JPWO2007100136A1 - Liquid crystalline composition - Google Patents

Abstract

The present invention provides a liquid crystalline composition having flexibility and / or flexibility, and a method for producing the same. The present invention has a cyclic molecule, a linear molecule that includes the cyclic molecule in a skewered manner, and blocking groups that are arranged at both ends of the linear molecule so that the cyclic molecule is not detached from the linear molecule. A polyrotaxane; and a liquid crystalline composition, wherein the polyrotaxane is a group in which a cyclic molecule exhibits compatibility with the liquid crystalline substance, for example, a mesogenic group, specifically, in the following formulas 1 to 3: A liquid crystal composition having a biphenyl group represented by the present invention is provided.

Description

  The present invention relates to a liquid crystalline composition having a polyrotaxane and a liquid crystalline substance and a method for producing the same.

  Many kinds of liquid crystals are used in recent electrical appliances, particularly displays. Here, portable terminals such as notebook computers, PDAs, and mobile phones are required to be further miniaturized, and as one form, for example, development of wearable computers is also required. Therefore, the wearable computer display and the like are required to have flexibility and flexibility.

On the other hand, at the both ends (both ends of the linear molecule) of the pseudopolyrotaxane in which the opening of the cyclic molecule (rotator) is skewered by the linear molecule (axis) Patent Document 1 discloses a crosslinked polyrotaxane obtained by crosslinking a plurality of polyrotaxanes in which blocking groups are arranged so as not to leave. This crosslinked polyrotaxane has viscoelasticity generated by the movement of cyclic molecules. For this reason, even if tension is applied to the crosslinked polyrotaxane, the tension can be uniformly dispersed in the crosslinked polyrotaxane by this action.
Japanese Patent No. 3475252.

Therefore, an object of the present invention is to meet the above needs.
Specifically, an object of the present invention is to provide a liquid crystal material having flexibility and / or flexibility, and a method for manufacturing the same.

  As a result of intensive studies to achieve the above object, the present inventors have found that a composition comprising a polyrotaxane having a group that exhibits compatibility with a liquid crystal substance in a cyclic molecule, for example, a polyrotaxane having a mesogenic group, and the liquid crystal substance is the above problem. I found out that it could be solved. Specifically, the present inventors have found the following invention.

<1> A cyclic molecule, a linear molecule that claws the cyclic molecule in a skewered manner, and a polyrotaxane having blocking groups arranged at both ends of the linear molecule so that the cyclic molecule is not detached from the linear molecule And a liquid crystalline composition, wherein the polyrotaxane has a group in which a cyclic molecule exhibits compatibility with the liquid crystalline substance.
<2> In the above item <1>, the group exhibiting compatibility with the liquid crystalline substance may be a mesogenic group.
<3> In the above <2>, the mesogenic group is A—X—B—C—Y— (wherein A and B are 6-membered rings, C is a single bond or a linear group, X And Y is a linking group).

<4> In the above <3>, the 6-membered rings of A and B are each independently a saturated or unsaturated homocyclic or heterocyclic ring, preferably an optionally substituted benzene It should be a ring. More preferably, A is a p-cyanophenyl group and B is an unsubstituted benzene ring.
<5> In the above <3> or <4>, C has 0 to 100 elements, preferably 0 to 70 elements, more preferably 0 to 30 elements, forming the straight chain of C. Is good. C may include —O— or a benzene ring in a straight chain. Here, when a benzene ring is included, the “number of elements forming a straight chain” of the benzene ring is four in the present application for convenience. Preferably, C is a linear alkyl chain or a linear alkyl ether chain.

<6> In any one of the above items <3> to <5>, X is a single bond, —CO—O—, —O—CO—, —N═N—, an azoxy group, —N═CH—, — It may be selected from the group consisting of CH═N—, —CH═CH— and —C≡C—. Preferably, X is a group consisting of a single bond, —CO—O—, —O—CO—, —N═N—, an azoxy group, —N═CH—, —CH═N— and —CH═CH—. And more preferably a single bond, —CO—O— or —O—CO—.
<7> In any one of the above items <3> to <6>, Y represents a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NH—CO—, —CO. It may be selected from the group consisting of —NH—, —NH—CO—O— and —O—CO—NH—. Preferably, Y is selected from the group consisting of —CO—O—, —O—, —NH—CO—O— and —O—CO—, more preferably —CO—O—. Is good.

<8> In any one of the above items <3> to <7>, AX-B- represents D-1 to D-20 (wherein R ^{1 to} R ²⁰ each independently represents a substituent) Preferably selected from the group consisting of R ^{1 to} R ²⁰ are each independently a cyano group, F, Cl, a C 1-20, preferably a C 1-15 (preferably linear) alkyl group, a C 1-20, preferably C1-C15 (preferably linear) alkoxy group, C1-C20, preferably C1-C15 (preferably linear) alkylcarbonyloxy group or alkyloxycarbonyl group, C1 It may be ˜20, preferably a C 1-15 (preferably linear) fluorocarbon, or a nitro group. In particular, A-X-B- represents D-1 to D-14, D-19 or D-20, preferably D-2 to D-14, D-19 or D-20, more preferably D-4. ~ D-14, D-19 or D-20, in particular D-6.

<9> In any one of the above items <1> to <8>, a group that exhibits compatibility with a liquid crystalline substance, for example, a mesogenic group is represented by the following formulas 1 to 3 (where n is an integer of 1 to 20) M is an integer of 1 to 10, R ²¹ , R ²³ and R ²⁵ are each independently 0 to 5 substituents, and R ²² , R ²⁴ and R ²⁶ are each independently , 0 to 4 substituents).

<10> In the above item <9>, the biphenyl substituent may be represented by the formula 1, R ²¹ may be one, be present at the p-position, be a cyano group, and R ²² may be zero.
<11> In the above <9>, the biphenyl substituent is represented by the formula 2, n is an integer of 2 to 10, preferably an integer of 3 to 8, particularly 5, R ²³ is 1, and p-position. And a cyano group, and R ²⁴ is preferably zero.
<12> In the above <9>, the biphenyl substituent is represented by formula 3, m is an integer of 1 to 5, preferably an integer of 2 to 4, particularly 2, R ²⁵ is 1, and p-position. And a cyano group, and R ²⁶ is preferably 0.

