Complex

Abstract

The purpose of the present disclosure is to provide a slide-ring material capable of shortening a manufacturing process of a complex (preferably, a complex containing a (poly)rotaxane), and also capable of improving fracture toughness and fracture strength.　This complex is obtained from a composition containing a polymer (A) having an epoxy group at a terminal and a cyclic compound (B) encapsulating the polymer (A) and having a reactive group r1, and includes a crosslinked structure provided by the polymer (A).

Description

complex

[0001] This disclosure relates to a complex.

[0002] Rotaxanes and pseudorotaxanes are known as composites formed by combining cyclic compounds and polymers. A rotaxane is a structure having a cyclic compound, a polymer penetrating the ring of the cyclic compound, and a sealing site located at the end of the polymer. A pseudorotaxane is a structure having a cyclic compound and a polymer penetrating the ring of the cyclic compound, but without a sealing site at the polymer end.

[0003] Patent Document 1 describes a polyrotaxane in which a cyclic molecule having active hydrogen, selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, has its opening encapsulated by a linear molecule in a skewer-like manner, and a sealing group is arranged at both ends of the pseudopolyrotaxane to prevent the cyclic molecule from being removed, wherein at least a portion of the active hydrogen is -(CO(CH) ２ ) ｎ O) ｍ Polyrotaxanes substituted with polymerization chains represented by -H (where n is a number from 1 to 8 and m is a number from 1 to 12 as an average) are described.

[0004] Patent Document 2 describes a resin composition comprising a thermosetting resin, an inorganic filler, an organic filler, and a tacky softener, and states that the content of the organic filler is 5% by mass or more when the non-volatile components in the resin composition are taken as 100% by mass. Epoxy resin is described as the thermosetting resin.

[0005] Patent Document 3 describes a resin composition containing a polyrotaxane, an epoxy resin, and a curing agent, wherein the resin composition contains 0.1 parts by mass or more and less than 10 parts by mass of an acid anhydride as a curing agent, per 100 parts by mass of the total of the polyrotaxane, epoxy resin, and curing agent.

[0006] International Publication No. 2015 / 041322, Japanese Patent Publication No. 2020-158704, International Publication No. 2020 / 095928

[0007] In a conventionally known complex (preferably, a complex containing a (poly)rotaxane), a large number of steps are required for synthesis, and there is room for improvement in terms of yield and cost.

[0008] The present disclosure aims to provide a sliding ring material capable of shortening the manufacturing process of a complex (preferably, a complex containing a (poly)rotaxane) and improving fracture toughness and fracture strength.

[0009] The present disclosure includes the following aspects. [1] A complex obtained from a composition containing a polymer (A) having an epoxy group at its terminal and a cyclic compound (B) that includes the polymer (A) and has a reactive group r １ and including a crosslinked structure formed by the polymer (A). [2] The complex according to [1], wherein the crosslinked structure includes a crosslinked structure between one or more epoxy groups contained in the polymer (A) and another epoxy group contained in the polymer (A). [3] The complex according to [1] or [2], which is a (poly)rotaxane. [4] The complex according to any one of [1] to [3], wherein the crosslinked structure includes a crosslinked structure between one or more epoxy groups contained in the polymer (A) and the group r １ contained in the cyclic compound (B). [5] A complex which is a (poly)rotaxane and includes a polymer having no stopper structure at its terminal and a cyclic compound that includes the polymer and includes a crosslinked structure formed by the polymer. [6] The complex according to any one of [1] to [5], wherein the reactive group r １ is a group capable of reacting with an epoxy group. [7] The complex according to any one of [1] to [6], wherein the reactive group r １ is a group capable of reacting with a group capable of reacting with an epoxy group. [8] The complex according to any one of [1] to [7], wherein the reactive group r １ includes one or more selected from a hydroxy group, a carboxy group, an amino group, a thiol group, an acid anhydride group, an epoxy group, and a highly reactive carbon atom. [9] The reactive group r １The composite according to any one of [1] to [8], comprising a hydroxyl group.

[10] The composite according to any one of [1] to [9], wherein the polymer (A) comprises one or more selected from ether bonds, carbonyl bonds, ester bonds and ketone bonds.

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

[10] , wherein the polymer (A) comprises a polyether chain and a polyester chain.

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

[11] , wherein the polymer (A) comprises a polyalkylene oxide chain.

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

[12] , wherein the cyclic compound (B) comprises one or more selected from the group consisting of cyclodextrin, crown ether, calixarene, cucurbituryl, pillararene and derivatives thereof.

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

[13] , wherein the cyclic compound (B) comprises pillararene and / or a derivative thereof.

[15] The cyclic compound (B) is the following formula (I): [In formula (I), A is a divalent C containing one or more selected independently from -OR and CO-] ４－５０ Formula (I) represents an organic group, where R independently represents an organic group or hydrogen atom which may contain one or more fluorine atoms, n represents an integer from 4 to 20, and formula (I) contains at least one reactive group r １ A composite according to any one of [1] to

[14] , comprising a cyclic compound represented by ].

[16] The composite according to

[15] , wherein the cyclic compound (B) comprises a compound in formula (I) where A is a 1,4-dihydroxybenzene-2,5-diyl group or a 1,4-benzoquinone-2,5-diyl group and n is 5.

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

[16] , further comprising a crosslinking agent (C) in the composition.

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

[17] , which is a slide ring material.

[19] A polymer (A) having epoxy groups at its terminals, and a reactive group r that encloses the polymer (A). １A method for producing a composite, comprising using a composition containing a cyclic compound (B) having and a polymer (A) to form a crosslinked structure with the polymer (A).

[20] The method for producing a composite according to

[19] , wherein the crosslinked structure comprises a crosslinked structure of one or more epoxy groups contained in the polymer (A) and another epoxy group contained in the polymer (A).

[21] The method for producing a composite according to

[19] or

[20] , wherein the composite is a (poly)rotaxane.

[22] The crosslinked structure comprises one or more epoxy groups contained in the polymer (A) and a group r contained in the cyclic compound (B). １ A manufacturing method according to any one of

[19] to

[21] , comprising a crosslinking structure with the reactive group r １ The method for producing an epoxy group according to any one of

[19] to

[22] , wherein the reactive group r １ The composite according to any one of

[19] to

[23] , wherein the reactive group r １ A method for producing carbon atoms according to any one of

[19] to

[24] , wherein the reactive group r １The method for producing the polymer according to any one of

[19] to

[25] , wherein the polymer (A) comprises one or more selected from ether bonds, carbonyl bonds, ester bonds and ketone bonds. The method for producing the polymer according to any one of

[19] to

[26] . The method for producing the polymer according to any one of

[19] to

[27] , wherein the polymer (A) comprises one or more selected from polyether chains and polyester chains. The method for producing the polymer according to any one of

[19] to

[28] , wherein the polymer (A) comprises a polyalkylene oxide. The method for producing the polymer according to any one of

[19] to

[28] . The method for producing the polymer according to any one of

[19] to

[29] , wherein the cyclic compound (B) comprises one or more selected from the group consisting of cyclodextrin, crown ether, calixarene, cucurbituryl, pillararene and derivatives thereof. The method for producing the polymer according to any one of

[19] to

[29] . The method for producing the polymer according to any one of

[19] to

[30] , wherein the cyclic compound (B) comprises pillararene and / or a derivative thereof.

[32] The cyclic compound (B) is of the following formula (I): [In formula (I), A is a divalent C containing one or more selected independently from -OR and CO-] ４－５０ Formula (I) represents an organic group, where R independently represents an organic group or hydrogen atom which may contain one or more fluorine atoms, n represents an integer from 4 to 20, and formula (I) contains at least one reactive group r １ A method for producing a cyclic compound represented by

[19] to

[31] , comprising

[33] the cyclic compound (B) comprising a compound in formula (I) where A is a 1,4-dihydroxybenzene-2,5-diyl group or a 1,4-benzoquinone-2,5-diyl group and n is 5, as described in

[32] , as described in

[34] the method for producing a cyclic compound according to any one of

[19] to

[33] , wherein the composition further comprises a crosslinking agent (C), as described in

[35] the method for producing a composite according to any one of

[19] to

[34] , wherein the composite is a slide ring material, as described in

[36] a composite composition comprising the composite according to any one of [1] to

[18] , as described in

[37] a molded article comprising the composite according to any one of [1] to

[18] , as described in [1] to

[18] , as described in

[32] , as described in

[34] , as described in

[34] , as described in

[19] to

[34] , as described in

[36] a composite composition comprising the composite according to any one of [1] to

[18] , as described in

[37] a molded article comprising the composite according to any one of [1] to

[18] , as described in [1] to

[18] , as described in

[32] , as described in

[34] , as described in

[36]

[0010] According to this disclosure, it is possible to realize a slide ring material that allows for a shortening of the manufacturing process and also improves fracture toughness and fracture strength.

[0011] Figure 1 is a photograph of the composite of Example 6 punched into a micro dumbbell. Figure 2 is a photograph of the cured product of Comparative Example 2. Figure 3 is a photograph of the composite of Example 14 punched into a micro dumbbell. Figure 4 is a photograph of the composite of Example 16 punched into a micro dumbbell. Figure 5 is a photograph of the cured product of Comparative Example 4. Figure 6 is a photograph of the composite of Example 18 punched into a micro dumbbell. Figure 7 is a photograph of the film of Example 30. Figure 8 shows the stress-strain curves of Examples 28, 32, and 33. Figure 9 is a photograph of the film of Example 33. Figure 10 is a photograph of the film of Example 37. Figure 11 is a photograph of the film of Example 40.

[0012] The composite of the present disclosure comprises a polymer (A) having epoxy groups at its termini, and a reactive group r that encloses the polymer (A). １ Obtained from a composition comprising a cyclic compound (B) having and a crosslinked structure by the polymer (A).

[0013] According to this disclosure, the manufacturing process can be shortened, and the cyclic compound (B) has a reactive group r １ By crosslinking via this material, a slide ring material can be realized that also offers improved fracture toughness and fracture strength. This disclosure should not be interpreted as being limited to any particular theory, but the reasons why this disclosure may produce such effects are thought to be as follows.

[0014] In other words, by using a polymer with epoxy groups at its ends as the stem polymer (axial polymer) in the composite, and a cyclic compound with reactive groups as the cyclic molecule, a crosslinked structure can be formed between the stem polymer and the cyclic molecule, and the ends of the stem polymer can be sealed without providing bulky sealing groups. Since the crosslinked structure involving the epoxy groups can be formed by a single reaction step, the manufacturing process can be shortened, preferably by a significant amount. Furthermore, the resulting composite corresponds to a slide-ring material that includes a structure in which the cyclic molecule can move freely within the stem polymer, and it is believed that this can improve fracture toughness and fracture strength.

