JP2013258834A - Actuator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an actuator capable of greatly deforming in a low voltage.SOLUTION: An actuator includes a first deformation material layer 11, a second deformation material layer 12, and an intermediate layer 13 provided between the first deformation material layer 11 and the second deformation material layer 12. The first deformation material layer 11 includes a first deformation material containing a first stimulation responsiveness chemical compound which changes its molecule structure by an oxidation reduction reaction. The second deformation material layer 12 includes a second deformation material containing a second stimulation responsiveness chemical compound which changes its molecule structure by an oxidation reduction reaction. The first stimulation responsiveness chemical compound and/or the second stimulation responsiveness chemical compound is a polymer constituted by polymerization of constitutional units each having a polymerizable functional group. The intermediate layer 13 includes an ion exchanger which exchanges anions.

Description

  The present invention relates to an actuator.

In recent years, the need for small actuators has increased in the medical field, the micromachine field, and the like.
Such a small actuator is required to be small and to be driven at a low voltage. Various attempts have been made to achieve such a low voltage (see, for example, Patent Document 1).
However, in the conventional actuator, the driving voltage cannot be made sufficiently low, and a high voltage is required for deformation. Further, in the conventional actuator, it is difficult to make the deformation amount (displacement amount) sufficiently large.

JP 2005-224027 A

  An object of the present invention is to provide an actuator that can be largely displaced at a low voltage.

Such an object is achieved by the present invention described below.
The actuator of the present invention includes a first deformable material layer,
A second deformable material layer;
An intermediate layer provided between the first deformable material layer and the second deformable material layer;
The first deformable material layer includes a first deformable material including a first stimulus-responsive compound whose molecular structure is changed by a redox reaction,
The second deformable material layer includes a second deformable material including a second stimulus-responsive compound whose molecular structure is changed by a redox reaction,
The first stimulus responsive compound and / or the second stimulus responsive compound is a polymer in which a structural unit having a polymerizable functional group is polymerized,
The intermediate layer includes an ion exchanger that exchanges anions.
Thereby, it is possible to provide an actuator that can be largely displaced at a low voltage.

In the actuator of the present invention, the deformable material is preferably a gel.
Thereby, the deformable material which deforms more flexibly and operates smoothly can be obtained. In addition, the shape stability and handleability as a deformable material (actuator) are particularly excellent.
In the actuator according to the aspect of the invention, it is preferable that the first deformable material layer and / or the second deformable material layer include an electron conductive substance.
Thereby, the actuator which can be displaced more largely with a low voltage can be provided.

In the actuator according to the aspect of the invention, it is preferable that the electronic conductive material contains carbon.
Thereby, the electron transport function is improved, and the deformable material (actuator) can be greatly displaced at a relatively low voltage.
In the actuator according to the aspect of the invention, it is preferable that the electron conductive substance is a particle.
As a result, the electron conductive substance can be uniformly dispersed throughout the deformable material, and the transport of electrons in the deformable material can be suitably performed.

In the actuator of the present invention, it is preferable that the average particle diameter of the electron conductive material is 1 nm or more and 10 μm or less.
Thereby, the transport of electrons in the deformable material can be suitably performed, and the electron supply efficiency to the stimulus-responsive compound can be made particularly excellent.
In the actuator according to the aspect of the invention, it is preferable that the structural unit includes a functional group having liquid crystallinity.
Thereby, the response speed of a structural unit can be improved more effectively, and the response speed of the stimulus-responsive compound (deformation material, actuator) formed by polymerizing the structural unit can be made particularly excellent. Further, it is possible to more suitably amplify the displacement of the deformable material (actuator) that accompanies the expansion and contraction of the stimulus-responsive compound composed of the structural unit.

In the actuator according to the aspect of the invention, it is preferable that the structural unit is a unit in which the functional group having liquid crystallinity and the polymerizable functional group are arranged via a linking group.
Thereby, when the group which has liquid crystallinity aligns, it can suppress that each group which has liquid crystallinity becomes obstruction. As a result, since the movement performance when the group having liquid crystallinity is aligned can be made higher, the movement speed of the stimulus-responsive compound (deformable material, actuator) obtained by polymerizing the structural unit becomes faster. .
In the actuator of the present invention, it is preferable that the structural unit includes a polyalkylene oxide structure in which an alkylene oxide having 2 and / or 3 carbon atoms is polymerized.
Thereby, the flexibility of the deformable material and the operability in the low temperature region can be further improved. In addition, the deformable material can be adjusted to a more optimal hardness.

In the actuator of the present invention, the structural unit includes a unit A having a coupling functioning as a rotating shaft,
A first unit B disposed at a first binding site of the unit A;
A second unit B disposed at a second binding site of the unit A;
A first unit C;
A second unit C,
The first unit B and the second unit B are combined by a reduction reaction,
It is preferable that the first unit C and the second unit C have the polymerizable functional group.
Thereby, the response speed and displacement amount of the stimulus-responsive compound (deformation material, actuator) can be made particularly excellent.

In the actuator of the present invention, the unit C preferably has a functional group having liquid crystallinity.
Thereby, the response speed of the stimulus-responsive compound (deformable material) can be improved more effectively. In addition, the displacement of the entire deformable material accompanying the expansion and contraction of the stimulus responsive compound can be further suitably amplified, and the displacement amount of the entire actuator can be further increased. Further, the actuator can be deformed at a lower voltage.

In the actuator of the present invention, the deformable material is further one or two selected from the group consisting of vinylidene fluoride-hexafluoropropylene copolymer, poly (meth) methyl acrylate, and an organic electrolyte oligomer. It is preferable that the above is included.
Thereby, the whole deformation | transformation material can be adjusted to more optimal hardness. Further, the deformable material (actuator) can be deformed more flexibly and operate smoothly. In addition, in the deformable material in the gel state, since the holding power of the solvent (liquid component) can be made particularly excellent, it is possible to more effectively prevent the volume of the deformable material from decreasing unintentionally over time. .

In the actuator of the present invention, the ion exchanger is preferably composed of an anion exchange resin and / or a both ion exchange resin.
Thereby, the whole actuator can be deformed more flexibly and operated smoothly.
In the actuator of the present invention, the ion exchanger preferably has a quaternary ammonium group.
Thereby, the deformation amount of the actuator can be increased.
In the actuator of the present invention, it is preferable that the first deformable material layer and / or the second deformable material layer have an electrolyte.
Thereby, the expansion / contraction rate as the whole actuator can be made especially large.

It is sectional drawing which shows typically suitable embodiment of the actuator of this invention. It is sectional drawing which shows typically suitable embodiment of the actuator of this invention. It is a figure for demonstrating the structure before and behind the oxidation-reduction reaction of the structural unit of the stimulus responsive compound which comprises the actuator of this invention. It is a figure for demonstrating the molecular structure before and behind the oxidation reduction reaction of the stimulus responsive compound which comprises the actuator of this invention. It is a figure for demonstrating the structure before and behind the oxidation-reduction reaction of the structural unit of the stimulus responsive compound which comprises the actuator of this invention. It is a figure for demonstrating the molecular structure before and behind the oxidation reduction reaction of the stimulus responsive compound which comprises the actuator of this invention. It is sectional drawing which shows typically the behavior of the anion and solvent which comprise the actuator of this invention.

Hereinafter, preferred embodiments of the present invention will be described in detail.
1 and 2 are cross-sectional views schematically showing a preferred embodiment of the actuator of the present invention.
As shown in FIGS. 1 and 2, the actuator 100 according to the present embodiment includes a first deformable material layer 11, a second deformable material layer 12, a first deformable material layer 11, and a second deformable material layer. And an intermediate layer 13 provided therebetween. The drive device 200 includes an actuator 100, a DC power supply 10, and a switch 14 that selects energization / disconnection of the actuator 100. The actuator 100 is connected to the power supply 10 via the switch 14. It is connected.