<13> In any one of the above items <1> to <12>, the liquid crystalline substance is an azo compound group, an azoxy compound group, a substituted group of p-substituted benzoic acid ester, a cholesteryl ester, a p-substituted biphenyl, At least selected from the group consisting of cyclohexanecarboxylic acid ester substituents, Schiff bases, p-substituted cyclohexyl-p-substituted phenyls, 2-phenyl substituted-1,3-dioxane substituted groups, and phenylpyrimidines It should be one type.
<14> In any one of the above items <1> to <13>, the liquid crystalline substance is represented by formula C-1, C-2, E, F-1, F-2, G, or H (wherein X ⁵ to X ⁸ and X ^{10 to} X ¹⁹ are each independently a cyano group, F, Cl, a C 1-20, preferably a C 1-15 (preferably linear) alkyl group (preferably linear). A C 1-20, preferably a C 1-15 (preferably linear) alkoxy group, a C 1-20, preferably a C 1-15 (preferably linear) alkylcarbonyloxy group. Alternatively, it may be a compound represented by an alkyloxycarbonyl group, a C1-20, preferably a C1-15 (preferably linear) fluorocarbon, or a nitro group).

<15> In any one of the above items <1> to <14>, the liquid crystalline substance may be present in the crosslinked polyrotaxane.
<16> In any one of the above items <1> to <15>, at least a part of the polyrotaxane may be a crosslinked polyrotaxane that is crosslinked between the polyrotaxanes.

  <17> In any one of the above items <1> to <16>, the linear molecule is polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, cellulose resin (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.) , Polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, and / or copolymers thereof, polyethylene, polypropylene, and other olefins Polyolefin resins such as copolymer resins with monomers, polyester resins, polyvinyl chloride resins, polystyrene and acrylonitrile-styrene copolymers Polystyrene resins such as fat, acrylic resins such as polymethyl methacrylate and (meth) acrylic acid ester copolymers, acrylonitrile-methyl acrylate copolymer resins, polycarbonate resins, polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl Butyral resin, etc .; and derivatives or modified products thereof, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polydienes such as polyimides, polyisoprene, and polybutadiene , Polysiloxanes such as polydimethylsiloxane, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenyle Preferably selected from the group consisting of polyethylene, polyhaloolefins, and derivatives thereof, such as polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene. And is preferably selected from the group consisting of polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene, and particularly preferably polyethylene glycol.

<18> In any one of the above items <1> to <17>, the linear molecule may have a molecular weight of 500 or more, preferably 1000 or more, more preferably 2000 or more.
<19> In any one of the above items <1> to <18>, the blocking group is a dinitrophenyl group, a cyclodextrin, an adamantane group, a trityl group, a fluorescein, a pyrene, a substituted benzene (as a substituent) , Alkyl, alkyloxy, hydroxy, halogen, cyano, sulfonyl, carboxyl, amino, phenyl, etc., but are not limited to them. Selected from the group consisting of polynuclear aromatics (substituents may include, but are not limited to, the same as those described above. One or more substituents may be present) and steroids It is good. In addition, it is preferably selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, and pyrenes, more preferably an adamantane group or a trityl group. .

<20> In any one of the above items <1> to <19>, the cyclic molecule may be a cyclodextrin molecule which may be substituted.
<21> In any one of the above items <1> to <20>, the cyclic molecule may be a substituted cyclodextrin molecule, and the cyclodextrin molecule is α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. , As well as the derivatives thereof.

<22> In any one of the above items <1> to <21>, the cyclic molecule may be a substituted α-cyclodextrin, and the linear molecule may be polyethylene glycol.
<23> In any one of the above items <1> to <22>, when the amount of cyclic molecules included to the maximum when the cyclic molecules are included in a skewered manner by linear molecules is 1, Cyclic molecules may be skewered into linear molecules in an amount of 0.01 to 0.99, preferably 0.1 to 0.9, more preferably 0.2 to 0.8.

  <24> In any one of the above items <1> to <23>, the liquid crystalline composition is a display material, a display element, a recording material, a lithium ion battery, a fuel cell, a solar cell, an actuator, an electric double layer capacitor, or a light emitting element. And at least one selected from the group consisting of an electrochromic element, a sensor, an ionic circuit, a polymer electrolyte, an electrochemical material, a catalyst, a separation membrane, and a coating agent.

<25> a polyrotaxane; and a liquid crystal material;
a) mixing a cyclic molecule and a linear molecule in a liquid and including the cyclic molecule in a skewered manner in the linear molecule; and b) preventing the cyclic molecule from detaching from the linear molecule. Preparing a polyrotaxane by disposing blocking groups at both ends of the linear molecule.
Furthermore, the method comprises:
c) introducing a group that expresses compatibility with a liquid crystalline substance into the cyclic molecule; performing any of the following i) to v):
i) before step a);
ii) during step a);
iii) after step a) and before step b);
iv) during step b); or v) after step b):
d) Step of introducing a liquid crystalline substance into the system in any one of the following i ′) to vii ′):
Having the above method:
i ′) a) before step;
ii ′) during the a) step;
iii ′) after step a) and before step b);
iv ′) during step b) above;
v ′) after step b);
vi ′) before step c); or vii ′) after step c).

<26> In the above item <25>, the group exhibiting compatibility with the liquid crystalline substance may be a mesogenic group.
<27> In the above <25> or <26>, the step c) may be performed after the step v) b).
<28> In any one of the above items <25> to <27>, step d) is performed after step v ′) b) and before step vi ′) c), or after step vii ′) c) The step c) is preferably performed after the step b).
<29> In any one of the above items <25> to <28>, it may further include e) a step of reacting or physically adsorbing polyrotaxanes to obtain a crosslinked polyrotaxane.

<30> In the above item <29>, the step of obtaining a crosslinked polyrotaxane is preferably performed by a chemical crosslinking method using a crosslinking agent or a photocrosslinking method using light irradiation.
<31> In any one of the above items <26> to <30>, the mesogenic group is A—X—B—C—Y— (wherein A and B are 6-membered rings, and C is a single bond or a direct bond). A chain group, and X and Y are bonding groups).