[0015] In this disclosure, rotaxane is not limited to rotaxane in the narrow sense (a composite in which the detachment of cyclic molecules from the stem polymer is suppressed by providing encapsulating groups at the ends), but also includes composites in which the detachment of cyclic molecules from the stem polymer is suppressed.

[0016] In this disclosure, inclusion means that at least a portion of the polymer is present inside the ring of the cyclic compound. In one embodiment, polymer (A) may penetrate the ring structure of cyclic compound (B). Also, there may be one or more cyclic compounds (B) that inclusion one polymer (A), preferably one in one embodiment and preferably two or more in another embodiment. As an upper limit, on average there are 5 or fewer, or 3 or fewer, and preferably 1 or fewer, per repeating unit of polymer (A). For example, if the number of repeating units of polymer (A) is j, the number of cyclic compounds (B) contained in one complex is preferably 5 × j or less, more preferably 3 × j or less, and even more preferably j or less.

[0017] Polymer (A) Polymer (A) is not particularly limited as long as it is a polymer having epoxy groups at its ends. Having epoxy groups at its ends makes it possible to obtain a composite containing a crosslinked structure of polymer (A).

[0018] Polymer (A) is preferably a chain polymer, star polymer, dendrimer, or hyperbranched polymer, more preferably a chain polymer (e.g., linear or branched polymer), and even more preferably a linear polymer. The number of epoxy groups in polymer (A) is 1 or more, preferably 1 to 100, and more preferably 2 to 50. In polymer (A), epoxy groups may be present at locations other than the ends.

[0019] Polymer (A) may or may not contain groups other than epoxy groups at its ends. It is preferable that polymer (A) does not contain a stopper structure (also called a "end group," "sealing group," or "blocking group"). The stopper structure may, for example, be a group containing a cyclic ring of six or more members. Examples of cyclic rings of six or more members include phenyl groups, naphthyl groups, fluorescenyl groups, pyrenyl groups, triphenylmethyl groups, etc. ６－２０ Aromatic hydrocarbon groups; such as adamantyl groups, etc. ８－２０ Examples include alicyclic hydrocarbon groups. The above-mentioned groups containing a cyclic group with six or more members may include the above-mentioned aromatic hydrocarbon group and the above-mentioned alicyclic hydrocarbon group with substituents (halogen atom; hydroxyl group; substituted or unsubstituted amino group; C １－４ The group may have an alkyl group or the like attached to it, and the above aromatic hydrocarbon group or the above alicyclic hydrocarbon group may be a group that is linked via a linking group (amide bond, urethane bond, carbonyl bond, ester bond, etc.).

[0020] The polymer (A) preferably contains one or more selected from ether bonds (-O-), carbonyl bonds (-CO-), ester bonds (-CO-O), and ketone bonds (R-CO-R', where R and R' each represent an organic group), and preferably contains a polymer chain containing one or more selected from ether bonds (-O-), carbonyl bonds (-CO-), ester bonds (-CO-O), and ketone bonds (-CO-).

[0021] Polymer (A) has amine bonds (-NR-, where R is a hydrogen atom or C １－４ It may further contain alkyl groups, thioether bonds (-S-), etc.

[0022] Examples of such polymer chains include polyether chains, polyester chains, polycarbonate chains, polyarylate chains, polyamide chains, polyetherketone chains, and polyetheretherketone polyurethane chains. In particular, polymer (A) preferably contains one or more selected from polyether chains and polyester chains, and more preferably contains polyether chains. Examples of polyester chains include aliphatic polyester chains and aromatic polyester chains, with aliphatic polyester chains being preferred, and biodegradable polyester being preferred among aliphatic polyester chains. Examples of polyether chains include aliphatic polyether chains and aromatic polyether chains, with aliphatic polyether chains being preferred, and polyalkylene oxide chains being preferred.

[0023] Examples of polyalkylene oxide chains include polyethylene oxide chains and polypropylene oxide chains.

[0024] The number-average molecular weight of polymer (A) may be, for example, 200 to 1,000,000, preferably 300 to 500,000, more preferably 400 to 300,000, and even more preferably 400 to 250,000, for example 400 to 250,000. In this disclosure, the number-average molecular weight can be measured by gel permeation chromatography and can be measured as a converted value with polystyrene as the standard sample.

[0025] The crosslinked structure of polymer (A) can be any crosslinked structure involving one or more epoxy groups contained in polymer (A), such as a crosslinked structure between one or more epoxy groups contained in polymer (A) and another epoxy group contained in polymer (A); or a crosslinked structure between one or more epoxy groups contained in polymer (A) and a reactive group r contained in cyclic compound (B). １ A cross-linking structure is one example.

[0026] The above crosslinked structure may be a crosslinked structure formed by the direct reaction of an epoxy group and a group that forms a crosslinked structure together with the epoxy group; or it may be a crosslinked structure formed via a crosslinking agent (C) described later, between the epoxy group and the group that forms a crosslinked structure together with the epoxy group.

[0027] Cyclic compound (B) Cyclic compound (B) is a compound having a ring capable of enclosing a polymer, wherein the reactive group r １ It is not particularly limited as long as it has a reactive group r on the cyclic compound (B). １ By having this, a slide ring material can be obtained in which at least one end of the crosslinked structure is fixed to the cyclic compound (B).

[0028] In this disclosure, the reactive group r １ This refers to a reactive group.

[0029] In one embodiment, the reactive group r1 is preferably a group that can react with an epoxy group, and more preferably a group that can react with an epoxy group to form a covalent bond. １ A crosslinked structure can be formed by a direct reaction between the epoxy group and the hydroxyl group (-OH), carboxyl group (-COOH), amino group (-NR ２ R is a hydrogen atom or C １－４ Alkyl group (-SH), thiol group (-O-CO-O-), acetyl group (-CO-CH ３ Examples include ), and preferably include hydroxyl groups, amino groups, thiol groups, acid anhydride groups, etc.

[0030] In another embodiment, the reactive group r １ The crosslinking agent is preferably a group that can react with the epoxy group, and more preferably a group that can react with the epoxy group to form a covalent bond. This allows a crosslinking structure to be formed between the polymer (A) and the cyclic compound (B) using a crosslinking agent that can react with the epoxy group. Such groups include epoxy groups, isocyanate groups (-NCO), and nitrile groups (-NO). ２ Examples of highly reactive carbon atoms include, for example, the carbon atom of the formula: -C=C １ Carbon atoms C in the group represented as H-CO- １ This includes the reactive group r. １This can be an epoxy group, an isocyanate group, a nitrile group, and a group represented by the formula: -C=CH-CO-. A highly reactive carbon atom (preferably, the formula: -C=C １ Carbon atoms C in the group represented as H-CO- １ ) can readily react with an amino group, which is a group that can react with an epoxy group.

[0031] Reactive group r １ Specifically, these are hydroxyl groups (-OH), carboxyl groups (-COOH), and amino groups (-NR ２ R is a hydrogen atom or C １－４ Alkyl group (-SH), thiol group (-O-CO-O-), acid anhydride group (-NCO), isocyanate group (-NCO), nitrile group (-NO ２ ), epoxy groups and highly reactive carbon atoms (preferably, formula: -C=C) １ Carbon atoms C in the group represented as H-CO- １ Preferably, it contains one or more selected from ), a hydroxyl group, a carboxyl group, an amino group, a thiol group, an acid anhydride group, an epoxy group, and a highly reactive carbon atom (preferably, formula: -C=C １ Carbon atoms C in the group represented as H-CO- １ It is more preferable to include one or more selected from ) and even more preferable to include a hydroxyl group.

[0032] Reactive group r １ This may be included as a substituent in the ring structure of the cyclic compound (B), or it may be included in the ring structure itself.

[0033] The cyclic compound (B) preferably contains cyclodextrin, crown ether, calixarene, cucurbituryl, pillararene, and derivatives thereof as a ring structure, and more preferably contains pillararene and derivatives thereof.

[0034] Cyclic compound (B) is a pillararene and its derivatives, as given by formula (I): [In formula (I), A is a divalent C containing one or more selected independently from -OR and CO-] ４－５０Formula (I) represents an organic group, where R independently represents an organic group or hydrogen atom which may contain one or more fluorine atoms, n represents an integer from 4 to 20, and formula (I) contains at least one reactive group r １ It is preferable that it contains a cyclic compound represented by ].

[0035] In this disclosure, in formula (I), a compound in which A contains -OR may be called a pillar[n]arene, and a compound in which A contains -CO- may be called a pillar[n]quinone.

[0036] In equation (I), A is independently a divalent C ４－５０ Represents an organic group and includes one or more selected from -OR and CO-. The above C ４－５０ The organic group is preferably C ４－２０ Organic group, comfort C ４－１０ It can be an organic group.

[0037] In this disclosure, a monovalent or divalent "organic group" means a monovalent or divalent group containing carbon. A monovalent or divalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A hydrocarbon group derivative means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc., at the terminal or molecular chain of a hydrocarbon group. When simply referred to as "organic group," it means a monovalent organic group.

[0038] Furthermore, in this disclosure, "hydrocarbon group" means a group containing carbon and hydrogen, obtained by removing one hydrogen atom from a hydrocarbon. Such hydrocarbon groups are not particularly limited, but C １－２０ Hydrocarbon groups, for example, C １－２０ Aliphatic hydrocarbon group, C ６－２０ Examples include aromatic hydrocarbon groups. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. Furthermore, the hydrocarbon group may contain one or more ring structures. Furthermore, the hydrocarbon group may have one or more substituents.

[0039] In this disclosure, the substituents of the "hydrocarbon group" are not particularly limited, but include, for example, halogen atoms; C may be substituted with one or more halogen atoms. １－６ Alkyl alkyl group, C ２－６ Alkenyl group, C ２－６ Alkynyl group, C ３－１０ Cycloalkyl groups, C ３－１０ Unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, C ６－１０ Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0040] In a divalent organic group containing one or more selected from -OR and CO- represented by A above, the "divalent C ４－５０ The "organic group" is preferably a divalent C ６－２０ Aromatic hydrocarbon group or divalent C ３－２０ It may be an alicyclic hydrocarbon group. The above divalent C ６－２０ The aromatic hydrocarbon group is preferably a divalent C ６－１０ Aromatic hydrocarbon group, more preferably divalent C ６－８ Aromatic hydrocarbon groups, particularly preferably phenylene groups. The above divalent C ３－２０ The alicyclic hydrocarbon group may be either a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group. The above divalent C ３－２０ The alicyclic hydrocarbon group is preferably a divalent C ６－１０ Unsaturated alicyclic hydrocarbon group, more preferably divalent C ６－８ The group may be an unsaturated hydrocarbon group, particularly preferably a cyclohexadienyl group.

