Polyrotaxane having long-chain alkyl groups on cyclic molecules, composition containing said polyrotaxane, and method for producing said polyrotaxane

Abstract

The present invention provides a polyrotaxane of high compatibility with silicones, such as silicone oil, a highly insulative polyrotaxane, and / or a material comprising said polyrotaxane. The present invention provides a polyrotaxane obtained by disposing blocking groups at both ends of a pseudopolyrotaxane, in which the opening in a cyclic molecule is clathrated in a skewered manner by a straight-chain molecule, so that the cyclic molecule does not escape, wherein the cyclic molecule comprises a first group represented by formula I (in formula I, X is a single bond or NH; n is 0 or 1; R is a straight-chain, branched, or cyclic alkyl group, alkenyl group, or alkynyl group comprising 12–20 carbon atoms, with some of the hydrogen in the alkyl group, alkenyl group, or alkynyl group being optionally substituted by an OH group, a CN group, or an NH2 group; and * is the position of the bond to the cyclic molecule).

Description

[Technical field]

[0001] The present invention relates to a polyrotaxane having a long-chain alkyl group or the like on a cyclic molecule, a composition containing the polyrotaxane, a crosslinked body comprising the polyrotaxane, a method for producing the polyrotaxane, and a method for producing the crosslinked body. [Background technology]

[0002] Polyrotaxanes, which are pseudo-polyrotaxanes in which the openings of cyclic molecules are pierced by linear molecules and have blocking groups placed on both ends to prevent the cyclic molecules from detaching, are expected to be applied to a variety of materials because materials using them exhibit excellent elongation and flexibility. In order to utilize the properties of polyrotaxane, there are various reports of modifying the hydroxyl groups of cyclic molecules of polyrotaxane, such as α-cyclodextrin (hereinafter sometimes simply abbreviated as “α-CD”), with various modifying groups to improve compatibility with solvents and impart functionality.

[0003] For example, Patent Document 1 discloses a polyrotaxane in which the hydroxyl group of α-CD, a cyclic molecule of polyrotaxane, is modified with (i) an acyl group, and (ii) a group selected from the group consisting of an alkyloxy, an alkyloxy, an alkylcarbonate group, an alkylcarbamoyl group, a silyl group, and a photoreactive group, and discloses that the modified polyrotaxane has improved solubility in various solvents.

[0004] Patent Document 2 discloses a modified polyrotaxane in which a hydroxypropyl group is bonded to a hydroxyl group of α-CD of a polyrotaxane, and a part or all of the hydroxyl groups are further modified with a modifying group derived from ε-caprolactone, and the terminal hydroxyl group of the caprolactone-derived modifying group is further modified with a hydrocarbon group having an alicyclic structure having 3 to 29 carbon atoms, and discloses that the compatibility ratio with polypropylene glycol is improved by the modified polyrotaxane.

[0005] Furthermore, Patent Document 3 discloses a composition containing polyrotaxane, a polysiloxane-containing block copolymer, and a polymer not containing polysiloxane, and discloses that an elastomer made from the composition exhibits excellent moisture resistance. The polyrotaxane specifically disclosed in Patent Document 3 has a polycaprolactone side chain. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] WO2008 / 108411. [Patent Document 2] JP 2019-1990 A. [Patent Document 3] JP 2017-66318 A. Summary of the Invention [Problem to be solved by the invention]

[0007] However, none of the above Patent Documents 1 to 3 discloses the compatibility of the modified polyrotaxane with silicone. For example, Patent Document 1 does not disclose anything about the compatibility of the modified polyrotaxane of Patent Document 1 with silicone. Furthermore, Patent Document 2 discloses that the compatibility of the modified polyrotaxane of Patent Document 2 with polypropylene glycol is improved in the presence of a solvent, but there is no disclosure whatsoever regarding compatibility with silicones. Furthermore, although Patent Document 3 discloses a block copolymer containing a polyrotaxane having a polycaprolactone side chain and a polysiloxane, when a non-copolymerized polysiloxane is used, it is found that the modified polyrotaxane is not compatible with silicone, as disclosed in Comparative Example 2 of Patent Document 3.

[0008] On the other hand, there is a demand for polyrotaxanes that are compatible with silicones at high concentrations. If such polyrotaxanes can be provided, it will be possible to provide materials that have excellent elastic properties, such as a desired Young's modulus and / or a desired hysteresis loss, as well as materials that exhibit high insulating properties.

[0009] Therefore, an object of the present invention is to provide a polyrotaxane that is highly compatible with silicones, such as silicone oil. Another object of the present invention is to provide a polyrotaxane exhibiting high insulating properties or a material comprising said polyrotaxane, other than or in addition to the above object. Furthermore, an object of the present invention is to provide a method for producing the polyrotaxane, other than or in addition to the above object. Further, an object of the present invention is to provide a composition comprising the polyrotaxane, a crosslinked body comprising the polyrotaxane, and a method for producing the crosslinked body, other than or in addition to the above object.

[0010] In order to achieve the above object, the present inventors have discovered the following invention. <1> A polyrotaxane in which a pseudo-polyrotaxane in which an opening of a cyclic molecule is pierced by a linear molecule and a blocking group is arranged at both ends of the pseudo-polyrotaxane so that the cyclic molecule does not detach, (Wherein, X is a single bond or NH; n is 0 or 1; R represents a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 12 to 20 carbon atoms (a portion of hydrogen in the alkyl group, alkenyl group or alkynyl group may be substituted with an OH group, a CN group or an NH group); * is the position where it bonds to the cyclic molecule) A polyrotaxane having a first group represented by:

[0011] [ka]

[0012] <2> the above <1> In the above, the cyclic molecule has hydroxyl groups, some of which are substituted with the first group, and when the amount of hydroxyl groups before substitution is taken as 100%, the first group is substituted at 20 to 80%, preferably 25 to 75%, more preferably 30 to 70%, and most preferably 40 to 60%. <3> the above <1> or <2> In the above, the polyrotaxane has a hydroxyl group and has a hydroxyl value of 60 to 300 mgKOH / g, preferably 70 to 250 mgKOH / g, more preferably 80 to 200 mgKOH / g, and most preferably 90 to 150 mgKOH / g.