<32> In the above <31>, the 6-membered rings of A and B may each independently be substituted, a saturated or unsaturated homocyclic ring or heterocyclic ring, preferably benzene that may be substituted It should be a ring. More preferably, A is a p-cyanophenyl group and B is an unsubstituted benzene ring.
<33> In the above <31> or <32>, C has 0 to 100 elements, preferably 0 to 70 elements, more preferably 0 to 30 elements, forming the straight chain of C. Is good. C may include —O— or a benzene ring in a straight chain. Here, when a benzene ring is included, the “number of elements forming a straight chain” of the benzene ring is four in the present application for convenience. Preferably, C is a linear alkyl chain or a linear alkyl ether chain.

<34> In any one of the above items <31> to <33>, X is a single bond, -CO-O-, -O-CO-, -N = N-, an azoxy group, -N = CH-,- It may be selected from the group consisting of CH═N—, —CH═CH— and —C≡C—. Preferably, X is a group consisting of a single bond, —CO—O—, —O—CO—, —N═N—, an azoxy group, —N═CH—, —CH═N— and —CH═CH—. And more preferably a single bond, —CO—O— or —O—CO—.
<35> In any one of the above items <31> to <34>, Y represents a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NH—CO—, —CO. It may be selected from the group consisting of —NH—, —NH—CO—O— and —O—CO—NH—. Preferably, Y is selected from the group consisting of —CO—O—, —O—, —NH—CO—O— and —O—CO—, more preferably —CO—O—. Is good.

<36> In any one of the above items <31> to <35>, A-X-B- is from the above D-1 to D-20 (wherein R ^{1 to} R ²⁰ have the same meanings as described above). It is better to be selected from the group consisting of R ^{1 to} R ²⁰ are each independently a cyano group, F, Cl, a carbon number of 1 to 20, preferably a C ^{1 to} C 15 (preferably linear) alkyl group, and a carbon number of 1 to 20, preferably C1-C15 (preferably linear) alkoxy group, C1-C20, preferably C1-C15 (preferably linear) alkylcarbonyloxy group or alkyloxycarbonyl group, C1 It may be ˜20, preferably a C 1-15 (preferably straight chain) fluorocarbon, or a nitro group. In particular, A-X-B- represents D-1 to D-14, D-19 or D-20, preferably D-2 to D-14, D-19 or D-20, more preferably D-4. ~ D-14, D-19 or D-20, in particular D-6.
<37> In any one of the above items <25> to <36>, a group that exhibits compatibility with a liquid crystalline substance, for example, a mesogenic group is represented by the above formulas 1 to 3 (wherein n, m, and R ^{21 to} R ²⁶ may be any of the biphenyl substituents as defined above.

<38> In the above <37>, the biphenyl substituent may be represented by Formula 1, R ²¹ may be one, be present at the p-position, be a cyano group, and R ²² may be zero.
<39> In the above <37>, the biphenyl substituent is represented by formula 2, n is an integer of 2 to 10, preferably 3 to 8, particularly 5, R ²³ is 1, and p-position And a cyano group, and R ²⁴ is preferably zero.
<40> In the above <37>, the biphenyl substituent is represented by formula 3, m is an integer of 1 to 5, preferably an integer of 2 to 4, particularly 2, R ²⁵ is 1, and p-position. And a cyano group, and R ²⁶ is preferably 0.

<41> In any one of the above items <25> to <40>, the liquid crystalline substance is an azo compound group, an azoxy compound group, a substituted group of p-substituted benzoic acid esters, cholesteryl esters, p-substituted biphenyls, At least selected from the group consisting of cyclohexanecarboxylic acid ester substituents, Schiff bases, p-substituted cyclohexyl-p-substituted phenyls, 2-phenyl substituted-1,3-dioxane substituted groups, and phenylpyrimidines It should be one type.
<42> In any one of the above items <25> to <41>, the liquid crystalline substance is represented by formula C-1, C-2, E, F-1, F-2, G, or H (wherein X ⁵ to X ⁸ and X ^{10 to} X ¹⁹ are the same as described above.

<43> In any one of the above items <25> to <42>, the liquid crystalline substance may be present in the crosslinked polyrotaxane.
<44> In any one of the above items <25> to <43>, at least a part of the polyrotaxane may be a crosslinked polyrotaxane that is crosslinked between the polyrotaxanes.

  <45> In any one of the above items <25> to <44>, the linear molecule is polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, cellulose resin (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.) , Polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, and / or copolymers thereof, polyethylene, polypropylene, and other olefins Polyolefin resin such as copolymer resin with monomer, polyester resin, polyvinyl chloride resin, polystyrene and acrylonitrile-styrene copolymer Polystyrene resins such as resins, acrylic resins such as polymethyl methacrylate and (meth) acrylic acid ester copolymers, acrylonitrile-methyl acrylate copolymer resins, polycarbonate resins, polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl Butyral resin, etc .; and derivatives or modified products thereof, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polydienes such as polyimides, polyisoprene, and polybutadiene , Polysiloxanes such as polydimethylsiloxane, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polypheny Selected from the group consisting of polyethylenes, polyhaloolefins, and derivatives thereof, such as polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene. Preferably, it is selected from the group consisting of polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene, and particularly preferably polyethylene glycol.

<46> In any one of the above items <25> to <45>, the linear molecule may have a molecular weight of 500 or more, preferably 1000 or more, more preferably 2000 or more.
<47> In any one of the above items <25> to <46>, the blocking group is a dinitrophenyl group, a cyclodextrin, an adamantane group, a trityl group, a fluorescein, a pyrene, a substituted benzene (as a substituent) , Alkyl, alkyloxy, hydroxy, halogen, cyano, sulfonyl, carboxyl, amino, phenyl, etc., but are not limited to them. Selected from the group consisting of polynuclear aromatics (substituents may include, but are not limited to, the same as those described above. One or more substituents may be present) and steroids It is good. In addition, it is preferably selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, and pyrenes, more preferably an adamantane group or a trityl group. .