[0041] A divalent C containing one or more selected from -OR and CO- represented by A above ４－５０ Each organic group is independently preferably a divalent C having -OR as a substituent. ６－２０ Aromatic hydrocarbon group; C ３－２０ In alicyclic hydrocarbon groups, the hydrogen atoms bonded to the carbon atoms constituting the ring are substituted with -OR; and C ３－２０ In alicyclic hydrocarbon groups, the ring is composed of -CH ２It may be one selected from groups in which - is replaced by -CO-; more preferably a divalent C having -OR as a substituent. ６－１０ Aromatic hydrocarbon groups; and C ６－１０ In alicyclic hydrocarbon groups, the ring is composed of -CH ２ It can be one of the groups selected from those in which the - is replaced by -CO-.

[0042] The total number of -OR and CO- groups in A is between 1 and 4, and preferably 2.

[0043] Each R independently represents an organic group or hydrogen atom that may contain one or more fluorine atoms.

[0044] Examples of organic groups represented by R include alkyl groups, alkyloxy groups, alkyl ether groups, tosyl groups, triflate groups, or phenyl groups, and these groups may have one or more substituents.

[0045] The organic group represented by R may contain a fluorine atom, and the fluorine atom may be included as a substituent of the organic group. The substituents that the organic group represented by R may have are not particularly limited, but include, for example, reactive groups such as hydroxyl groups, amino groups, carboxyl groups, thiol groups, acid anhydride groups, isocyanate groups, nitrile groups, epoxy groups, and acetyl groups. １ (Preferably hydroxyl groups, amino groups, thiol groups, acid anhydride groups, epoxy groups); aliphatic hydrocarbon groups such as alkyl groups, vinyl groups, and ethynyl groups; and halogen atoms. Examples of such halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and preferably fluorine atoms or chlorine atoms.

[0046] The alkyl group in R is preferably C １－３０ It is an alkyl group. Such alkyl group may be linear or branched. In one embodiment, C １－３０ Alkyl alkyl groups are C １－２０ Alkyl alkyl group, preferably C １－１０ Alkyl alkyl group, comfortable C １－３０ It may be an alkyl group. In another embodiment, C １－３０The alkyl group is C １７－３０ alkyl group, preferably C １８－３０ alkyl group, more preferably C ２６－３０ alkyl group.

[0047] As substituents of the alkyl group in R, there may be mentioned a halogen atom; a C １－６ alkyl group, a C ２－６ alkenyl group, a C ２－６ alkynyl group, a C ３－１０ cycloalkyl group, a C ３－１０ unsaturated cycloalkyl group, a 5- to 10-membered heterocyclyl group, a C ６－１０ aryl group and a 5- to 10-membered heteroaryl group, one or more groups selected therefrom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably may be a fluorine atom or a chlorine atom.

[0048] The alkyloxy group in the above R is typically —O—R ２１ (wherein R ２１ is an alkyl group which may have one or more substituents).

[0049] The alkyl group in R ２１ may be substituted with the above-mentioned substituents, and preferably may be substituted with a fluorine atom, and the alkyl group is preferably a C １－３０ alkyl group which may be substituted with a fluorine atom. The alkyl group may be linear or branched. In one embodiment, the C １－３０ alkyl group may be a C １－２０ alkyl group, preferably a C １－１０ alkyl group, more preferably a C １－３ alkyl group.

[0050] R ２１ is preferably —R ２２ —R ２３ (wherein R ２２ is an unsubstituted C １－３０ alkylene group, preferably a C １－２０ ]]alkylene group, more preferably a C １－１０It is an alkylene group, R ２３ C １－１０ Perfluoroalkyl groups, preferably C １－６ It is a perfluoroalkyl group.

[0051] The alkyl ether group in R above is a compound having one or more etheric oxygen atoms in the molecular chain of the alkyl group. Such an alkyl ether group is typically -R ２６ -R ２７ - (O-R ２８ ) ｍ -R ２９ It is a group represented by the formula. In the formula, R ２６ R is a single bond or an oxygen atom. ２７ is a single bond or C １－１０ It is an alkylene group. ２８ C １－１０ It is an alkylene group. ２９ is a hydrogen atom or C １－１０ It is an alkyl group. m represents an integer from 1 to 20, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0052] In one embodiment, the organic group has a reactive group r at its terminal end. １ This may be an alkyl group, alkyloxy group, or alkyl ether group substituted by the substituted group. Such a group may be further substituted by another substituent.

[0053] In one embodiment, preferably, R may have one or more substituents C. １－３０ Represents an alkyl group or a hydrogen atom.

[0054] 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.

[0055] In formula (I), the reactive group r １ -OH may be included as a substituent of the organic group in -OH;R when A contains -OR and R is a hydrogen atom.

[0056] The cyclic compound (B) preferably includes a compound in formula (I) where A is a 1,4-dihydroxybenzene 2,5-diyl group or a 1,4-benzoquinone-2,5-diyl group, and n is 5.

[0057] The above cyclic compounds are preferably the following formulas (1) to (3): [In formula (1), R １ , R ２ , R ３ , R ４ Each of these independently represents a hydrogen atom or an organic group, however, R ３ and R ４ At least one of them is a hydrogen atom, n1 is an integer between 4 and 20, and in formula (1), at least one reactive group r １ In a preferred embodiment, R １ ~R ４ One or more selected from are preferably fluorine-containing organic groups, C ２－６ More preferably, the organic group contains a fluoroalkyl group, and in another preferred embodiment, R ３ and R ４ One or more selected from are hydrogen atoms, more preferably R ３ and R ４ This could be a hydrogen atom. [In formula (2), R ５ , R ６ Each of these independently represents a hydrogen atom or an organic group, n2 is an integer between 4 and 20, and in formula (2), at least one reactive group r １ This includes [...] [In formula (3), R ７ , R ８ , R ９ , R １０ , R １１ , R １２ Each independently represents a hydrogen atom or an organic group, n3 is an integer from 1 to 19, n4 is an integer from 1 to 19, the sum of n3 and n4 is from 4 to 20, the order of existence of the units enclosed in parentheses with n3 or n4 is arbitrary in formula (3), and in formula (3), at least one reactive group r１ It is preferable that it contains a compound represented by any of the following:

[0058] In formula (1), R １ Each of these independently represents a hydrogen atom or an organic group, R ２ Each of these independently represents a hydrogen atom or an organic group, R ３ Each of these independently represents a hydrogen atom or an organic group, R ４ Each of these independently represents either a hydrogen atom or an organic group.

[0059] R １ , R ２ , R ３ or R ４ Examples of organic groups represented by include alkyl groups, alkyloxy groups, alkyl ether groups, tosyl groups, triflate groups, phenyl groups, or fluorine-containing organic groups, and these groups may have one or more substituents.

[0060] R １ , R ２ , R ３ or R ４ The substituents that the organic group represented by the organic group may have are not particularly limited, but for example, a reactive group r １ (Preferably hydroxyl groups, amino groups, thiol groups, acid anhydride groups, epoxy groups); aliphatic hydrocarbon groups such as alkyl groups, vinyl groups, and ethynyl groups.

[0061] R １ , R ２ , R ３ or R ４ The alkyl group in is preferably C １－３０ It is an alkyl group. Such alkyl group may be linear or branched. In one embodiment, C １－３０ Alkyl alkyl groups are C １－２０ Alkyl alkyl group, preferably C １－１０ Alkyl alkyl group, comfortable C １－３０ It may be an alkyl group. In another embodiment, C １－３０ Alkyl alkyl groups are C １７－３０ Alkyl alkyl group, preferably C １８－３０ Alkyl alkyl group, comfortable C ２６－３０It can be an alkyl group.

[0062] R １ , R ２ , R ３ or R ４ The substituents on the alkyl group in C may be halogen atoms; C may be substituted with one or more halogen atoms. １－６ alkyl group, C ２－６ Alkenyl group, C ２－６ Alkynyl group, C ３－１０ Cycloalkyl groups, C ３－１０ Unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, C ６－１０ Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0063] The above R １ , R ２ , R ３ or R ４ The alkyloxy group in this is typically -O-R ２１ (In the formula, R ２１ This is an alkyl group which may have one or more substituents.

[0064] R ２１ The alkyl group in C may be substituted with the substituents described above, and preferably with a fluorine atom. １－３０ It is an alkyl group. Such alkyl group may be linear or branched. In one embodiment, C １－３０ Alkyl alkyl groups are C １－２０ Alkyl alkyl group, preferably C １－１０ Alkyl alkyl group, comfortable C １－３ It can be an alkyl group.

[0065] R ２１ Preferably, -R ２２ -R ２３ (In the formula, R ２２ is an unsubstituted C １－３０ Alkylene group, preferably C １－２０ Alkylene group, more preferably C １－１０ It is an alkylene group, R２３ C １－１０ Perfluoroalkyl groups, preferably C １－６ It is a perfluoroalkyl group.

[0066] The above R １ , R ２ , R ３ or R ４ The alkyl ether group in is a compound having one or more etheric oxygen atoms in the molecular chain of the alkyl group. Such alkyl ether groups are typically -R ２６ -R ２７ - (O-R ２８ ) ｍ -R ２９ It is a group represented by the formula. In the formula, R ２６ R is a single bond or an oxygen atom. ２７ is a single bond or C １－１０ It is an alkylene group. ２８ C １－１０ It is an alkylene group. ２９ is a hydrogen atom or C １－１０ It is an alkyl group. m represents an integer from 1 to 20, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0067] The above R １ , R ２ , R ３ or R ４ The fluorine-containing organic group in is preferably an organic group having 2 or more carbon atoms and a fluoroalkyl group, and more preferably a fluoroalkyl group or a fluoro(poly)ether group. The fluoroalkyl group is preferably C １－１０ Fluoroalkyl groups, more preferably C ２－６ It is a fluoroalkyl group. Such a fluoroalkyl group may be linear or branched, and is preferably linear. Such a fluoroalkyl group is preferably a perfluoroalkyl group. The above fluoro(poly)ether group represents a fluoroether group and / or a fluoropolyether group.

[0068] In one embodiment, the above fluorine-containing organic group is given by the following formula: -(O ｐ１ -R２０ ｑ１ )-Rf ａ [In the formula: R ２０ Each of them is independent of C １－１０ Represents an alkylene group. Rf ａ C １－１０ Represents an fluoroalkyl group. p1 is an integer from 0 to 2. q1 is an integer from 0 to 3. (O ｐ１ -R ２０ ｑ１ ) in which O and R １１ａ The order of existence of these is not limited. They are bases represented by ].

[0069] R ２０ C in １－１０ The alkylene group is preferably C １－６ Alkylene group, more preferably C ２－６ This is an alkylene group. Such an alkylene group may be linear or branched, and is preferably linear.