In the configuration shown in FIG. 1, the first deformable material layer 11 is connected to the positive electrode of the power source 10 via the switch 14, and the second deformable material layer 12 is connected to the negative electrode of the power source 10. . On the other hand, in the configuration shown in FIG. 2, the first deformable material layer 11 is connected to the negative electrode of the power supply 10 via the switch 14, and the second deformable material layer 12 is connected to the positive electrode of the power supply 10. ing.
The first deformable material layer 11 and the second deformable material layer 12 are both composed of a deformable material containing a stimulus-responsive compound that changes its molecular structure by an oxidation-reduction reaction.
The intermediate layer 13 has a function of exchanging anions.

Hereinafter, the configuration of the actuator 100 will be described in detail.
As shown in FIGS. 1 and 2, the actuator 100 according to the present embodiment includes a first deformable material layer 11, a second deformable material layer 12, a first deformable material layer 11, and a second deformable material layer. 12 and an intermediate layer 13 provided in contact therewith.
≪First deformation material layer≫
First, the first deformable material layer will be described.
The first deformable material layer 11 is made of a material containing a stimulus responsive compound. Furthermore, the first deformable material layer 11 may contain an electrolyte, an electronic conductive material, a solvent, a gelling agent, a liquid crystal polymer, and the like.

  The first deformable material layer 11 may be in any form such as solid, gel (semi-solid), liquid, etc., but is in the form of a gel (semi-solid). Is preferred. Thereby, while being excellent in the handleability (easiness of handling) of a deformable material, the application range of a deformable material can be expanded. In addition, it is possible to provide the actuator 100 that is flexibly deformed and operates smoothly.

Hereinafter, each component constituting the first deformable material will be described in detail.
<Stimulus responsive compound>
First, the stimulus-responsive compound will be described.
3 and 5 are diagrams for explaining the structure before and after the oxidation-reduction reaction of the structural unit of the stimulus-responsive compound constituting the actuator of the present invention. 4 and 6 are diagrams for explaining the molecular structure before and after the oxidation-reduction reaction of the stimulus-responsive compound constituting the actuator. 3 and 4 show a stimulus-responsive compound having no unit D, which will be described in detail later, and FIGS. 5 and 6 show a stimulus-responsive compound having a unit D, which will be described in detail later. FIG. 5 corresponds to FIG. 3, and FIG. 6 corresponds to FIG. 3, 4, 5, and 6, ◯ means a functional group (atomic group), and a line means a bond.

A stimulus-responsive compound is a compound having a function of deforming (displacement) the three-dimensional structure of a molecule by stimulation, in other words, a function of expanding and contracting a molecular chain.
In the present invention, the stimulus-responsive compound is a compound in which the three-dimensional structure of a molecule is changed by an oxidation-reduction reaction, and the stimulus-responsive compound is a polymer obtained by polymerizing structural units having a polymerizable functional group. This can greatly displace the entire deformable material with a relatively low voltage. As a result, for example, the actuator can obtain a sufficiently large displacement force and displacement amount at a low voltage. In addition, the response speed of the actuator can be made excellent, and the reproducibility of deformation is also excellent. In addition, the weight of the actuator can be reduced.

[Unit]
The structural unit constituting the stimulus-responsive compound has a function in which the three-dimensional structure of the molecule changes due to the oxidation-reduction reaction, and the molecular chain expands and contracts. Thereby, the stimulus responsive compound as a polymer obtained by polymerizing the structural units can increase the degree of deformation (change rate). Further, the displacement amount of the actuator 100 as a whole can be made particularly large.

  The structural unit shown in FIG. 3A and the like includes a unit A having a bond that functions as a rotation axis, and two units B (bonded to both ends (first binding site and second binding site) of unit A ( A first unit B and a second unit B), and two units C (a first unit C and a second unit C). Is bonded by an oxidation-reduction reaction, and the first unit C and the second unit C are functional groups having liquid crystallinity. Thereby, the response speed and displacement of the stimulus-responsive compound (deformable material, actuator 100) can be made particularly excellent.

Hereinafter, a structural unit as shown in FIG. 3 will be mainly described.
The unit A that constitutes the structural unit is a group (unit) that has a bond that functions as a rotation axis and is rotatable about the bond. By having such a unit, the stimulus-responsive compound can be deformed (displaced).
As the unit A, for example, a group in which two aromatic rings are bonded can be used. Among them, one type selected from the group consisting of the following formula (1), the following formula (2), and the following formula (3) is used. It is preferable that Thereby, the structural unit can be deformed (displaced) more smoothly, and the actuator 100 is driven at a lower voltage.

As shown in FIG. 3A, the unit B (the first unit B and the second unit B) has both ends in the rotation axis direction of the unit A (the first coupling site and the second coupling of the unit A). Group). That is, the first unit B is bonded to the first binding site of unit A, and the second unit B is bonded to the second binding site of unit A.
Unit B is a group that forms a bond between units B by an oxidation-reduction reaction (see FIG. 3B). In other words, it is a group that forms a bond by receiving (reducing) electrons from the outside. Further, it is a group that releases bonds by releasing (oxidizing) electrons to the outside. Such a redox reaction can be advanced by applying a voltage, for example. Further, by stopping the application of voltage, the redox reaction of the structural unit can be stopped, and as a result, the shape of the first deformable material layer 11 can be maintained.

In particular, as shown in FIG. 3, the following effects can be obtained when the structural unit is extended (expanded) and positively charged by an oxidation reaction.
That is, when the structural unit itself expands (expands), the volume of the entire first deformable material layer 11 increases, and an effect of expanding (expanding) is obtained. By electrostatically repelling each other, it is possible to obtain an effect that the volume of the entire first deformable material layer 11 increases at a rate larger than the increase rate of the volume of the molecule of the structural unit. Furthermore, when an oxidation reaction is performed, an anion (anion) derived from an electrolyte, which will be described in detail later, flows in, so the volume of the first deformable material layer 11 is the anion (for example, BF ₄ ^{− and the} like). ) Is increased by an amount corresponding to the volume. By synergistically acting these effects, the volume of the first deformable material layer 11 in which the oxidation reaction occurs can be increased particularly efficiently. On the other hand, when the reduction reaction proceeds, the structural unit itself contracts, and further, the electrostatic repulsion and the inflow of ions as described above do not occur. Therefore, the contraction of the first deformable material layer 11 occurs. The rate can be high. From the above, as shown in FIG. 3, when the structural unit expands (expands) by the oxidation reaction and is positively charged, the first deformable material layer 11 as a whole The amount of deformation of can be made large. As a result, the deformation amount of the actuator 100 as a whole can be increased, and driving at a lower voltage is possible.
The unit B (the first unit B and the second unit B) is particularly a group that forms a bond by oxidation-reduction reaction between the units B (the first unit B and the second unit B). Although not limited, the unit B (the first unit B and the second unit B) is preferably a group represented by the following formula (4). Thereby, the coupling | bonding state and the non-bonding state of units B can be reversibly advanced more easily by adjusting reaction conditions. Moreover, since the reactivity is high, the structural unit can be deformed more smoothly and at a lower voltage.

  Unit C (first unit C and second unit C) has a polymerizable functional group. A structural unit is polymerized by this polymerizable functional group, whereby a stimulus-responsive compound having a longer molecular chain can be formed. Further, by lengthening the molecular chain in this way, the degree of molecular deformation (displacement) can be increased as will be described in detail later, and the structural unit can be driven with a stronger force (stress). It becomes possible.