<48> In any one of the above items <25> to <47>, the cyclic molecule may be a cyclodextrin molecule which may be substituted.
<49> In any one of the above items <25> to <48>, the cyclic molecule may be a substituted cyclodextrin molecule, and the cyclodextrin molecule is α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. , As well as the derivatives thereof.

<50> In any one of the above items <25> to <49>, the cyclic molecule may be a substituted α-cyclodextrin, and the linear molecule may be polyethylene glycol.
<51> In any one of the above items <25> to <50>, when the amount of cyclic molecules included to the maximum when the cyclic molecules are included in a skewered manner by linear molecules is 1, Cyclic molecules may be skewered into linear molecules in an amount of 0.01 to 0.99, preferably 0.1 to 0.9, more preferably 0.2 to 0.8.

  <52> In any one of the above items <25> to <51>, the liquid crystalline composition includes a display material, a display element, a recording material, a lithium ion battery, a fuel cell, a solar cell, an actuator, an electric double layer capacitor, and a light emitting device. And at least one selected from the group consisting of an electrochromic element, a sensor, an ionic circuit, a polymer electrolyte, an electrochemical material, a catalyst, a separation membrane, and a coating agent.

  According to the present invention, it is possible to provide a liquid crystal material having flexibility and / or flexibility and a method for manufacturing the same.

Hereinafter, the present invention will be described in detail.
The present invention provides a liquid crystal composition having a polyrotaxane; and a liquid crystal substance.

<Liquid crystalline material>
The liquid crystalline composition of the present invention has a liquid crystalline substance. A liquid crystalline substance refers to a molecule or substance that can form an intermediate phase by temperature change such as heating or cooling, or by the action of a certain amount of solvent. The liquid crystal substance is not particularly limited, and includes conventionally known liquid crystal substances and liquid crystal substances that will be developed in the future. The liquid crystalline substance contained in the composition of the present invention may be one type, two types, or more.

As liquid crystalline substances, azo compound group, azoxy compound group, substituted group of p-substituted benzoic acid ester, cholesteryl ester, p-substituted biphenyl, substituted group of cyclohexanecarboxylic acid ester, Schiff base, p-substituted Examples thereof include, but are not limited to, cyclohexyl-p-substituted phenyls, 2-phenyl substituted-1,3-dioxane substituted groups, and phenylpyrimidines. Here, the azo compound group is Formula A, the azoxy compound group is Formula B, the substituted group of p-substituted benzoic acid ester is Formula C-1 or C-2, the cholesteryl esters are Formula D, p- Substituted biphenyls are of formula E, cyclohexanecarboxylic acid ester groups are of formula F-1 or F-2, Schiff bases are of formula G, p-substituted cyclohexyl-p-substituted phenyls are of formula H, The 2-phenyl-substituted-1,3-dioxane-substituted group can be represented by Formula J, and the phenylpyrimidines can be represented by Formula K. In the formula, X ^{1 to} X ²³ each independently represent a substituent. Preferably, X ^{1 to} X ²³ are each independently a cyano group, F, Cl, a C 1-20, preferably a C 1-15 (preferably straight chain) alkyl group, a C 1-20, Preferably it is a C1-C15 (preferably linear) alkoxy group, C1-C20, preferably C1-C15 (preferably linear) alkylcarbonyloxy group or alkyloxycarbonyl group, carbon It may be a fluorocarbon having 1 to 20, preferably 1 to 15 (preferably linear) carbon, or a nitro group.

Preferably, the liquid crystalline substance may be a compound represented by the formula C-1, C-2, E, F-1, F-2, G or H, and X ^{5 to} X ⁸ and X ¹⁰ to X ¹⁹ is each independently a cyano group, F, Cl, a C 1-20, preferably a C 1-15 (preferably linear) alkyl group, a C 1-20, preferably a C 1 15 (preferably linear) alkoxy group, 1 to 20 carbon atoms, preferably 1 to 15 (preferably linear) alkylcarbonyloxy group or alkyloxycarbonyl group, 1 to 20 carbon atoms, preferably Is preferably a fluorocarbon having 1 to 15 carbon atoms (preferably linear) or a nitro group.

  In the liquid crystal composition, the liquid crystal substance has a weight ratio of liquid crystal substance: polyrotaxane of 0.999: 0.001 to 0.1: 0.9, preferably 0.99: 0.01 to 0.2: It is preferable to be included so as to be 0.8, more preferably 0.98: 0.02 to 0.3: 0.7.

<Polyrotaxane>
Here, the polyrotaxane is a cyclic molecule, a linear molecule that includes the cyclic molecule in a skewered manner, and blocking groups that are arranged at both ends of the linear molecule so that the cyclic molecule is not detached from the linear molecule. Have

  In addition, the polyrotaxane has a group in which a cyclic molecule expresses compatibility with the liquid crystal substance. By having this group, the polyrotaxane can be made compatible with a liquid crystal substance. The compatibility between the polyrotaxane and the liquid crystalline substance includes a case where both of these have direct compatibility, but in addition, the composition has other components other than the polyrotaxane and the liquid crystalline substance, The case where the compatibility between the polyrotaxane and the liquid crystalline substance is brought about through the other components is also included. Examples of such other components include, but are not limited to, good solvents for both the polyrotaxane and the liquid crystal substance. Other components (third component) will be described later.

The group that exhibits compatibility with the liquid crystal substance is preferably a mesogenic group.
The mesogenic group refers to a group that expresses the formation of an intermediate phase by a temperature change such as heating or cooling or by the action of a certain amount of solvent.
The mesogenic group is AX—B—C—Y— (wherein A and B are 6-membered rings, C is a single bond or a linear group, and X and Y are linking groups). It may be a group represented.
The 6-membered rings of A and B are each independently an optionally substituted saturated or unsaturated homologous or heterocyclic ring, preferably an optionally substituted benzene ring. More preferably, A is a p-cyanophenyl group and B is an unsubstituted benzene ring.