[0070] Rf ａ C in １－１０ The fluoroalkyl group is preferably C １－６ It is a fluoroalkyl group. Such a fluoroalkyl group may be linear or branched, and is preferably linear. Such a fluoroalkyl group is preferably a perfluoroalkyl group.

[0071] p1 is an integer between 0 and 2, preferably 1 or 2. In one embodiment, p1 is 1. In another embodiment, p1 is 2.

[0072] q1 is an integer between 0 and 3, preferably an integer between 1 and 3, more preferably 1 or 2. In one embodiment, q1 is 1. In another embodiment, q1 is 2.

[0073] In a preferred embodiment, the fluoro(poly)ether group is -O-R ２０ - (O-R ２０ ) ｒ１ -Rf ａ [In the formula: R ２０ Each of them is independent of C １－１０ Represents an alkylene group. Rf ａ C１－１０ It represents an fluoroalkyl group. r1 is 0 or 1. It is a group represented by [ ].

[0074] In a more preferred embodiment, the fluoro(poly)ether group is -O-R ２０ - (O-R ２０ ) ｒ１ -Rf ａ [In the formula: R ２０ Each of them is independent of C １－１０ Represents an alkylene group. Rf ａ C １－１０ It represents a perfluoroalkyl group. r1 is 0 or 1. It is a group represented by ].

[0075] n1 is an integer between 4 and 20, preferably between 4 and 6, and more preferably 5 or 6.

[0076] In a particularly preferred embodiment, R １３ and R １６ is -O-R ２０ - (O-R ２０ ) ｒ１ -Rf ａ And R １４ and R １５ is either a hydrogen atom or R １４ and R １５ is -O-R ２０ - (O-R ２０ ) ｒ１ -Rf ａ And R １３ and R １６ R is a hydrogen atom. ２０ Each of them is independent of C １－１０ Alkylene group, preferably C １－６ It is an alkylene group, Rf ａ C １－１０ Perfluoroalkyl groups, preferably C １－６ It is a perfluoroalkyl group, where r1 is 0 or 1, and n1 is an integer from 4 to 6, preferably 5 or 6.

[0077] In one embodiment, the organic group has a reactive group r at its terminal end. １This may be an alkyl group, alkyloxy group, or alkyl ether group substituted by the substituted group. Such a group may be further substituted by another substituent.

[0078] In one embodiment, preferably, R １ C may have one or more substituents. １－３０ R represents an alkyl group or a hydrogen atom. ２ C may have one or more substituents. １－３０ R represents an alkyl group or a hydrogen atom. ３ C may have one or more substituents. １－３０ R represents an alkyl group or a hydrogen atom. ４ C may have one or more substituents. １－３０ Represents an alkyl group or a hydrogen atom.

[0079] In a preferred embodiment, R １ ~R ４ One or more selected from are preferably fluorine-containing organic groups, C ２－６ It is more preferable that the organic group contains a fluoroalkyl group.

[0080] In another preferred embodiment, R ３ and R ４ One or more of those selected are hydrogen atoms, more preferably R ３ and R ４ This could be a hydrogen atom.

[0081] n1 is preferably 4 to 20, more preferably 4 to 10, even more preferably 4 to 7, and even more preferably 5 to 6. In one embodiment, n1 is 5. In another embodiment, n1 is 6.

[0082] In formula (1), the reactive group r １ R ３ or R ４ -OH;R when it is a hydrogen atom １ , R ２ , R ３ , R ４ It may be included as a substituent of the organic group in the compound.

[0083] In a preferred embodiment, R １ , R ２ , R ３ , R ４ Each of these C atoms may independently have one or more substituents. １－３０ Represents an alkyl group or a hydrogen atom, except R ３ and R ４ At least one of them represents a hydrogen atom, and n1 can be an integer from 4 to 20. In this embodiment, R ３ and R ４ At least one of them is a hydrogen atom, preferably R ３ and R ４ R may be a hydrogen atom; or R １ and R ２ is a hydrogen atom, R ３ and R ４ This may be a hydrogen atom or a methyl group.

[0084] In another preferred embodiment, R １ , R ２ , R ３ , R ４ Each of these independently represents a hydrogen atom or an organic group, however, R １ , R ２ , R ３ , R ４ At least one of them is a fluorine-containing organic group, R ３ and R ４ At least one of them is a hydrogen atom, and n1 can be an integer from 4 to 20. In this embodiment, R １ and R ２ Each of these may be an independent organic group; R １ and R ２ At least one of them may be a fluorine-containing organic group; R ３ and R ４ Each of these may be an organic group; R ３ and R ４ At least one of them may be a fluorine-containing organic group.

[0085] In yet another preferred embodiment, R １ , R ２ , R ３ , R ４Each of these C atoms may independently have one or more substituents. １－３０ Represents an alkyl group or a hydrogen atom, except R ３ and R ４ At least one of them is a hydrogen atom, and n1 can be an integer from 4 to 20. In this embodiment, R １ , R ２ , R ３ and R ４ At least one of them may be a hydrogen atom; R １ , R ２ , R ３ and R ４ One or two of those selected may be hydrogen atoms; R １ and R ２ is a hydrogen atom, R ３ and R ４ This may be a hydrogen atom or a methyl group.

[0086] In formula (2), R ５ Each of these independently represents a hydrogen atom or an organic group, R ６ Each of these independently represents either a hydrogen atom or an organic group.

[0087] R ５ or R ６ Examples of organic groups represented by include alkyl groups, alkyloxy groups, alkyl ether groups, tosyl groups, triflate groups, or phenyl groups, and these groups may have one or more substituents.

[0088] R ５ or R ６ The substituents that the organic group represented by the organic group may have are not particularly limited, but for example, a reactive group r １ (Preferably a hydroxyl group, carboxyl group, amino group, thiol group, acid anhydride group, epoxy group, highly reactive carbon atom (preferably, formula: -C=C) １ Carbon atoms C in the group represented as H-CO- １ Examples include aliphatic hydrocarbon groups such as alkyl groups, vinyl groups, and ethynyl groups. Highly reactive carbon atoms (preferably, formula: -C=C) １ Carbon atoms C in the group represented as H-CO- １) can readily react with amino groups, which are groups that can react with epoxy groups.

[0089] R ５ or R ６ The alkyl group in is preferably C １－３０ It is an alkyl group. Such alkyl group may be linear or branched. In one embodiment, C １－３０ Alkyl alkyl groups are C １－２０ Alkyl alkyl group, preferably C １－１０ Alkyl alkyl group, comfortable C １－３０ It may be an alkyl group. In another embodiment, C １－３０ Alkyl alkyl groups are C １７－３０ Alkyl alkyl group, preferably C １８－３０ Alkyl alkyl group, comfortable C ２６－３０ It can be an alkyl group.

[0090] R ５ or R ６ The substituents on the alkyl group in C may be halogen atoms; C may be substituted with one or more halogen atoms. １－６ alkyl group, C ２－６ Alkenyl group, C ２－６ Alkynyl group, C ３－１０ Cycloalkyl groups, C ３－１０ Unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, C ６－１０ Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0091] The above R ５ or R ６ The alkyloxy group in this is typically -O-R ２１ (In the formula, R ２１ This is an alkyl group which may have one or more substituents.

[0092] R ２１ The alkyl group in C may be substituted with the substituents described above, and preferably with a fluorine atom. １－３０It is an alkyl group. Such alkyl group may be linear or branched. In one embodiment, C １－３０ Alkyl alkyl groups are C １－２０ Alkyl alkyl group, preferably C １－１０ Alkyl alkyl group, comfortable C １－３ It can be an alkyl group.

[0093] The above R ５ or R ６ The alkyl ether group in is a compound having one or more etheric oxygen atoms in the molecular chain of the alkyl group. Such alkyl ether groups are typically -R ２６ -R ２７ - (O-R ２８ ) ｍ -R ２９ It is a group represented by the formula. In the formula, R ２６ R is a single bond or an oxygen atom. ２７ is a single bond or C １－１０ It is an alkylene group. ２８ C １－１０ It is an alkylene group. ２９ is a hydrogen atom or C １－１０ It is an alkyl group. m represents an integer from 1 to 20, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0094] In one embodiment, the organic group has a reactive group r at its terminal end. １ The alkyl group may be an alkyl group, alkyloxy group, or alkyl ether group substituted with a hydroxyl group, amino group, thiol group, acid anhydride group, or epoxy group. Such a group may be further substituted with another substituent.

[0095] In one embodiment, preferably, R ５ C may have one or more substituents. １－３０ R represents an alkyl group or a hydrogen atom. ６ C may have one or more substituents. １－３０ Represents an alkyl group or a hydrogen atom.

[0096] n2 is preferably 4 to 20, more preferably 4 to 10, even more preferably 4 to 7, and even more preferably 5 to 6. In one embodiment, n2 is 5. In another embodiment, n2 is 6.

[0097] In formula (2), the reactive group r １ R ５ , R ６ It may be included as a substituent of the organic group in the compound.

[0098] In a preferred embodiment, R ５ , R ６ Each of these C atoms may independently have one or more substituents. １－３０ R represents an alkyl group or a hydrogen atom, and n2 can represent an integer from 4 to 20. In this embodiment, R ５ and R ６ It may be a hydrogen atom.

[0099] In formula (3), R ７ Each of these independently represents a hydrogen atom or an organic group, R ８ Each of these independently represents a hydrogen atom or an organic group, R ９ Each of these independently represents a hydrogen atom or an organic group, R １０ Each of these independently represents a hydrogen atom or an organic group, R １１ Each of these independently represents a hydrogen atom or an organic group, R １２ Each of these independently represents either a hydrogen atom or an organic group.

[0100] R ７ , R ８ , R ９ , R １０ , R １１ or R １２ Examples of organic groups represented by include alkyl groups, alkyloxy groups, alkyl ether groups, tosyl groups, triflate groups, or phenyl groups, and these groups may have one or more substituents.

[0101] R ７ , R ８ , R ９ , R １０ , R １１ or R １２The substituents that the organic group represented by the organic group may have are not particularly limited, but for example, a reactive group r １ (Preferably hydroxyl groups, amino groups, thiol groups, acid anhydride groups, epoxy groups); aliphatic hydrocarbon groups such as alkyl groups, vinyl groups, and ethynyl groups.

[0102] R ７ , R ８ , R ９ , R １０ , R １１ or R １２ The alkyl group in is preferably C １－３０ It is an alkyl group. Such alkyl group may be linear or branched. In one embodiment, C １－３０ Alkyl alkyl groups are C １－２０ Alkyl alkyl group, preferably C １－１０ Alkyl alkyl group, comfortable C １－３０ It may be an alkyl group. In another embodiment, C １－３０ Alkyl alkyl groups are C １７－３０ Alkyl alkyl group, preferably C １８－３０ Alkyl alkyl group, comfortable C ２６－３０ It can be an alkyl group.

