Liquid-crystal compound, thermally responsive material, and production method therefor

Abstract

One purpose of the present invention is to provide a liquid-crystal compound which exhibits liquid crystallinity at low temperatures. Another purpose of the present invention is to provide a thermally responsive material which exhibits liquid crystallinity and rubber elasticity at low temperatures (around room temperature) ever, though a large amount of a liquid-crystal compound is contained therein, and a method for producing this thermally responsive material. A liquid-crystal compound according to the present invention is obtained by adding an alkylene oxide and/or styrene oxide to a mesogenic group-containing compound that has an active hydrogen group.

Claims

1. A liquid-crystal compound obtained by adding an alkylene oxide and/or styrene oxide to a mesogenic group-containing compound represented by a general formula (1) below: ##STR00008## wherein X is an active hydrogen group; R.sub.1 is a single bond, NN, CO, COO, or CHN; R.sub.2 is a single bond or O; and R.sub.3 is an alkylene group having 1 to 20 carbon atoms.

2. The liquid-crystal compound according to claim 1, wherein the alkylene oxide is at least one kind selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide.

3. The liquid-crystal compound according to claim 2, wherein 2 to 10 moles of the alkylene oxide and/or styrene oxide are added to 1 mole of the compound represented by the general formula (1).

4. A thermally responsive material obtained by reacting the liquid-crystal compound according to claim 1 with a compound that reacts with an active hydrogen group of the liquid-crystal compound.

5. The thermally responsive material according to claim 4, comprising 50 to 90% by weight of the liquid-crystal compound as a raw material.

6. The thermally responsive material according to claim 4, wherein a transition temperature from a liquid-crystal phase to an isotropic phase or from an isotropic phase to a liquid-crystal phase is from 0 to 100 C.

7. A thermally responsive material obtained by reacting the liquid-crystal compound according to claim 1 with a compound that reacts with an active hydrogen group of the liquid-crystal compound.

8. The thermally responsive material according to claim 7, comprising 50 to 90% by weight of the liquid-crystal compound as a raw material.

9. The thermally responsive material according to claim 7, wherein a transition temperature from a liquid-crystal phase to an isotropic phase or from an isotropic phase to a liquid-crystal phase is from 0 to 100 C.

Description

MODE FOR CARRYING OUT THE INVENTION

(1) The liquid-crystal compound of the present invention is a compound obtained by adding an alkylene oxide and/or styrene oxide to a mesogenic group-containing compound having an active hydrogen group.

(2) 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 said mesogenic group-containing compound is preferably a compound represented by the following general formula (1):

(3) ##STR00003##
wherein X is an active hydrogen group; R.sub.1 is a single bond, NN, CO, COO, or CHN; R.sub.2 is a signle bond or O; and R.sub.3 is a single bond or an alkylene group having 1 to 20 carbon atoms, provided that the compound when R.sub.2 is O and R.sub.3 is a single bond is excluded.

(4) Examples of X include OH, SH, NH.sub.2, COOH, secondary amines, and the like.

(5) In order to obtain a thermally responsive material having a transition temperature (Ti) of 0 to 100 C. from a liquid-crystal phase to an isotropic phase or from the isotropic phase to the liquid-crystal phase, it is preferable to use a compound having a biphenyl skeleton (R.sub.1 is a single bond). When R.sub.3 is an alkylene group, the number of carbon atoms is preferably 2 to 10.

(6) 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, allyl glycidyl ether, and the like. 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.

(7) In order to obtain a thermally responsive material having a transition temperature (Ti) of 0 to 100 C. at which phase transition from a liquid-crystal phase to an isotropic phase or from the isotropic phase to the liquid-crystal phase occurs, it is preferable to use at least one oxide selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and styrene oxide.

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

(9) The transition temperature (Ti) from a liquid-crystal phase to an isotropic phase or from the isotropic phase to the liquid-crystal phase of the liquid-crystal compound is preferably from 15 to 150 C., more preferably from 25 to 125 C.

(10) The liquid-crystal compound may be used singly or in combination of two or more thereof.