In addition, the polymerizable functional group of the unit C (the first unit C and the second unit C) is preferably a vinyl group or a (meth) acryl group. Thereby, the stimulus-responsive compound can be easily polymerized.
The unit C (the first unit C and the second unit C) preferably has a group having liquid crystallinity. Thereby, when an electric field or a magnetic field is applied to the unit C, the unit C is arranged in a predetermined direction. As a result, the structural unit shows a predetermined direction for its driving. Here, liquid crystallinity means that the orientation direction of molecules can be changed by applying an electric field or a magnetic field.

Further, the unit C (the first unit C and the second unit C) has a group having liquid crystallinity, so that the displacement of the entire deformable material accompanying the expansion and contraction of the stimulus responsive compound formed by polymerizing the structural units can be reduced. Amplification can be performed more suitably, and the amount of displacement of the entire deformable material can be made particularly large. In addition, the deformable material can be deformed at a lower voltage.
When the unit C (the first unit C and the second unit C) includes a group exhibiting liquid crystallinity, a group having a plurality of ring structures, for example, a plurality of aromatic rings (for example, phenyl groups) is converted into an ester group , An aromatic ring (for example, benzene ring) or a cyclohexane ring directly connected. In particular, the group having a plurality of ring structures preferably contains two or more aromatic rings.

  As the unit C, it is particularly preferable to use a group in which one or more halogen atoms are bonded to one ring structure among a plurality of ring structures. Thereby, the movement performance at the time of orientation of the unit C can be made higher, and the movement speed becomes faster. As a result, the deformable material can be deformed (displaced) faster and more smoothly, and can be driven at a lower voltage.

  Moreover, when a structural unit has a functional group which has liquid crystallinity, it is preferable that the functional group and liquid crystalline functional group which have liquid crystallinity are arrange | positioned through the coupling group. Thereby, when the group which has liquid crystallinity aligns, it can suppress that each group which has liquid crystallinity becomes obstruction | occlusion, and becomes difficult to align. Moreover, the movement performance at the time of orientation of the unit C having a group having liquid crystallinity can be made higher, and the movement speed of the stimuli-responsive compound obtained by polymerizing the structural unit becomes faster. In addition, the deformable material can be deformed (displaced) faster and more smoothly.

As the linking group joining the functional group and a polymerizable functional group having liquid crystallinity, C _n H _2n or C _{n H} 2n _{O (where,} n is an integer of 1 or more) those represented by Can be mentioned. In this case, n may be an integer of 1 or more, but is particularly preferably an integer of 2 to 10. As a result, the movement performance of the unit C having a group having liquid crystallinity during alignment can be made particularly high, and the movement speed of the stimulus-responsive compound formed by polymerizing the structural units can be made particularly fast. it can.
As described above, the unit C (the first unit C and the second unit C) having a polymerizable functional group, a group having a liquid crystal group, and a linking group for joining the functional group having liquid crystallinity and the polymerizable functional group. Specific examples of the unit C) include the following.

  The unit C may be bonded to any site in the molecule of the structural unit. For example, the unit C may be bonded to the unit B, but is preferably bonded to the unit A. In particular, when the unit includes two units C (a first unit C and a second unit C), the first unit C includes the third binding site (the first binding site, the first unit, and the second unit C). The second unit C is arranged in the fourth binding site of the unit A (first binding site, second binding site, third binding site). It is preferable that they are arranged at different sites. Thereby, it can deform | transform suitably at a still lower voltage. As a result, the flexibility of the deformable material and the operability in the low temperature region can be further improved.

  As described above, the structural unit is the unit A that can rotate the axis and the two units that are bonded to both ends (the first binding site and the second binding site) of the unit A. A unit B (first unit B and second unit B) capable of forming a coupling between units, and two units coupled to unit B (first unit B and second unit B) In the case where the liquid crystallinity unit C (the first unit C and the second unit C) is included, it can be deformed (displaced) with lower power and the degree of displacement. Can be made relatively large. This is considered to be due to the following reasons.

  That is, a plurality of structural units can be aligned (arranged) by the unit C having liquid crystallinity, and a voltage or the like is applied in the aligned state so that the units B in one molecule can undergo oxidation-reduction reactions. To bond (crosslink). Thus, by utilizing the orientation (liquid crystallinity) of the unit C and the binding property by the stimulation of the unit B, the state shown in FIG. 3 (a) is surely changed to the state shown in FIG. 3 (b). It can be deformed (displaced). In particular, since the orientation of the unit C and the coupling between the units B proceed at a low voltage, a large deformation (displacement) is possible at a low voltage.

  In addition to the unit A, unit B (first unit B, second unit B) and unit C (first unit C, second unit C) described above, the structural unit is further in the molecule. A unit D containing a polyalkylene oxide structure obtained by polymerizing alkylene oxides having 2 and / or 3 carbon atoms may be included (see FIGS. 5 and 6). Thereby, it can deform | transform suitably with a lower voltage. Further, the flexibility of the first deformable material layer 11 (actuator 100) can be further improved. In addition, crystallization of the stimulus-responsive compound (deformable material) containing the structural unit can be reliably prevented even at a low temperature, and the operability in a low temperature region (for example, −10 ° C. or lower) is particularly excellent. be able to. In addition, since the structural unit includes unit D, the stimulus-responsive compound as a whole can have excellent affinity and compatibility with the salt (electrolyte), and charge transfer can be more improved in the oxidation-reduction reaction. Promptly. As a result, the response speed of the actuator 100 including the stimulus-responsive compound becomes faster.

Moreover, when the structural unit includes the unit D, the ability to retain the solvent (liquid retention) can be made particularly excellent as the entire stimulus-responsive compound. For this reason, a deformable material can be adjusted to more optimal hardness. Further, the actuator 100 can be deformed more flexibly and operate smoothly.
The stimulus-responsive compound may include one unit D in the molecule, but in the configuration shown in FIG. 5, the unit D includes the first unit D and the second unit D. . Thereby, it can deform | transform suitably at a still lower voltage. Further, the flexibility of the actuator 100 and the operability in a low temperature region can be further improved.

The unit D may be bonded to any site in the molecule of the structural unit. For example, the unit D may be bonded to the unit B, but is preferably bonded to the unit A. In particular, when the unit includes two units D (a first unit D and a second unit D), the first unit D has a third binding site (a first binding site, a first unit, The second unit D is arranged in the fourth binding site of the unit A (first binding site, second binding site, third binding site). It is preferable that they are arranged at different sites. Thereby, it can deform | transform suitably at a still lower voltage. Further, the flexibility of the actuator 100 and the operability in a low temperature region can be further improved.
The first unit D is preferably coupled to the first unit C, and the second unit D is preferably coupled to the second unit C. Thereby, it can deform | transform suitably at a still lower voltage. Further, the flexibility of the actuator 100 and the operability in a low temperature region can be further improved.

As described above, the unit D (the first unit D and the second unit D) includes a polyalkylene oxide structure obtained by polymerizing alkylene oxides having 2 and / or 3 carbon atoms.
When the unit D has a structure obtained by polymerizing alkylene oxide having 2 carbon atoms (ethylene oxide), the flexibility of the actuator 100, the operability in the low temperature region, etc. can be made particularly excellent. Further, the response speed of the actuator 100 can be made particularly fast.

Further, when the unit D has a structure formed by polymerization of alkylene oxide (propylene oxide) having 3 carbon atoms, the durability of the deformable material / actuator 100 can be made particularly excellent.
The number of alkylene oxide polymerizations in the unit D (first unit D, second unit D) (number of molecules of alkylene oxide as a raw material) is preferably 4 or more and 20 or less, preferably 5 or more and 10 or less. Is more preferable. While the durability of the deformable material / actuator 100 is further improved, the flexibility of the actuator 100, the operability in the low temperature region, etc. can be made particularly excellent, and the response speed of the actuator 100 is particularly fast. can do.

