JP2016056113A - Liquid crystalline compound, heat-responsive material and production method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystalline compound that develops liquid crystallinity at low temperature, and to provide a heat-responsive material and a production method of the material, which has liquid crystallinity and rubber elasticity at low temperature (near room temperature) while having a large content of a liquid crystalline compound.SOLUTION: The liquid crystalline compound of the present invention is prepared by adding an alkylene oxide and/or styrene oxide to a mesogen group-containing compound having an active hydrogen group.SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal compound, a thermotropic thermoresponsive material, and a method for producing the same.

  The liquid crystal elastomer is a hybrid material of liquid crystal and elastomer. The characteristic response of liquid crystal elastomers is that when the degree of orientation of the liquid crystal is increased by applying external stimuli such as heat, light, electric field, and magnetic field, it expands in the orientation direction and decreases when the degree of orientation is reduced except for external stimuli. In order to show the behavior, application to various fields such as actuators has been attempted.

  For example, Patent Document 1 discloses a polymer liquid crystal polyurethane exhibiting liquid crystallinity obtained by reacting bis (ω-hydroxyalkyleneoxy) biphenyl and 1,4-phenylene diisocyanate.

  Patent Document 2 discloses a polymer liquid crystal polyurethane obtained by polymerizing a diol component having a mesogenic group and trans-1,4-cyclohexane diisocyanate.

  However, the conventional liquid crystal polyurethane has a very high temperature at which the liquid crystal develops, and it is difficult to exhibit liquid crystallinity at a low temperature (around room temperature). Further, the conventional liquid crystal polyurethane has increased fluidity when the liquid crystal is developed and has no rubber elasticity. Further, the conventional mesogenic diol as a raw material has a high temperature for developing liquid crystallinity, and it has been difficult to produce a liquid crystal polyurethane without a solvent.

JP-A-5-170860 JP 7-258369 A

  An object of this invention is to provide the liquid crystalline compound with low temperature which expresses liquid crystallinity. Another object of the present invention is to provide a heat-responsive material having liquid crystallinity and rubber elasticity at a low temperature (around room temperature) despite its high content of liquid crystal compounds, and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by a liquid crystalline compound and a thermoresponsive material described below, and have completed the present invention.

  That is, the present invention relates to a liquid crystal compound obtained by adding alkylene oxide and / or styrene oxide to a mesogen group-containing compound having an active hydrogen group.

  By adding alkylene oxide and / or styrene oxide to a mesogen group-containing compound having an active hydrogen group, the present inventor reduces the thermal stability of the mesogen group, thereby reducing the temperature range in which liquid crystallinity appears. I found out. By using the liquid crystalline compound, the reaction curing can be performed in a state without a solvent and exhibiting liquid crystallinity. By performing reaction curing in a state where liquid crystallinity is exhibited, the crystallinity of the mesogen can be inhibited and the formation of a crystal phase can be prevented.

（式中、Ｘは活性水素基であり、Ｒ_１は単結合、−Ｎ＝Ｎ−、−ＣＯ−、−ＣＯ−Ｏ−、又は−ＣＨ＝Ｎ−であり、Ｒ_２は単結合、又は−Ｏ−であり、Ｒ_３は単結合、又は炭素数１〜２０のアルキレン基である。ただし、Ｒ_２が−Ｏ−であり、かつＲ_３が単結合である場合を除く。） In the present invention, the mesogenic group-containing compound is preferably a compound represented by the following general formula (1).

(Wherein X is an active hydrogen group, R ₁ is a single bond, —N═N—, —CO—, —CO—O—, or —CH═N—, and R ₂ is a single bond, or -O- and R ₃ is a single bond or an alkylene group having 1 to 20 carbon atoms, except when R ₂ is -O- and R ₃ is a single bond.

  The alkylene oxide is preferably at least one selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide.

  Moreover, it is preferable that 2-10 mol is added with respect to 1 mol of compounds represented by General formula (1), and alkylene oxide and / or styrene oxide. When the number of added moles is less than 2 moles, it is difficult to sufficiently lower the temperature range in which the liquid crystal properties of the liquid crystal compound are exhibited, and it is difficult to perform reaction curing in a solvent-free and liquid crystal state. Tend to be. On the other hand, when the added mole number exceeds 10 moles, the liquid crystal compound tends not to exhibit liquid crystallinity.

