, -COR f4 , -SO2R f4 AND-O-COR f4 1 of

[0544] R f1 represents a divalent hydrocarbon group which may have one or more substituents or a single bond,

[0545] R f2 represents a divalent hydrocarbon group which may have one or more substituents or a single bond,

[0546] R f3 Each occurrence independently represents a C which may have one or more substituents. 1－16 Alkyl or hydrogen atom,

[0547] R f4 Each occurrence independently represents a C which may have one or more substituents. 1－16 an alkyl group, a hydrogen atom or a halogen atom,

[0548] q is 0 or 1.]

[0549] R F The preferred formula is: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - the group shown.

[0550] [Where:

[0551] R Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence,

[0552] a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of existence of each repeating unit indicated by a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary. Fa When it is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more. ].

[0553] R Fa Preferably, it is a hydrogen atom or a fluorine atom, and more preferably, it is a fluorine atom.Fa When it is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more.

[0554] Preferably, a, b, c, d, e and f are each independently an integer of 0 to 100.

[0555] The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. The sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, further preferably 60 or less, for example, 50 or less or 30 or less.

[0556] These repeating units can be straight-chain or branched, and can also contain ring structures. For example, -(OC6F 12 )- can be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10 )- may be any of -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)-(i.e. in the above formula, R Fa The -(OCF2CF2CF2)- may be any of -(OCF(CF3)CF2)-, -(OCF2CF(CF3))-, and -(OCF2CF(CF3))-. The -(OC2F4)- may be any of -(OCF2CF2)-, and -(OCF(CF3))-.

[0557] The ring structure may be a three-membered ring, a four-membered ring, a five-membered ring or a six-membered ring.

[0558]

[0559] [Wherein, * represents the bonding position.]

[0560] The above ring structure may preferably be a four-membered ring, a five-membered ring or a six-membered ring, and more preferably a four-membered ring or a six-membered ring.

[0561] The repeating unit having a ring structure may preferably be the following units.

[0562]

[0563] [Wherein, * represents the bonding position.]

[0564] In one embodiment, the repeating unit is linear. By making the repeating unit linear, the surface smoothness and wear durability of the surface treatment layer can be improved.

[0565] In one embodiment, the repeating unit is branched. By making the repeating unit branched, the dynamic friction coefficient of the surface treatment layer can be increased.

[0566] In one approach, R F Each occurrence is independently a group represented by any one of the following formulae (f1) to (f7), preferably a group represented by the following formula (f7).

[0567] -(OC3F6) d -(OC2F4) e - (f1)

[0568] [Wherein, d is an integer from 1 to 200, and e is 0 or 1. ];

[0569] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f2)

[0570] [wherein, c and d are each independently an integer from 0 to 30, e and f are each independently an integer from 1 to 200,

[0571] The sum of c, d, e and f is greater than 2,

[0572] The order of presence of the repeating units marked with the subscript c, d, e or f and enclosed in brackets in the formula is arbitrary. ];

[0573] -(R 36 -R 37 ) g - (f3)

[0574] [Where R36 For OCF2 or OC2F4,

[0575] R 37 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0576] g is an integer from 2 to 100. ];

[0577] -(R 36 -R 37 ) g -R r -(R 37’ -R 36’ ) g’ - (f4)

[0578] [Where R 36 For OCF2 or OC2F4,

[0579] R 37 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0580] R 36’ For OCF2 or OC2F4,

[0581] R 37’ is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0582] g is an integer from 2 to 100,

[0583] g' is an integer from 2 to 100,

[0584] R r for

[0585]

[0586] (Where * represents the bonding position.) ];

[0587] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6)d -(OC2F4) e -(OCF2) f - (f5)

[0588] [In the formula, e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[0589] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f6)

[0590] [In the formula, f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula. ];

[0591] -(CF2CF2CH2O) d - (f7)

[0592] [In the formula, d represents an integer of 1 to 200.]

[0593] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, further preferably 15 to 50, for example, 25 to 35. OC3F6 in the above formula (f1) is preferably (OCF2CF2CF2), (OCF(CF3)CF2) or (OCF2CF(CF3)), more preferably (OCF2CF2CF2). (OC2F4) in the above formula (f1) is preferably (OCF2CF2) or (OCF(CF3)), more preferably (OCF2CF2). In one embodiment, e is 0. In another embodiment, e is 1.

[0594] In the above formula (f2), e and f are each independently preferably an integer of 5 to 200, more preferably an integer of 10 to 200. In addition, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e-(OCF2) f In another embodiment, formula (f2) may be -(OC2F4) e -(OCF2) f - the group shown.

[0595] In the above formula (f3), R 36 Preferably, it is OC2F4. In the above (f3), R 37 It is preferably a group selected from OC2F4, OC3F6 and OC4F8, or a combination of two or three groups independently selected from these groups, and more preferably a group selected from OC3F6 and OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8 is not particularly limited, and examples thereof include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2F 4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4- and -OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably an integer of 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It may be a straight chain or a branched chain, preferably a straight chain. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g -or-(OC2F4-OC4F8) g -

[0596] In the above formula (f4), R 36 , R 37 and g have the same meanings as those in the above formula (f3) and have the same aspects. 36’ , R 37’ and g' respectively have the same meanings as R described in the above formula (f3). 36 , R 37 Same as g, in the same way. r Preferably

[0597]

[0598] [Wherein, * represents the bonding position.],

[0599] More preferably

[0600]

[0601] [Wherein, * represents the bonding position. ].

[0602] In the above formula (f5), e is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 to 100.

[0603] In the above formula (f6), f is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 to 100.

[0604] In the above formula (f7), d is preferably an integer of 1 to 100, more preferably 5 to 100, and even more preferably 10 to 100.

[0605] In one embodiment, the above R F It is a group represented by the above formula (f1).

[0606] In one embodiment, the above R F It is a group represented by the above formula (f2).

[0607] In one embodiment, the above R F It is a group represented by the above formula (f3).

[0608] In one embodiment, the above R F It is a group represented by the above formula (f4).

[0609] In one embodiment, the above R F It is a group represented by the above formula (f5).

[0610] In one embodiment, the above R F It is a group represented by the above formula (f6).

[0611] In one embodiment, the above R F It is a group represented by the above formula (f7).

[0612] In the above R FIn the embodiment of the present invention, the ratio of e to f (hereinafter referred to as "e / f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, further preferably 0.2 to 1.5, and further more preferably 0.2 to 0.85. By making the e / f ratio less than 10, the smoothness, wear durability and chemical resistance (for example, durability to artificial sweat) of the surface treatment layer obtained from the compound are further improved. The smaller the e / f ratio, the more the smoothness and wear durability of the surface treatment layer are improved. On the other hand, by making the e / f ratio greater than 0.1, the stability of the compound can be further improved. The larger the e / f ratio, the more the stability of the compound is improved.

[0613] The above R F The number average molecular weight of the moiety shown is not particularly limited, and is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. F The number average molecular weight of the parts shown is calculated using 19 The value measured by F-NMR.

[0614] In another way, R F The number average molecular weight of the moiety shown is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, further preferably 2,000 to 10,000, and for example, may be 3,000 to 6,000.

[0615] In another embodiment, R F The number average molecular weight of the moiety shown may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0616] R f1 Each occurrence independently represents a divalent hydrocarbon group which may have one or more substituents or a single bond.