C has 0 to 100 elements, preferably 0 to 70 elements, more preferably 0 to 30 elements, forming the straight chain of C. C may include —O— or a benzene ring in a straight chain. Here, when a benzene ring is included, the “number of elements forming a straight chain” of the benzene ring is four in the present application for convenience. Preferably, C is a linear alkyl chain or a linear alkyl ether chain.
X represents a single bond, —CO—O—, —O—CO—, —N═N—, an azoxy group, —N═CH—, —CH═N—, —CH═CH— and —C≡C—. Preferably selected from the group consisting of Preferably, X is a group consisting of a single bond, —CO—O—, —O—CO—, —N═N—, an azoxy group, —N═CH—, —CH═N— and —CH═CH—. And more preferably a single bond, —CO—O— or —O—CO—.
Y represents a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NH—CO—, —CO—NH—, —NH—CO—O— and —O—CO. It is preferable to be selected from the group consisting of —NH—. Preferably, Y is selected from the group consisting of —CO—O—, —O—, —NH—CO—O— and —O—CO—, more preferably —CO—O—. Is good.

A-X-B- may be selected from the group consisting of the above-described D-1 to D-20 (wherein R ^{1 to} R ²⁰ are as defined above). R ^{1 to} R ²⁰ are each independently a cyano group, F, Cl, a C 1-20, preferably a C 1-15 (preferably straight chain) alkyl group, a C 1-20, preferably C1-C15 (preferably linear) alkoxy group, C1-C20, preferably C1-C15 (preferably linear) alkylcarbonyloxy group or alkyloxycarbonyl group, C1 It may be ˜20, preferably a C 1-15 (preferably linear) fluorocarbon, or a nitro group. In particular, A-X-B- represents D-1 to D-14, D-19 or D-20, preferably D-2 to D-14, D-19 or D-20, more preferably D-4. ~ D-14, D-19 or D-20, in particular D-6.

The mesogenic group may be any of the biphenyl substituents represented by the above formulas 1 to 3 (wherein n, m, and R ^{21 to} R ²⁶ have the same meanings as described above).
It is preferred that the biphenyl substituent is represented by formula 1, R ²¹ is 1, is in the p-position and is a cyano group, and R ²² is 0.
In addition, the biphenyl substituent is represented by formula 2, n is an integer of 2 to 10, preferably 3 to 8, particularly 5, R ²³ is 1, and is present at the p-position and is a cyano group. Yes, R ²⁴ should be zero.
Furthermore, the biphenyl substituent is represented by formula 3, m is an integer from 1 to 5, preferably an integer from 2 to 4, especially 2, R ²⁵ is 1, is present at the p-position and is a cyano group Yes, R ²⁶ should be zero.

In the composition of the present invention, at least a part of the polyrotaxane may be a crosslinked polyrotaxane that is crosslinked with the polyrotaxane. The crosslinked polyrotaxane may be physically crosslinked or chemically crosslinked with each other.
In the case of chemical cross-linking, the polyrotaxanes are preferably cross-linked with the cyclic molecules bonded through some group or directly bonded.
Further, when the polyrotaxane forms a crosslinked polyrotaxane, the liquid crystalline substance is preferably present in the crosslinked polyrotaxane. For example, the liquid crystalline substance may be present in the crosslinked polyrotaxane as a solvent.

  In the polyrotaxane of the liquid crystal composition of the present invention, the linear molecule is polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, cellulose resin (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene Oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, etc. and / or copolymers thereof, polyethylene, polypropylene, and other olefinic monomers Polyolefin resins such as copolymer resins, polyester resins, polyvinyl chloride resins, polystyrene and acrylonitrile-styrene copolymer resins Polystyrene resins such as polymethyl methacrylate, (meth) acrylic acid ester copolymers, acrylic resins such as 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 copolymer (ABS resin), polyamides such as nylon, polyimides, polydienes such as polyisoprene and polybutadiene, Polysiloxanes such as polydimethylsiloxane, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenyle Selected from the group consisting of polyethylenes, polyhaloolefins, and derivatives thereof, such as polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene. It is preferably selected from the group, preferably selected from the group consisting of polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene, and particularly preferably polyethylene glycol.

  The linear molecule should have a molecular weight of 500 or more, preferably 1000 or more, more preferably 2000 or more.

  In the polyrotaxane of the liquid crystal composition of the present invention, the blocking group includes dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes, substituted benzenes (alkyl, alkyloxy as substituents). , Hydroxy, halogen, cyano, sulfonyl, carboxyl, amino, phenyl, etc., but are not limited to these.One or more substituents may be present), an optionally substituted polynuclear aromatic (The substituents may be the same as those described above, but are not limited thereto. One or more substituents may be present) and steroids. In addition, it is preferably selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, and pyrenes, more preferably an adamantane group or a trityl group. .

  In the polyrotaxane of the liquid crystalline composition of the present invention, the cyclic molecule may be an optionally substituted cyclodextrin molecule. In particular, the cyclic molecule is an optionally substituted cyclodextrin molecule, and the cyclodextrin molecule may be selected from the group consisting of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and derivatives thereof. .

  In the polyrotaxane of the liquid crystal composition of the present invention, the cyclic molecule may be an α-cyclodextrin which may be substituted, and the linear molecule may be polyethylene glycol.

  In the polyrotaxane of the liquid crystalline composition of the present invention, when the maximum amount of cyclic molecules included when the cyclic molecules are included in a skewered manner by linear molecules is 1, the cyclic molecules are 0. It is good to be included in a skewered form in a linear molecule in an amount of 01 to 0.99, preferably 0.1 to 0.9, more preferably 0.2 to 0.8.

If the inclusion amount of the cyclic molecule is close to the maximum value, the movement distance of the cyclic molecule on the linear molecule tends to be limited. When the moving distance is limited, there is a tendency that the degree of expansion and contraction of the polyrotaxane is limited.
The maximum inclusion amount of the cyclic molecule can be determined by the length of the linear molecule and the thickness of the cyclic molecule. For example, when the linear molecule is polyethylene glycol and the cyclic molecule is an α-cyclodextrin molecule, the maximum inclusion amount is experimentally determined (see Macromolecules 1993, 26, 5698-5703. The contents of this document are all incorporated herein).