[0013] <4> (A) The above <1> ~ <3> The polyrotaxane according to any one of the preceding claims; and (B) a first compound having a polysiloxane structure; A composition comprising: <5> the above <4> In the above, when the total weight of the polyrotaxane (A) and the first compound (B) is 100 parts by weight, the polyrotaxane (A) is 3 to 70 parts by weight, preferably 5 to 60 parts by weight, and more preferably 8 to 55 parts by weight, out of the 100 parts by weight. <6> the above <4> or <5> In the above, (B) the first compound may have a hydroxyl group.

[0014] <7> the above <4> ~ <6> In any one of the above, the (B) first compound may have a polydimethylsiloxane structure. <8> the above <4> ~ <7> A crosslinked body formed from the composition according to any one of claims 1 to 5. <9> the above <8> In the above, when the total weight of the polyrotaxane (A) and the first compound (B) is 100 parts by weight, the polyrotaxane (A) is 3 to 70 parts by weight, preferably 5 to 60 parts by weight, and more preferably 8 to 55 parts by weight, out of the 100 parts by weight. <10> the above <8> or <9> A substance having a crosslinked structure.

[0015] <11> (I) a step of preparing a polyrotaxane in which a pseudo-polyrotaxane in which an opening of a cyclic molecule is pierced and enclosed by a linear molecule in a skewered manner is provided at both ends of the pseudo-polyrotaxane, and blocking groups are arranged at the both ends of the pseudo-polyrotaxane so that the cyclic molecule does not detach, the cyclic molecule having (1) a hydroxyl group or (2) a hydroxypropyl group; (II) preparing a second compound selected from the group consisting of RCOOH, RCOCl, and RNCO (wherein R represents a linear, branched, or cyclic alkyl group, alkenyl group, or alkynyl group having 12 to 20 carbon atoms (a portion of hydrogen atoms in the alkyl group, alkenyl group, or alkynyl group may be substituted with an OH group, a CN group, or an NH group)); (III) reacting the polyrotaxane prepared in the step (I) with the second compound prepared in the step (II); By having A polyrotaxane in which a pseudo-polyrotaxane in which an opening of a cyclic molecule is pierced by a linear molecule and a blocking group is arranged at both ends of the pseudo-polyrotaxane so that the cyclic molecule does not detach, (Wherein, X is a single bond or NH; n is 0 or 1; R represents a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 12 to 20 carbon atoms (some of the hydrogen atoms in the alkyl group, alkenyl group or alkynyl group may be substituted with OH groups, CN groups or NH groups); * is the position where it bonds to the cyclic molecule) The present invention relates to a method for producing a polyrotaxane, the method comprising the steps of:

[0016] [ka]

[0017] <12> the above <11> When the cyclic molecule in step (I) has (1) a hydroxyl group and / or (2) a hydroxyl group derived from a hydroxypropyl group, and the amount of the hydroxyl groups is taken as 100%, the polyrotaxane obtained in step (III) has 20 to 80% of the hydroxyl groups substituted with the first groups, preferably 25 to 75%, more preferably 30 to 70%, and most preferably 40 to 60%.

[0018] <13> (X) A polyrotaxane in which a pseudo-polyrotaxane in which an opening of a cyclic molecule is pierced by a linear molecule and a blocking group is arranged at both ends of the pseudo-polyrotaxane so that the cyclic molecule does not detach, (Wherein, X is a single bond or NH; n is 0 or 1; R represents a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 12 to 20 carbon atoms (some of the hydrogen atoms in the alkyl group, alkenyl group or alkynyl group may be substituted with OH groups, CN groups or NH groups); * is the position where it bonds to the cyclic molecule) preparing a polyrotaxane (A) having a first group represented by (XI)(B) preparing a first compound having a polysiloxane structure; (XII) a step of reacting (A) a polyrotaxane with (B) a first compound, for example, a step of reacting under conditions of room temperature to 150°C and normal pressure; By having A method for producing a crosslinked body formed from (A) a polyrotaxane and (B) a first compound, the method comprising obtaining a crosslinked body formed from (A) a polyrotaxane and (B) a first compound. Effect of the Invention

[0019] According to the present invention, it is possible to provide a polyrotaxane that is highly compatible with silicones, for example, silicone oil. Furthermore, the present invention can provide a polyrotaxane exhibiting high insulating properties or a material comprising the polyrotaxane. Furthermore, the present invention can provide a method for producing the polyrotaxane, other than or in addition to the above effects. Furthermore, other than or in addition to the above-mentioned effects, the present invention can provide a composition comprising the polyrotaxane, a crosslinked product comprising the polyrotaxane, and a method for producing the crosslinked product. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The invention described in this application will now be described in detail. The present invention provides a polyrotaxane having a long-chain alkyl group or the like on a cyclic molecule, a composition comprising the polyrotaxane, a crosslinked body comprising the polyrotaxane, a method for producing the polyrotaxane, and a method for producing the crosslinked body. The following describes each in turn.

[0021] <Polyrotaxanes with long-chain alkyl groups on cyclic molecules> The present invention provides a polyrotaxane having a long-chain alkyl group or the like in a cyclic molecule. Specifically, the present invention provides a polyrotaxane in which a blocking group is arranged at both ends of a pseudopolyrotaxane in which an opening of a cyclic molecule is pierced and enclosed by a linear molecule, so that the cyclic molecule does not detach, and the cyclic molecule is represented by the above formula I (Wherein, X is a single bond or NH, preferably a single bond; n is 0 or 1, preferably 1; R represents a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 12 to 20 carbon atoms (a portion of hydrogen in the alkyl group, alkenyl group or alkynyl group may be substituted with an OH group, a CN group or an NH group); * is the position where it bonds to the cyclic molecule) The present invention provides a polyrotaxane having a first group represented by:

[0022] In the above formula I, R is preferably a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 11 to 18 carbon atoms, preferably 12 to 17 carbon atoms, and more preferably 14 to 16 carbon atoms, and is preferably a linear alkyl group, a linear alkenyl group or a linear alkynyl group, and more preferably a linear alkyl group or a linear alkenyl group. Specifically, in the first group, X is preferably a single bond, n is preferably 1, and R is preferably an alkyl group having 14 to 16 carbon atoms.