[0103] R ７ , R ８ , R ９ , R １０ , R １１ or R １２ The substituents on the alkyl group in C may be halogen atoms; C may be substituted with one or more halogen atoms. １－６ alkyl group, C ２－６ Alkenyl group, C ２－６ Alkynyl group, C ３－１０ Cycloalkyl groups, C ３－１０ Unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, C ６－１０ Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0104] The above R ７ , R ８ , R ９ , R １０ , R １１ or R１２ The alkyloxy group in this is typically -O-R ２１ (In the formula, R ２１ This is an alkyl group which may have one or more substituents.

[0105] R ２１ The alkyl group in C may be substituted with the substituents described above, and preferably with a fluorine atom. １－３０ It is an alkyl group. Such alkyl group may be linear or branched. In one embodiment, C １－３０ Alkyl alkyl groups are C １－２０ Alkyl alkyl group, preferably C １－１０ Alkyl alkyl group, comfortable C １－３ It can be an alkyl group.

[0106] 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 alkyl group. Such alkyl ether groups are typically -R ２６ -R ２７ - (O-R ２８ ) ｍ -R ２９ It is a group represented by the formula. In the formula, R ２６ R is a single bond or an oxygen atom. ２７ is a single bond or C １－１０ It is an alkylene group. ２８ C １－１０ It is an alkylene group. ２９ is a hydrogen atom or C １－１０ It is an alkyl group. m represents an integer from 1 to 20, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0107] In one embodiment, the above R ７ , R ８ , R ９ , R １０ , R１１ or R １２ The represented organic group has a reactive group r at its terminal end. １ The alkyl group may be an alkyl group, alkyloxy group, or alkyl ether group substituted with a hydroxyl group, amino group, thiol group, acid anhydride group, or epoxy group. Such a group may be further substituted with another substituent.

[0108] In one embodiment, preferably, R ７ C may have one or more substituents. １－３０ R represents an alkyl group or a hydrogen atom. ８ C may have one or more substituents. １－３０ R represents an alkyl group or a hydrogen atom. ９ C may have one or more substituents. １－３０ R represents an alkyl group or a hydrogen atom. １０ C may have one or more substituents. １－３０ R represents an alkyl group or a hydrogen atom. １１ C may have one or more substituents. １－３０ R represents an alkyl group or a hydrogen atom. １２ C may have one or more substituents. １－３０ Represents an alkyl group or a hydrogen atom.

[0109] n3 is preferably 1 to 19, more preferably 1 to 9, even more preferably 1 to 6, and even more preferably 1 to 5. n4 is preferably 1 to 19, more preferably 1 to 9, even more preferably 1 to 6, and even more preferably 1 to 5. n3 + n4 is preferably 4 to 20, more preferably 4 to 10, even more preferably 4 to 7, and even more preferably 5 to 6.

[0110] In formula (3), the reactive group r １ R ９ or R １０ -OH;R when it is a hydrogen atom ７ , R ８ , R ９ , R １０ , R １１ , R １２It may be included as a substituent of the organic group in the compound.

[0111] In a preferred embodiment, R ７ , R ８ , R ９ , R １０ , R １１ , R １２ Each of these C atoms may independently have one or more substituents. １－３０ Represents an alkyl group or a hydrogen atom, where n3 is an integer from 1 to 19, n4 is an integer from 1 to 19, and the sum of n3 and n4 is from 4 to 20, provided that the order of existence of the units enclosed in parentheses with n3 or n4 is arbitrary in formula (3). In such an embodiment, R ７ , R ８ , R １１ and R １２ Preferably, is a hydrogen atom, R ９ and R １０ This is preferably a methyl group.

[0112] In another preferred embodiment, R ７ , R ８ , R ９ , R １０ , R １１ , R １２ Each of these independently represents a hydrogen atom or an organic group, however, R ９ and R １０ 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 sum of n3 and n4 is from 4 to 20, and the order of existence of the units enclosed in parentheses with n3 or n4 may be arbitrary in equation (3). In such an embodiment, R ９ and R １０ At least one of them may be a hydrogen atom; preferably R ９ｂ and R １０ｂ It may be a hydrogen atom.

[0113] The above-mentioned cyclic compound (B) may preferably include one or more compounds selected from formulas (1), (2), and (3).

[0114] In one embodiment, the cyclic compound (B) preferably includes a compound represented by formula (1), where R １ , R ２ , R ３ , R ４ It is preferable that the compound contains a hydrogen atom and n1 is 5.

[0115] In another embodiment, the cyclic compound (B) preferably includes a compound represented by formula (2), where R ５ , R ６ It is preferable that the compound contains a hydrogen atom and n2 is 5.

[0116] In yet another embodiment, the cyclic compound (B) preferably includes a compound represented by formula (3).

[0117] If the composition contains two or more cyclic compounds (B), these two or more cyclic compounds (B) may be the same or different.

[0118] The proportion of cyclic compound (B) is preferably 0.01% to 99% by mass, more preferably 0.1% to 95% by mass, and even more preferably 1% to 90% by mass, in 100 parts by mass of the total of polymer (A) and cyclic compound (B). The tensile strength of the composite is good when the proportion of cyclic compound (B) is within the above range.

[0119] In the above composition, the total content of polymer (A) and cyclic compound (B) is preferably 80% to 100% by mass, more preferably 90% to 100% by mass, and even more preferably 95% to 100% by mass, based on 100% by mass of the total amount of the composition.

[0120] Crosslinking agent (C) The above composition may further contain a crosslinking agent (C). The crosslinking agent is typically a group that can react with epoxy groups and / or a reactive group r １ It is preferable that the compound has two or more groups in one molecule that can react with [the specified substance].

[0121] Examples of such crosslinking agents (C) include phenolic crosslinking agents, carbodiimide crosslinking agents, acid anhydride crosslinking agents, amine crosslinking agents, benzoxazine crosslinking agents, cyanate ester crosslinking agents, thiol crosslinking agents, and the like.

[0122] As phenolic crosslinking agents, crosslinking agents having one or more, preferably two or more, hydroxyl groups bonded to aromatic rings such as benzene rings and naphthalene rings per molecule can be used. Crosslinking agents such as biphenyl type, naphthalene type, phenol novolac type, naphthylene ether type, and triazine skeleton-containing phenol type can be used.

[0123] As carbodiimide-based crosslinking agents, crosslinking agents having one or more, preferably two or more, carbodiimide structures in one molecule can be used. Examples of carbodiimide-based crosslinking agents include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); and poly(phenylenecarbodiimide) and poly(naphtholonecarbodiimide). Examples of polycarbodiimides include aromatic polycarbodiimides such as ethylenecarbodiimide, poly(tylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide].

[0124] As an acid anhydride crosslinking agent, a crosslinking agent having one or more acid anhydride groups in one molecule can be used, and a crosslinking agent having two or more acid anhydride groups in one molecule is preferred. Examples of acid anhydride crosslinking agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexen-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride, and bensophenone tetracarboxylic acid di Examples include anhydrides, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenylsulfontetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymer-type acid anhydrides such as styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid.

[0125] As an amine-based crosslinking agent, a crosslinking agent having one or more, preferably two or more, amino groups in one molecule can be used. Examples of amine-based crosslinking agents include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and the like, with aromatic amines being preferred. The amino groups contained in the amine-based crosslinking agent are preferably primary or secondary amino groups, with primary amino groups being more preferred. Specific examples of amine-based crosslinking agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, Examples include 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, dicyandiamide, etc.

[0126] As a benzoxazine-based crosslinking agent, a phenolic resin produced by ring-opening of a benzoxazine compound can be used.

[0127] Examples of cyanate ester crosslinking agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl) thioether, and bis(4-cyanatephenyl) ether; polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs; and prepolymers in which these cyanate resins are partially triazined.

[0128] Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl) isocyanurate.

[0129] In one embodiment, the amount of crosslinking agent (C) is preferably 0.5 moles to 2 moles, more preferably 0.8 moles to 1.2 moles, per mole of epoxy groups contained in polymer (A).

[0130] The above composition may contain additives in addition to the polymer (A), cyclic compound (B), and optionally used crosslinking agent (C). Examples of such additives include curing accelerators, reactive diluents, fillers, flame retardants, defoamers, wetting agents, leveling agents, emulsifiers, surfactants, thickeners, viscoelastic modifiers, dispersants, preservatives, plasticizers, penetrating agents, fragrances, bactericides, acaricides, fungicides, ultraviolet absorbers, antioxidants, antistatic agents, dyes, pigments, and the like.

[0131] Examples of curing accelerators include well-known ones such as imidazole compounds, amine compounds, and phosphorus compounds. Examples of amine compounds include tertiary amines and tertiary amine salts, and examples of phosphorus compounds include triphenylphosphine and phosphonium salts. Examples of imidazole compounds include 1-isobutyl-2-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and benzimidazole. Other curing accelerators include sulfonium salts and 3-phenyl-1,1'dimethylurea. The curing accelerator should be appropriately selected in combination with the crosslinking agent.

[0132] Examples of reactive diluents include low-viscosity liquid epoxy resins having glycidyl ether groups at their termini. Specific examples of these include neopentyl glycol diglycidyl ether, glycidylaniline, glycidyl orthotoluidine, and hexahydrophthalate diglycidyl ester.

[0133] Examples of fillers include metal hydroxides such as aluminum hydroxide and magnesium hydroxide; metal oxides such as magnesium oxide and aluminum oxide; metal carbonates such as calcium carbonate, aluminum carbonate and magnesium carbonate; and other materials such as glass balloons, silica, mica, talc, wollastonite, titanium dioxide, carbon black, graphite, iron oxide, gold, aluminum powder, and iron powder.

[0134] The composite of the present disclosure comprises a polymer (A) having epoxy groups at its termini and a reactive group r that encloses polymer (A). １ The composite is obtained from a composition containing a cyclic compound (B) having and a polymer (A), and because it contains a crosslinked structure by the polymer (A), the cyclic compound (B) can maintain an inclusion state without detaching from the polymer (A). Therefore, the composite of this disclosure corresponds to a (poly)rotaxane.

[0135] Because the composites of this disclosure include a crosslinked structure by polymer (A), the inclusion state by the cyclic compound (B) can be maintained even if polymer (A) does not have a stopper structure at its terminals. In other words, the technical scope of this disclosure includes composites that include a polymer without a stopper structure at its terminals and a cyclic compound that inclusions the polymer, and that include a crosslinked structure by the polymer.