[0617] The "hydrocarbon group" in the above-mentioned hydrocarbon group which may have one or more substituents may be preferably a divalent C 1－20 A hydrocarbon group, more preferably a divalent C 1－20 Aliphatic hydrocarbon group, more preferably C 1－16 Alkylene.

[0618] The hydrocarbon group which may have one or more substituents is preferably a C 1－16 Alkylene. C may be substituted with one or more fluorine atoms 1－16 The "C" in the alkylene 1－16 The "alkylene" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C1－10 Alkylene, more preferably a linear or branched C 1－6 Alkylene, more preferably a linear or branched C 1－3 Alkylene, more preferably a straight chain C 1－6 Alkylene, especially straight chain C 1－3 Alkylene.

[0619] Examples of the substituent that the hydrocarbon group may have include: -COOR f13 ,-OR f13 , -NR f13 2. -NR f13 -CO-R f13 , -CO-NR f13 2. -NO2, -CN, -COR 14 ,-SO3R f14 , -O-COR f14 and halogen atoms. f13 and R f14 The meaning is the same as above.

[0620] The substituent that the above hydrocarbon group may have may be preferably selected from -COOH, -OH, -NH2, -CONR f13 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f14 and halogen atoms, more preferably a halogen atom, and still more preferably a fluorine atom or a chlorine atom.

[0621] In one embodiment, the above R f1 The hydrocarbon group which may have one or more substituents is preferably a C 1－16 Alkylene.

[0622] The above C may be substituted with one or more fluorine atoms 1－16 The "C" in the alkylene 1－16 The "alkylene" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Alkylene, especially C 1－3 Alkylene, more preferably a straight chain C 1－6 Alkylene, especially C 1－3 Alkylene.

[0623] The above R f1 Preferably, C is substituted with one or more fluorine atoms. 1－16 Alkylene, more preferably C 1－16 Perfluoroalkylene.

[0624] C 1－16The perfluoroalkylene group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Perfluoroalkylene, especially C 1－3 Perfluoroalkylene, more preferably linear C 1－6 Perfluoroalkylene, especially C 1－3 Perfluoroalkylene is specifically -CF2-, -CF2CF2- or -CF2CF2CF2-.

[0625] In the above formula, R f2 It represents a divalent hydrocarbon group which may have one or more substituents or a single bond.

[0626] The "hydrocarbon group" in the above-mentioned hydrocarbon group which may have one or more substituents may preferably be C 1－20 Hydrocarbyl, more preferably C 1－20 Aliphatic hydrocarbon group, more preferably C 1－16 alkyl.

[0627] The hydrocarbon group which may have one or more substituents is preferably a C 1－16 Alkyl. C may be substituted with one or more fluorine atoms 1－16 The "C" in the alkyl 1－16 The "alkyl" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－10 Alkyl, more preferably a linear or branched C 1－6 Alkyl, more preferably a linear or branched C 1－3 Alkyl, preferably a straight chain C 1－6 Alkyl groups, especially straight-chain C 1－3 alkyl.

[0628] Examples of the substituent that the hydrocarbon group may have include: -COOR f13 ,-OR f13 , -NR f13 2. -NR f13 -CO-R f13 , -CO-NR f13 2. -NO2, -CN, -COR 14 , -SO2R f14 , -O-COR f14 and halogen atoms. f13 and R f14 The meaning is the same as above.

[0629] The substituent that the above hydrocarbon group may have may be preferably selected from -COOH, -OH, -NH2, -CONR f13, -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f14 and halogen atoms, more preferably a halogen atom, and still more preferably a fluorine atom or a chlorine atom.

[0630] In one approach, R f2 The hydrocarbon group which may have one or more substituents is preferably a C 1－16 alkyl.

[0631] The above C may be substituted with one or more fluorine atoms 1－16 The "C" in the alkyl 1－16 The "alkyl" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Alkyl groups, especially C 1－3 Alkyl, more preferably a straight chain C 1－6 Alkyl groups, especially C 1－3 alkyl.

[0632] The above R f2 Preferably, C is substituted with one or more fluorine atoms. 1－16 Alkyl, more preferably C 1－16 Perfluoroalkyl.

[0633] C 1－16 The perfluoroalkyl group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl, more preferably linear C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl group, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0634] In the above formula, Y 1 represents a halogen atom, a hydrogen atom, -COOR f3 ,-OR f3 , -NR f3 2. -NR f3 -CO-R f3 , -CO-NR f3 2. -NO2, -CN, -COR f4 , -SO2R f4 AND-O-COR f4 1 of them.

[0635] In addition, in the above formula, Y 2 represents a halogen atom, a hydrogen atom, -COOR f3 ,-OR f3 , -NRf3 2. -NR f3 -CO-R f3 , -CO-NR f3 2. -NO2, -CN, -COR f4 , -SO2R f4 AND-O-COR f4 1 of them.

[0636] R f3 Each occurrence independently represents a C which may have one or more substituents. 1－16 an alkyl group or a hydrogen atom.

[0637] The above C may be substituted with one or more fluorine atoms 1－16 The "C" in the alkylene 1－16 The "alkylene" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Alkylene, especially C 1－3 Alkylene, more preferably a straight chain C 1－6 Alkylene, especially C 1－3 Alkylene.

[0638] As the above R f3 C shown 1－16 The substituent that the alkylene group may have is selected from -COOR f13 ,-OR f13 , -NR f13 2. -NR f13 -CO-R f13 , -CO-NR f13 2. -NO2, -CN, -COR 14 ,-SO3R f14 , -O-COR f14 and halogen atoms. f13 and R f14 The meaning is the same as above.

[0639] The above R f3 C shown 1－16 The substituent that the alkylene group may have may be preferably selected from -COOH, -OH, -NH2, -CONR f13 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f14 and halogen atoms, more preferably a halogen atom, and still more preferably a fluorine atom or a chlorine atom.

[0640] In one embodiment, the above R f3 The C shown may have one or more substituents. 1－16The alkylene group may be preferably a C 1－16 Alkylene.

[0641] The above R f3 The C shown may be substituted with one or more fluorine atoms 1－16 The alkylene group is preferably a C 1－16 Alkylene, more preferably C 1－16 Perfluoroalkylene.

[0642] The above R f3 C 1－16 The perfluoroalkylene group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Perfluoroalkylene, especially C 1－3 Perfluoroalkylene, more preferably linear C 1－6 Perfluoroalkylene, especially C 1－3 Perfluoroalkylene is specifically -CF2-, -CF2CF2- or -CF2CF2CF2-.

[0643] R f4 Each occurrence independently represents a C which may have one or more substituents. 1－16 an alkyl group, a hydrogen atom or a halogen atom.

[0644] The above C which may have one or more substituents 1－16 The "C" in the alkyl 1－16 The "alkyl" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－5 Alkyl groups, especially C 1－3 Alkyl, more preferably a straight chain C 1－6 Alkyl groups, especially C 1－3 alkyl.

[0645] As the above R f4 C shown 1－16 The substituent that the alkyl group may have is selected from -COOR f13 ,-OR f13 , -NR f13 2. -NR f13 -CO-R f13 , -CO-NR f13 2. -NO2, -CN, -COR 14 , -SO2R f14 , -O-COR f14 and halogen atoms. f13 and R f14 The meaning is the same as above.

[0646] The above Rf4 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.

[0647] In one embodiment, the above R f4 The C shown may have one or more substituents. 1－16 The alkyl group may be preferably a C 1－16 alkyl.