[0023] The cyclic molecule has hydroxyl groups, and a portion of the hydroxyl groups are substituted with the first group. When the amount of hydroxyl groups before substitution is taken as 100%, the first group is substituted at 20 to 80%, preferably 25 to 75%, more preferably 30 to 70%, and most preferably 40 to 60%.

[0024] The cyclic molecule of the polyrotaxane of the present invention preferably has a first functional group capable of reacting with other materials in addition to the first group. Examples of the first functional group include a hydroxyl group, an amino group, a thiol group, a carboxylic acid group, an acid anhydride group, and an epoxy group, and the first functional group preferably has a hydroxyl group. When the polyrotaxane of the present invention, particularly the cyclic molecule of the polyrotaxane of the present invention, has a hydroxyl group, the hydroxyl value is preferably 60 to 300 mgKOH / g, preferably 70 to 250 mgKOH / g, more preferably 80 to 200 mgKOH / g, and most preferably 90 to 150 mgKOH / g.

[0025] The "cyclic molecule," "linear molecule," and "blocking group" constituting the polyrotaxane will be described below. Conventionally known molecules can be used for these. <<Cyclic molecules>> The cyclic molecules of the polyrotaxane of the present invention are not particularly limited as long as they are cyclic, have an opening, and are included in the polyrotaxane in a skewered manner by the linear molecules. The cyclic molecule has a first group via an arbitrary linking group. Examples of the linking group include, but are not limited to, -CH-CH-, -CH-CH-CH-, -CHCH(OH)-CH-, -CH-CH-CH-CH-, -CO-CH-CH-, -CO-C(CH)-CH-, -CO-CH(OH)-CH-, -CO-CH-CH-CH-CH(CH)-, and the like.

[0026] The cyclic molecule may have a group other than the first group. For example, the group other than the first group may include, but is not limited to, an acetyl group, a propionyl group, a butyl ester group, a methoxy group, a propyl ether group, a butyl ether group, a butyl carbamoyl group, a cyclohexyl carbamoyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a 2,3-dihydroxypropyl group, a phenyl group, a benzyl carbamoyl group, a phenylethyl carbamoyl group, a benzyl ester group, and a butyl benzyl ester group. The cyclic molecule may be, for example, selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. For example, as described above, it is preferable to replace some of the -OH groups of α-cyclodextrin, etc. with the above-mentioned first group. Note that some of the -OH groups of α-cyclodextrin, etc. may be replaced with groups other than the above-mentioned first group.

[0027] <<Linear molecule>> The linear molecule of the polyrotaxane of the present invention is not particularly limited as long as it can be included in the opening of the cyclic molecule used in a skewered manner. For example, linear molecules include polyvinyl alcohol, polyvinylpyrrolidone, poly(meth)acrylic acid, cellulose-based resins (such as carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal-based resins, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, and / or copolymers thereof, polyolefin-based resins such as polyethylene, polypropylene, and copolymer resins with other olefin-based monomers, polyester resins, polyvinyl chloride resins, polystyrene-based resins such as polystyrene and acrylonitrile-styrene copolymer resins, polymethyl methacrylate and (meth)acrylic acid, and the like. ) acrylic resins such as acrylic acid ester copolymers, acrylonitrile-methyl acrylate copolymer resins, polycarbonate resins, polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, etc.; and derivatives or modified products thereof, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymers (ABS resins), polyamides such as nylon, polyimides, polyisoprene, polybutadiene, polysiloxanes such as polydimethylsiloxane, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and derivatives thereof. For example, it is preferably selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol, and polyvinyl methyl ether. In particular, polyethylene glycol is preferable.

[0028] The linear molecule has a weight average molecular weight of 1,000 or more, preferably 3,000 to 100,000, and more preferably 6,000 to 50,000. In the polyrotaxane of the present application, the combination of (cyclic molecules, linear molecules) is preferably (derived from α-cyclodextrin, derived from polyethylene glycol).

[0029] <<Blocking group>> The blocking groups of the polyrotaxane of the present invention are not particularly limited as long as they are arranged at both ends of the pseudopolyrotaxane and act to prevent the cyclic molecule used from being detached. For example, the blocking group may be selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, pyrenes, substituted benzenes (substituents include, but are not limited to, alkyl, alkyloxy, hydroxy, halogen, cyano, sulfonyl, carboxyl, amino, phenyl, etc., and one or more substituents may be present), optionally substituted polynuclear aromatics (substituents include, but are not limited to, the same as those described above, and one or more substituents may be present), and steroids. It is preferable to select from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, and pyrenes, and more preferably adamantane groups or cyclodextrins.

[0030] The polyrotaxane of the present invention has the first group represented by formula I, thereby making it possible to improve compatibility with silicones.

[0031] <Composition containing the polyrotaxane of the present invention> The present invention provides a composition comprising: (A) a polyrotaxane having a first group represented by formula I above on a cyclic molecule thereof. In particular, the present invention relates to a composition comprising the above-mentioned component (A); and (B) a first compound having a polysiloxane structure; A composition comprising: The composition of the present invention may contain components other than the above component (A) and component (B).

[0032] <<(B) First Compound Having a Polysiloxane Structure>> The (B) first compound having a polysiloxane structure contained in the composition of the present invention is not particularly limited as long as it has a polysiloxane structure. The first compound preferably has a hydroxyl group. Moreover, the first compound preferably has a polydimethylsiloxane (PDMS) structure as a main component. The first compound may have at least one second functional group in the main chain or in a side chain. The first compound is preferably a polysiloxane that is not block copolymerized with other oligomers or polymers. Examples of the second functional group include, but are not limited to, a hydroxyl group, an amino group, a thiol group, a carboxylic acid group, an acid anhydride group, and an epoxy group.