  The heat-responsive material of the present invention is obtained by reacting a liquid crystal compound with a compound that reacts with an active hydrogen group of the liquid crystal compound, and has liquid crystallinity and rubber elasticity at a low temperature (near room temperature). .

  The heat-responsive material preferably contains 50 to 90% by weight of a liquid crystal compound as a raw material, and more preferably 60 to 80% by weight. By increasing the compounding amount of the liquid crystal compound and increasing the content of the mesogenic group, a heat-responsive material that is largely deformed by a temperature change can be obtained. In the present invention, since the liquid crystal compound is used, the heat-responsive material obtained even when the content of the liquid crystal compound is increased has a low elastic modulus. When the content of the liquid crystal compound is less than 50% by weight, the liquid crystal tends to hardly appear. On the other hand, when the content of the liquid crystal compound exceeds 90% by weight, it is difficult to introduce a crosslinking point in the molecule, and therefore, it tends to be hard to be cured.

  The thermoresponsive material preferably has a transition temperature (Ti) from 0 to 100 ° C. from the liquid crystal phase to the isotropic phase or from the isotropic phase to the liquid crystal phase.

  The present invention also provides a process A in which an alkylene oxide and / or styrene oxide is added to a mesogen group-containing compound having an active hydrogen group to obtain a liquid crystalline compound, the liquid crystalline compound and the liquid crystalline compound under solvent-free conditions Heat including step B of obtaining a raw material composition for a thermoresponsive material by mixing a compound that reacts with the active hydrogen group, and a step C of curing the raw material composition for the thermoresponsive material at a temperature at which liquid crystallinity develops The present invention relates to a method for manufacturing a responsive material.

（式中、Ｘは活性水素基であり、Ｒ_１は単結合、−Ｎ＝Ｎ−、−ＣＯ−、−ＣＯ−Ｏ−、又は−ＣＨ＝Ｎ−であり、Ｒ_２は単結合、又は−Ｏ−であり、Ｒ_３は単結合、又は炭素数１〜２０のアルキレン基である。ただし、Ｒ_２が−Ｏ−であり、かつＲ_３が単結合である場合を除く。） In the manufacturing method of the thermoresponsive material of this invention, it is preferable that a mesogen group containing compound is a compound represented by following General formula (1).

(Wherein X is an active hydrogen group, R ₁ is a single bond, —N═N—, —CO—, —CO—O—, or —CH═N—, and R ₂ is a single bond, or -O- and R ₃ is a single bond or an alkylene group having 1 to 20 carbon atoms, except when R ₂ is -O- and R ₃ is a single bond.

  The alkylene oxide is preferably at least one selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide.

  Moreover, it is preferable that 2-10 mol is added with respect to 1 mol of compounds represented by General formula (1), and alkylene oxide and / or styrene oxide.

  Moreover, it is preferable that content of the liquid crystalline compound in the raw material composition for thermoresponsive materials is 50 to 90 weight%, More preferably, it is 60 to 80 weight%. By increasing the compounding amount of the liquid crystal compound and increasing the content of the mesogenic group, a heat-responsive material that is largely deformed by a temperature change can be obtained. In the present invention, since the liquid crystal compound is used, the heat-responsive material obtained even when the content of the liquid crystal compound is increased has a low elastic modulus. When the content of the liquid crystal compound is less than 50% by weight, the liquid crystal tends to hardly appear. On the other hand, when the content of the liquid crystal compound exceeds 90% by weight, it is difficult to introduce a crosslinking point in the molecule, and therefore, it tends to be hard to be cured.

  In Step C, it is preferable to align the mesogenic groups of the liquid crystalline compound while curing the raw material composition for a thermoresponsive material at a temperature at which liquid crystallinity develops.