  The composition of the present invention may contain components other than the above-described polyrotaxane and liquid crystal substance (hereinafter sometimes abbreviated as “third component”). Examples of the third component include solvents (including the above-mentioned good solvents for both polyrotaxane and liquid crystal substance), pigments, surfactants, plasticizers, carbon compounds such as carbon nanotubes, salts, and various polymers. Can do. For example, when the third component is a polymer, the polymer and the polyrotaxane in the composition of the present invention may be physically or chemically bonded. For example, a third component (for example, a polymer) and the polyrotaxane may be chemically crosslinked via a cyclic molecule.

  The liquid crystalline composition of the present invention includes a display material, a display element, a recording material, a lithium ion battery, a fuel cell, a solar battery, an actuator, an electric double layer capacitor, a light emitting element, an electrochromic element, a sensor, an ionic circuit, and a polymer electrolyte. And at least one selected from the group consisting of an electrochemical material, a catalyst, a separation membrane, and a coating agent.

<Method for preparing liquid crystalline composition>
The above-mentioned liquid crystalline composition can be prepared as follows, for example.
a) a step of mixing a cyclic molecule and a linear molecule in a liquid and including the cyclic molecule in a skewered manner in the linear molecule; and b) a linear shape so that the cyclic molecule is not detached from the linear molecule. Preparing a polyrotaxane by placing blocking groups at both ends of the molecule;
Furthermore, the method comprises:
c) a step of introducing a group that exhibits compatibility with the liquid crystalline substance into the cyclic molecule, for example, a mesogenic group; and d) a step of introducing the liquid crystalline substance into the system, that is, the composition. A liquid crystal composition can be obtained.

  Step a) and step b) can be performed by a conventionally known method. For example, it can be obtained by a method described in Japanese Patent No. 3475252, Japanese Patent Application Laid-Open No. 2005-154675, and the like.

Hereinafter, step c) will be described.
Step c) is a step of introducing a group that expresses compatibility with the liquid crystalline substance into the cyclic molecule, for example, a mesogenic group. This step is either i) a) before step; ii) a) during step; iii) after step a) and b) before step; iv) b) during step; or v) b) after step. Preferably in step v), i.e. after step b).

In the step c), the step of introducing a group exhibiting compatibility with the liquid crystal substance, for example, a mesogenic group, can be introduced by using various conventionally known methods. For example, the conditions used in the introduction step depend on the mesogenic group to be introduced and the type of polyrotaxane, but are not particularly limited, and various reaction methods and reaction conditions can be used. Specifically, when the mesogenic group bonding group (for example, Y described above) is an ether group (—O—), the following can be mentioned. In general, a technique in which an appropriate base coexists with a halide in a polar solvent such as dimethyl sulfoxide or dimethylformamide is used. Sodium methoxide, sodium ethoxide, potassium t-butoxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, potassium carbonate, cesium carbonate, silver oxide, barium hydroxide, barium oxide, hydrogenated as base Alkali or alkaline earth metal salts such as sodium and potassium hydride can be used. In addition, when the bonding group of the mesogenic group (for example, Y) is a carbonyl group (—CO—), the mesogenic group can be introduced by reacting an acid chloride that can be a mesogenic group in the presence of triethylamine.
In particular, when groups represented by formulas 1 to 3 are introduced as mesogenic groups, acid chloride derivatives of these groups are preferably reacted with polyrotaxane in the presence of triethylamine.

  Furthermore, the method of the present invention has step d). Step d) is a step of introducing a liquid crystalline substance into the system, that is, into the composition. This step is i ′) a) before step; ii ′) during step a); iii ′) after step a) and b) before step; iv ′) b) during step; v ′) b) after step Vi ′) c) before step; or vii ′) c) after step. Preferably, it is performed after step v ') b) and before step vi') c), or after step vii ') c) and step c) is performed after step b).

  The step d) depends on the type of liquid crystal substance and polyrotaxane used, but can be performed, for example, under the following conditions. That is, step d) can be performed by mixing the liquid crystalline substance and the polyrotaxane by various methods. Specific examples include a method in which both the liquid crystalline substance and / or polyrotaxane are heated and mixed in a fluid state; a technique in which both are dissolved and mixed in a good solvent for the liquid crystalline substance and polyrotaxane. However, it is not limited to these.

The method of the present invention may further include e) a step of reacting or physically adsorbing polyrotaxanes to obtain a crosslinked polyrotaxane.
The step e) is preferably performed after the step b). The step e) can be performed by a chemical crosslinking method using a crosslinking agent or the like, or a photocrosslinking method by irradiating with light. In addition, as a method for bonding a polyrotaxane cyclic molecule via a bonding group, a conventionally known method, for example, a method described in Japanese Patent No. 3475252, Japanese Patent Application Laid-Open No. 2005-154675, or the like can be used.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to a present Example.

  Polyrotaxane was prepared according to the method described in Japanese Patent Application Laid-Open No. 2005-154675, and was actually purchased from Advanced Soft Materials and used as it is. The linear molecule is PEG (weight average molecular weight 35000), the cyclic molecule is α-cyclodextrin, the blocking group is an adamantane group, and the number of cyclodextrins included is 90 to 100 per molecule, The inclusion amount was 0.25 to 0.3 when the maximum inclusion amount was 1. Other chemicals were purchased from Wako Pure Chemicals, Aldrich, Tokyo Kasei, etc., and used without any particular purification.

P. A. G. Cormac, B.M. D. Moore, D.C. C. Sherrington. J. et al. Mater. Chem. , 7, 1977-1983 (1997), ethyl-6- (4-cyanobiphenyl-4′-yloxy) hexanoate was synthesized from 4-cyano-4′-hydroxybiphenyl (CNBP) and ethyl 6-bromohexanoate. Thereafter, it was hydrolyzed with potassium hydroxide to give ethyl-6- (4-cyanobiphenyl-4′-yloxy) hexanoic acid (hereinafter referred to as CNBP-C ₅ —COOH). Subsequently, CNBP-C ₅ -COOH (2.48 mmol) was dissolved in 5 ml of thionyl chloride, stirred at room temperature for 4 hours under a stream of argon, and then excess thionyl chloride was distilled off by evaporation. - to give the cyano-4'-yloxy) hexanoic acid chloride (hereinafter referred to as _{CNBP-C 5} -COCl). The obtained CNBP-C ₅ -COCl was not further purified, and the entire amount was directly used for the following coupling reaction.