[0033] Specifically, examples of the (B) first compound include, but are not limited to, carbinol-terminated PDMS, bis(hydroxyethylamine)-terminated PDMS, silanol-terminated PDMS, PDMS having a portion of the side chain modified with an OH group, vinyl-terminated PDMS, PDMS having a portion of the side chain modified with a vinyl group, hydride-terminated PDMS, PDMS having a portion of the side chain modified with a hydride, aminopropyl-terminated PDMS, PDMS having a portion of the side chain modified with an aminopropyl group, epoxypropoxypropyl-terminated PDMS, (meth)acrylyloxypropyl-terminated PDMS, succinic anhydride-terminated PDMS, carboxyalkyl-terminated PDMS, chloromethyl-terminated PDMS, and mercaptopropyl-terminated PDMS.

[0034] <<Components other than the above component (A) and the above component (B)>> As described above, the composition of the present invention can contain components other than the above component (A) and the above component (B). These components include, but are not limited to, (C1) a component having a reactive group capable of reacting with the above-mentioned (A) component and / or (B) component, (C2) a polyol component not containing a siloxane component, and the like.

[0035] (C1) As for the component having a reactive group capable of reacting with the above-mentioned (A) component and / or (B) component, examples of the "reactive group" include an isocyanate group, an acid anhydride group, a thioisocyanate group, an epoxy group, a carboxylic acid group, a carboxylic acid chloride, an amino group, and the like, but are not limited thereto. The "reactive group" is preferably an isocyanate group, a blocked isocyanate group, or an epoxy group, more preferably an isocyanate group or a blocked isocyanate group, and most preferably an isocyanate group.

[0036] (C1) A component having a reactive group capable of reacting with the above component (A) and / or the above component (B), specifically, polyisocyanate compounds such as hexamethylene diisocyanate, phenylene diisocyanate, triethylene diisocyanate, isophorone diisocyanate, biuret type polyisocyanate, isocyanurate type polyisocyanate, adduct type polyisocyanate, or blocked isocyanate compounds thereof; diacid anhydrides such as pyromellitic anhydride, 4,4'-carbonyldiphthalic anhydride, cyclohexanetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, etc. Examples of the isocyanate compounds include, but are not limited to, polyols having terminal isocyanate groups, such as polypropylene glycol, polycarbonate diol, polyethylene glycol, and carbinol-terminated polysiloxane, whose terminal hydroxyl groups are modified with diisocyanate compounds. In addition, when the isocyanate group is present, the isocyanate group may be blocked with a compound such as ε-caprolactam, diethyl malonate, 2-butanone oxime, or dimethylpyrazole.

[0037] (C2) The polyol component not containing a siloxane component refers to an oligomer or polymer polyol that does not have a siloxane structure in its molecular structure. Specific examples include, but are not limited to, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyester polyol, and polycarbonate polyol.

[0038] Examples of components other than the above (C1) and (C2) include, but are not limited to, polyrotaxanes other than the above polyrotaxanes, polymers other than polyrotaxanes or monomers or oligomers that form such polymers, and solvents. In addition, various components for providing the crosslinked body formed from the composition of the present invention with desired properties can be included, including, but not limited to, antioxidants, UV absorbers, crosslinking assistants, surfactants, emulsifiers, plasticizers, polymerization initiators, polymerization inhibitors, polymer particles, metal oxides such as silica and alumina, surface conditioners, and flame retardants.

[0039] Further, examples of polymers other than polyrotaxane include, but are not limited to, polyethers, polyesters, polycarbonates, polyacrylates, polyurethanes, polyureas, polysiloxanes, polyolefins, polyamides, polyamic acids, polyenes, polyvinyl ethers, polyvinyl esters, and copolymers thereof, or modified products thereof.

[0040] Plasticizers include, but are not limited to, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, dihexyl phthalate, dioctyl adipate, bis(2-ethylhexyl) adipate, tris(2-ethylhexyl) trimellitate, tricresyl phosphate, and the like.

[0041] Examples of UV absorbers include, but are not limited to, 2-ethylhexyl paradimethylaminobenzoate, 2-ethylhexyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octylbenzophenone, 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole, bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, 2-ethylhexyl paramethoxycinnamate, isopropyl paramethoxycinnamate, ethylhexyl methoxycinnamate, and octyl methoxycinnamate.

[0042] The photoinitiator may include, but is not limited to, benzoylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Lucirin® TPO); or bisacylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure® 819); 1-hydroxyphenyl ketones such as 1-hydroxycyclohexylphenyl ketone (Irgacure® 184); and the like.

[0043] Examples of the thermal polymerization initiator include organic peroxide-based polymerization initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, diisopropyl peroxydicarbonate, and bis(4-t-butylcyclohexyl)peroxydicarbonate; and azo-based polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), but are not limited to these. Examples of the solvent include, but are not limited to, acetone, methyl ethyl ketone, toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol, water, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetonitrile, ethyl cellosolve, butyl cellosolve, and other cellosolve-based solvents.

[0044] <Crosslinked body formed from the composition of the present invention; and substance having the crosslinked body> The present invention provides a crosslinked body formed from a composition containing the above-mentioned (A) polyrotaxane; and (B) a first compound having a polysiloxane structure. In the crosslinked body of the present invention, when the total weight of the polyrotaxane (A) and the first compound (B) is 100 parts by weight, the polyrotaxane (A) is 3 to 70 parts by weight, preferably 5 to 60 parts by weight, and more preferably 8 to 55 parts by weight, of the 100 parts by weight.

[0045] The polyrotaxane (A) of the present invention has good compatibility with silicones including the first compound having a polysiloxane structure (B), and therefore the polyrotaxane (A) can be contained at a high concentration within the above range. Furthermore, since A) polyrotaxane can be contained at a high concentration within the above range, the crosslinked body of the present invention can have desired properties, such as a desired Young's modulus, a desired hysteresis loss, and / or a desired insulating property. Furthermore, the present invention can provide a substance having the above-mentioned crosslinked structure. The substance is not particularly limited as long as it has the above-mentioned crosslinked structure.