[0648] The above R f4 The C shown may be substituted with one or more fluorine atoms 1－16 The alkyl group is preferably a C 1－16 Alkyl, more preferably C 1－16 Perfluoroalkyl.

[0649] The above R f4 C 1－16 The perfluoroalkyl group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl, more preferably linear C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl group, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0650] As the above Y 1 or Y 2 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or a chlorine atom is preferred.

[0651] Y 1 It may be preferably selected from -COOH, -OH, -NH2, -CONR f3 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f4 and halogen atoms.

[0652] Y 2 It may be preferably selected from -COOH, -OH, -NH2, -CONR f3 , -NO2, -CN, -COH, -COCl, -SO3H, -O-COR f4 and halogen atoms.

[0653] In the above formula, q is 0 or 1. In one embodiment, q is 0, and in another embodiment, q is 1.

[0654] The number average molecular weight of the fluoropolyether is not particularly limited, and is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. 19 The measurement was performed by F-NMR.

[0655] In another embodiment, the number average molecular weight of the fluoropolyether is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, further preferably 2,000 to 10,000, and for example, may be 3,000 to 6,000.

[0656] In another embodiment, the number average molecular weight of the fluoropolyether may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0657] Examples of the chlorine-containing polymer include chlorine-containing olefin polymers; chlorine-containing acrylic polymers; polymers having repeating structural units containing chlorine atoms as substituents in the above formulae (B1) to (B6), and preferably chlorine-containing olefin polymers.

[0658] Preferred examples of the chlorine-containing polymer include polymers having a repeating structural unit represented by the following formula (B7).

[0659] -[CR b3 2-CR b3 2]-(B7)

[0660] [In formula (B7),

[0661] R b3 Each occurrence independently represents a hydrogen atom, a chlorine atom and a C 1－5 One of the chloroalkyl groups,

[0662] R b3 One or more of them are chlorine atoms.]

[0663] In the above formula, R b3 Each occurrence independently represents a hydrogen atom, a chlorine atom, a C 1－5 Chloroalkyl and C 1－5 A type of chloroalkoxy.

[0664] R b3 C shown 1－5The chloroalkyl group may be a straight chain or a branched chain, and may preferably be a straight chain or a branched chain C 1－5 Chloroalkyl, especially C 1－3 Chloroalkyl, more preferably linear C 1－3 Chloroalkyl. As R b3 C shown 1－5 Specific examples of the fluoroalkyl group include -CH2Cl, -CHCl2 and CCl3.

[0665] The repeating structural unit represented by the above formula (B6) may preferably be -[CH2-CHCl]- or -[CH2-CCl2]-.

[0666] The number average molecular weight of the chlorine-containing polymer may preferably be 1,000 to 1,000,000, more preferably 2,000 to 500,000, and even more preferably 3,000 to 300,000.

[0667] Preferred examples of the polymer containing a proton donating group or an unsaturated group include polymers having one or more repeating structural units selected from the following formulae (B8), (B9), (B10), (B1) and (B2).

[0668] -[CR b4 2-CR b4 =CR b4 -CR b4 2]- (B8)

[0669] -[CR b4 2-CR b4 OH]- (B9)

[0670] -[CR b4 2-CR b4 OH] n -[CR b4 2-CR b4 2] m -(B10)

[0671] -[NH-CO-R b2 -CO-NH-R b2 ]- (B1)

[0672] -[NH-CO-R b2 ]-(B2)

[0673] [In formulas (B7) to (B9), (B1) and (B2),

[0674] R b2The meanings are the same as above, and each occurrence independently represents a C which may have one or more substituents. 6－20 A divalent aromatic hydrocarbon group, or a C 1－16 Alkylene,

[0675] R b4 Each occurrence independently represents a C which may have one or more substituents. 1－16 Alkyl or hydrogen atom,

[0676] The order of the units marked with m and n and enclosed in parentheses is arbitrary in formula (B9).

[0677] R b4 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, more preferably a linear or branched C 1－4 The alkyl group may specifically be -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)CH3, -C(CH3)3, -CH2CH2CH2CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)CH3, -C(CH3)2CH3.

[0678] As R b4 C shown 1－16 The substituent that the alkyl group may have is selected from -COOR f13 ,-OR f13 , -NR f13 2. -NR f13 -CO-R f13 , -CO-NR f13 2. -NO2, -CN, -COR 14 ,-SO3R f14 , -O-COR f14 and halogen atoms. f13 and R f14 The meaning is the same as above.

[0679] The above R b4 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-CORf14 and halogen atoms, more preferably a halogen atom, and still more preferably a fluorine atom or a chlorine atom.

[0680] Examples of the polymer containing the group containing hydrogen atoms having a charge density of 0.25 or more include: b2 Preferably C 6－16 Alkylene, more preferably C 6－10 Specific examples of polymers of repeating structural units of an alkylene group include poly-ε-caprolactone and 6-nylon.

[0681] In poly-ε-caprolactone, the charge density of hydrogen bonded to the carbon adjacent to the carbonyl group is 0.27, and in 6-nylon, the charge density of hydrogen bonded to the carbon adjacent to the carbonyl group of polyamide is 0.268. In fact, it is necessary to calculate which hydrogen atom has a charge density of 0.25 or more, but from the above example, it can be seen that there is a tendency for the charge density of hydrogen bonded to the carbon adjacent to the carbonyl group to be high. It should not be limited to a specific theory for explanation, but it is speculated that this may be due to the high electron-attracting property of the carbonyl group, which affects the charge density of hydrogen atoms bonded to the adjacent carbon. It can be considered that based on such a relationship, polymer design and charge density calculation can determine the structure in the composite that can be expected to interact.