(11) The thermally responsive material of the present invention is a material obtained by reacting the 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, an alcohol, and the like. In particular, it is preferable to use an isocyanate compound. Hereinafter, the thermally responsive material will be described by exemplifying a liquid-crystal polyurethane elastomer.

(12) The known compounds in the field of polyurethanes can be used as the isocyanate compound which is a raw material of a liquid-crystal polyurethane elastomer without any particular limitation. The isocyanate compounds include, for example, aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2-diphenyl methane diisocyanate, 2,4-diphenyl methane diisocyanate, 4,4-diphenyl methane diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate and m-xylylene diisocyanate, aliphatic diisocyanates such as ethylene diisocyanate, 2,2,4-trimethyl hexamethylene di isocyanate and 1,6-hexamethylene diisocyanate, and cycloaliphatic diisocyanates such as 1,4-cyclohexane diisocyanate, 4,4-dicyclohexyl methane diisocyanate, isophorone diisocyanate and norbornane diisocyanate. These may be used alone or as a mixture of two or more thereof.

(13) In order to introduce a crosslinking point into the liquid-crystal polyurethane elastomer to form a network, it is preferable to use a tri- or more functional isocyanate compound in combination, and it is particularly preferable to use a trifunctional isocyanate compound in combination. The isocyanate compounds having a functionality of 3 or more include, for example, triisocyanates (e.g., triphenylmethane triisocyanate, tris(isocyanatephenyl)thio-phosphate, lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, and bicycloheptane triisocyanate) and tetraisocyanates (e.g., tetraisocyanate silane). These may be used alone or in combination of two or more thereof. It may also be possible to use a polymerized diisocyanate. As used herein, the term polymerized diisocyanate refers to any of polymerized isocyanate derivatives produced by addition of three or more molecules of diisocyanate, or refers to a mixture of the isocyanate derivatives. For example, the isocyanate derivative may be of (1) trimethylolpropane adduct type, (2) biuret type, (3) isocyanurate type, or the like.

(14) When the diisocyanate and the trifunctional isocyanate compound are used in combination, it is preferable to blend the former/the latter at a ratio of 19/1 to 1/1 (weight ratio).

(15) A high molecular weight polyoi 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 introduce a crosslinking point into the liquid-crystal polyurethane elastomer to form a network. The number of hydroxyl groups is preferably 3. Examples of the high molecular weight polyol include polyether polyol, polyester polyol, polycarbonate polyol, polyester polycarbonate polyol, and the like. These may be used singly, or two or more of them may be used in combination.

(16) 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, and examples thereof include low molecular weight polyols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 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, glycerol, 1,2,6-hexanetriol, pentaerythritol, tetramethyiolcyclohexane, methyl glucoside, sorbitol, mannitol, dulcitol, sucrose, 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol, diethanolamine, N-methyldiethanolamine, and triethanolamine; low molecular weight polyaraines such as ethylenediamine, tolylenediamine, diphenylmethanediamine, and diethylenetriamine; alcohol amines such as monoethanolamine, 2-(2-aminoethylamino)ethanol, and monopropanolamine. These active hydrogen group-containing low molecular weight compounds may be used singly, or two or more of them may be used in combination.

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

(18) The liquid-crystal polyurethane elastomer may be produced by a prepolymer method or may be produced by a one-shot method. Incidentally, a catalyst promoting a known urethane reaction, such as tertiary amine type catalyst, may be used.

(19) The liquid-crystal polyurethane elastomer is obtained by heating a polyurethane raw material composition and curing the composition by urethanication reaction. Then, during the urethanization reaction, the mesogenic groups of the liquid-crystal compound are oriented in a uniaxial direction while the liquid-crystal compound exhibits liquid crystallinity, and the composition is cured with the mesogenic group being in an oriented state. There is no particular limitation on the method of orienting the mesogenic group in the uniaxial direction, and examples of such a method include a method of performing the urethanization reaction on the oriented film, a method of orientation by applying an electric or magnetic field at the time of urethanization reaction, a method of stretching in the semi-cured state.