  The liquid crystalline compound of the present invention has a low temperature range in which liquid crystallinity is manifested. By using the liquid crystalline compound, the reaction curing can be performed in a state without a solvent and exhibiting liquid crystallinity. The thermoresponsive material of the present invention has a liquid crystallinity and rubber elasticity at a low temperature (around room temperature) because the temperature range in which the liquid crystallinity of the liquid crystal compound as a raw material is low and the network structure is formed by crosslinking. In the thermoresponsive material, mesogenic groups are oriented in a uniaxial direction, so when heat is applied, the orientation of the mesogenic groups decreases and shrinks in the orientation direction, and by removing heat, the orientation of the mesogenic groups increases. Characteristic response behavior of extending in the orientation direction.

  The liquid crystalline compound of the present invention is obtained by adding alkylene oxide and / or styrene oxide to a mesogen group-containing compound having an active hydrogen group.

（式中、Ｘは活性水素基であり、Ｒ_１は単結合、−Ｎ＝Ｎ−、−ＣＯ−、−ＣＯ−Ｏ−、又は−ＣＨ＝Ｎ−であり、Ｒ_２は単結合、又は−Ｏ−であり、Ｒ_３は単結合、又は炭素数１〜２０のアルキレン基である。ただし、Ｒ_２が−Ｏ−であり、かつＲ_３が単結合である場合を除く。） The mesogenic group-containing compound having an active hydrogen group is not particularly limited as long as it is a compound having an active hydrogen group and a mesogenic group, but is preferably a compound represented by the following general formula (1).

(Wherein X is an active hydrogen group, R ₁ is a single bond, —N═N—, —CO—, —CO—O—, or —CH═N—, and R ₂ is a single bond, or -O- and R ₃ is a single bond or an alkylene group having 1 to 20 carbon atoms, except when R ₂ is -O- and R ₃ is a single bond.

Examples of X include OH, SH, NH ₂ , COOH, and secondary amine.

In order to obtain a thermoresponsive material having a transition temperature (Ti) from the liquid crystal phase to the isotropic phase or from the isotropic phase to the liquid crystal phase, 0 to 100 ° C., the biphenyl skeleton (R ₁ is a single bond) It is preferable to use a compound. Further, when _{R 3} is an alkylene group, it is preferred that 2 to 10 carbon atoms.

  The alkylene oxide to be added is not particularly limited, and examples thereof include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, and allyl. Examples thereof include glycidyl ether. The styrene oxide to be added may have a substituent such as an alkyl group, an alkoxyl group, or a halogen on the benzene ring.

  In order to obtain a thermoresponsive material having a transition temperature (Ti) from the liquid crystal phase to the isotropic phase or from the isotropic phase to the liquid crystal phase, 0 to 100 ° C., ethylene oxide, propylene oxide, 1,2-butylene oxide 1, at least one oxide selected from the group consisting of 2,3-butylene oxide and styrene oxide is preferably added.

  The alkylene oxide and / or styrene oxide is preferably added in an amount of 2 to 10 mol, more preferably 2 to 8 mol, per 1 mol of the compound represented by the general formula (1).

  The liquid crystalline compound preferably has a transition temperature (Ti) from a liquid crystal phase to an isotropic phase or from an isotropic phase to a liquid crystal phase of 15 to 150 ° C, more preferably 25 to 125 ° C.

  A liquid crystalline compound may be used by 1 type and may use 2 or more types together.

  The thermoresponsive material of the present invention is obtained by reacting a liquid crystal compound with a compound that reacts with an active hydrogen group of the liquid crystal compound. Examples of the compound that reacts with the active hydrogen group of the liquid crystal compound include an isocyanate compound, an epoxy compound, a silanol group-containing compound, a halide, a carboxylic acid, and an alcohol. In particular, it is preferable to use an isocyanate compound. Hereinafter, the thermoresponsive material will be described by taking a liquid crystal polyurethane elastomer as an example.

  As the isocyanate compound which is a raw material of the liquid crystal polyurethane elastomer, a known compound in the field of polyurethane can be used without any particular limitation. For example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene Aromatic diisocyanates such as diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate 1,4-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, Cycloaliphatic diisocyanates such as Rubo Renan diisocyanate. These may be used alone or in combination of two or more.