[0682] The polymer represented by the above formula (B8) may be partially cross-linked with double bonds. As the crosslinking agent, a peroxide crosslinking agent can be used, and any organic peroxide that can easily generate peroxyl radicals in the presence of heat or a redox system can be used. Specific examples thereof include 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-tert-butyl peroxide (PERBUTYL D), tert-butyl peroxide isopropylbenzene (PERBUTYL C), diisopropylbenzene peroxide (PERCUMYL D, PERCUMYL D-40, PERCUMYL D-40MB(T)), α,α-bis(tert-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (PERHEXA25B, PERHEXA25B-40), 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexyne-3-yl (PERHEXYNE 25B, PERHEXYNE 25B-40), benzoyl peroxide, tert-butylbenzene peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane (PERHEXA 25Z), tert-butyl peroxymaleate (tert-butyl MA), tert-butyl peroxyisopropyl carbonate (PERBUTYL I-75), methyl ethyl ketone peroxide (PERMEK D (DR), PERMEK H (HR, HY), PERMEK N (NR, NY), PERMEK S (SR), PERMEK F (FR), PERMEK G (GR, GY)), cyclohexanone peroxide (PERHEXAH), acetylacetone peroxide (PERCURE AH, AL), 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane (PERHEXATMH), 1,1-di(tert-hexylperoxy)cyclohexane (PERHEXAHC), 1,1-di(tert-butylperoxy)-2-methylcyclohexane (PERHEXAMC), 1,1-di(tert-butylperoxy)cyclohexane (PERHEXA C-80(S), PERHEXA C-75(EB), PERHEXAC(C), PERHEXA C-40, PERHEXA C-40MB(S)), 2,2-di(tert-butylperoxy)butane (PERHEXA22), 4,4-di(tert-butylperoxy)butyl valerate (PERHEXA V, PERHEXA V-40(F)), 2,2-di(4,4-di(tert-butylperoxy)cyclohexyl)propane (PERTETRA A), hydrogen peroxide Permethrin (PERMENTAH), diisopropylbenzene hydroperoxide (PERCUMYL P), 1,1,3,3-tetramethylbutyl hydroperoxide (PEROCTA H), cumene hydroperoxide (PERCUMYL H-80), tert-butyl hydroperoxide (PERBUTYL H-69), di(2-tert-butylperoxyisopropyl)benzene (PERBUTYL P, PERBUTYL P-40, PEROXYMON F-40, PERBUTYL P-40MB(K)), di-tert-hexyl peroxide (PERHEXYL D), diisobutyryl peroxide (PEROYL IB), di(3,5,5-trimethylhexanoyl peroxide) (PEROYL355(S)), dilauroyl peroxide (PEROYL L), disuccinic acid peroxide (PEROYL NYPER BMT-K40, NYPER BMT-M), dibenzoyl peroxide (NYPER BW, NYPER BO, NYPER FF, NYPER BS, NYPER E, NYPER NS), di(4-methylbenzoyl) peroxide (NYPER PMB), di-n-propyl peroxydicarbonate (PEROYL NPP-50M), diisopropyl peroxydicarbonate (PEROYL IPP-50, PEROYL IPP-27), di(4-tert-butylcyclohexyl) peroxydicarbonate (PEROYL TCP), di(2-ethylhexyl) peroxydicarbonate (PEROYLOPP), di-sec-butyl peroxydicarbonate (PEROYL SBP), cumyl peroxyneodecanoate (PERCUMYL ND, PERCUMYLND-50E), 1,1,3,3-tetramethylbutyl peroxyneodecanoate (PEROCTA ND, PEROCTA ND-50E), tert-hexyl peroxyneodecanoate (PERHEXYL ND, PERHEXYL ND-50E), tert-butyl peroxyneodecanoate (PERBUTYL ND, PERBUTYL ND-50E), tert-butyl peroxyneoheptanoate (PERBUTYL NHP), tert-hexyl peroxypivalate (PERHEXYLPV, PERHEXYL PV-50E), tert-butyl peroxypivalate (PERBUTYL PV, PERBUTYL PV-40E), 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate (PEROCTA O), 2,5-dimethyl-2,5-Di(2-ethylhexanoylperoxy)hexane (PERHEXA 25O), tert-hexyl peroxy-2-ethylhexanoate (PERHEXYL O, PERCURE HO(N)), tert-butyl peroxy-2-ethylhexanoate (PERBUTYL O, PERCURE O), tert-hexyl peroxyisopropyl monocarbonate (PERHEXYLI), tert-butyl peroxy-3,5,5-trimethylhexanoate (PERBUTYL355), tert-butyl peroxylaurate (PERBUTYLL), tert-butyl peroxy-2-ethylhexyl monocarbonate (PERBUTYL E), tert-hexyl peroxybenzoate (PERHEXYL Z), tert-butyl peroxyacetate (PERBUTYL A), mixture of tert-butyl peroxy-3-methylbenzoate and tert-butyl peroxybenzoate (PERBUTYL ZT), tert-butyl peroxybenzoate (PERBUTYL Z), tert-butyl peroxyallyl monocarbonate (PERROMER AC), 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone (BTTB-25), 2,3-dimethyl-2,3-diphenylbutane (NOFMER BC-90), etc. Among them, the dialkyl type is preferred. In addition, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane is particularly preferred. Usually, the type and amount of organic peroxide are selected in consideration of the amount of active -O-O-, decomposition temperature, etc.

[0683] The number average molecular weight of the polymer having a group containing a hydrogen atom capable of interacting with -CO-, a nitrogen atom or a halogen atom is, for example, 500 to 1,000,000, preferably 1,000 to 500,000, more preferably 2,000 to 300,000, further preferably 2,000 to 250,000, for example, 3,000 to 250,000.

[0684] The polymer may be crystalline or non-crystalline. In one embodiment, in differential scanning calorimetry of the polymer, when a crystallization temperature is observed, the polymer may be determined to be a crystalline polymer, and when a crystallization temperature is not observed, the polymer may be determined to be a non-crystalline polymer. In one embodiment, the polymer may be crystalline. In another embodiment, the polymer may be non-crystalline.

[0685] The polymer preferably has at least one of a glass transition temperature and a melting point at or above 50°C. In other words, it is preferred that the glass transition temperature of the polymer is 50°C or above, or the melting point of the polymer is 50°C or above. In detail, 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 only needs to be 50°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 only needs to be 50°C or above. By having at least one of the glass transition temperature and the melting point at or above 50°C, the heat resistance of the obtained composite is good. For example, the polymer may have at least one of the glass transition temperature and the melting point at or above 100°C and at or below 400°C, and may have at least one of the glass transition temperature and the melting point at or above 150°C and at or below 300°C.

[0686] The polymer may or may not have a capping site at the end. The capping site may be a C 6－30 Aromatic hydrocarbon group, or C optionally having one or more substituents 6－30 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.

[0687] The number average molecular weight of the polymer may be, for example, 500 to 1,000,000, preferably 1,000 to 700,000, more preferably 2,000 to 500,000, further preferably 2,000 to 300,000, for example 3,000 to 300,000.

[0688] In one embodiment, it is preferred that the polymer includes a polymer containing one or more selected from -CO-, a nitrogen atom and a halogen atom, and the cyclic compound includes a polymer having a group containing a hydrogen atom capable of interacting with -CO-, a nitrogen atom or a halogen atom. In this embodiment, it is preferred that the polymer includes a polymer containing one or more selected from -CO-, a nitrogen atom and a halogen atom, and the cyclic compound includes a compound represented by any one of the above formulas (1-B) and (3-B); it is more preferred that the polymer includes a polymer containing one or more selected from -CO-, a nitrogen atom and a halogen atom, and the cyclic compound includes a compound represented by the above formula (1-B). In this embodiment, in formula (1-B), R 3b and R 4b One or more of them are preferably hydrogen atoms.

[0689] In another embodiment, it is preferred that the polymer includes a polymer having a group containing a hydrogen atom capable of interacting with -CO-, a nitrogen atom or a halogen atom, and the cyclic compound includes one or more selected from -CO-, a nitrogen atom and a halogen atom. In this embodiment, it is preferred that the polymer includes a polymer having a group containing a hydrogen atom capable of interacting with -CO-, a nitrogen atom or a halogen atom, and the cyclic compound includes a compound represented by any one of the above formulas (2) or (3); it is more preferred that the polymer includes a polymer having an unsaturated bond or a polymer containing a hydroxyl group or a polymer containing an NH group, and the cyclic compound includes a compound represented by any one of the above formulas (2) or (3); it is further preferred that the polymer includes a diene polymer, and the cyclic compound includes a compound represented by any one of the above formulas (2) or (3); it is further preferred that the polymer includes a polymer having a repeating structural unit represented by formula (B5), and the cyclic compound includes a compound represented by formula (2).

[0690] The thermal decomposition temperature of the composite is preferably 170° C. or higher, more preferably 200° C. or higher, and for example, may be 400° C. or lower. The composite of the present invention has excellent heat resistance and can be suitably used in applications requiring high heat resistance.

[0691] 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.