[0046] <Method of producing polyrotaxane having long-chain alkyl groups on cyclic molecules according to the present invention> The polyrotaxane of the present invention having a long-chain alkyl group or the like on the cyclic molecule can be produced as follows. That is, (I) a step of preparing a polyrotaxane in which a pseudo-polyrotaxane in which an opening of a cyclic molecule is pierced and enclosed by a linear molecule in a skewered manner is provided at both ends of the pseudo-polyrotaxane, and blocking groups are arranged at the both ends of the pseudo-polyrotaxane so that the cyclic molecule does not detach, the cyclic molecule having (1) a hydroxyl group or (2) a hydroxypropyl group; (II) preparing a second compound selected from the group consisting of RCOOH, RCOCl, and RNCO, wherein R has the same definition as above; (III) reacting the polyrotaxane prepared in the step (I) with the second compound prepared in the step (II); By having It is possible to obtain a polyrotaxane in which blocking groups are arranged on both ends of a pseudopolyrotaxane in which the opening of a cyclic molecule is pierced and included by a linear molecule, so that the cyclic molecule does not detach, and the cyclic molecule has a first group represented by the above formula I.

[0047] <(I) Process> The above step (I) is a step of preparing a polyrotaxane in which the cyclic molecule has (1) a hydroxyl group or (2) a hydroxypropyl group. This step can be carried out by the method described in WO2008 / 10841. In step (I), the cyclic molecule has (1) a hydroxyl group and / or (2) a hydroxyl group derived from a hydroxypropyl group, and assuming the amount of the hydroxyl groups to be 100%, the polyrotaxane obtained in step (III) has 20 to 80% of the hydroxyl groups substituted with first groups, preferably 25 to 75%, more preferably 30 to 70%, and most preferably 40 to 60%.

[0048] <(II) Process> The above step (II) is a step of preparing a second compound selected from the group consisting of RCOOH, RCOCl, and RNCO, where R has the same definition as above. Examples of RCOOH include, but are not limited to, lauric acid, myric acid, palmitic acid, and oleic acid. Examples of RCOCl include, but are not limited to, lauric acid chloride, myricitic acid chloride, palmitic acid chloride, and oleic acid chloride. Further, RNCOs can include, but are not limited to, dodecyl isocyanate, tetradecyl isocyanate, octadecyl isocyanate, and the like. The second compound may be commercially available or may be prepared separately.

[0049] <(III) Process> The above step (III) is a step of reacting the polyrotaxane prepared in step (I) with the second compound prepared in step (II). Specifically, the reaction is preferably carried out under the following conditions: temperature: room temperature to 150° C., and pressure: normal pressure.

[0050] The above method may include steps other than the above steps (I) to (III). Examples of the step other than steps (I) to (III) include, but are not limited to, a step of removing a solvent.

[0051] <Method for producing a crosslinked body formed with the polyrotakin of the present invention> The present invention also provides a method for producing a crosslinked body formed from the polyrotakine of the present invention, particularly a crosslinked body formed from a composition comprising the polyrotakine of the present invention and (B) a first compound. The method comprises: (X) a step of preparing (A) a polyrotaxane, which is a pseudo-polyrotaxane in which an opening of a cyclic molecule is pierced and enclosed by a linear molecule in a skewered manner, and which has blocking groups disposed on both ends of the pseudo-polyrotaxane so that the cyclic molecule does not detach, and the cyclic molecule has a first group represented by the above formula I; (XI)(B) preparing a first compound having a polysiloxane structure; (XII) a step of reacting (A) a polyrotaxane with (B) a first compound under conditions of, for example, a temperature of room temperature to 150° C. and a pressure of normal pressure; By having A crosslinked body formed having (A) the polyrotaxane and (B) the first compound can be obtained.

[0052] <<(X) Process>> Step (X) is a step of preparing (A) a polyrotaxane in which a cyclic molecule has a first group represented by the above formula I. This step can be performed using the above-mentioned production method for "a polyrotaxane in which a cyclic molecule has a first group represented by the above formula I."

[0053] <<(XI) Process>> Step (XI) is a step of preparing (B) a first compound having a polysiloxane structure. As (B) the first compound having a polysiloxane structure, the above-mentioned compounds can be used, and the first compound may be commercially purchased or separately prepared.

[0054] <<(XII) Process>> Step (XII) is a step of reacting (A) a polyrotaxane with (B) a first compound. The reaction conditions include, but are not limited to, room temperature to 150° C., in the presence or absence of a solvent.

[0055] The above method may include steps other than the above steps (X) to (XII). Examples of the step other than the above steps (X) to (XII) include, but are not limited to, a step of mixing C1, C2, and other components, and a step of removing the solvent.

[0056] The polyrotaxane of the present invention, a composition containing the polyrotaxane, and a molded article containing the polyrotaxane have various applications due to their characteristics, including, but not limited to, electrical and electronic component materials, electrical insulating materials for actuators, pressure sensitive adhesives, sensor materials, scratch resistant films, vibration-proofing, vibration-damping, and vibration-isolating materials, sound absorbing materials, paints, coating agents, sealants, ink additives and binders, binders for metals and metal oxides, binders for abrasives, optical materials, friction control agents, cosmetic materials, rubber and elastomer additives, foaming materials, resin modifiers and toughening agents, compatibilizers for resins, electrolyte materials, rheology control agents, thickeners, fibers, medical biomaterials, cosmetic materials, machine and automotive materials, building materials, and clothing and sporting goods. The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0057] (Example) Analytical equipment for each compound 1H-NMR measurements were performed using a 400 MHz JEOL JNM-AL400 (manufactured by JEOL Ltd.). The molecular weight and molecular weight distribution were measured using a TOSOH HLC-8220GPC device under the following conditions: Column: TSK guard column Super AW-H and TSKgel Super AWM-H (two columns connected), Eluent: dimethyl sulfoxide (DMSO) / 0.01M LiBr, Column oven: 50°C, Flow rate: 0.5ml / min, Sample concentration: about 0.2wt / vol%, Injection volume: 20μl, Pretreatment: Filtration with a 0.2μm filter, Standard molecular weight: PEO. The hydroxyl value and acid value were measured according to a method in accordance with JIS 0070-1992.