Anhydrous lithium chloride (1.13 g) was dissolved in dehydrated dimethylacetamide (11.4 g), and polyrotaxane (126 mg) was added thereto and dissolved at room temperature to 60 ° C. Then, after the obtained mixture was cooled to room temperature, triethylamine (0.345 ml) was mixed. A solution obtained by dissolving CNBP-C ₅ -COCl obtained above in 3 ml of dehydrated dimethylacetamide was added dropwise over 20 minutes under ice-cooling, followed by stirring for 24 hours under an argon flow. After the reaction, twice with methanol, precipitated once with ion exchanged water (each 200ml) _{CNBP-C 5} - groups, to give bound to α- cyclodextrin polyrotaxane _CNBP-C 5 APR a (185 mg) as a white solid .

<Composition having polyrotaxane CNBP-C ₅ APR and liquid crystal substance>
The polyrotaxane CNBP-C ₅ APR obtained above was dissolved in 4-cyano-4′-n-pentylbiphenyl (hereinafter simply referred to as “5CB”), which is a low-molecular liquid crystal substance, at high temperatures.
On the other hand, unmodified polyrotaxane as raw material, methylated polyrotaxane in which —OH group of α-cyclodextrin of unmodified polyrotaxane as raw material is substituted with —OCH ₃ group, —OH of α-cyclodextrin of unmodified polyrotaxane as raw material hydroxypropylated polyrotaxane obtained by substituting groups -OCH ₂ CH (OH) CH ₃ groups, did not dissolve in 5CB.
FIG. 1 shows the temperature change of the CNBP-C ₅ APR / 5CB composition. Aggregation or precipitation was observed at the bottom up to 55 ° C, but at 90 ° C it completely dissolved and became a transparent solution. Further, when the temperature was returned to 20 ° C. again, the solution became a cloudy gel as a whole, but such gelation did not occur in the mixture of unmodified polyrotaxane and 5CB.

In the same manner as in Example 1, polyrotaxane CNBP-C ₅ APR was obtained.
This polyrotaxane CNBP-C ₅ APR could be uniformly mixed with 5CB, which is a low-molecular liquid crystal substance, using tetrahydrofuran (hereinafter abbreviated as “THF”) as a solvent. This composition, that is, a composition obtained by dissolving CNBP-C ₅ APR (10 mg) and 5CB (100 μL) in THF (150 μL) was cast on a glass slide and dried on a hot plate at 50 ° C. To form a film.
FIG. 2 shows the temperature change of the CNBP-C ₅ APR / 5CB mixed film.
This film was white at room temperature but became transparent when heated to 37 ° C. or higher, and became cloudy again when the temperature was lowered to room temperature. All of these changes were completed within a few seconds and were found to show rapid temperature responsiveness. When this film was placed between crossed polarizers and the temperature responsiveness was observed in the same manner, it showed birefringence at room temperature, but the birefringence decreased at 37 ° C. or higher. Since 5CB transitions from a nematic phase to an isotropic phase at 35 ° C., it was suggested that the properties of this film reflect the liquid crystallinity exhibited by 5CB contained in the film.
On the other hand, since unmodified polyrotaxane (that is, unmodified polyrotaxane as a raw material) does not dissolve in THF, such a mixture with 5CB could not be formed.

In the same manner as in Example 1, polyrotaxane CNBP-C ₅ APR was obtained.
This CNBP-C ₅ APR (20 mg) was dried under reduced pressure at 80 ° C. for 1 hour, and then mixed with 5CB (100 μL) and THF (100 μL) in a glove box and dissolved. Carbonyldiimidazole (2.5 mg) was added thereto and dissolved well, and then placed in a sealed container and allowed to stand at 60 ° C. for 1 day to carry out a crosslinking reaction to obtain a crosslinked polyrotaxane CL-CNBP-C ₅ APR. The prepared CL-CNBP-C ₅ APR was taken out from the container and allowed to stand at 60 ° C. for 2 days to volatilize THF to prepare a composition containing 5CB as a solvent.
FIG. 3 shows the temperature change of the composition obtained. At 20 ° C., 5CB contained as a solvent is cloudy because it is a nematic phase, but at 50 ° C., 5CB is isotropic and transparent.
Moreover, FIG. 4 shows a mode that the same composition was observed between orthogonal polarizers. It can be seen that the composition exhibits birefringence at 20 ° C., whereas the birefringence disappears at 50 ° C.
From this, it can be seen that the composition of this example having a low-molecular liquid crystal such as 5CB and a crosslinked polyrotaxane CL-CNBP-C ₅ APR exhibits liquid crystallinity. In addition, since the composition of the present invention has the crosslinked polyrotaxane CL-CNBP-C ₅ APR, it has a pulley effect produced by sliding the cyclic molecule of the crosslinked polyrotaxane on the linear molecule (Japanese Patent No. 3475252). See the publication).

FIG. 3 is a view showing a temperature change of the composition obtained in Example 1. FIG. 3 is a view showing a temperature change of the composition obtained in Example 2. (A) is observed under normal light, and (b) is observed between orthogonal polarizers. It is a figure which shows the temperature change observed under normal light of the composition obtained in Example 3. FIG. It is a figure which shows the temperature change observed between orthogonal polarizers of the composition obtained in Example 3. FIG.