[0692] The present invention should not be limited to a specific theory for interpretation. In the composite of the present invention, since the polymer and the cyclic compound interact with each other, the thermal decomposition temperature is greatly increased even if the composite is formed 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, and more preferably 50°C or more.

[0693] 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.

[0694] The above-mentioned complex is not easily decomposed even when mixed with a solvent, for example, because the above-mentioned polymer and the above-mentioned cyclic compound interact with each other through hydrogen bonds. When the above-mentioned complex is mixed with a good solvent for the above-mentioned polymer, assuming that the mass of the complex before mixing is w0, and the mass of the complex after mixing is w1, w1 / w0 is preferably 4% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more, for example, 80% by mass or less. The mass of the above-mentioned complex before mixing can be set to the total mass of the polymer and the cyclic compound used to make the complex.

[0695] As a good solvent for the above-mentioned polymer, there is no particular limitation as long as it is a solvent in which more than 10% by mass of the polymer is dissolved. For example, in the case of polylactic acid (PLA), chloroform and trichloroethylene can be listed; in the case of PBR, ethyl acetate and chloroform can be listed. In addition, when the above-mentioned cyclic compound and the above-mentioned complex are mixed, the good solvent for the above-mentioned cyclic compound can be preferably 500 parts by mass or more and 10,000 parts by mass or less, more preferably 300 parts by mass or more and 5,000 parts by mass or less, and further preferably 150 parts by mass or more and 1,000 parts by mass or less, relative to 1 part by mass of the above-mentioned cyclic compound.

[0696] <Method for producing composite material>

[0697] The composite can be produced by a production method comprising the step of bringing the polymer into contact with the cyclic compound represented by the formula (I) in the absence of a solvent to obtain the composite.

[0698] 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.

[0699] The contact method is not particularly limited, and examples thereof include methods using a ball mill, a rotation / revolution mixer, a homogenizer, ultrasonic dispersion, and the like.

[0700] 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.

[0701] 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.

[0702] 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.

[0703] <Composition>

[0704] A composition containing the above-mentioned complex is also included in the technical scope of the present invention.

[0705] The composition may contain, in addition to the above-mentioned complex, one or more selected from a resin, a solvent and other additives.

[0706] In the composition, the content of the complex may be preferably 0.1 mass % or more and less than 100 mass %, more preferably 1 mass % or more and 99 mass % or less, based on 100 mass % of the solid content of the composition.

[0707] Examples of the resin include acrylic resins, polyurethane resins, polyolefin resins, polyester resins, polyamide resins, styrene resins, vinyl ether resins, polyvinyl alcohol resins, polycarbonate resins, and polysulfone resins.

[0708] 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.

[0709] 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.

[0710] 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.

[0711] Example

[0712] 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.

[0713] (Synthesis example 1)

[0714] In a 2 L single-necked round-bottom flask, 25.0 g of the compound represented by formula (1-2) and 350 mL of MeCN were added, and a solution prepared by dissolving 122.9 g of potassium monopersulfate complex salt (OXONE) (2KHSO5·KHSO4·K2SO4) in 350 mL of water was added.

[0715]

[0716] Next, 7.5 mL of iodobenzene was added and the mixture was vigorously stirred at room temperature for 48 hours. The reaction solution was then poured into water and filtered by suction. The resulting yellow precipitate was washed with a large amount of water and methanol and dried.

[0717] First, 18.264 g of the washed and dried precipitate was dissolved in 350 mL of boiling 1,1,2,2-tetrachloroethane, and the insoluble matter was removed by suction filtration. The resulting red transparent filtrate was allowed to stand at room temperature for 6 hours, and then allowed to stand at 6 to 10°C for 8 hours. The precipitated fine crystals were suction filtered, washed three times with a small amount of 1,1,2,2-tetrachloroethane, and then washed three times with a small amount of methanol, and dried to obtain the compound represented by formula (3-2).

[0718]

[0719] pass 1 H NMR,13 C NMR, time-of-flight mass spectrometry (ESI-TOF-MS), melting point measurement and IR measurement confirmed that the compound represented by formula (3-2) was obtained.

[0720] 1 H NMR (500.13MHz, TFA-d, ppm): δ = 6.93 (s, 10H, CH), 3.61 (s, 10H, CH2).

[0721] 13 C NMR (125.72MHz, TFA-d, ppm): δ = 190.5 (s, C = O), 146.8 (s, C-CH2), 138.1 (CH), 28.0 (CH2).

[0722] HRMS(ESI-TOF-MS):

[0723] m / z[M+Na]+(calculated for)C 35 H 21 O 10 Theoretical calculated value: 601.1129; measured value (found): 601.1132

[0724] m / z[M+Na]+C 35 H 20 O 10 Na theoretical calculated value: 623.0949; measured value: 623.0930

[0725] Melting point: No melting point is shown. It decomposes at temperatures above 250°C.

[0726] IR (paraffin paste (Nujol mull), cm -1 ):1654,1610,1461,1377,1286,1250,1125,921,722

[0727] The structures of the cyclic compounds used in Examples are shown.

[0728]

[0729] The polymers used in Examples and Comparative Examples are shown.

[0730] 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.

[0731]

[0732] 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)

[0733] PVDF2: PVDF Kyner HSV900 manufactured by Arkema, melting point 162°C, MFR 230°C 10kgf: 0.2g / 10min

[0734] 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.

[0735]

[0736] High melting point PLA (PLLA): A commercially available product having a melting point of 180° C. and having a ratio of 99% or more of the L form of optical isomers is used. The structural formula is shown below.

[0737]

[0738] PeC: Commercially available poly-ε-caprolactone having a weight average molecular weight of 10,000 and a melting point of 60° C. was used. The structural formula is shown below.

[0739]

[0740] The measuring methods used in the examples are shown.

[0741] (1) NMR

[0742] The measurement was performed using an NMR measuring apparatus manufactured by JEOL Ltd. (JNM-ECZ500R or JEOL JNM-ECS400).

[0743] 1 H-NMR measurement conditions: 500 MHz (tetramethylsilane = 0 ppm)

[0744] (2) IR analysis

[0745] The measurement was performed at room temperature using a Fourier transform infrared spectrophotometer (IRPrestige-21) manufactured by Shimadzu Corporation.

[0746] (3) Thermal decomposition temperature

[0747] The measurement was performed using a TG / DTA analyzer (thermogravimetric differential thermal analyzer) (STA7200) manufactured by Hitachi Hightech Solutions, Inc., in a nitrogen atmosphere, with a nitrogen flow rate of 200 mL / min for a sample of about 10 mg, in a temperature range of 23° C. to 600° C. and a temperature increase rate of 10° C. / min. The thermal decomposition temperature is the temperature at which the mass of the object to be measured decreases by 5% compared to the mass of the object to be measured before the start of the measurement.

[0748] (4)DSC

[0749] Using DSC (Differential Scanning Calorimeter: Hitachi Hightech 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.

[0750] (5) X-ray diffraction

[0751] The measurement was performed under the following conditions using a fully automatic multifunctional X-ray diffractometer (SmartLab: manufactured by Rigaku Corporation).

[0752] ·Measurement angle: 10~30°(light source: Cu / Kα, wavelength: )

[0753] (6) Rotational viscometer

[0754] The measurement device used was a Discovery HR20 rotational rheometer manufactured by TA Instruments, with an environmental test chamber and LN2 low temperature accessories as the temperature control system and a geometric structure. The measurement was performed using a parallel plate (made of SUS).