[Stimulus-responsive compound]
The stimulus-responsive compound is a polymer obtained by polymerizing the structural units as described above.
Since the structural unit as described above has a polymerizable functional group in the unit C (the first unit C and the second unit C), polymerization is performed using this polymerizable functional group. Thus, a stimuli-responsive compound that is a polymer obtained by polymerizing the structural units can be obtained. Thereby, the degree of deformation (displacement) of the molecule of the stimulus-responsive compound can be increased. As a result, a larger amount of displacement can be obtained as the deformable material, and the operability of the actuator 100 can be improved.

  That is, the stimuli-responsive compound, which is a polymer obtained by polymerizing the structural units using the polymerizable functional group of the unit C, is in a state in which the structural units are successively connected like the structure shown in FIG. And in the state which the stimulus responsive compound was oxidized, as shown to Fig.4 (a), the structural unit exists in the state extended in a line in the longitudinal direction. Thereby, the three-dimensional structure of the molecule is in an expanded (expanded) state. In the state where the stimuli-responsive compound is reduced, as shown in FIG. 4B, the unit A rotates about the axis, the adjacent units B are bonded together by an oxidation-reduction reaction, and further, the liquid crystalline unit When C is oriented, it is folded with unit B as a base point. Thereby, the three-dimensional structure of the molecule is in a contracted state. Thus, as a whole stimulus-responsive compound, the three-dimensional structure of the molecule changes greatly. Here, the stimuli-responsive material formed by polymerizing the structural unit having the unit B has a plurality of units B serving as the base points of the bending. For this reason, the degree of displacement can be made large as a whole stimulus-responsive material. As a result, the degree of displacement of the actuator 100 including the stimulus responsive compound can be increased.

Further, by applying a voltage to the stimulus-responsive compound, the units C having functional groups having liquid crystallinity are arranged in a predetermined direction. For this reason, the stimulus-responsive material as a whole has a greater degree of displacement due to the synergistic effect of the plurality of units B serving as the base points of bending as described above and the orientation of the units C of each constituent unit. It can be. As a result, the degree of displacement of the actuator 100 including the stimulus responsive compound can be increased.
Further, the change in the three-dimensional structure of the molecule described above is reversible, and can return from the contracted state to the expanded (expanded) state as described above. Further, the change in the three-dimensional structure of the molecule can be performed a plurality of times, and the reproducibility is excellent.

  As described above, the stimulus-responsive compound has a change in the three-dimensional structure of the molecule and its reversibility and reproducibility. For this reason, the deformable material containing the stimulus-responsive compound has the same effect. As a result, the deformable material can increase the degree of deformation (deformation rate), and can impart directionality to the deformation. Then, by stopping the application of voltage, the shape of the first deformable material layer 11 can be maintained, and the shape of the actuator 100 can be maintained.

  In addition, when the deformable material containing the stimulus-responsive compound is in a gel form, the stimulus-responsive compound obtained by polymerizing the structural unit itself forms a gel (the stimulus-responsive compound is made into a gel alone. In addition to the above, a gel is formed by adding a solvent to the stimuli-responsive compound. The same shall apply hereinafter.) The deformable material is in the form of a gel, and a gelling agent is added separately to form the deformable material. Some gels.

  When the stimulus-responsive compound obtained by polymerizing the structural unit forms a gel by itself, the deformable material can be gelled by incorporating a solvent into the stimulus-responsive polymer. Thereby, the deformable material can more suitably perform anisotropic expansion and contraction. Further, the deformable material has more suitable elasticity. Furthermore, when the stimuli-responsive compound is a polymer obtained by polymerizing a structural unit having a unit D containing a polyalkylene oxide structure, the stimuli-responsive compound as a whole has an ability to retain a solvent (liquid retention), in particular. It can be excellent. As a result, the deformable material can be gelled, and the shape stability and handleability as the deformable material are particularly excellent. As a result, the shape stability of the actuator 100 can be made excellent.

  Further, the stimulus-responsive compound may be composed only of a polymer obtained by polymerizing the structural units as described above, but the polymer may include other components. For example, the polymer as described above may be further partially chemically modified to introduce a substituent. Thereby, for example, the response speed of the stimulus-responsive compound as a whole can be further improved. In addition, for example, as a whole stimulus-responsive compound, the ability to retain a solvent (liquid retention) can be made particularly excellent.

The weight average molecular weight (Mw) of the stimulus-responsive compound is preferably 1,000 or more and 500,000 or less, and more preferably 10,000 or more and 100,000 or less. Thereby, the effect of this invention is exhibited more notably.
The content of the stimulus-responsive compound in the deformable material is preferably 10% by mass to 80% by mass, and more preferably 20% by mass to 60% by mass. Thereby, the effect of this invention is exhibited more notably.

<Electrolyte>
The deformation material constituting the first deformation material layer 11 preferably contains an electrolyte.
As the electrolyte, various acids, bases and salts can be used, but it is preferable to use a salt. Thereby, the durability of the deformable material can be made particularly excellent. Examples of the electrolyte salt include lithium chloride, potassium chloride, sodium chloride, lithium perchlorate, and lithium trifluoromethanesulfonate, cesium chloride, sodium iodide, sodium bromide, sodium sulfide, sodium fluoride, and hexafluoride. Inorganic salts of lithium phosphate; tetraethylammonium chloride, tetrabutylammonium tetrafluoroboron, sodium dodecylbenzenesulfonate, lithium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (BMPTFSI) ), Methyl-trioctylammonium bis (trifluoromethylsulfonyl) imide (MTOATFSI), triethylsulfonium bis (trifluoromethylsulfonyl) imide ( ESTFSI), 1- ethyl-3-methylimidazolium trifluoromethanesulfonate (EMICF ₃ SO ₃₎ may be an organic salt such as. The structural formulas of BMPTFSI, MTOATFSI, TESTFSI, and EMICF ₃ SO ₃ are represented by the following formula (6), the following formula (7), the following formula (8), and the following formula (9), respectively.

  In particular, the deformable material is preferably an electrolyte containing chloride ions, more preferably lithium chloride, sodium chloride, or cesium chloride. As a result, the response speed of the stimulus-responsive compound (deformable material, actuator 100) can be further effectively improved, and the displacement of the entire actuator 100 associated with the expansion and contraction of the stimulus-responsive compound can be further amplified.

By including the electrolyte as described above, stable power supply by the power supply 10 is possible. Moreover, the charge delivery to the stimulus-responsive compound can be advanced more rapidly, and the high-speed response of the first deformable material layer 11 can be made particularly excellent. In addition, the stimuli-responsive compound constituting the deformable material can be efficiently expanded and contracted over the entire deformed first deformable material layer 11 (in particular, the entire thickness direction of the first deformable material layer 11). As a result, the expansion / contraction rate of the actuator 100 as a whole can be made particularly large.
The content of the electrolyte in the deformable material is preferably 3% by mass or more and 80% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. Thereby, the effects as described above are more remarkably exhibited.

<Electronic conductive material>
Further, the deformable material constituting the first deformable material layer 11 may include an electron conductive material having a function of transporting electrons in the deformable material.
Examples of the electronic conductive substance include a metal material, a carbon material, a compound thereof, or an organic material. Specific examples include, for example, various carbon materials such as graphite, carbon nanotubes, graphene, carbon nanoparticles, acetylene black and activated carbon; polyaniline, polythiol, polypyrrole, semiconductor materials such as Si-based and Ga-based materials, PEDOT: PSS (3, Examples include conductive polymers such as 4-polyethylenedioxythiophene-polystyrene sulfonic acid), transparent conductive oxide materials (for example, ITO (indium tin oxide)), and various metal nanowires. Among these, carbon materials are particularly preferable, and carbon nanoparticles (particularly porous carbon nanoparticles) are more preferable. Thereby, the electron transport function is improved, and the first deformable material layer 11 (actuator 100) can be greatly displaced at a relatively low voltage.