Claims (29)

  A cyclic molecule, a linear molecule that includes the cyclic molecule in a skewered manner, and a polyrotaxane having blocking groups arranged at both ends of the linear molecule so that the cyclic molecule is not detached from the linear molecule; and A liquid crystalline composition having a liquid crystalline substance, wherein the polyrotaxane has a group in which the cyclic molecule exhibits compatibility with the liquid crystalline substance.   2. The composition according to claim 1, wherein the group exhibiting compatibility with the liquid crystal substance is a mesogenic group.   The mesogenic group is A—X—B—C—Y— (wherein A and B are 6-membered rings, C is a single bond or a linear group, and X and Y are bonding groups). The composition of Claim 1 or 2 which is group represented by these.   The composition according to claim 3, wherein the six-membered rings of A and B are each independently a saturated or unsaturated homocyclic ring or heterocyclic ring which may be substituted.   The composition according to claim 3 or 4, wherein the C has 0 to 100 elements forming the straight chain of the C.   X is a single bond, —CO—O—, —O—CO—, —N═N—, an azoxy group, —N═CH—, —CH═N—, —CH═CH— and —C≡C. The composition according to any one of claims 3 to 5, which is selected from the group consisting of-.   Y represents a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NH—CO—, —CO—NH—, —NH—CO—O— and —O—. The composition according to claim 3, which is selected from the group consisting of CO—NH—. The composition according to claim 3, wherein AX-B- is selected from the group consisting of D-1 to D-20 (wherein R ^{1 to} R ²⁰ each independently represents a substituent). .
The mesogenic group is represented by the following formulas 1 to 3 (wherein n is an integer of 1 to 20, m is an integer of 1 to 10, and R ²¹ , R ²³ and R ²⁵ are each independently 0 9 to 5 substituents, wherein R ²² , R ²⁴ and R ²⁶ are each independently 0 to 4 substituents). The composition of any one of these.
The composition according to claim 9, wherein the biphenyl substituent is represented by the formula 1, R ²¹ is 1, p-position is a cyano group, and R ²² is 0. 10. The biphenyl substituent is represented by formula 2, n is an integer of 2 to 10, R ²³ is 1, is p-position and is a cyano group, and R ²⁴ is 0. The composition as described. 10. The biphenyl substituent is represented by formula 3, m is an integer of 1 to 5, R ²⁵ is 1, is p-position and is a cyano group, and R ²⁶ is 0. The composition as described.   Liquid crystalline substances are azo compound group, azoxy compound group, substituted group of p-substituted benzoic acid ester, cholesteryl ester, p-substituted biphenyl, substituted group of cyclohexanecarboxylic acid ester, Schiff base, p-substituted The at least one selected from the group consisting of cyclohexyl-p-substituted phenyls, 2-phenyl substituted-1,3-dioxane substituted groups, and phenylpyrimidines. Composition. The liquid crystalline substance has formulas C-1, C-2, E, F-1, F-2, G or H (wherein X ^{5 to} X ⁸ and X ^{10 to} X ¹⁹ are each independently a cyano group, F, Cl, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylcarbonyloxy group or alkyloxycarbonyl group having 1 to 20 carbon atoms, a fluorocarbon having 1 to 20 carbon atoms, or a nitro group. 14. The composition according to any one of claims 1 to 13, wherein
  The composition according to claim 1, wherein the liquid crystalline substance is present in a crosslinked polyrotaxane.   The composition according to any one of claims 1 to 15, wherein at least a part of the polyrotaxane is a crosslinked polyrotaxane that is crosslinked between the polyrotaxanes.   The linear molecule is polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, cellulose resin, polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine. , Casein, gelatin, starch and the like and / or copolymers thereof, polyolefin resins such as polyethylene, polypropylene, and other copolymer resins with olefin monomers, polyester resins, polyvinyl chloride resins, polystyrene resins, Acrylic resin, polycarbonate resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, etc .; and derivatives or modified products thereof, polyisobuty , Polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polyimides, polydienes such as polyisoprene and polybutadiene, polysiloxanes such as polydimethylsiloxane, polysulfones, 17. Any one of claims 1 to 16, selected from the group consisting of polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and derivatives thereof. A composition according to item.   The composition according to any one of claims 1 to 17, wherein the linear molecule has a molecular weight of 500 or more.   The blocking group is selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes, substituted benzenes, optionally substituted polynuclear aromatics, and steroids. The composition according to claim 1, which is selected.   The composition according to any one of claims 1 to 19, wherein the cyclic molecule is a cyclodextrin molecule which may be substituted.   21. The cyclodextrin molecule in which the cyclic molecule may be substituted, and the cyclodextrin molecule is selected from the group consisting of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and derivatives thereof. The composition of any one of these.   The composition according to any one of claims 1 to 21, wherein the cyclic molecule is α-cyclodextrin which may be substituted, and the linear molecule is polyethylene glycol.   The amount of the cyclic molecule is 0.01 to 0.99, where 1 is the maximum amount of the cyclic molecule included when the cyclic molecule is included in a skewered manner by the linear molecule. The composition according to any one of claims 1 to 22, which is included in a skewered manner in the linear molecule.   The liquid crystalline composition includes a display material, a display element, a recording material, a lithium ion battery, a fuel cell, a solar battery, an actuator, an electric double layer capacitor, a light emitting element, an electrochromic element, a sensor, an ionic circuit, a polymer electrolyte, an electric The composition according to any one of claims 1 to 23, which is used for at least one selected from the group consisting of a chemical material, a catalyst, a separation membrane, and a coating agent. A liquid crystal composition comprising: a polyrotaxane; and a liquid crystal substance,
a) mixing a cyclic molecule and a linear molecule in a liquid and including the cyclic molecule in a skewered manner in the linear molecule; and b) preventing the cyclic molecule from detaching from the linear molecule. Preparing a polyrotaxane by disposing blocking groups at both ends of the linear molecule.
Furthermore, the method comprises:
c) introducing a group that expresses compatibility with a liquid crystalline substance into the cyclic molecule; performing any of the following i) to v):
i) before step a);
ii) during step a);
iii) after step a) and before step b);
iv) during step b); or v) after step b):
d) Step of introducing a liquid crystalline substance into the system in any one of the following i ′) to vii ′):
Having the above method:
i ′) a) before step;
ii ′) during the a) step;
iii ′) after step a) and before step b);
iv ′) during step b) above;
v ′) after step b);
vi ′) before step c); or vii ′) after step c).   The method according to claim 25, wherein the group exhibiting compatibility with the liquid crystal substance is a mesogenic group.   The method according to claim 25 or 26, wherein the step c) is performed after the step v) b).   The step d) is performed after the step v ′) b) and before the step vi ′) c), or after the step vii ′) c), and the step c) is performed after the step b). The method according to any one of 25 to 27. The method according to any one of claims 25 to 28, further comprising a step of e) reacting or physically adsorbing the polyrotaxanes to obtain a crosslinked polyrotaxane.