[0755] The measurement conditions were set as follows.

[0756] Measuring temperature range: -120℃~50℃

[0757] Heating rate: 5℃ / min

[0758] Frequency: 1Hz constant

[0759] Deformation: 0.1% (the low elastic modulus area automatically changes according to stress)

[0760] The glass transition temperature was determined from the peak temperature of tan δ calculated from the obtained storage modulus and loss modulus.

[0761] (7) Residual rate

[0762] The total mass of the polymer and the cyclic compound used to prepare the composite is w0. Next, the composite obtained is mixed with a good solvent for the polymer in an amount 100 times the mass of w0 and the mass after the solvent is removed is w1. The residual polymer ratio is calculated as w1 / w0 (mass %).

[0763] Example 1 (Melt compounding of PLA and P5OH)

[0764] 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.

[0765] 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.

[0766] From the above results, it was confirmed that the inclusion complex was obtained by treating at 150° C. for at least 15 hours.

[0767] 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.

[0768] 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).

[0769] Example 2 (Confirmation of the interaction between PLA and P5OH)

[0770] The IR of the composite obtained in Example 1 was measured. For comparison, the results of PLA and P5OH alone are also shown. An enlarged view of the carbonyl stretching vibration absorption region is also shown.

[0771] Since P5OH does not have a carbonyl group, the -1 There is no absorption near this region. On the other hand, PLA with carbonyl groups has an absorption at 1755 cm -1 The absorption peak of C=O is shown. The peak of C=O of the composite obtained in Example 1 is 1747 cm -1 , a low wave number shift of the absorption of C=O was observed. This is considered to be the result of the interaction caused by the hydrogen bond between the C=O group of PLA and the OH group of P5OH of the cyclic compound. This is considered to be because the polymer side has C=O as a proton accepting group and the cyclic compound has an OH group as a proton donating group, so the complex after inclusion forms hydrogen bonds and the solubility changes. Even if chloroform, which is a good solvent for the polymer alone, is used for washing, it does not dissolve.

[0772] In addition, since the complex does not have polymer end-blocking, it is a pseudorotaxane structure, but it is believed that due to the above-mentioned interaction (hydrogen bond), the cyclic compound becomes difficult to dissociate. The polymer end-blocking needs to be modified by a bulky compound in subsequent reactions after the inclusion of the cyclic compound, so the operation becomes very complicated. Since it is not necessary to carry out such polymer end-blocking, the industrial utilization value of the structure stabilization achieved by interaction is high.

[0773] Example 3 (compounding by mixing PLA and P5OH solution)

[0774] For 10 mg (0.016 mmol) of P5OH, 23.6 mg (0.328 mmol) of PLA (P5OH:PLA=1:20 (molar ratio)) was uniformly dissolved in 1 mL of acetone and dried at 40°C for 2 hours. After that, it was heated at 150°C for 15 hours to obtain a composite. The composite was uniform, and the Tg was 58.6°C by DSC. Similarly, a composite with P5OH:PLA=1:15 (molar ratio) was prepared, and after DSC measurement, the Tg was 60.0°C.

[0775] Considering that the glass transition temperature of PLA alone is about 51°C, the rigidity of the main chain of the polymer is increased by complexing (inclusion) and utilizing the interaction between the cyclic compound and the polymer, and the glass transition temperature is increased by nearly 10°C.

[0776] Example 4 (complex of high melting point PLA and P5OH)

[0777] 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.

[0778] 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 3 For comparison, the results of PLA alone and P5OH alone are also shown.

[0779] Example 5 (Melt method of PeC and P5Q composite)

[0780] After adding 0.57 g (5 mmol) of PeC to a 5 mL glass tube, the temperature was raised to 70 ° C to completely melt PeC. 0.06 g (0.1 mmol) of P5Q as a cyclic compound was added thereto, and after standing at 70 ° C for 15 hours, it was returned to room temperature to obtain a solid complex. The obtained complex was washed 5 times in total with 15 mL of acetone as a good solvent for PeC, and then centrifuged 3 times (2000 rpm, 10 minutes) with acetone as the dispersion medium to purify it.

[0781] The purified complex was dissolved in chloroform and assayed 1 After H-NMR, peaks derived from PeC and P5Q were observed.

[0782] In addition, the ratio of the P5Q unit to the repeating unit of PeC was determined from the integrated ratio of NMR, and it was P5Q:PeC=1:2.7 (molar ratio).

[0783] Example 6 (Thermal Decomposition Resistance of the Composite of PeC and P5Q)

[0784] The thermal decomposition temperature of the composite of PeC and P5Q obtained in Example 5 was determined by TGA. For comparison, the results of PeC alone and P5Q alone are also shown. Figure 4The thermal decomposition temperature of PeC is 244°C, the thermal decomposition temperature of P5Q is 263°C, and the thermal decomposition temperature of the composite is 320°C. The thermal decomposition temperature of the composite is more than 50°C higher than that of the raw material alone. The reason is not clear, but it is considered that the heat resistance is improved by inclusion compared with the heat resistance of the single material.

[0785] Example 7 (Compound of PeC and P5OH)

[0786] 0.57 g (5 mmol) of PeC and 0.061 g (0.1 mmol) of P5OH as a cyclic compound were dissolved in 5 mL of acetone, and the resulting solution was added to a 5 mL glass tube. The acetone was removed by vacuum drying, and the mixture was heated to 70°C to completely melt the mixture. After standing at 70°C for 15 hours, the mixture was returned to room temperature to obtain a solid complex. After washing the resulting complex with 300 mL of chloroform, a good solvent for PeC, an undissolved complex was observed. This is considered to be because P5OH is encapsulated by PeC, thereby changing its solubility. Through this treatment, the unencapsulated PeC is distilled off, so that the complex can be purified.

[0787] The purified complex was dissolved in acetone d6 and assayed 1 After H-NMR analysis, peaks derived from PeC and P5OH were observed as predicted.

[0788] In addition, the ratio of the P5OH unit to the repeating unit of PeC was determined from the integrated ratio of NMR, and it was P5OH:PeC=1:6.6 (molar ratio).

[0789] Example 8 (complex of PBR and P5Q)

[0790] After adding 0.27 g (5 mmol) of PBR (liquid polymer) to a 5 mL glass tube, 0.06 g (0.1 mmol) of P5Q 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 complex. The obtained complex was washed 3 times, 4 times, and 8 times in total with 30 mL of ethyl acetate as a good solvent for PBR, and a purified product was obtained.

[0791] Each purified product was dissolved in chloroform d and measured 1 After H-NMR, peaks derived from PBR and P5Q were observed. The results are shown in Figure 5 .

[0792] Although the number of washings with ethyl acetate was changed to 3 to 10 times, the graph hardly changed.

[0793] The ratio of the P5Q unit to the PBR repeating unit was calculated from the NMR integral ratio, which was P5Q:PBR = 1:8.3. This ratio was calculated from the integral value of hydrogen a of PBR at about 5.3 ppm (equivalent to H, 2) and the integral value of hydrogen b of P5Q at about 6.8 ppm (equivalent to H, 10).

[0794] Example 9 (Confirmation of the interaction between PBR and P5Q)

[0795] The IR of the carbonyl region of the complex obtained in Example 8 was measured. For comparison, the results of PBR and P5Q alone are also shown together. Figure 6 .