[0136] In such a composite, the crosslinking structure of the polymer may be a crosslinking structure formed between polymers, or a crosslinking structure formed between a polymer and a cyclic compound. The polymer is preferably polymer (A). The cyclic compound is preferably cyclic compound (B).

[0137] The composite of the present disclosure comprises a polymer and a cyclic compound that can move on the polymer while encapsulating the polymer, and corresponds to a slide ring material. In the slide ring material of the present disclosure, it is believed that the crosslinking points in the polymer can move freely within the material while maintaining the function of the macrostructure, thereby improving impact resistance.

[0138] Furthermore, the composite of the present disclosure comprises a polymer (A) having an epoxy group and a cyclic compound (B) having a reactive group r １ Although it has such a feature, in another embodiment, the polymer (A) may have a reactive group r1 and the cyclic compound (B) may have an epoxy group. That is, the technical scope of this disclosure is such that the reactive group r at the terminal is ２ The composite is obtained from a composition comprising a polymer (A') having a reactive group r, and a cyclic compound (B') having an epoxy group that encloses the polymer (A'), and also includes a crosslinked structure by the cyclic compound (B2). ２ Examples of such groups include those that can react with epoxy groups, or groups that can react with epoxy groups, specifically hydroxyl groups, carboxyl groups, amino groups, thiol groups, and acid anhydride groups.

[0139] Examples of the polymer (A') mentioned above include polyalkylene oxides having hydroxyl groups at the terminals (especially linear polyalkylene oxides having hydroxyl groups at both ends); and polyalkylene oxides having amino groups at the terminals (especially linear polyalkylene oxides having amino groups at both ends).

[0140] Examples of the above cyclic compound (B') include derivatives of pillararenes, the following being examples (where * represents a bond in the formula).

[0141] Manufacturing Method The manufacturing method disclosed herein involves a polymer (A) having epoxy groups at its terminals, and a reactive group r that encloses polymer (A). １ The method involves using a composition containing a cyclic compound (B) having and forming a crosslinked structure with a polymer (A). The composition preferably further contains a crosslinking agent (C) and may further contain additives.

[0142] According to the manufacturing method of this disclosure, a crosslinked structure is formed using a polymer having epoxy groups at its ends and a cyclic compound having reactive groups that encloses the polymer. This method allows for a shortened manufacturing process and improves the tensile strength, thereby providing a slide ring material.

[0143] Polymer (A), cyclic compound (B), crosslinking agent (C), additive, and crosslinked structure have the same meaning as described above.

[0144] The conditions for forming the above crosslinked structure are not particularly limited. In the presence or absence of a solvent, epoxy group, reactive group r １ Furthermore, by reacting with a crosslinking agent (C) as needed, a crosslinked structure can be formed and a composite can be obtained.

[0145] Examples of solvents that can be used in the reaction include aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-cymene; aliphatic hydrocarbons such as hexane and heptane; cyclic alkanes such as methylcyclohexane; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; carbonate esters such as ethylene carbonate and propylene carbonate; and amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone (NMP).

[0146] Furthermore, the reaction temperature may preferably be 20 to 250°C, more preferably 60 to 180°C, and the reaction time may preferably be 10 minutes to 24 hours, more preferably 60 minutes to 12 hours. The reaction temperature and reaction time may be changed in stages.

[0147] The technical scope of this disclosure also includes composite compositions comprising the composites of the disclosure.

[0148] The composite content in the composite composition is preferably 1% to 90% by mass, more preferably 5% to 80% by mass, and even more preferably 10% to 60% by mass, out of 100% by mass of the total amount of the composite composition.

[0149] The composite composition may also contain epoxy resin, resin, filler, and the above-mentioned additives, in addition to the composite.

[0150] The scope of this disclosure also includes molded articles comprising the composites of the disclosure.

[0151] The composite content in the molded article is preferably 1% to 80% by mass, more preferably 2% to 60% by mass, and even more preferably 5% to 50% by mass, based on 100% by mass of the total amount of the molded article.

[0152] The molded article may contain, in addition to the composite, resin, filler, and the above-mentioned additives.

[0153] The shape of the above molded body is not particularly limited and may be, for example, film-like, plate-like, block-like, three-dimensional shape, etc.

[0154] The composite of the present disclosure enables shortening of the manufacturing process and is excellent in fracture toughness and fracture strength. Therefore, the molded body containing the composite is also excellent in fracture toughness and fracture strength. Therefore, the composite of the present disclosure can be preferably used in medical devices, electronic devices, vehicle parts, building parts, textile products, etc.

[0155] The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. (1) NMR Measured using an NMR measuring device manufactured by JEOL Ltd. １ H-NMR measurement conditions: 500 MHz (tetramethylsilane = 0 ppm) (2) Thermal decomposition temperature Measured in accordance with JIS K7120 using a TGA measuring device under measurement conditions consisting of a temperature range from 23°C to 600°C and a heating rate of 10°C / min in a nitrogen gas atmosphere. The thermal decomposition temperature was defined as the temperature at which the mass of the measurement object decreased by 5% compared to the mass of the measurement object before the start of the measurement. (3) Tensile test Using a desktop tensile compression tester MCT-2150 manufactured by A&D, a sample punched out in the shape of a JIS micro dumbbell was subjected to a tensile test at room temperature and a condition of 200 mm / min, and the fracture strength, fracture elongation, tensile elastic modulus, and fracture toughness (the area surrounded by the SS curve and the horizontal axis) were determined.

[0156] The following polymers were used as the polymer (A). A-1:

[0157] A-1 is polyethylene glycol having an epoxy group at both ends and a molecular weight of 400.

[0158] A-2:

[0159] A-2 is polyethylene glycol having an epoxy group at both ends and a molecular weight of 1,000.

[0160] A-3:

[0161] A-3 is a polyethylene glycol with a molecular weight of 5,000, having epoxy groups at both ends.

[0162] A-4:

[0163] A-4 is a polyethylene glycol with a molecular weight of 10,000, having epoxy groups at both ends.

[0164] The following compound was used as the cyclic compound (B).

[0165] B-1: A compound represented by formula (1-2) was used as a cyclic compound. Hereinafter referred to as P5OH.

[0166] B-1 has a hydroxyl group that can react with an epoxy group.

[0167] B-2: A compound represented by formula (3-2) was used as a cyclic compound. This will be referred to as P5Q below.

[0168] B-2 has a carbonyl group as a reactive group.

[0169] The following compound was used as the crosslinking agent (C).

[0170] C-1: Amine curing agent

[0171] Triethylenetetramine (TEA)

[0172] C-2: Amine curing agent

[0173] Diethylmethylbenzenediamine (DEMBA)

[0174] C-3: Amine curing agent 2,2'-dimethyl-4,4'-methylenebis(cyclohexylamine) (DMCA)

[0175] The following compound was used as a curing accelerator (D).

[0176] D-1: Phosphorus-based triphenylphosphine (TPP)

[0177] D-2: Imidazole derivative 2-ethyl-4-methylimidazole (2E4MZ)

[0178] Reference Example 1: 550 mg of A-1, a polymer having epoxy groups at both ends, and 100 mg of B-1, a cyclic compound having reactive groups, were mixed at room temperature and held for 48 hours. Then, 2 mL of water, a good solvent for A-1, was added and the mixture was stirred uniformly. After washing with another 20 mL of water and centrifuging, a precipitated solid was obtained. The obtained solid was dissolved in heavy DMSO and subjected to NMR analysis. The results showed that A-1 and B-1 were observed in a molar ratio of 0.8:1. It was considered that the solubility in water changed when B-1 was inclusionated into A-1, and that the inclusionated A-1 remained.

[0179] Example 1: 550 mg of A-1, a polymer having epoxy groups at its ends, was uniformly dissolved with 150 mg of B-1, a cyclic compound having reactive groups. The mixture was then held at room temperature for 48 hours. 110 mg of 2E4MZ was added as a curing accelerator and uniformly mixed. The mixture was then sandwiched between two Daikin Industries NF-0100 sheets, placed in a press, and heated at 90°C for 2 hours, followed by heating at 150°C for 6 hours.

[0180] After cooling to room temperature, the film was removed and a cured film was obtained. The obtained film was punched out using a micro-dumbbell die and then measured using a tensile testing machine. The results are shown in Table 1. Furthermore, the obtained film did not dissolve in water, which is a good solvent for A-1.

[0181] Examples 2-5: Cured films were prepared in the same manner as in Example 1, except that the amount of 2E4MZ used as a curing accelerator was changed to 90 mg, 130 mg, 150 mg, and 170 mg, and measured using a tensile testing machine. The results are shown in Table 1.

[0182] Example 6 A cured film was prepared in the same manner as in Example 4, except that B-1 was used as the cyclic compound at 175 mg, and measured using a tensile testing machine. The results are shown in Table 1.

[0183]

[0184] Comparative Example 1: 550 mg of A-1, a polymer having epoxy groups at its ends, was uniformly mixed with 150 mg of 2E4MZ as a curing accelerator. The mixture was then held in a heat press at 90°C for 2 hours and 150°C for 6 hours, as in Example 1. Upon removal and observation, no cured product was obtained.

[0185] As shown in Comparative Example 1, in the curing reaction of epoxy, the cured product was obtained by the participation of the hydroxy group of cyclic molecule B-1. That is, it was considered that the crosslinking points of the cured product with the cyclic molecules had a so-called slide ring structure.

[0186] Example 7: After uniformly dissolving 550 mg of A-1 as a polymer having an epoxy group at the terminal and 150 mg of B-1 as a cyclic compound having a reactive group, it was held at room temperature for 48 hours. Then, 238 μL of DMCA was added as a crosslinking agent and uniformly mixed. After that, it was sandwiched between two sheets of NF-0100 sheets manufactured by Daikin Industries, Ltd., placed between the presses, held at 80 °C for 1 hour, 100 °C for 1 hour, 120 °C for 1 hour, and 150 °C for 4 hours, cooled to room temperature, and taken out. As a result, a cured film was obtained. After punching out the obtained film in the shape of a micro dumbbell, it was measured with a tensile tester. The results are shown in Table 2. Also, the obtained film did not dissolve in water, which is a good solvent for A-1.

[0187] Examples 8 to 10: Cured films were produced in the same manner as in Example 7 except that the amounts of DMCA used as the crosslinking agent were changed to 297.5 μL, 178 μL, and 119 μL, and measured with a tensile tester. The results are shown in Table 2.

[0188] Examples 11 and 12: Cured films were produced in the same manner as in Example 7 except that the amounts of B-1 as the cyclic compound were changed to 200 mg and 100 mg, and measured with a tensile tester. The results are shown in Table 2.

[0189]

[0190] Fig. 1 shows a photograph of the composite (punched into a micro dumbbell) of Example 6.