(20) The transition temperature (Ti) from a liquid-crystal phase to an isotropic phase or from the isotropic phase to the liquid-crystal phase of the thermally responsive material of the present invention is preferably from 0 to 100 C., more preferably from 0 to 85 C.

EXAMPLES

(21) Description will be given of the invention with examples, while the invention is not limited to description in the examples.

(22) [Measurement and Evaluation Method]

(23) (Calculation of Content of Liquid-Crystal Compound)

(24) The content of the liquid-crystal compound in the polyurethane elastomer was calculated by the following expression.
Content (% by weight) of liquid-crystal compound={(Weight of liquid-crystal compound)/(Weight of all raw material components of polyurethane elastomer)}100

(25) (Measurement of (Liquid-Crystal Phase)-to-(Isotropic Phase) Transition Temperature (Ti) of Liquid-crystal Compound and Polyurethane Elastomer)

(26) The Ti was measured under the condition of 20 C./min using a differential scanning calorimeter DSC (manufactured by Hitachi High-Tech science Corp., trade name: X-DSC 7000).

(27) (Evaluation of Liquid Crystallinity)

(28) The presence or absence of liquid crystallinity of the liquid-crystal compound and polyurethane elastomer were evaluated by using a polarization microscope (manufactured by Nikon Corporation, trade name: LV-100POL) and a differential scanning calorimeter DSC (manufactured by Hitachi High-Tech Science Corp., trade name: X-DSC 7000) under the condition of 20 C./min.

(29) (Measurement of Storage Elastic Modulus (E) when Liquid Crystallinity is Exhibited)

(30) The storage elastic modulus of the polyurethane elastomer when the liquid crystallinity is exhibited was measured under conditions of 2 C./min, strain 2%, and 10 Hz using a VES (trade name: Full Automatic Viscoelasticity Analyzer VR-7110, manufactured by Ueshima Seisakusho Co., Ltd.).

Example 1

Synthesis of Mesogenic Diol A, Liquid-Crystal Compound

(31) ##STR00004##

(32) To a reaction vessel were added 100 g of 4,4-biphenol (BHO), 3.8 g of KOH and 600 ml of DMF, and then 4 equivalents of propylene oxide was added thereto relative to 1 mole of 4,4-biphenol. The resulting mixture was allowed to react at 120 C. for 2 hours. Subsequently, 3.0 g of oxalic acid was added to the reaction solution to stop the addition reaction. After removal of the salt by suction filtration, the filtrate was evaporated under reduced pressure to remove the DMF, thereby obtaining a mesogenic diol A (which may contain a structural isomer).

(33) (Synthesis of Polyurethane Elastomer)

(34) A mixture was obtained from 2 g of mesogenic did A, 0.92 g of hexamethylene diisocyanate, and 0.10 g of HDI type isocyanurate (Sumidur N3300, manufactured by Sumika Bayer Urethane Co., Ltd.) by mixing them at 100 C. Thereafter, the mixture was poured into a mold preheated to 100 C. and was reacted to cure at 100 C. for 30 minutes to obtain a semi-cured polyurethane. After releasing the semi-cured polyurethane from the mold, the polyurethane was elongated twice in the uniaxial direction at 20 C. Thereafter, a polyurethane elastomer was obtained by allowing the polyurethane to stand at 20 C. until it was cured while maintaining the state of being twice elongated.

Example 2

(35) A polyurethane elastomer was obtained in the same manner as in Example 1 except that the raw materials and compositions shown in Table 1 were employed.

Example 3

Synthesis of Mesogenic Diol B, Liquid-Crystal Compound

(36) ##STR00005##

(37) To a reaction vessel were added 100 g of BH6, 3.8 g of KCH and 600 ml of DMF, and then 2 equivalents of propylene oxide was added thereto relative to 1 mole of BH6. The resulting mixture was allowed to react at 120 C. for 2 hours under pressure. Subsequently, 3.0 g of oxalic acid was added to the reaction solution to stop the addition reaction. After removal of the salt by suction filtration, the filtrate was evaporated under reduced pressure to remove the DMF, thereby obtaining a mesogenic diol B (which may contain a structural isomer).