[0796] Since PBR does not have a carbonyl group, the -1 There is no absorption. On the other hand, P5Q with carbonyl group has an absorption at 1654 cm -1 and 1610cm -1 The absorption peak of C=O is shown. The peak of C=O of the composite obtained in Example 9 is 1651 cm -1 and 1605cm -1 , a low wavenumber shift was observed. This is considered to be the result of the interaction caused by the hydrogen bond between the C=C-H group of PBR and the C=O group of P5Q of the cyclic compound. This is considered to be because the polymer side has C=C-H as a proton donating group, and the cyclic compound has a C=O group as a proton accepting group, so hydrogen bonds are effectively formed, the solubility changes, and even if the polymer is washed with a good solvent alone, it will not dissolve. In addition, since the complex is not specifically end-capped, it is a so-called pseudo-rotaxane structure, but it is believed that due to the interaction, the cyclic compound becomes difficult to detach. End-capping requires the use of bulky compounds to modify the ends in subsequent reactions, so if this end-capping is not required, the industrial utilization value is high.

[0797] Comparative Example 1 (composite of PBR and P5OH)

[0798] 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.

[0799] 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 7For comparison, the results of P5OH alone and PBR alone are also shown.

[0800] Comparative Example 2 (composite of PBR and C2P5A)

[0801] 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 four times in total with 30 mL of hexane as a good solvent for PBR to obtain a purified product.

[0802] 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 8 For comparison, the results for PBR alone are also shown.

[0803] Example 10 (Compound 2 of PBR and P5Q)

[0804] After adding 2 g (36.7 mmol) of PBR (liquid polymer) to a 5 mL glass tube, a solution of 0.2 g (0.33 mmol) of the cyclic compound P5Q dissolved in 30 mL of dichloromethane was added while maintaining the room temperature, and the mixture was allowed to stand at room temperature for 15 hours to obtain a liquid complex. The obtained complex was washed with 200 mL of ethyl acetate, a good solvent for PBR, to obtain a purified product.

[0805] The purified product was dissolved in acetone d6 and measured 1 After H-NMR, peaks derived from PBR and P5Q were observed. The results are shown in Fig. 9 .

[0806] The ratio of the repeating unit of P5Q unit to PBR was determined from the integrated ratio of NMR, and it was P5Q:PBR=1:12.2 (molar ratio). The obtained composite was vacuum dried at 50° C. for 12 hours. The yield was 91 mg.

[0807] Relative to PBR (2g) and P5Q (0.2g) before compounding, the obtained composite is 91mg, so the mass w0 of the composite before mixing is 2.2g, and the mass w1 of the composite after mixing is 0.091g. When the residual rate is w1 / w0 (mass %), the residual rate is 4.13 mass %.

[0808] Example 11 (Three-solution method of the composite of PBR and P5Q)

[0809] 0.259 g (4.8 mmol) of PBR and 0.01 g (0.016 mmol) of P5Q were added to a 5 mL sample tube, 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.

[0810] Example 12 (Four-solution method of the composite of PBR and P5Q)

[0811] A composite was obtained in the same manner as in Example 12 except that the amount of PBR was changed to 0.518 g (9.6 mmol).

[0812] Example 13 Comparison of thermal decomposition temperature using TGA

[0813] The thermal decomposition temperatures of the composites obtained in Examples 10 to 12 were determined by TGA method. The temperature at which the weight decreased by 5% was defined as the thermal decomposition temperature.

[0814] The results are shown in the table.

[0815] [Table 1]

[0816]

[0817] According to the results of Examples 11 and 12, the thermal decomposition temperature of PBR increased significantly by adding a very small amount of P5Q. The exact reason for this is not clear, but it is believed that the heat resistance is improved by the inclusion structure and the interaction (hydrogen bonding, confirmed in Example 10). It is believed that the thermal decomposition temperature of Example 11, in which the weight ratio of P5Q is large, is slightly reduced due to the influence of the thermal decomposition of P5Q itself.

[0818] Example 14 Comparison of glass transition temperature and storage modulus using a rotational viscoelasticity measuring apparatus

[0819] The glass transition temperatures of PBR alone and the composites obtained in Examples 11 and 12 were evaluated using a rotary viscoelasticity measuring apparatus. The glass transition temperature was determined based on the peak temperature of tan δ. The results are shown in the table below.

[0820] [Table 2]

[0821]

[0822] It is known that the glass transition temperature rises as the amount of P5Q inclusion increases. It is believed that the inclusion and interaction have an effect of making the main chain rigid.

[0823] Examples 15 to 17 (PLA and P5OH complex solution method)

[0824] PLA was used instead of PBR, and P5OH was used instead of P5Q in the amount ratios shown in the table below. The same operation as in Example 12 was carried out to obtain a composite.

[0825] [Table 3]

[0826]

[0827] Examples 18 to 21 (PeC and P5Q complex solution method)

[0828] A composite was obtained by the same operation as in Example 12 except that PeC was used instead of PBR in the amount ratio shown in the table below.

[0829] [Table 4]

[0830]

[0831] Examples 22 to 25 (PeC and P5OH complex solution method)

[0832] A composite was obtained by the same operation as in Example 12 except that PeC was used instead of PBR and P5OH was used instead of P5Q in the amount ratios shown in the table below.

[0833] [Table 5]

[0834]

[0835] Example 26 Comparison of thermal decomposition temperature using TGA

[0836] The thermal decomposition temperatures of the composites obtained in Examples 15 to 25 and Examples 1, 5, and 7 were determined by TGA method. The temperature at which the weight decreased by 5% was defined as the thermal decomposition temperature.

[0837] The results are shown in the table.

[0838] [Table 6]

[0839]

[0840] [Table 7]

[0841]

[0842] [Table 8]

[0843]

[0844] In either case, the thermal decomposition start temperature of the complex with a small amount of cyclic compound was significantly higher than that of the polymer alone. The reason is not clear, but it is believed that the inclusion effect is exhibited.

[0845] Regarding the above-mentioned cyclic compounds and polymers, the charge density of each atom below was calculated by electron density analysis (Gaussian) using the natural bond orbital (NBO) method. During the calculation, Gaussian 16 revision A.03 (Gaussian) was used, B3LYP was used as the functional, 6-31G (d) was used as the basis function set, and the structural formula of the atom to be calculated was assumed to perform structural optimization calculations and determine the optimized structure. Next, using this optimized structure, the electron density analysis was performed using the natural bond orbital (NBO) method to calculate the charge density. The calculation results are shown in Table 9.

[0846] Among the charge densities of hydrogen atoms in -CH2- in PeC, the charge density of hydrogen atoms contained in -CH2- adjacent to -CO- is the largest, and Table 9 lists the values ​​of the charge density of these hydrogen atoms.

[0847] [Table 9]

[0848]

[0849] In the above-mentioned Examples 1 to 4, 7, 15 to 17, and 22 to 25, P5OH containing hydrogen atoms with a charge density of 0.492 was used as a cyclic compound. In Examples 1 to 4, 15 to 17, PLA or PLLA containing oxygen atoms with a charge density of -0.594 was used as a polymer, and in Examples 7 and 22 to 25, PeC containing oxygen atoms with a charge density of -0.579 was used. In all of these Examples, it was confirmed that a composite was formed, and it was confirmed that the heat resistance and residual rate of the obtained composite were good.