  Moreover, the form of particles, such as a carbon material, is not specifically limited, Any forms, such as dense, porous, and hollow, may be sufficient. Further, for example, when carbon nanoparticles are used as the electronic conductive material, it is preferable to use carbon nanoparticles having a hollow shell structure. This improves the electron transport function. Further, the entire deformable material can be greatly displaced with a relatively low voltage, and the actuator 100 can be deformed (displaced) faster and more smoothly.

  When porous carbon nanoparticles are used as the electronic conductive material, the porosity (porosity) of the carbon nanoparticles is preferably 90% by volume or less, and 30% by volume or more and 90% by volume or less. Is more preferable, and it is further more preferable that it is 60 volume% or more and 90 volume% or less. Thereby, the above effects can be exhibited more significantly while maintaining the stability of the shape of the carbon nanoparticles (electronic conductive material). As a result, the above-described effects can be exhibited stably over a long period of time, and the uniformity of characteristics among the lots of the actuator 100 can be made particularly excellent.

The electron conductive substance may be dissolved in other components in the deformable material, but is preferably present as an insoluble component in the deformable material, particularly in a solid state. Are preferred.
Examples of the shape of the electron conductive material include various shapes such as a particle shape, a flat plate shape, and a fiber shape (for example, a tube shape). In particular, the electron conductive material has a particle shape. Is preferred. The shape of the particles may be spherical or non-spherical (for example, scaly, spindle, or spheroid). As a result, the electron conductive material can be uniformly dispersed throughout the deformable material, the entire deformable material can be uniformly and largely displaced at a relatively low voltage, and the entire actuator 100 can be uniformly and largely displaced. .

  When the electron conductive substance is in the form of particles, the average particle diameter is preferably 1 nm or more and 10 μm or less, and more preferably 2 nm or more and 90 nm or less. Thereby, the electron in a deformable material can be reliably supplied by providing an electron conductive material of a required density | concentration to the whole deformable material. In addition, the electron supply efficiency to the stimulus-responsive compound can be made particularly excellent, and the actuator 100 can be deformed (displaced) faster and more smoothly. On the other hand, when the average particle size is less than the lower limit, the electron conductive material aggregates, and a treatment for preventing aggregation is necessary. On the other hand, when the average particle diameter exceeds the upper limit, it is necessary to increase the content of the electronic conductive material, and further improvement of the effects as described above is not observed.

In the present specification, “average particle diameter” refers to a volume-based average particle diameter (volume average particle diameter (D ₅₀ )). Examples of the measuring apparatus include a laser diffraction / scattering particle size analyzer Microtrac MT-3000 (manufactured by Nikkiso Co., Ltd.). The volume average particle diameter _{(D 50)} in Examples described later is a value measured with Microtrac MT-3000 of the.

  By including the electronic conductive material as described above, the entire first deformable material layer 11 can be greatly displaced at a relatively low voltage. In particular, even when the thickness of the first deformable material layer 11 is relatively large, the entire first deformable material layer 11 can be efficiently deformed. As a result, a larger displacement force and displacement amount can be obtained at a low voltage. In addition, the deformable material (first deformable material layer 11) can be displaced more greatly without contacting the wiring drawn from the power supply 10 over a large area of the deformable material (first deformable material layer 11). . As a result, the actuator 100 can deform more flexibly and operate smoothly. Further, even if the thickness of the deformable material is relatively large, the difference in deformation amount between the vicinity of the surface and the vicinity of the center portion becomes small, so that the deformation amount can be easily controlled.

  Further, the content of the electron conductive substance in the deformable material is preferably 10% by mass or more and 90% by mass or less, and more preferably 30% by mass or more and 70% by mass or less. Thereby, the transport of electrons in the deformable material can be suitably performed, and the actuator 100 can be deformed (displaced) faster and more smoothly. On the other hand, when the content of the electron conductive material is less than the lower limit value, the function of assisting the movement of electrons in the deformable material decreases. On the other hand, when the content of the electronic conductive material exceeds the upper limit, further improvement of the effects as described above is not observed.

  Also, the dispersion state of the electronic conductive material in the deformable material is preferably uniform, but the concentration of the electronic conductive material in the deformable material changes continuously and intermittently (intermittently). There may be parts. When the dispersion state of the electronic conductive substance in the deformable material is uniform, the entire deformable material can be uniformly and largely displaced with a relatively low voltage. In particular, even when the thickness of the deformable material is relatively large, the deformable material can be more efficiently deformed.

<Solvent>
Moreover, the deformation material which comprises the 1st deformation material layer 11 may contain a solvent. When the solvent is taken into the stimulus-responsive polymer or the like, the deformable material can be suitably gelled, so that it can be easily solidified and the handleability of the deformable material can be improved. Furthermore, the first deformable material layer 11 can be adjusted to an optimum hardness, and the flexibility of the actuator 100 can be made particularly excellent. In addition, in the case of including an electrolyte that is solid as a single substance, the electrolyte can be dissolved in the deformable material, and can be suitably ionized.

Examples of the solvent include aprotic solvents such as dimethyl sulfoxide (DMSO), acetonitrile, methylformamide, dimethylformamide (DMF), dimethylacetamide (DMA), ethyl acetate, acetone, tetrahydrofuran, distilled water, RO water, and ion exchange. Protic solvents such as water, pure water, tap water, etc., alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, glycerin, alkoxyethanol, carboxylic acids such as formic acid, acetic acid, propionic acid, etc. Can do.
The content of the solvent in the deformable material is preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 60% by mass or less. Thereby, the handleability of a deformable material can be made higher.

<Gelling agent>
Further, the deformable material constituting the first deformable material layer 11 may include a gelling agent as a material capable of gelling the entire deformable material. Thereby, the 1st deformable material layer 11 can be adjusted to the optimal hardness by selection of the kind, compounding quantity, etc. of a gelatinizer for the whole deformable material.
In particular, even when the stimulus-responsive compound is difficult to gel, by including the gelling agent, the entire deformable material can be adjusted to the optimal hardness of the first deformable material layer 11. Further, not only when the stimulus-responsive compound does not form a gel by itself, but also when the stimulus-responsive compound forms a gel by itself, a gelling agent can be similarly used.

  Examples of the gelling agent constituting the deformable material include various resin materials, materials such as agar, gelatin, alginate, gellan gum and the like. It is preferable to include one or more selected from the group consisting of a fluorinated propylene copolymer, methyl (meth) acrylate, and an organic electrolyte oligomer. Thereby, the 1st deformation | transformation material layer 11 can be adjusted to optimal hardness by selection, such as a kind and compounding quantity of a gelatinizer. Further, the deformable material (actuator 100) can be deformed more flexibly and operate smoothly. Thereby, the holding power of the solvent (liquid component) contained in the gel-like first deformable material layer 11 can be made excellent. As a result, the intermediate layer 13 can improve the temporal stability. Furthermore, the volume reduction of the actuator 100 over time can be prevented more effectively.

  In particular, when the deformable material constituting the first deformable material layer 11 includes a vinylidene fluoride-hexafluoropropylene copolymer, the deformable material can be made more flexible. In addition, it can be made less susceptible to fluctuations in moisture concentration. As a result, unintentional moisture absorption of the deformable material can be more effectively prevented, and the deformation amount of the actuator 100 can be adjusted more reliably.