[0058] <Synthesis Example 1: Synthesis of hydroxypropyl group-modified polyrotaxane HAPR> A polyrotaxane consisting of a linear molecule: polyethylene glycol (number average molecular weight Mn = 20,000), a cyclic molecule: α-cyclodextrin, and a blocking group: adamantane group, and a polyrotaxane modified with a hydroxypropyl group (HAPR) were prepared by the method described in WO2008-108411. The weight average molecular weight Mw of the obtained HAPR was measured by GPC and found to be 129,000. In addition, NMR analysis showed that 50% of the hydroxyl groups of cyclodextrin were replaced with hydroxypropyl. The hydroxyl value was measured and found to be 398 mg KOH / g.

[0059] <Synthesis Example 2: Preparation of crosslinker PPG-B> After adding 91.6 g of 1,3-bis(isocyanatemethyl)cyclohexane (Takenate 600, manufactured by Mitsui Chemicals) to the reaction flask, the mixture was stirred under a nitrogen stream in an oil bath at 80°C. 100 g of polypropylene glycol, diol type (Mn=700) was added dropwise to the solution over a period of 2 hours, and the mixture was stirred for another 2 hours. After the reaction, the temperature was lowered to room temperature, and then 76.6 g of 2-butanone oxime (manufactured by Tokyo Chemical Industry) was added dropwise, and the mixture was stirred at room temperature for 8 hours to obtain polypropylene glycol (crosslinking agent PPG-B) having a blocked isocyanate group blocked at the end with butanone oxime.

[0060] <Synthesis Example 3: Preparation of crosslinker solution PDMS-g-PCL-B> 100 g of polydimethylsiloxane modified with carbinol at both ends (X-22-160AS, Shin-Etsu Silicone) and 200 g of ε-caprolactone (Daicel) were added to a three-necked eggplant flask, and the mixture was dehydrated by stirring for 2 hours under a nitrogen stream in an oil bath at 110°C. After the oil bath was heated to 130°C, 0.1 g of tin 2-ethylhexanoate (Aldrich) was added and stirred for 6 hours to obtain a polycaprolactone-polydimethylsiloxane block copolymer with polycaprolactone grafted to both ends.

[0061] 31.6 g of 1,3-bis(isocyanatemethyl)cyclohexane (Takenate 600, manufactured by Mitsui Chemicals) was added to another three-necked flask, and the mixture was stirred under a nitrogen stream in an oil bath at 90°C. 152.7 g of the polydimethylsiloxane with polycaprolactone grafted to both ends, dissolved in 152.7 g of toluene, was slowly added dropwise to the solution over 2 hours, and the mixture was stirred for another 2 hours. After the reaction, the liquid temperature was lowered to room temperature, and 22.9 g of 2-butanone oxime (manufactured by Tokyo Chemical Industry) was slowly added dropwise so that the liquid temperature did not exceed 60°C. After the addition, the mixture was stirred at room temperature for 5 hours to obtain a crosslinker solution (concentration 57.6 wt%) containing polydimethylsiloxane (PDMS) with terminal blocked isocyanate groups, PDMS-g-PCL-B.

[0062] (Example 1: Preparation of modified polyrotaxane A1) 10 g of HAPR obtained in Synthesis Example 1 and 40 ml of dimethylacetamide were added to a reactor to dissolve, and 6 ml of triethylamine was added with stirring. 9.6 ml of myricitic acid chloride was slowly added dropwise while cooling the reactor with water, and the reaction was continued for 15 hours. The resulting solution was reprecipitated in water, and the solid was washed several times with water and then dried under reduced pressure in a dryer at 80°C to obtain modified polyrotaxane A1 having myricitic acid ester groups on the cyclic molecule α-CD. GPC analysis revealed that the weight average molecular weight was 174,000. The hydroxyl value was 133 mgKOH / g.

[0063] (Example 2: Preparation of a composition of modified polyrotaxane A1 and polysiloxane) 1.90 g of polydimethylsiloxane (PDMS) X-22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) having hydroxyl groups at both ends and 0.10 g of the modified polyrotaxane A1 obtained in Example 1 were placed in a sample bottle and stirred with a magnetic stirrer to obtain a transparent composition containing no insoluble matter. The composition of this example consists only of modified polyrotaxane A1, which is a polyrotaxane of the present invention, and polydimethylsiloxane, and it is possible to provide a composition in which modified polyrotaxane A1 accounts for 5% by weight when the total weight of modified polyrotaxane A1 and polydimethylsiloxane is 100% by weight.

[0064] (Comparative Example 1: Solubility of hydroxypropylated polyrotaxane SH2400P having polycaprolactone chains in polysiloxane) Using hydroxypropylated polyrotaxane SH2400P (manufactured by Advanced Soft Materials) having polycaprolactone chains, a solubility experiment similar to that in Example 2 was carried out, that is, using 1.90 g of polydimethylsiloxane (PDMS) X-22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.10 g of SH2400P. As a result, insoluble matter was found and a homogeneous composition was not obtained. SH2400P has the following structure (hydroxyl value: 76 mgKOH / g): linear molecule: polyethylene glycol (number average molecular weight Mn = 20,000), cyclic molecule: α-CD, blocking group: adamantane group; cyclic molecule: α-CD, OH group of the polyrotaxane is substituted with hydroxypropyl group, and the OH group of the hydroxypropyl group is further substituted with polycaprolactone chain.

[0065] [ka]

[0066] (Comparative Example 2: Preparation of HAPR having butylcarbamoyl group and its solubility in polysiloxane) In a reactor, 10 g of HAPR obtained in Synthesis Example 1 was dissolved in 40 ml of dimethylacetamide, and 4 ml of butyl isocyanate was added dropwise under nitrogen flow conditions and reacted for 15 hours. The reaction solution was reprecipitated in isopropanol (IPA), and the solid was washed twice with IPA and dried at 80°C to obtain butylcarbamoyl-modified polyrotaxane (PR-X1). NMR analysis confirmed that 51% of the hydroxyl groups in CD were substituted with butylcarbamoyl groups. GPC analysis showed that the weight-average molecular weight was 165,000. A solubility experiment similar to that in Example 2 was carried out using PR-X1, that is, using 1.90 g of polydimethylsiloxane (PDMS) X-22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.10 g of PR-X1. As a result, insoluble matter was found and a homogeneous composition was not obtained.