  In order to introduce a crosslinking point into the liquid crystal polyurethane elastomer to form a network, it is preferable to use a trifunctional or higher functional isocyanate compound, and it is particularly preferable to use a trifunctional isocyanate compound in combination. Examples of the trifunctional or higher functional isocyanate compound include triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate. 1,8-diisocyanate-4-isocyanatomethyloctane, triisocyanates such as bicycloheptane triisocyanate, and tetraisocyanates such as tetraisocyanate silane. These may be used alone or in combination of two or more. Also, multimerized diisocyanate may be used. The multimerized diisocyanate is an isocyanate-modified product or a mixture thereof that has been multimerized by adding three or more diisocyanates. Examples of the modified isocyanate include 1) trimethylolpropane adduct type, 2) burette type, and 3) isocyanurate type.

  When diisocyanate and a trifunctional isocyanate compound are used in combination, the former / the latter is preferably blended at 19/1 to 1/1 (weight ratio).

  High molecular weight polyols may be used as long as the object of the present invention is not impaired. As the high molecular weight polyol, a high molecular weight polyol having 3 or more hydroxyl groups may be used in order to form a network by introducing a crosslinking point into the liquid crystal polyurethane elastomer. The number of hydroxyl groups is preferably 3. Examples of the high molecular weight polyol include polyether polyol, polyester polyol, polycarbonate polyol, and polyester polycarbonate polyol. These may be used alone or in combination of two or more.

  In addition to the high molecular weight polyol, an active hydrogen group-containing low molecular weight compound may be used as long as the object of the present invention is not impaired. The active hydrogen group-containing low molecular weight compound is a compound having a molecular weight of less than 400, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butane. Diol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene Glycol, 1,4-bis (2-hydroxyethoxy) benzene, trimethylolpropane, glycerin, 1,2,6-hexanetriol, pentaerythritol, tetramethylolcyclohexane, methylglucoside, sorbitol, mannitol, dulcitol, sucrose, 2 Low molecular weight polyols such as 2,6,6-tetrakis (hydroxymethyl) cyclohexanol, diethanolamine, N-methyldiethanolamine, and triethanolamine; low molecular weight polyamines such as ethylenediamine, tolylenediamine, diphenylmethanediamine, and diethylenetriamine; monoethanol Examples include amines, alcohol amines such as 2- (2-aminoethylamino) ethanol, and monopropanolamine. These active hydrogen group-containing low molecular weight compounds may be used alone or in combination of two or more.

  The content of the liquid crystal compound in the polyurethane raw material composition is preferably 50 to 90% by weight, more preferably 60 to 80% by weight. The polyurethane raw material composition is prepared by mixing the raw material components under solvent-free conditions.

  The liquid crystal polyurethane elastomer may be produced by a prepolymer method or a one-shot method. In addition, you may use the catalyst which accelerates | stimulates well-known urethane reactions, such as a tertiary amine type | system | group.

  The liquid crystal polyurethane elastomer is obtained by heating a polyurethane raw material composition and curing it by a urethanization reaction. Then, during the urethanization reaction, in a state where the liquid crystalline compound exhibits liquid crystallinity, the mesogenic groups of the liquid crystalline compound are aligned in a uniaxial direction and cured in a state where the mesogenic groups are aligned. The method for aligning mesogenic groups in a uniaxial direction is not particularly limited. For example, a method of performing a urethanization reaction on an alignment film, a method of aligning by applying an electric field or a magnetic field during the urethanization reaction, a method of stretching in a semi-cured state Etc.

  In the thermoresponsive material of the present invention, the transition temperature (Ti) from the liquid crystal phase to the isotropic phase or from the isotropic phase to the liquid crystal phase is preferably 0 to 100 ° C, more preferably 0 to 85 ° C. It is.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[Measurement and evaluation methods]
(Calculation of content of liquid crystal compound)
The content of the liquid crystalline compound in the polyurethane elastomer was calculated by the following formula.
Content of liquid crystal compound (% by weight) = {(weight of liquid crystal compound) / (weight of all raw material components of polyurethane elastomer)} × 100

(Measurement of transition temperature (Ti) from liquid crystal phase to isotropic phase of liquid crystalline compound and polyurethane elastomer)
Ti was measured using a differential scanning calorimeter DSC (manufactured by Hitachi High-Tech Science Co., Ltd., trade name: X-DSC 7000) at 20 ° C./min.