[0191] Comparative Example 2: After uniformly mixing 550 mg of A-1 as a polymer having an epoxy group at the terminal and 238 μL of DMCA as a crosslinking agent, it was held in a heat press at 80 °C for 1 hour, 100 °C for 1 hour, 120 °C for 1 hour, and 150 °C for 4 hours in the same manner as in Example 7, and then taken out and observed. As a result, a cured product capable of a tensile test was not obtained. Fig. 2 shows a photograph of the cured product of Comparative Example 2.

[0192] As shown in Comparative Example 2, the composites obtained in Examples 7 to 10 were thought to have significantly improved mechanical strength of the cured product due to the involvement of cyclic molecule B-1 in the epoxy curing reaction. In other words, although the reason is unknown, it was thought that crosslinking with cyclic molecule B-1 occurred in the cured product, i.e., a sliding ring structure was formed.

[0193] Example 13: The thermal decomposition temperatures of the composites from Examples 7 to 10 were measured. The results are shown in Table 3.

[0194] Comparative Example 3: The thermal decomposition temperature of A-1 alone was measured as a polymer having epoxy groups at both ends. The results are shown in Table 3.

[0195]

[0196] Example 14 A cured film was prepared in the same manner as in Example 7, except that A-2 was used instead of A-1 as a polymer having epoxy groups at both ends, and the curing time was changed from 48 hours at room temperature to 48 hours at 60°C. The film was then measured using a tensile testing machine. The results are shown in Table 4. The individual compositions are also shown in Table 4. Figure 4 shows a photograph of the obtained composite (punched into a micro dumbbell).

[0197]

[0198] Example 15 A composite was obtained in the same manner as in Example 14, except that A-3 and A-4 were used instead of A-2 as polymers having epoxy groups at both ends, and the curing time was changed from 48 hours at 60°C to 18 hours at 100°C.

[0199] Example 16: 250 mg of A-3 was used as a polymer having epoxy groups at both ends, and 50 mg of B-1 was used as a cyclic compound having a reactive group. After uniform dissolution, the mixture was held at 100°C for 18 hours. 10 mg of TPP was added as a curing accelerator and uniformly mixed. The mixture was then sandwiched between two sheets of Daikin Industries' NF-0100, placed in a press, and heated at 100°C for 0.5 hours, followed by heating at 100°C for 5.5 hours. After cooling to room temperature, the film was removed to obtain a cured film. The obtained film was punched out using a micro dumbbell die and then measured using a tensile testing machine. The results are shown in Table 5.

[0200]

[0201] Figure 4 shows a photograph of the composite obtained in Example 16 (punched into a micro dumbbell).

[0202] Comparative Example 4: 250 mg of A-3 was used as the polymer having epoxy groups at its ends, and 10 mg of TPP was used as a curing accelerator. After uniform mixing, the mixture was heated in the same manner as in Example 16, removed, and observed. As a result, no cured product was obtained. Figure 5 shows a photograph of the cured product of Comparative Example 4.

[0203] Example 17: Using 275 mg of A-1 as a polymer having epoxy groups at its ends and 75 mg of B-1 as a cyclic compound having reactive groups, the mixture was homogeneously dissolved and held at room temperature for 48 hours. After adding 89 μL of DEMBA as a crosslinking agent and mixing homogeneously, the mixture was sandwiched between two sheets of Daikin Industries' NF-0100 and placed in a press machine, held at 100°C for 2 hours and 175°C for 6.5 hours. After cooling to room temperature, the mixture was removed to obtain a cured film. The obtained film did not dissolve in water, which is a good solvent for A-1.

[0204] Example 18: 550 mg of A-1 was used as a polymer having epoxy groups at its ends, and 150 mg of B-1 was used as a cyclic compound having reactive groups. After homogeneous dissolution, the mixture was held at room temperature for 48 hours. 109.5 μL of TEA was added as a crosslinking agent and homogeneously mixed. The mixture was then sandwiched between two sheets of Daikin Industries' NF-0100, placed in a press machine, and held at 60°C for 6 hours. After cooling to room temperature, the mixture was removed to obtain a cured film. The obtained film was punched out using a micro dumbbell die and then measured using a tensile tester. The results are shown in Table 6. Furthermore, the obtained film did not dissolve in water, which is a good solvent for A-1.

[0205] Examples 19 and 20: Cured films were prepared in the same manner as in Example 18, except that B-1 was used as the cyclic compound in 100 mg and 75 mg doses, respectively, and measured using a tensile testing machine. The results are shown in Table 6.

[0206]

[0207] Figure 6 shows a photograph of the composite material from Example 18 (punched into a micro dumbbell).

[0208] Reference Example 2: 500 mg of A-1, a polymer having epoxy groups at both ends, and 10 mg of B-2, a cyclic compound having reactive groups, were used. They were mixed at room temperature and held for 3 hours. Then, 2 mL of water, a good solvent for A-1, was added and the mixture was stirred uniformly. After washing with another 20 mL of water and centrifuging, a precipitated solid was obtained. The obtained solid was dissolved in heavy DMSO and subjected to NMR analysis. The results showed that A-1 and B-2 were observed in a molar ratio of 0.28:1. It was considered that the solubility in water changed when B-2 was inclusionated into A-1, and that the inclusionated A-2 remained.

[0209] Example 21: 550 mg of A-1 was used as a polymer having epoxy groups at its ends, and 150 mg of B-2 was used as a cyclic compound having reactive groups. After homogeneous dissolution, the mixture was held at room temperature for 48 hours. 238 μL of DMCA was added as a crosslinking agent and homogeneously mixed. The mixture was then sandwiched between two sheets of Daikin Industries' NF-0100 and placed in a press machine. After being held at 80°C for 1 hour, 100°C for 1 hour, 120°C for 1 hour, and 150°C for 4 hours, the mixture was cooled to room temperature and removed to obtain a cured film. The obtained film did not dissolve in water, which is a good solvent for A-1.

[0210] Example 22: Composition and molded article 1 Liquid epoxy 1 550 mg of A-1 was used as a polymer having epoxy groups at its ends, and 150 mg of B-1 was used as a cyclic compound having reactive groups. After homogeneous dissolution, it was held at room temperature for 48 hours, 110 mg of 2E4MZ was added as a curing accelerator and homogeneously mixed, and then 100 mg of neopentyl glycol diglycidyl ether was added as a reactive diluent and homogeneously mixed. The mixture was then cured under the same conditions as in Example 1 to obtain a cured film. The obtained film did not dissolve in water, which is a good solvent for A-1.

[0211] Example 23: Composition and molded article No. 2 Liquid epoxy No. 2 A cured film was obtained under the same conditions as in the above example, except that 100 mg of bisphenol A type JER819 (manufactured by Mitsubishi Chemical Corporation) was used as a reactive diluent. Furthermore, the obtained film did not dissolve in water, which is a good solvent for A-1.

[0212] Example 24: Composition and molded body No. 3 (liquid epoxy) + filler To 100 parts of the homogeneous mixture of the above example, 10 parts of SO-C6 manufactured by Admatec Co., Ltd. were added as silica filler, and a cured film was obtained under the same conditions as in the above example. Furthermore, the obtained film did not dissolve in water, which is a good solvent for A-1.

[0213] Example 25: 250 mg of A-2 was used as a polymer having epoxy groups at its ends, and 75 mg of B-1 was used as a cyclic compound having reactive groups. After homogeneous dissolution, the mixture was held at 60°C for 48 hours. 50 mg of 2E4MZ was added as a curing accelerator and mixed uniformly. The mixture was then mixed in an ultrasonic cleaner at 40°C for 10 minutes. After removal, it was held at 70°C for 5 minutes. The mixture was then sandwiched between two Daikin Industries NF-0100 sheets and heated in a press machine at 90°C for 2 hours. Subsequently, it was heated at 110°C for 1 hour, 130°C for 1 hour, and 150°C for 6 hours.

[0214] After cooling to room temperature, the material was removed, yielding a cured film. The resulting film was punched out using a micro-dumbbell die and then measured using a tensile testing machine. The results are shown in Table 7.

[0215] Examples 26-31: Cured films were prepared in the same manner as in Example 25, except that the amount of B-1 used as a cyclic compound was varied to 100 mg, 125 mg, 150 mg, 153.2 mg, 175 mg, and 200 mg. The films were then measured using a tensile testing machine. The results are shown in Table 7.

[0216] A photograph of the film from Example 30 is shown in Figure 7.

[0217] Example 32: 250 mg of A-1 was used as a polymer having epoxy groups at its ends, and 150 mg of B-1 was used as a cyclic compound having reactive groups. After homogeneous dissolution, the mixture was held at room temperature for 48 hours. 50 mg of 2E4MZ was added as a curing accelerator and mixed uniformly. The mixture was then mixed in an ultrasonic cleaner at 40°C for 10 minutes. After removal, it was held at 70°C for 5 minutes. The mixture was then sandwiched between two Daikin Industries NF-0100 sheets and placed in a press machine, where it was heated at 90°C for 2 hours. Subsequently, it was heated at 110°C for 1 hour, 130°C for 1 hour, and 150°C for 6 hours.

[0218] After cooling to room temperature, the material was removed, yielding a hardened film. The resulting film was punched out using a micro-dumbbell die and then measured using a tensile testing machine.

[0219] Example 33: 250 mg of A-4, a polymer having epoxy groups at its ends, was dissolved in 2 mL of methanol. Then, 150 mg of B-1, a cyclic compound having reactive groups, was uniformly dissolved. The mixture was then held at room temperature for 31 hours. After the methanol was volatilized at 50°C, 50 mg of 2E4MZ was added as a curing accelerator and uniformly mixed. The mixture was then held at 70°C for 5 minutes. Finally, the mixture was placed between two Daikin Industries NF-0100 sheets and heated in a press at 90°C for 2 hours. After that, it was heated at 110°C for 1 hour, 130°C for 1 hour, and 150°C for 6 hours.

[0220] After cooling to room temperature, the film was removed and a cured film was obtained. The obtained film was punched out using a micro dumbbell die and then measured using a tensile testing machine. The results for Examples 28 and 32 are shown in Table 8. The SS curves of the measurement results in Table 8 are shown in Figure 8. A photograph of the film from Example 33 is shown in Figure 9.

[0221] Example 34 A cured film was prepared in the same manner as in Example 33, except that 2E4MZ-CN (2-ethyl-4-methyl-1H-imidazole-1-propanenitrile) was used instead of 2E4MZ as the curing accelerator, and measured using a tensile testing machine. The results are shown in Table 9.