[0067] (Comparative Example 3: Preparation of HAPR having a cyclohexylbamoyl group and its solubility in polysiloxane) In Comparative Example 2, a similar experiment was carried out using 4.5 ml of cyclohexyl isocyanate instead of 4 ml of butyl isocyanate, and as a result, a cyclohexylcarbamoyl-modified polyrotaxane (PR-X2) was obtained. NMR analysis confirmed that 48% of the hydroxyl groups in CD were substituted with cyclohexylcarbamoyl groups. GPC analysis showed that the weight-average molecular weight was 172,000. A solubility experiment similar to that in Example 2 was carried out using PR-X2, that is, using 1.90 g of polydimethylsiloxane (PDMS) X-22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.10 g of PR-X2. As a result, insoluble matter was found and a homogeneous composition was not obtained.

[0068] (Example 3: Preparation of composition B1 containing modified polyrotaxane A1 and polysiloxane; and preparation of film C1 from the composition) <Preparation of Composition B1> Composition B1 having the composition shown in Table 1 was prepared using modified polyrotaxane A1 of Example 1. In Table 1, Thanox1726 manufactured by Rianlon Corp. was used as the antioxidant (the same applies to the following Examples). In addition, in the composition B1, the amount of the crosslinking agent PPG-B was adjusted so that the total amount of hydroxyl groups in the modified polyrotaxane A1, polypropylene glycol, and polydimethylsiloxane (PDMS) X-22-160AS was equivalent to the amount of isocyanate groups in the crosslinking agent PPG-B. In composition B1, when the total weight of modified polyrotaxane A1 and polydimethylsiloxane (PDMS) X-22-160AS was taken as 100% by weight, the amount (% by weight) of modified polyrotaxane A1 in said 100% by weight was 64.5% by weight.

[0069] <Preparation of Film C1> The above composition B1 was applied to a release agent-treated PET sheet to a film thickness of 50 μm, and cured for 1 hour at 80° C. and 5 hours at 130° C. The composition B1 was peeled off from the PET sheet to obtain a transparent film C1. In the film C1, when the total weight of the modified polyrotaxane A1 and polydimethylsiloxane (PDMS) X-22-160AS is 100% by weight, the amount (weight%) of the modified polyrotaxane A1 in the 100% by weight was 64.5% by weight, similar to the weight% in the composition B1. In addition, in the film C1, the weight ratio (weight%) based on the polydimethylsiloxane (PDMS) structure in the total weight of the film C1 was measured and found to be 15.5% by weight.

[0070] [Table 1]

[0071] (Example 4: Preparation of composition B2 containing modified polyrotaxane A1 and polysiloxane; and preparation of film C2 from the composition) <Preparation of Composition B2> Using the modified polyrotaxane A1 of Example 1, composition B2 having the composition shown in Table 2 below was prepared. Note that, compared to the above composition B1, composition B2 was a system that did not contain polypropylene glycol. In composition B2, the amount of crosslinker PPG-B was adjusted so that the total amount of hydroxyl groups in modified polyrotaxane A1 and polydimethylsiloxane (PDMS) X-22-160AS was equivalent to the amount of isocyanate groups in crosslinker PPG-B. In composition B2, when the total weight of modified polyrotaxane A1 and polydimethylsiloxane (PDMS) X-22-160AS was taken as 100% by weight, the amount (% by weight) of modified polyrotaxane A1 in said 100% by weight was 47.6% by weight.

[0072] <Preparation of Film C2> A transparent film C2 was obtained in the same manner as in Example 3, except that the composition B1 in Example 3 was replaced with the composition B2. In the film C2, when the total weight of the modified polyrotaxane A1 and polydimethylsiloxane (PDMS) X-22-160AS was 100% by weight, the amount (weight%) of the modified polyrotaxane A1 in the 100% by weight was 47.6% by weight, similar to the weight% in the composition B2. In addition, in the film C2, the weight ratio (weight%) based on the polydimethylsiloxane (PDMS) structure in the total weight of the film C2 was measured and found to be 29.7% by weight.

[0073] [Table 2]

[0074] (Comparative Example 4: Preparation of film C3 of composition B3 containing polyrotaxane SH2400P and polysiloxane) <Composition B3> Composition B3 having the composition shown in Table 3 was prepared using the hydroxypropylated polyrotaxane SH2400P having polycaprolactone chains used in Comparative Example 1. Note that, since polydimethylsiloxane (PDMS) X-22-160AS used in Examples 3 and 4 is not compatible with SH2400P as shown in Comparative Example 1, the crosslinker solution PDMS-g-PCL-B prepared in Synthesis Example 3 was used instead of polydimethylsiloxane (PDMS) X-22-160AS.

[0075] <Film C3> A transparent film C3 was obtained in the same manner as in Example 3, except that composition B3 was used instead of composition B1 in Example 3. In addition, when the weight ratio (weight %) based on the polydimethylsiloxane (PDMS) structure in the total weight of film C3 was measured, it was 5.2 weight %.

[0076] [Table 3]

[0077] (Example 5: Tensile properties and voltage resistance of film) <Tensile test> The tensile test of the film was performed using Shimadzu Autograph AGS-5kNX. In accordance with JIS K-6251, the film was cut into a dumbbell-shaped No. 7 model, with an effective tensile length of 20 mm, and a tensile speed of 100 mm / min. Young's modulus was calculated from the stress and displacement (elongation) curve. Hysteresis loss was also calculated by the relaxation caused by repeated pulling at the same speed and constant elongation (in accordance with JIS K6400). In other words, it was calculated as {(area of ​​the curve when stretched - area when relaxed) / area when stretched} x 100% in the stress-strain curve. <Voltage Test> The dielectric breakdown field of the prepared film was measured at room temperature and normal pressure according to JIS8703. The cured film was attached to the disk electrode on the installation side, and another disk electrode was placed on top of the film, and degassed using a vacuum device to ensure that there were no air bubbles between the film and the electrode. The electrode was connected to the power supply of the dielectric breakdown measuring device, and a voltage was applied at a voltage increase rate of 10V / 0.1 seconds. Measurements were made from a state where no current flows to the dielectric breakdown field (V / μm).