(Evaluation of liquid crystal properties)
The presence or absence of liquid crystallinity of the liquid crystalline compound and the polyurethane elastomer is determined by a polarizing microscope (Nikon Corporation, trade name: LV-100POL) and a differential scanning calorimeter DSC (Hitachi High-Tech Science Corporation, trade name: X-DSC 7000). ) Was evaluated under the conditions of 20 ° C./min.

(Measurement of storage elastic modulus (E ') when liquid crystal appears)
The storage elastic modulus at the time of liquid crystal expression of the polyurethane elastomer is 2 ° C./min, 2% strain, and 10 Hz using VES (manufactured by Ueshima Seisakusho Co., Ltd., trade name: fully automatic viscoelasticity analyzer VR-7110). Measured with

反応容器に４，４’−ビフェノール（ＢＨ０）１００ｇ、ＫＯＨ３．８ｇ、及びＤＭＦ６００ｍｌを入れて混合し、その後、プロピレンオキシドを４，４’−ビフェノール１モルに対して４当量添加し、加圧条件下で１２０℃で２時間反応させた。その後、シュウ酸３．０ｇを添加して付加反応を停止させ、吸引ろ過により塩を除去し、さらにＤＭＦを減圧蒸留により除去して、目的物であるメソゲンジオールＡ（構造異性体を含んでいてもよい）を得た。 Example 1
(Synthesis of mesogenic diol A which is a liquid crystal compound)

In a reaction vessel, 100 g of 4,4′-biphenol (BH0), 3.8 g of KOH, and 600 ml of DMF were mixed, and then 4 equivalents of propylene oxide was added to 1 mol of 4,4′-biphenol, and pressure conditions The reaction was carried out at 120 ° C. for 2 hours. Thereafter, 3.0 g of oxalic acid was added to stop the addition reaction, the salt was removed by suction filtration, DMF was further removed by distillation under reduced pressure, and the target mesogendiol A (containing structural isomers) was obtained. Also good).

(Synthesis of polyurethane elastomer)
2 g of mesogenic diol A, 0.92 g of hexamethylene diisocyanate, and 0.10 g of HDI isocyanurate (manufactured by Sumika Bayer Urethane Co., Ltd., Sumidur N3300) were mixed at 100 ° C. to obtain a mixture. Thereafter, the mixture was poured into a mold preheated to 100 ° C. and reacted and cured at 100 ° C. for 30 minutes to obtain a semi-cured polyurethane. After releasing from the mold, the polyurethane was stretched twice in a uniaxial direction at 20 ° C. Thereafter, the polyurethane elastomer was obtained by leaving it at 20 ° C. with the polyurethane stretched twice.

Example 2
A polyurethane elastomer was obtained in the same manner as in Example 1 except that the raw materials and blends shown in Table 1 were employed.

反応容器にＢＨ６（１００ｇ）、ＫＯＨ３．８ｇ、及びＤＭＦ６００ｍｌを入れて混合し、その後、プロピレンオキシドをＢＨ６（１モル）に対して２当量添加し、加圧条件下で１２０℃で２時間反応させた。その後、シュウ酸３．０ｇを添加して付加反応を停止させ、吸引ろ過により塩を除去し、さらにＤＭＦを減圧蒸留により除去して、目的物であるメソゲンジオールＢ（構造異性体を含んでいてもよい）を得た。 Example 3
(Synthesis of mesogenic diol B which is a liquid crystal compound)

BH6 (100 g), 3.8 g of KOH, and 600 ml of DMF are mixed in a reaction vessel, and then 2 equivalents of propylene oxide is added to BH6 (1 mol) and reacted at 120 ° C. for 2 hours under pressure. It was. Thereafter, 3.0 g of oxalic acid was added to stop the addition reaction, the salt was removed by suction filtration, DMF was further removed by distillation under reduced pressure, and the target mesogendiol B (containing structural isomers) was obtained. Also good).

(Synthesis of polyurethane elastomer)
2 g of mesogenic diol B, 0.79 g of hexamethylene diisocyanate, and 0.09 g of HDI-based isocyanurate (manufactured by Sumika Bayer Urethane Co., Ltd., Sumidur N3300) were mixed at 100 ° C. to obtain a mixture. Thereafter, the mixture was poured into a mold preheated to 100 ° C. and reacted and cured at 100 ° C. for 30 minutes to obtain a semi-cured polyurethane. After releasing from the mold, the polyurethane was stretched twice in a uniaxial direction at 20 ° C. Thereafter, the polyurethane elastomer was obtained by leaving it at 20 ° C. with the polyurethane stretched twice.