[0850] In Examples 8 to 13, PBR containing hydrogen atoms with a charge density of 0.224 or 0.241 was used as the polymer. In Examples 8 to 13, P5Q containing oxygen atoms with a charge density of -0.511 was used as the cyclic compound. In all of these Examples, it was confirmed that a composite was formed, and it was confirmed that the heat resistance and residual rate of the obtained composite were good.

[0851] In the above-mentioned Examples 5, 18 to 21, PeC containing hydrogen atoms with a charge density of 0.270 was used as a polymer. In Examples 5, 18 to 21, P5Q containing oxygen atoms with a charge density of -0.511 was used as a cyclic compound. In all of these Examples, it was confirmed that a composite was formed, and it was confirmed that the heat resistance and residual rate of the obtained composite were good.

[0852] On the other hand, P5OH was used as the cyclic compound and PBR was used as the polymer in Comparative Example 1. Neither the cyclic compound nor the polymer used in Comparative Example 1 contained a proton acceptor, and formation of a complex was not confirmed.

[0853] In Comparative Example 2, P2P5A was used as the cyclic compound and PBR was used as the polymer. Neither the cyclic compound nor the polymer used in Comparative Example 2 contained a proton acceptor, and formation of a complex was not confirmed.

[0854] Embodiment 27

[0855] Results of cross-linking of PBR in PBR / P5Q system

[0856] (Preparation method of premix)

[0857] After solid P5Q was crushed in a mortar in advance, 0.8 g of P5Q was weighed into a sample bottle with respect to 19.2 g of PBR, and mixed with a mixing rotor for more than 16 hours to prepare a slurry-like premix. In addition, as a sample with a different concentration, 3.6 g of P5Q was mixed with respect to 16.4 g of PBR to prepare a premix.

[0858] (Method for preparing mixed samples)

[0859] The prepared premix and PH25B (PERHEXA 25B; manufactured by NOF Corporation) were stirred with a spatula to obtain a kneaded sample. A kneaded sample of PBR and PH25B was also obtained.

[0860] The composition of each kneaded sample is shown in the table below.

[0861] [Table 10]

[0862]

[0863] (Method for forming a cross-linked rubber sheet)

[0864] The kneaded sample was poured into a frame of 100 mm×150 mm×1 mm, vacuum dried (degassing) at 50°C for 30 minutes, and then press-molded at 170°C for 40 minutes to prepare a crosslinked rubber sheet.

[0865] (Evaluation of Thermal Decomposition Temperature)

[0866] The temperature (Td5) at which the weight of the crosslinked rubber sheet decreased by 5% and the temperature (Td1) at which the weight of the crosslinked rubber sheet decreased by 1% were evaluated by TGA method.

[0867] [Table 11]

[0868]

[0869] Embodiment 28

[0870] Research on PA11 / P5Q

[0871] Study on polyamide 11 (purchased from Sigma-Ardrich as a reagent) (PA11) and P5Q

[0872]

[0873] (Mixing Research)

[0874] 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.

[0875] (Evaluation of Thermal Decomposition Temperature)

[0876] The temperature (Td5) at which the weight of the strand decreased by 5% was evaluated by the TGA method.

[0877] [Table 12]

[0878] sample Td5(℃) PA11 Single 382 PA11 / P5Q 379 P5Q alone 263

[0879] (FT-IR measurement)

[0880] according to Fig.10 Compared 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 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 from 4 to 20, One of the polymer and the cyclic compound contains one or more selected from -CO-, a nitrogen atom and a halogen atom, and the other has a group containing a hydrogen atom capable of interacting with -CO-, a nitrogen atom or a halogen atom.

2. The composite according to claim 1, characterized in that: The group containing a hydrogen atom capable of interacting with -CO-, a nitrogen atom or a halogen atom contains one or more selected from the group consisting of a proton donating group, an unsaturated group and a group containing a hydrogen atom having a charge density of 0.25 or more.

3. The composite according to claim 1 or 2, 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, Among them, R 3 and R 4 At least one of them is a hydrogen atom, 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).

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

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

6. The composite according to any one of claims 1 to 5, 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, Among them, R 3a and R 4a At least one of represents a 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, The order of existence of the units indicated by n3 or n4 and enclosed in parentheses is arbitrary in formula (3-A).

7. The composite according to any one of claims 2 to 6, characterized in that: The proton donating group contains a hydrogen atom having a charge density of 0.22 or more.

8. The composite according to any one of claims 2 to 7, characterized in that: The charge density of the hydrogen atom bonded to the carbon atom constituting the unsaturated group is 0.22 or more.

9. The composite according to any one of claims 2 to 8, characterized in that: The proton donating group is a group containing a hydrogen atom bonded to one atom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom.

10. The composite according to any one of claims 1 to 9, characterized in that: The polymer is a linear polymer which may have a substituent.

11. The composite according to any one of claims 1 to 10, characterized in that: The polymer is a polymer containing one or more selected from -CO-, a nitrogen atom and a halogen atom, and the cyclic compound contains a proton donating group.

12. The composite according to any one of claims 1 to 11, characterized in that: The polymer is a polymer containing one or more selected from -CO-, a nitrogen atom and a halogen atom, and the cyclic compound is a compound represented by any one of the following formulas (1-B) and (3-B). In formula (1-B), R 1b Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 2b Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 3b Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, R 4b Each occurrence independently represents a C which may have one or more substituents. 1－30 Alkyl or hydrogen atom, Among them, R 3b and R 4b At least one of them is a hydrogen atom, n1 is an integer from 4 to 20; In formula (3-B), R 7b represents independently at each occurrence a hydrogen atom or an organic group, R 8b represents independently at each occurrence a hydrogen atom or an organic group, R 9b represents independently at each occurrence a hydrogen atom or an organic group, R 10b represents independently at each occurrence a hydrogen atom or an organic group, R 11b represents independently at each occurrence a hydrogen atom or an organic group, R 12b represents independently at each occurrence a hydrogen atom or an organic group, Among them, R 9b and R 10b At least one of them is a 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, The order of existence of the units indicated by n3 or n4 and enclosed in parentheses is arbitrary in formula (3-B).

13. The composite according to any one of claims 1 to 12, characterized in that: The polymer contains ester groups in the main chain backbone.

14. The composite according to any one of claims 3 to 13, characterized in that: The polymer includes a protogenic group, and the cyclic compound includes a compound represented by any one of the formulas (2) and (3).

15. The composite according to any one of claims 1 to 14, characterized in that: The polymer includes a polymer having an unsaturated bond.

16. The composite according to any one of claims 1 to 15, characterized in that: The polymer includes a diene polymer.

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

18. The composite according to any one of claims 1 to 17, characterized in that: When the composite and the good solvent for the polymer are mixed, assuming that the mass of the composite before mixing is w0 and the mass of the composite after mixing is w1, w1 / w0 is 4 mass % or more.

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

20. The composite according to any one of claims 1 to 19, 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.

21. A method for producing a composite, which is the method for producing a composite according to any one of claims 1 to 20, 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. One of the polymer and the cyclic compound contains one or more selected from -CO-, a nitrogen atom and a halogen atom, and the other has a group containing a hydrogen atom capable of interacting with -CO-, a nitrogen atom or a halogen atom.

22. The manufacturing method according to claim 21, 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.

23. A composition, characterized in that: A composite comprising the composite according to any one of claims 1 to 20.

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

25. The composition of claim 23, wherein: It is in liquid form.

Images