[0078] The tensile properties (specifically, Young's modulus and hysteresis loss) and withstand voltage were measured by the above-mentioned tests using the films C1 to C3 obtained in Example 3, Example 4, and Comparative Example 4. The results are shown in Table 4. From Table 4, it was found that films C1 and C2 using the modified polyrotaxane of the present invention exhibit small average leakage current values ​​and exhibit high insulating properties. Furthermore, films C1 and C2 have low Young's modulus. Therefore, it is found that films C1 and C2 using the modified polyrotaxane of the present invention have low Young's modulus and high insulating properties. On the other hand, film C3 not using the modified polyrotaxane of the present invention has a Young's modulus similar to that of films C1 and C2, but has a relatively large average leakage current and does not exhibit insulating properties.

[0079] [Table 4]

Claims

1. A polyrotaxane in which a pseudopolyrotaxane in which an opening of a cyclic molecule is pierced by a linear molecule and a blocking group is arranged at both ends of the pseudopolyrotaxane so that the cyclic molecule does not detach, (Wherein, X is a single bond or NH; n is 0 or 1; R is a linear, branched or cyclic alkyl, alkenyl or alkynyl group having 12 to 20 carbon atoms (wherein some of the hydrogen atoms in the alkyl, alkenyl or alkynyl group are OH, CN or NH ２ group); * indicates the position where the cyclic molecule is bonded.) A polyrotaxane having a first group represented by: 【Chemistry 1】

2. The polyrotaxane according to claim 1, wherein the cyclic molecule has hydroxyl groups, a part of the hydroxyl groups is substituted with the first group, and the amount of the hydroxyl groups before substitution is taken as 100%, so that 20 to 80% of the first group is substituted.

3. The polyrotaxane according to claim 1 or 2, which has a hydroxyl group and a hydroxyl value of 60 to 300 mgKOH / g.

4. (A) the polyrotaxane according to any one of claims 1 to 3; and (B) a first compound having a polysiloxane structure; A composition comprising:

5. The composition according to claim 4, wherein, when the total weight of the polyrotaxane (A) and the first compound (B) is 100 parts by weight, the polyrotaxane (A) is contained in an amount of 3 to 70 parts by weight per 100 parts by weight.

6. The composition according to claim 4 or 5, wherein the first compound (B) has a hydroxyl group.

7. The composition according to any one of claims 4 to 6, wherein the first compound (B) has a polydimethylsiloxane structure.

8. The composition according to any one of claims 4 to 7, The polyrotaxane (A) has a hydroxyl group, The first compound (B) has a hydroxyl group, The composition further comprises (C) a component having a reactive group capable of reacting with the (A) polyrotaxane and the (B) first compound, the reactive group being selected from the group consisting of an isocyanate group, a blocked isocyanate group, and an epoxy group. A crosslinked body formed from the above composition and comprising the (A) polyrotaxane; and the (B) first compound.

9. A substance having the crosslinked structure according to claim 8.

10. (I) a step of preparing a polyrotaxane in which a pseudo-polyrotaxane in which an opening of a cyclic molecule is pierced and enclosed by a linear molecule in a skewered manner has blocking groups arranged on both ends of the pseudo-polyrotaxane so that the cyclic molecule does not detach, the cyclic molecule having (1) a hydroxyl group or (2) a hydroxypropyl group; (II) RCOOH, RCOCl, and RNCO (wherein R is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 12 to 20 carbon atoms (wherein some of the hydrogen atoms in the alkyl group, alkenyl group or alkynyl group are OH groups, CN groups or NH groups) ２ providing a second compound selected from the group consisting of: (III) reacting the polyrotaxane prepared in the step (I) with the second compound prepared in the step (II); By having A polyrotaxane in which a pseudopolyrotaxane in which an opening of a cyclic molecule is pierced by a linear molecule and a blocking group is arranged at both ends of the pseudopolyrotaxane so that the cyclic molecule does not detach, (Wherein, X is a single bond or NH; n is 0 or 1; R represents a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 12 to 20 carbon atoms (wherein some of the hydrogens in the alkyl group, alkenyl group or alkynyl group may be substituted with an OH group, a CN group or an NH ２ group). * indicates the position where the cyclic molecule is bonded.) A method for producing a polyrotaxane, comprising the steps of: obtaining a polyrotaxane having a first group represented by 【Chemistry 2】

11. The method according to claim 10, wherein the cyclic molecule in the step (I) has the (1) hydroxyl group and / or the (2) hydroxyl group derived from a hydroxypropyl group, and when the amount of the hydroxyl groups is taken as 100%, the polyrotaxane obtained in the step (III) has 20 to 80% of the hydroxyl groups substituted with the first groups.

12. (X) A polyrotaxane in which a pseudopolyrotaxane in which an opening of a cyclic molecule is pierced by a linear molecule and a blocking group is arranged at both ends of the pseudopolyrotaxane so that the cyclic molecule does not fall off, wherein the cyclic molecule is represented by the following formula I: (Wherein, X is a single bond or NH; n is 0 or 1; R represents a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 12 to 20 carbon atoms (wherein some hydrogens in the alkyl group, alkenyl group or alkynyl group may be substituted with an OH group, a CN group or an NH ２ group); * indicates the position where the cyclic molecule is bonded.) preparing a polyrotaxane (A) having a first group represented by the following formula (I) and having a hydroxyl group; (XI) (B) preparing a first compound having a polysiloxane structure and a hydroxyl group; (XIII) (C) preparing a component having a reactive group capable of reacting with the (A) polyrotaxane and the (B) first compound, the reactive group being selected from the group consisting of an isocyanate group, a blocked isocyanate group, and an epoxy group; (XII) reacting the (A) polyrotaxane with the (B) first compound in the presence of the (C) component; By having A method for producing a crosslinked body formed from (A) a polyrotaxane and (B) a first compound, the method comprising obtaining a crosslinked body formed from (A) a polyrotaxane and (B) a first compound. 【Chemistry 3】

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