Examples 4-12
A polyurethane elastomer was obtained in the same manner as in Example 1 except that the raw materials and blends shown in Table 1 were employed. TDI in Table 1 is toluene diisocyanate, and MDI is diphenylmethane diisocyanate.

反応容器にＢＨＢＡ６（１００ｇ）、ＫＯＨ３．８ｇ、及びＤＭＦ６００ｍｌを入れて混合し、その後、プロピレンオキシドをＢＨＢＡ６（１モル）に対して４当量添加し、加圧条件下で１２０℃で２時間反応させた。その後、シュウ酸３．０ｇを添加して付加反応を停止させ、吸引ろ過により塩を除去し、さらにＤＭＦを減圧蒸留により除去して、目的物であるメソゲンジオールＣ（構造異性体を含んでいてもよい）を得た。 Example 13
(Synthesis of mesogenic diol C, a liquid crystalline compound)

BHBA6 (100 g), 3.8 g of KOH, and 600 ml of DMF are mixed in a reaction vessel, and then 4 equivalents of propylene oxide are added to BHBA6 (1 mol) and reacted at 120 ° C. for 2 hours under pressure. It was. Thereafter, 3.0 g of oxalic acid was added to stop the addition reaction, the salt was removed by suction filtration, DMF was removed by distillation under reduced pressure, and the target mesogendiol C (containing structural isomers) was obtained. Also good).

(Synthesis of polyurethane elastomer)
2 g of mesogenic diol C, 0.59 g of hexamethylene diisocyanate, and 0.07 g of HDI-based isocyanurate (manufactured by Sumika Bayer Urethane Co., Ltd., Sumidur N3300) were mixed at 100 ° C. to obtain a mixture. Thereafter, the mixture was poured into a mold preheated to 100 ° C. and reacted and cured at 100 ° C. for 30 minutes to obtain a semi-cured polyurethane. After releasing from the mold, the polyurethane was stretched twice in a uniaxial direction at 20 ° C. Thereafter, the polyurethane elastomer was obtained by leaving it at 20 ° C. with the polyurethane stretched twice.

反応容器にＢＡ６（１００ｇ）、ＫＯＨ３．８ｇ、及びＤＭＦ６００ｍｌを入れて混合し、その後、プロピレンオキシドをＢＡ６（１モル）に対して４当量添加し、加圧条件下で１２０℃で２時間反応させた。その後、シュウ酸３．０ｇを添加して付加反応を停止させ、吸引ろ過により塩を除去し、さらにＤＭＦを減圧蒸留により除去して、目的物であるメソゲンジオールＤ（構造異性体を含んでいてもよい）を得た。 Example 14
(Synthesis of mesogenic diol D, a liquid crystalline compound)

BA6 (100 g), 3.8 g of KOH, and 600 ml of DMF are mixed in a reaction vessel, and then 4 equivalents of propylene oxide are added to BA6 (1 mol) and reacted at 120 ° C. for 2 hours under pressurized conditions. It was. Thereafter, 3.0 g of oxalic acid was added to stop the addition reaction, the salt was removed by suction filtration, DMF was removed by distillation under reduced pressure, and the target mesogendiol D (containing structural isomers) was obtained. Also good).

(Synthesis of polyurethane elastomer)
2 g of mesogenic diol D, 0.59 g of hexamethylene diisocyanate, and 0.07 g of HDI-based isocyanurate (manufactured by Sumika Bayer Urethane Co., Ltd., Sumidur N3300) were mixed at 100 ° C. to obtain a mixture. Thereafter, the mixture was poured into a mold preheated to 100 ° C. and reacted and cured at 100 ° C. for 30 minutes to obtain a semi-cured polyurethane. After releasing from the mold, the polyurethane was stretched twice in a uniaxial direction at 20 ° C. Thereafter, the polyurethane elastomer was obtained by leaving it at 20 ° C. with the polyurethane stretched twice.