The weight average molecular weight (Mw) of the vinylidene fluoride-hexafluoropropylene copolymer is preferably 10,000 or more and 1,000,000 or less, more preferably 100,000 or more and 500,000 or less. The effects as described above are more remarkably exhibited.
In addition, the chemical structure of a vinylidene fluoride-hexafluoropropylene copolymer can be represented by the following formula (10).

In formula (10), a is preferably from 0.60 to 0.98, and more preferably from 0.75 to 0.95. As a result, the deformable material can have flexibility more suitable for deformation.
Moreover, when the deformable material which comprises the 1st deformable material layer 11 contains polymethyl methacrylate, it can prevent more reliably that a crack etc. arise when a deformable material deform | transforms.
The weight average molecular weight (Mw) of polymethyl methacrylate is preferably 10,000 or more and 100,000 or less, and more preferably 10,000 or more and 50,000 or less. The effects as described above are more remarkably exhibited.
The chemical structure of polymethyl methacrylate can be represented by the following formula (11).

Moreover, when the deformation material which comprises the 1st deformation material layer 11 contains an organic electrolyte oligomer, the said organic electrolyte oligomer can also serve as the function of the electrolyte described later.
In addition, as an organic electrolyte oligomer, what is represented by following formula (12) can be used, for example.

（式（１２）中、Ｘは、ハロゲン、（ＣＦ_３ＳＯ_２）Ｎ、ＰＦ_６、ＢＦ_４、ＳＣＮ、または、ＣＦ_３ＳＯ_３、ｎは、３以上３０以下の数である。）

(In the formula (12), X is halogen, (CF ₃ SO ₂ ) N, PF ₆ , BF ₄ , SCN, or CF ₃ SO ₃ , and n is a number of 3 or more and 30 or less.)

  The content of the gelling agent in the deformable material is preferably 5% by mass or more and 50% by mass or less. Thereby, the 1st deformation | transformation material layer 11 can acquire moderate softness | flexibility, and the reliability and durability of the actuator 100 improve.

<Liquid crystal polymer>
Further, the deformable material constituting the first deformable material layer 11 may include a liquid crystal polymer.
The liquid crystal polymer preferably has an assisting function so as to be advantageous for molecular deformation due to the three-dimensional structure of the stimulus-responsive compound as described above. In particular, when the deformable material constituting the first deformable material layer 11 includes a liquid crystal polymer as a stimulus responsive compound, the redox reaction of the stimulus responsive compound is achieved by including a liquid crystal polymer. As the orientation of the functional group having liquid crystallinity (unit C) changes, the orientation of the liquid crystal polymer also changes favorably for the deformation of the molecule due to the three-dimensional structure of the stimuli-responsive compound as described above. For this reason, the deformation of the deformable material (actuator 100) as a whole can be made greater in degree and faster in response speed. That is, the deformable material (actuator 100) has a particularly excellent high-speed response and a greater degree of anisotropic expansion and contraction.

The liquid crystal polymer can be obtained by polymerizing a monomer having a functional group having liquid crystallinity.
As the functional group having liquid crystallinity, a group having a plurality of ring structures, for example, a group in which a plurality of aromatic rings (for example, a phenyl group) are linked by an ester group, an aromatic ring (for example, a benzene ring), or a cyclohexane ring is directly used. The connected thing is mentioned.

Examples of the monomer include a monomer having a liquid crystallinity functional group and an acrylic group, and a monomer having a liquid crystallinity functional group and a (meth) acryl group.
Examples of such a monomer include compounds represented by the following formula (13) or (14).

（式（１３）、（１４）中、ｎは６以上の整数、Ｒは炭素数が１以上のアルキル基を示す。）

(In formulas (13) and (14), n represents an integer of 6 or more, and R represents an alkyl group having 1 or more carbon atoms.)

By using such a monomer, the deformable material can be deformed (displaced) faster and more smoothly, and is driven at a lower voltage.
When the deformable material includes a liquid crystal polymer, the liquid crystal polymer is preferably cross-linked by a cross-linking agent. Thereby, the first deformable material layer 11 can be adjusted to an optimum hardness. That is, by including a liquid crystal polymer having a crosslinked structure, a stimulus-responsive compound can be incorporated into the molecule, and the first deformable material layer 11 can be adjusted to an optimum hardness. As a result, the shape stability and handleability of the deformable material as a whole are particularly excellent. Thereby, the deformable material (actuator 100) can perform anisotropic expansion and contraction more suitably. Moreover, the deformable material has more suitable elasticity by having a crosslinked structure.
The cross-linking agent is not particularly limited as long as it can cross-link the polymer formed of the above monomer, and any cross-linking agent may be used. By using a cross-linking agent represented by the following formula (15), liquid crystal The stimulus-responsive compound can be easily incorporated into the polymer molecule, and the deformable material can be gelled more reliably.

（式（１５）中、ｍは４以上の整数を示す。）

(In formula (15), m represents an integer of 4 or more.)

Specific examples of the crosslinking agent include bisacryloyloxyhexane, N, N-methylenebisacrylamide, and ethylene glycol dimethacrylate.
It is preferable that the liquid crystal polymer is cross-linked by adding 1 mol or more and 10 mol or less of a crosslinking agent to 100 mol of the monomer having a liquid crystalline functional group. Thereby, the displacement of the whole deformable material (actuator 100) accompanying the expansion and contraction of the stimulus responsive compound can be efficiently amplified.

  Further, when the deformable material is provided with a functional group having liquid crystallinity as the stimulus responsive compound, the liquid crystal polymer has the same functional group as the functional group having liquid crystallinity of the stimulus responsive compound in its molecule. Although it has, it is preferable. Thereby, the response speed of the stimulus-responsive compound (deformable material) can be improved more effectively. Further, the displacement of the entire actuator 100 due to the expansion and contraction of the stimulus-responsive compound can be further suitably amplified, and the displacement amount of the entire actuator 100 can be further increased. Further, the actuator 100 can be deformed at a lower voltage.

The weight average molecular weight (Mw) of the liquid crystal polymer is preferably 10,000 or more and 100,000 or less, and more preferably 10,000 or more and 50,000 or less. The effects as described above are more remarkably exhibited.
Further, when the deformable material constituting the first deformable material layer 11 includes a liquid crystal polymer together with a gelling agent, the above-described effects can be obtained, and these can act synergistically to form the deformable material. The strength can be further improved, and the amount of displacement can be increased.

By including the liquid crystal polymer as described above, the response speed of the stimulus-responsive compound (deformable material) can be effectively improved. In addition, the displacement of the entire deformable material accompanying the expansion and contraction of the stimulus responsive compound can be more suitably amplified, and the displacement amount of the actuator 100 as a whole can be made particularly large.
The content of the liquid crystal polymer in the deformable material is preferably 3% by mass or more and 50% by mass or less. Thereby, the effects as described above are more remarkably exhibited.

Further, the deformable material constituting the first deformable material layer 11 may include components other than those described above.
The conductivity of the first deformable material layer 11 is preferably 0.1 S / cm or more, and more preferably 1 S / cm or more. Thereby, the response speed of the actuator 100 can be made particularly excellent, and the actuator 100 can be downsized.

The thickness of the first deformable material layer 11 is not particularly limited, but is preferably 5 mm or less. Thereby, a larger displacement force can be obtained while the drive voltage is relatively low.
Further, when the deformable material layer contains an electron conductive substance, the thickness is preferably 0.01 mm or more and 10 mm or less, and more preferably 0.03 mm or more and 1 mm or less. Thereby, even if the thickness of the deformable material layer is relatively large, the actuator can be driven more suitably.