(38) (Synthesis of Polyurethane Elastomer)

(39) A mixture was obtained from 2 g of mesogenic diol B, 0.79 g of hexamethyiene diisocyanate, and 0.09 g of HDI type isocyanurate (sumidur N3300, manufactured by sumika Bayer Urethane Co., Ltd.) by mixing them at 100 C. Thereafter, the mixture was poured into a mold preheated to 100 C. and was reacted to cure at 100 C. for 30 minutes to obtain a semi-cured polyurethane. After releasing the semi-cured polyurethane from the mold, the polyurethane was elongated twice in the uniaxial direction at 20 C. Thereafter, a polyurethane elastomer was obtained by allowing the polyurethane to stand at 20 C. until it was cured while maintaining the state of being twice elongated.

Examples 4 to 12

(40) A polyurethane elastomer was obtained in the same manner as in Example 1 except that the raw materials and compositions shown in Table 1 were employed. In Table 1, TDI is toluene diisocyanate and MDI is diphenyl methane diisocyanate.

Example 13

Synthesis of Mesogenic Diol C, Liquid-Crystal Compound

(41) ##STR00006##

(42) To a reaction vessel were added 100 g of BHBA6, 3.8 g of KOH and 600 ml of DMF, and then 4 equivalents of propylene oxide was added thereto relative to 1 mole of BHBA6. The resulting mixture was allowed to react at 120 C. for 2 hours under pressure. Subsequently, 3.0 g of oxalic acid was added to the reaction solution to stop the addition reaction. After removal of the salt by suction filtration, the filtrate was evaporated under reduced pressure to remove the DMF, thereby obtaining a mesogenic diol C (which may contain a structural isomer).

(43) (Synthesis of Polyurethane Elastomer)

(44) A mixture was obtained from 2 g of mesogenic diol C, 0.59 g of hexamethyiene diisocyanate, and 0.07 g of HDI type isocyanurate (Sumidur N3300, manufactured by Sumika Bayer Urethane Co., Ltd.) by mixing them at 100 C. Thereafter, the mixture was poured into a mold preheated to 100 C. and was reacted to cure at 100 C. for 30 minutes to obtain a semi-cured polyurethane. After releasing the semi-cured polyurethane from the mold, the polyurethane was elongated twice in the uniaxial direction at 20 C. Thereafter, a polyurethane elastomer was obtained by allowing the polyurethane to stand at 20 C. until it was cured while maintaining the state of being twice elongated.

Example 14

Synthesis of Mesogenic Diol D, Liquid-Crystal Compound

(45) ##STR00007##

(46) To a reaction vessel were added 100 g of BA6, 3.8 g of KOH and 600 ml of DMF, and then 4 equivalents of propylene oxide was added thereto relative to 1 mole of BA6. The resulting mixture was allowed to react at 120 C. for 2 hours under pressure. Subsequently, 3.0 g of oxalic acid was added to the reaction solution to stop the addition reaction. After removal of the salt by suction filtration, the filtrate was evaporated under reduced pressure to remove the DMF, thereby obtaining a mesogenic diol D (which may contain a structural isomer).

(47) (Synthesis of Polyurethane Elastomer)

(48) A mixture was obtained from 2 g of mesogenic diol D, 0.59 g of hexamethyiene diisocyanate, and 0.07 g of HDI type isocyanurate (Sumidur N3300, manufactured by Sumika Bayer Urethane Co., Ltd.) by mixing them at 100 C. Thereafter, the mixture was poured into a mold preheated to 100 C. and was reacted to cure at 100 C. for 30 minutes to obtain a semi-cured polyurethane. After releasing the semi-cured polyurethane from the mold, the polyurethane was elongated twice in the uniaxial direction at 20 C. Thereafter, a polyurethane elastomer was obtained by allowing the polyurethane to stand at 20 C. until it was cured while maintaining the state of being twice elongated.