Comparative Examples 1-6
An attempt was made to produce a polyurethane elastomer by the same method as in Example 1 using the raw materials shown in Table 1, but the polyurethane elastomer could not be produced without a solvent because the Ti of the mesogenic diol was high. In Table 1, BH3 to 5 and BH11 are the following compounds.
BH3: Compound BH4 in the general formula (1), wherein X is OH, R ₁ is a single bond, R ₂ is —O—, and R ₃ is an alkylene group having 3 carbon atoms. In the general formula (1), X is OH , R ₁ is a single bond, R ₂ is —O—, and R ₃ is a C 4 alkylene group. In general formula (1), X is OH, R ₁ is a single bond, and R ₂ is —O. -, Compound BH11 in which R ₃ is an alkylene group having 5 carbon atoms: In general formula (1), X is OH, R ₁ is a single bond, R ₂ is -O-, and R ₃ is an alkylene group having 11 carbon atoms. A compound

  The heat-responsive material of the present invention exhibits a characteristic response behavior that when the degree of alignment of the liquid crystal is decreased by applying heat, the liquid crystal shrinks in the alignment direction, and when the degree of alignment of the liquid crystal is increased by removing heat, the liquid crystal expands. It can be applied to various fields such as actuators.

Claims (13)

A liquid crystal compound obtained by adding alkylene oxide and / or styrene oxide to a mesogen group-containing compound having an active hydrogen group. The liquid crystalline compound according to claim 1, wherein the mesogenic group-containing compound is a compound represented by the following general formula (1).

(Wherein X is an active hydrogen group, R ₁ is a single bond, —N═N—, —CO—, —CO—O—, or —CH═N—, and R ₂ is a single bond, or -O- and R ₃ is a single bond or an alkylene group having 1 to 20 carbon atoms, except when R ₂ is -O- and R ₃ is a single bond. 2. The liquid crystal compound according to claim 1, wherein the alkylene oxide is at least one selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide. The liquid crystalline compound according to any one of claims 1 to 3, wherein 2 to 10 mol of alkylene oxide and / or styrene oxide is added to 1 mol of the compound represented by the general formula (1). The heat-responsive material obtained by making the liquid crystalline compound in any one of Claims 1-4 react with the compound which reacts with the active hydrogen group of the said liquid crystalline compound. The thermoresponsive material according to claim 5, comprising 50 to 90% by weight of a liquid crystal compound as a raw material. The heat-responsive material according to claim 5 or 6, wherein a transition temperature from the liquid crystal phase to the isotropic phase or from the isotropic phase to the liquid crystal phase is 0 to 100 ° C. Step A to obtain a liquid crystalline compound by adding alkylene oxide and / or styrene oxide to a mesogenic group-containing compound having an active hydrogen group, reaction with the active hydrogen group of the liquid crystalline compound and the liquid crystalline compound under solvent-free conditions A process for producing a thermoresponsive material, comprising: a step B of mixing a compound to be obtained to obtain a raw material composition for a thermoresponsive material; and a step C of curing the raw material composition for the thermoresponsive material at a temperature at which liquid crystallinity develops. . The method for producing a thermoresponsive material according to claim 8, wherein the mesogen group-containing compound is a compound represented by the following general formula (1).

(Wherein X is an active hydrogen group, R ₁ is a single bond, —N═N—, —CO—, —CO—O—, or —CH═N—, and R ₂ is a single bond, or -O- and R ₃ is a single bond or an alkylene group having 1 to 20 carbon atoms, except when R ₂ is -O- and R ₃ is a single bond. The method for producing a thermoresponsive material according to claim 8 or 9, wherein the alkylene oxide is at least one selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide. The method for producing a thermoresponsive material according to any one of claims 8 to 10, wherein 2 to 10 moles of alkylene oxide and / or styrene oxide are added to 1 mole of the compound represented by the general formula (1). . The method for producing a thermoresponsive material according to any one of claims 8 to 11, wherein the content of the liquid crystal compound in the raw material composition for the thermoresponsive material is 50 to 90 wt%. The process for producing a thermoresponsive material according to any one of claims 8 to 12, wherein in step C, the mesogenic group of the liquid crystalline compound is aligned while curing the raw material composition for the thermoresponsive material at a temperature at which the liquid crystallinity develops. .