≪Second deformation material layer≫
Next, the second deformable material layer will be described.
The second deformable material layer 12 is made of a material containing a stimulus-responsive compound, similar to the first deformable material layer 11 described above, and further includes an electrolyte, an electronically conductive substance, a solvent, a gelling agent, A liquid crystal polymer or the like may be contained.

As the constituent material of the second deformable material layer 12, the materials described for the first deformable material layer 11 can be used. The second deformable material layer 12 may be composed of a material different from that of the first deformable material layer 11, or may be composed of the same or the same kind of material.
The second deformable material layer 12 preferably satisfies the same conditions as described in the first deformable material layer 11 with respect to conditions such as conductivity and thickness. Thereby, the same effect as described in the first deformable material layer 11 is obtained. In the actuator 100, the second deformable material layer 12 may have different conditions or the same conditions as the first deformable material layer 11.

≪Middle layer≫
Next, the intermediate layer will be described.
FIG. 7 is a cross-sectional view schematically showing the behavior of anions and solvents in the intermediate layer constituting the actuator of the present invention. FIG. 7A shows a state where the actuator has not been energized. 7 (b) and 7 (c) show a state where the actuator is energized, FIG. 7 (b) corresponds to FIG. 1, and FIG. 7 (c) corresponds to FIG. is there.

As shown in FIGS. 1, 2, and 7, the intermediate layer 13 is located between the first deformable material layer 11 and the second deformable material layer 12, and has a function of exchanging anions.
The intermediate layer 13 is made of a material including an ion exchanger having a function of exchanging anions, and may further include an electrolyte, a polar solvent, a gelling agent, and the like. The ion exchanger is composed of a material having an anion exchange group. Note that an ion refers to a positively or negatively charged atom or atomic group, and an anion refers to a negatively charged atom or atomic group among the ions.
The intermediate layer 13 has sufficient electrical conductivity for moving ions, and the ions move more smoothly between the first deformable material layer 11 and the second deformable material layer 12. It can be carried out. Therefore, the first deformable material layer 11 and the second deformable material layer 12 can surely be deformed by the molecular chain stretching function that changes the three-dimensional structure of the molecule by the oxidation-reduction reaction.

Furthermore, since the intermediate layer 13 has an anion exchanger, the intermediate layer 13 itself can be deformed. This is considered to be due to the following reasons. As shown in FIG. 7A, in the intermediate layer 13 constituting the actuator 100 that has not been energized, the anion and the solvent are present in the intermediate layer 13 in a uniform state. When the intermediate layer 13 is energized, as shown in FIG. 7B, the anions contained in the intermediate layer 13 move to the positive electrode side, and solvent molecules are transferred to the intermediate layer 13 along with the anions. Move in. For this reason, a difference in the amount of solvent occurs between the positive electrode side and the negative electrode side of the intermediate layer 13. As a result, the positive electrode side having a high rate including solvent molecules swells and the negative electrode side having a low rate including solvent molecules contracts, so that the intermediate layer 13 is curved and deformed so that the positive electrode side is convex. And even if the application of a voltage is stopped, the shape of the intermediate layer 13 is maintained. Moreover, as shown in FIG.7 (c), the intermediate | middle layer 13 can change the curve direction by changing the connection of a positive electrode and a negative electrode. That is, as shown in FIGS. 7B and 7C, the operation of the intermediate layer 13 is reversible. In addition, by continuously or intermittently inverting the characteristics of the current applied to the intermediate layer 13, the bending direction can be changed alternately and can be continuously repeated. Moreover, the reproducibility is also excellent. Further, when the actuator 100 is energized, the deformation of the intermediate layer 13 and the deformation of the first deformable material layer 11 and the second deformable material layer 12 described above are the same direction. The displacement amount of the entire 100 can be increased.
The intermediate layer 13 may be in any form, for example, solid, gel (semi-solid), liquid, etc., but it is in the form of a gel (semi-solid). preferable. Thereby, the actuator 100 whole can deform | transform more flexibly and can operate | move smoothly.

Hereinafter, each component which comprises the intermediate | middle layer 13 is demonstrated in detail.
<Ion exchanger>
In the present invention, the ion exchanger includes an anion exchange group having a function of exchanging anions. When the counter ion (anion) of the anion exchange group of the ion exchanger is replaced with another anion (for example, a hydroxide ion), movement of the counter ion (anion) occurs. As a result, the anion contained in the intermediate layer 13 moves to the positive electrode side, and the intermediate layer 13 itself can be deformed by the principle described above.

  Examples of ion exchangers having such functions include anion exchange resins, ion exchange resins such as both ion (anion and cation) exchange resins, organic ion exchangers such as fatty acid amines, zirconium hydroxide, Examples include inorganic ion exchangers such as hydrous bismuth and hydrotalcide. In particular, it is preferable to use at least one of an anion exchange resin and an anion exchange resin, and it is more preferable to use an anion exchange resin. Thereby, anions in the intermediate layer 13 can be efficiently moved, and ions can be moved between the first deformable material layer 11 and the second deformable material layer 12 via the intermediate layer 13. It can be performed more smoothly. Further, the response speed of the actuator 100 can be made particularly excellent even at a low voltage.

Examples of the anion exchange resin and the both ion (anion and cation) exchange resin as the ion exchanger having such a function include aliphatic ionenes such as 3,4-ionene and 8,8-ionene, Poly (ethyleneimine hydrochloride), poly (vinylpyridinium chloride), poly (vinyltrimethylammonium chloride), poly (allyltrimethylammonium chloride), poly (oxyethyl-1-methylenetrimethylammonium chloride), poly (N-chloride-N-) Methyl vinylpyridinium), poly (oxyethyl-1-methylenepyridinium chloride), poly (-2-hydroxy-3-methacryloxypropyltrimethylammonium chloride), poly (N-acrylamidopropyl-3-trimethylammonium chloride), poly (Chloride-N, N-dimethyl- , 5-methylenepiperidinium) poly (-2-acryloxyethyldimethylsulfonium chloride), poly (glycidyldimethylsulfonium chloride), poly (glycidyltributylphosphonium chloride), and various ion exchange resins mainly composed of polysulfone. Can be mentioned.
Moreover, when the intermediate layer 13 contains an anion exchange resin or both ion exchange resins, the resin layer containing carbon may be used as a skeleton and an anion exchange group may be introduced.

  Various resin materials can be used as the resin material that forms such a skeleton. For example, polyolefin resins such as polyethylene and polypropylene, styrene resins such as polystyrene and styrene-divinylbenzene copolymer, acrylic resins such as acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer Polymers, vinyl chloride resins such as vinyl chloride-vinylidene chloride copolymer, vinyl chloride-olefin copolymer, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer , Fluorocarbon resins such as tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, perfluorosulfonic acid resin, etc. Even some fluorine, chlorine, bromine, oxygen, nitrogen, silicon, sulfur, boron, those substituted with other atoms such as phosphorous, or a copolymer thereof, polymer alloy, and a blend and the like. In particular, a styrene resin is preferable, and a styrene-divinylbenzene copolymer is more preferable. Thereby, the intermediate | middle layer 13 can be made flexible and the actuator 100 whole can be made flexible.

  Examples of the anion exchange group include an amino group, a substituted amino group, a quaternary ammonium group, a pyridyl group, an imidazole group, a quaternary pyridinium group, and a quaternary imidazolium group, and a quaternary phosphonium group. And a cationic group such as a phosphorus functional group such as a group. In particular, at least one of a quaternary ammonium group and a quaternary phosphonium group is preferably used, and a quaternary ammonium group is more preferable. Thereby, the anion contained in the intermediate layer 13 is reliably moved to the positive electrode side, so that the intermediate layer 13 itself can be more reliably deformed.