Comparative Examples 1 to 6

(49) An attempt was made to prepare a polyurethane elastomer by using the raw materials shown in Table 1 in the same manner as in Example 1, but a polyurethane elastomer could not be prepared in the absence of a solvent since Ti of the mesogenic diol was high. BH3 to BH5 to BH11 in Table 1 are the following compounds.

(50) BH3: a compound in which X is OH, R.sub.1 is a single bond, R.sub.2 is O, and R.sub.3 is an alkylene group having 3 carbon atoms in the general formula (1).

(51) BH4: a compound in which X is OH, R.sub.1 is a single bond, R.sub.2 is O, and R.sub.3 is an alkylene group having 4 carbon atoms in the general formula (1).

(52) BH5: a compound in which X is OH, R.sub.1 is a single bond, R.sub.2 is O, and R.sub.3 is an alkylene group having 5 carbon atoms in the general formula (1).

(53) BH11: a compound in which X is OH, R.sub.1 is a single bond, R.sub.2 is O, and R.sub.3 is an alkylene group having 11 carbon atoms in the general formula (1).

(54) TABLE-US-00001 TABLE 1 Polyurethane elastomer Storage Composition of modulus Content Mesoogenic diol raw material during of Equivalent Meso- exhibiting meso- Meso- Kind of Liquid genic Diiso- Liquid liquid genic genic of addition Ti crystal- diol cyanate N3300 Ti crystal- crystallinity diol structure oxide oxide ( C.) linity (g) (g) (g) ( C.) linity (MPa) (%) Example 1 BH0 Propylene 4 73 Yes 2 HDI (0.92) 0.1 35 Yes 1-100 66 oxide Example 2 BH0 Ethylene 2 145 Yes 2 HDI (1.24) 0.14 70 Yes 1-100 69 oxide Example 3 BH6 Propylene 2 102 Yes 2 HDI (0.79) 0.09 67 Yes 1-100 69 oxide Example 4 BH6 Propylene 4 81 Yes 2 HDI (0.69) 0.08 44 Yes 1-100 72 oxide Example 5 BH6 Propylene 4 81 Yes 2 TDI (0.71) 0.08 54 Yes 1-100 72 oxide Example 6 BH6 Propylene 4 81 Yes 2 MDI (1) 0.11 56 Yes 1-100 64 oxide Example 7 BH6 Propylene 6 63 Yes 2 HDI (0.53) 0.06 33 Yes 0.1-10 77 oxide Example 8 BH6 Propylene 6 63 Yes 2 TDI (0.5) 0.06 36 Yes 0.1-10 78 oxide Example 9 BH6 Propylene 8 43 Yes 2 HDI (0.48) 0.05 21 Yes 0.01-1 79 oxide Example 10 BH6 Propylene 8 43 Yes 2 TDI (0.5) 0.06 28 Yes 0.01-1 76 oxide Example 11 BH6 Butylene 5 76 Yes 2 HDI (0.52) 0.06 19 Yes 1-100 78 oxide Example 12 BH6 Styrene 2 125 Yes 2 HDI (0.62) 0.07 75 Yes 1-100 74 oxide Example 13 BHBA6 Propylene 4 72 Yes 2 HDI (0.59) 0.07 38 Yes 1-100 75 oxide Example 14 BA6 Propylene 4 76 Yes 2 HDI (0.59) 0.07 42 Yes 1-100 75 oxide Comparative BH0 None Example 1 Comparative BH3 208 Yes Example 2 Comparative BH4 189 Yes Example 3 Comparative BH5 170 Yes Example 4 Comparative BH6 172 Yes Example 5 Comparative BH11 160 Yes Example 6

INDUSTRIAL APPLICABILITY

(55) Since the thermally responsive material of the present invention exhibits a characteristic response behavior of shrinking in the orientation direction when reducing the orientation degree of the liquid-crystal by applying heat and elongating in the orientation direction when removing the heat to increase the orientation degree of the liquid-crystal, the thermally responsive material can be applied to various fields such as actuators and the like.