[0222] Example 35 250 mg of A-4, a polymer having epoxy groups at its ends, was dissolved in 2 mL of methanol. Then, 150 mg of B-1, a cyclic compound having reactive groups, was uniformly dissolved. The mixture was held at room temperature for 24 hours, and methanol was removed by vacuum drying at 50°C and at room temperature for 24 hours. 50 mg of 2E4MZ-CN was added as a curing accelerator and uniformly mixed. After holding at 70°C for 5 minutes, the mixture was placed between two Daikin Industries NF-0100 sheets and heated in a press at 90°C for 1 hour. Subsequently, it was heated at 110°C for 1 hour, 130°C for 1 hour, and 150°C for 4 hours. After cooling to room temperature, the mixture was removed to obtain a cured film. The obtained film was punched out using a micro dumbbell die and measured using a tensile testing machine. The results are shown in Table 10.

[0223] Example 36: 250 mg of A-2 was used as a polymer having epoxy groups at its ends, and 175 mg of B-1 was used as a cyclic compound having reactive groups. 25 mg of JER828 manufactured by Mitsubishi Chemical Corporation was uniformly dissolved as a reactive diluent, and the mixture was held at 60°C for 48 hours. 50 mg of 2E4MZ was added as a curing accelerator and uniformly mixed. The mixture was held at 70°C for 5 minutes, then sandwiched between two NF-0100 sheets manufactured by Daikin Industries, Ltd., and heated in a press machine at 90°C for 2 hours. After that, it was heated at 110°C for 1 hour, 130°C for 1 hour, and 150°C for 6 hours.

[0224] After cooling to room temperature, the material was removed, yielding a cured film. The resulting film was punched out using a micro-dumbbell die and then measured using a tensile testing machine. The results are shown in Table 11.

[0225] Examples 37-39: In Example 36, the amounts of B-1 used as the cyclic compound, the reactive diluent JER828, and the curing accelerator 2E4MZ were changed as shown in Table 10. The resulting films were punched out using a microdumbbell die and then measured using a tensile testing machine. The results are shown in Table 10. A photograph of the film from Example 37 is shown in Figure 10.

[0226] Example 40 A cured film was prepared in the same manner as in Example 6, except that the heating conditions of the press machine were changed to heating at 90°C for 4 hours by placing the film between the presses, and then heating at 150°C for 6 hours. The film was then measured using a tensile testing machine. The results are shown in Table 12.

[0227] Example 41 A cured film was prepared in the same manner as in Example 31, except that the amount of B-1 was changed to 165 mg, and measured using a tensile testing machine. The results are shown in Table 13.

[0228] Example 42: 250 mg of A-4 was used as the polymer having epoxy groups at its ends, and 18.9 mg of JER828 was used as the reactive diluent. After homogeneous dissolution in 2 mL of methanol, 90 mg of B-1 was homogeneously dissolved as the cyclic compound having reactive groups, and the mixture was held at room temperature for 24 hours. Next, it was held at 50°C for 24 hours, and the methanol was volatilized by vacuum drying at room temperature for 1 hour. Then, 50 mg of 2E4MZ was added as the curing accelerator and homogeneously mixed. After holding at 70°C for 5 minutes, the mixture was placed between two Daikin Industries NF-0100 sheets and heated in a press machine at 90°C for 2 hours, and then heated at 110°C for 1 hour, 130°C for 1 hour, and 150°C for 6 hours.

[0229] After cooling to room temperature, the material was removed, yielding a cured film. The obtained film was punched out using a micro-dumbbell die and then measured using a tensile testing machine. The results are shown in Table 14. A photograph of the obtained film is shown in Figure 11.

[0230] Example 43: Using the method described in Chem. Commun., 2008, 5806-5808, ε-caprolactone was synthesized by lipase (Novozym 435) catalyzed ring-opening polymerization with glycidol as an initiator to obtain terminal epoxy-modified PCL. 550 mg of this terminal epoxy-modified PCL was homogeneously dissolved in 150 mg of B-1 as a cyclic compound having a reactive group, and the mixture was held at room temperature for 48 hours. 109.5 μL of TEA was added as a crosslinking agent and homogeneously mixed. The mixture was then sandwiched between two sheets of Daikin Industries' NF-0100, placed in a press machine, held at 60°C for 6 hours, cooled to room temperature, and removed to obtain a cured film. The obtained film did not dissolve in THF, which is a good solvent for epoxy-modified PCL.

[0231] The composite material of this disclosure allows for a shortened manufacturing process and exhibits excellent fracture toughness and fracture strength. As a result, molded articles containing the composite material also exhibit excellent fracture toughness and fracture strength. Therefore, the composite material of this disclosure can be preferably used in medical devices, electronic devices, vehicle parts, building components, textile products, and the like.

Claims

1. A polymer (A) having epoxy groups at its terminals, and a reactive group r that encloses the polymer (A). １ A composite obtained from a composition comprising a cyclic compound (B) having and a polymer (A), comprising a crosslinked structure by the polymer (A).

2. The composite according to claim 1, wherein the crosslinked structure comprises a crosslinked structure between one or more epoxy groups contained in the polymer (A) and another epoxy group contained in the polymer (A).

3. The composite according to claim 1 or 2, wherein the composite is a (poly)rotaxane.

4. The crosslinked structure comprises one or more epoxy groups contained in the polymer (A) and a group r contained in the cyclic compound (B). １ A composite according to any one of claims 1 to 3, comprising a crosslinking structure.

5. A (poly)rotaxane composite comprising a polymer that does not have a stopper structure at its terminals, and a cyclic compound that encloses the polymer, and comprising a crosslinked structure by the polymer.

6. The reactive group r １ The composite according to any one of claims 1 to 4, wherein is a group that can react with an epoxy group.

7. The reactive group r １ The composite according to any one of claims 1 to 4, wherein is a group that can react with an epoxy group.

8. The reactive group r １ The composite according to any one of claims 1 to 4, 6, or 7, wherein the composite comprises one or more selected from a hydroxyl group, a carboxyl group, an amino group, a thiol group, an acid anhydride group, an epoxy group, and a highly reactive carbon atom.

9. The reactive group r １ The composite according to claims 1 to 4, 6 to 8, comprising a hydroxyl group.

10. The composite according to any one of claims 1 to 9, wherein the polymer (A) comprises one or more selected from ether bonds, carbonyl bonds, ester bonds, and ketone bonds.

11. The composite according to any one of claims 1 to 10, wherein the polymer (A) comprises a polyether chain and a polyester chain.

12. The composite according to any one of claims 1 to 11, wherein the polymer (A) comprises a polyalkylene oxide chain.

13. The complex according to any one of claims 1 to 12, wherein the cyclic compound (B) comprises one or more selected from the group consisting of cyclodextrin, crown ether, calixarene, cucurbituryl, pillararene and derivatives thereof.

14. The complex according to any one of claims 1 to 13, wherein the cyclic compound (B) comprises pillararene and / or a derivative thereof.

15. The cyclic compound (B) is of the following formula (I): [In formula (I), A is a divalent C containing one or more selected independently from -OR and CO-] ４－５０ Formula (I) represents an organic group, where R independently represents an organic group or hydrogen atom which may contain one or more fluorine atoms, n represents an integer from 4 to 20, and formula (I) contains at least one reactive group r １ The complex according to any one of claims 1 to 14, comprising a cyclic compound represented by ].

16. The complex according to claim 15, wherein the cyclic compound (B) comprises a compound in formula (I) in which A is a 1,4-dihydroxybenzene-2,5-diyl group or a 1,4-benzoquinone-2,5-diyl group and n is 5.

17. The composite according to any one of claims 1 to 16, wherein the composition further comprises a crosslinking agent (C).

18. A composite material according to any one of claims 1 to 17, which is a slide ring material.

19. A polymer (A) having an epoxy group at its end, and a cyclic compound (B) that includes the polymer (A) and has a reactive group r １ A method for producing a composite, comprising forming a crosslinked structure with the polymer (A) using a composition containing the polymer (A) and the cyclic compound (B).

20. The manufacturing method according to claim 19, wherein the crosslinked structure comprises a crosslinked structure between one or more epoxy groups contained in the polymer (A) and another epoxy group contained in the polymer (A).

21. The manufacturing method according to claim 19 or 20, wherein the composite is a (poly)rotaxane.

22. The crosslinked structure comprises one or more epoxy groups contained in the polymer (A) and a group r contained in the cyclic compound (B). １ A manufacturing method according to any one of claims 19 to 21, comprising a crosslinking structure.

23. The reactive group r １ The manufacturing method according to any one of claims 19 to 22, wherein is a group that can react with an epoxy group.

24. The reactive group r １ The composite according to any one of claims 19 to 22, wherein is a group that can react with an epoxy group.

25. The reactive group r １ The method for producing carbon atoms according to any one of claims 19 to 24, wherein carbon atoms comprises one or more selected from a hydroxyl group, a carboxyl group, an amino group, a thiol group, an acid anhydride group, an epoxy group, and a highly reactive carbon atom.

26. The reactive group r １ The manufacturing method according to any one of claims 19 to 25, wherein the method comprises a hydroxyl group.

27. The manufacturing method according to any one of claims 19 to 26, wherein the polymer (A) comprises one or more selected from ether bonds, carbonyl bonds, ester bonds, and ketone bonds.

28. The manufacturing method according to any one of claims 19 to 27, wherein the polymer (A) comprises one or more selected from polyether chains and polyester chains.

29. The method for producing the polymer (A) according to any one of claims 19 to 28, wherein the polymer (A) comprises a polyalkylene oxide.

30. The method for producing the cyclic compound (B) according to any one of claims 19 to 29, wherein the cyclic compound (B) comprises one or more selected from the group consisting of cyclodextrin, crown ether, calixarene, cucurbituryl, pillararene, and derivatives thereof.

31. The manufacturing method according to any one of claims 19 to 30, wherein the cyclic compound (B) comprises pillararene and / or a derivative thereof.

32. The cyclic compound (B) is given by the following formula (I): [In formula (I), A is a divalent C containing one or more selected independently from -OR and CO-] ４－５０ Formula (I) represents an organic group, where R independently represents an organic group or hydrogen atom which may contain one or more fluorine atoms, n represents an integer from 4 to 20, and formula (I) contains at least one reactive group r １ A manufacturing method according to any one of claims 19 to 31, comprising a cyclic compound represented by ].

33. The method for producing the compound according to claim 32, wherein the cyclic compound (B) comprises a compound in formula (I) in which A is a 1,4-dihydroxybenzene-2,5-diyl group or a 1,4-benzoquinone-2,5-diyl group and n is 5.

34. The manufacturing method according to any one of claims 19 to 33, wherein the composition further comprises a crosslinking agent (C).

35. A method for manufacturing a composite according to any one of claims 19 to 34, wherein the composite is a slide ring material.

36. A composite composition comprising the composite according to any one of claims 1 to 24.

37. A molded article comprising the composite according to any one of claims 1 to 24.

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