  The quaternary ammonium group includes trimethylammonium group, triethylammonium group, tripropylammonium group, tributylammonium group, trioctylammonium group, diethylmethylammonium group, dipropylmethylammonium group, dibutylmethylammonium group, dimethylethyl. It preferably contains one or more selected from the group consisting of trialkylammonium groups such as an ammonium group and a methyldi (hydroxyethyl) ammonium group. Thereby, anions in the intermediate layer 13 can be efficiently moved, and ions can be moved between the first deformable material layer 11 and the second deformable material layer 12 via the intermediate layer 13. It can be performed more smoothly. As a result, the response of the actuator 100 is further improved.

Moreover, when using an anion exchange resin or a both ion exchange resin, as counter ions (anions), for example, chloride ions, bromide ions, fluoride ions, halide ions such as iodide ions, sulfate ions, nitrate ions, a perchlorate ion, dodecylbenzenesulfonate ion, trifluoromethanesulfonate ion, hexafluorophosphate (PF ₆ -), tetrafluoro boron ion (BF 4 _-), trifluoromethylsulfonylamide ions ( TFSI-) and the like. In particular, an electrolyte containing chloride ions is preferably used, and lithium chloride, sodium chloride, and cesium chloride are more preferably used. Thereby, the response speed of the intermediate layer 13 can be further increased, and the displacement of the intermediate layer 13 can be further improved.
In the intermediate layer 13, all of these counter ions may be the same, or some of them may be substituted differently.

  The shape of the ion exchanger constituting the intermediate layer 13 is not particularly limited, and examples thereof include various shapes such as a particle shape, a flat plate shape, a fiber shape, a rod shape, and a disk shape. It is preferable that it is in the form of particles. Thereby, the ion exchanger can be easily formed into a sheet shape as shown in FIGS. 1, 2, and 7. Moreover, when using a particulate thing as an ion exchanger, the shape of the particle | grains can use any thing of a spherical body and a non-spherical body (for example, a scaly shape, a spindle shape, a spheroid). Further, the form of the particles is not particularly limited, and may be any form such as dense, porous, and hollow.

Further, by using a sheet-like ion exchanger (ion exchange resin film), the thickness of the intermediate layer 13 can be made uniform. When the thickness of the intermediate layer 13 is set to be relatively thin, the actuator 100 can be lightweight. As a result, the driving speed and response speed of the intermediate layer 13 can be increased even with low power.
Specific examples of the sheet-like anion exchange resin include Aciplex A172 manufactured by Asahi Kasei Kogyo Co., Ltd., Selemion ASV manufactured by Asahi Glass Co., Ltd., and Neoceptor ACS manufactured by Tokuyama Co., Ltd.

  The anion exchange capacity of the ion exchanger is preferably from 0.5 meq / g to 3.0 meq / g, particularly preferably from 0.8 meq / g to 2.2 meq / g. Thereby, the movement of the anion in the intermediate | middle layer 13 can be improved by providing the ion exchanger of a required density | concentration. Further, ions can be moved more smoothly between the first deformable material layer 11 and the second deformable material layer 12 via the intermediate layer 13. On the other hand, if the anion exchange capacity of the ion exchanger is less than the lower limit value, the movement of anions in the intermediate layer 13 decreases, so the content of the ion exchanger in the intermediate layer 13 needs to be increased. There is. On the other hand, if the anion exchange capacity of the ion exchanger exceeds the upper limit, the actuator 100 may be deteriorated.

  The content of the ion exchanger in the intermediate layer 13 is preferably 40% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 70% by mass or less. Thereby, the movement of anions can be performed efficiently, and the deformation amount of the actuator 100 can be increased. On the other hand, if the content of the ion exchanger is less than the lower limit value, the movement of ions in the intermediate layer 13 is reduced, and sufficient improvement in deformation of the intermediate layer 13 itself is not observed. On the other hand, when the content of the ion exchanger exceeds the upper limit, further improvement of the effects as described above is not observed.

<Electrolyte>
The intermediate layer 13 preferably contains an electrolyte. Thereby, the movement of ions in the intermediate layer 13 can be made smooth. Moreover, the movement of the anion by the electrolyte between the first deformable material layer 11, the second deformable material layer 12, and the intermediate layer 13 can be performed more smoothly. As a result, the high-speed response of the actuator 100 can be made particularly excellent. Examples of the electrolyte include lithium chloride, potassium chloride, sodium chloride, cesium chloride, lithium perchlorate, lithium trifluoromethanesulfonate, lithium hexafluorophosphate, sodium iodide, sodium bromide, sodium sulfide, sodium fluoride. Inorganic salts such as tetrabutylammonium tetrafluoroboron, tetraethylammonium chloride, 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (BMPTFSI), methyl-trioctylammonium bis (trifluoromethylsulfonyl) Imido (MTOATFSI), triethylsulfonium bis (trifluoromethylsulfonyl) imide (TESTFSI), 1-ethyl-3-methylimidazolium trifluoromethanesulfo Organic salts such as nate (EMICF ₃ SO ₃ ) can be used, and it is particularly preferable to use an electrolyte containing chloride ions, and it is more preferable to use lithium chloride, sodium chloride, and cesium chloride. The response speed of the intermediate layer 13 can be further increased, and the displacement of the intermediate layer 13 can be further improved.

In addition, the anion of the electrolyte as the constituent component of the intermediate layer 13 and the counter ion (anion) of the anion exchanger may be different, but preferably include the same component. Thereby, the anion in the intermediate layer 13 can be efficiently moved, and the intermediate layer 13 itself can obtain a sufficiently large displacement.
Further, the electrolyte as the constituent component of the first deformable material layer 11 and the second deformable material layer 12 and the electrolyte as the constituent component of the intermediate layer 13 may be different, but they are the same or the same kind. It is preferable that it contains a component. Thereby, the movement of anions between the first deformable material layer 11 and the second deformable material layer 12 can be performed more smoothly via the intermediate layer 13. As a result, the displacement of the first deformable material layer 11 and the second deformable material layer 12 can be improved, and the deformation of the entire actuator 100 can be increased.
The content of the electrolyte in the intermediate layer 13 is preferably 3% by mass or more and 80% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. Thereby, the intermediate | middle layer 13 can maintain moderate softness | flexibility and the balance of electroconductivity.

<Polar solvent>
Moreover, the intermediate layer 13 preferably contains a polar solvent. Thereby, the intermediate layer 13 can be adjusted to an optimum hardness, and the flexibility of the actuator 100 as a whole can be made particularly excellent. In addition, in the case of including an electrolyte that is solid as a single substance, the electrolyte can be suitably dissolved and ionized in the intermediate layer 13.

Examples of polar solvents include dimethyl sulfoxide (DMSO), acetonitrile, methylformamide, dimethylformamide (DMF), dimethylacetamide (DMA), ethyl acetate, acetone, tetrahydrofuran and other aprotic solvents, distilled water, RO water, ions Examples include water such as exchange water, pure water, tap water, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, glycerin, and alkoxyethanol, and protic solvents such as carboxylic acids such as formic acid, acetic acid, and propionic acid. In particular, it is preferable to use a protic solvent, and it is more preferable to use ion-exchanged water.
Thereby, in the case of including an electrolyte that is solid as a single substance, the electrolyte can be suitably dissolved and ionized in the intermediate layer 13.

Moreover, the counter ion with respect to an ion exchanger can be easily exchanged by immersing the ion exchanger mentioned above in the solution which dissolved the electrolyte mentioned above in the polar solvent.
Further, when the intermediate layer 13 includes a solvent, the solvent may be different from the solvent as a constituent component of the first deformable material layer 11 and the second deformable material layer 12, or the same or The same kind may be sufficient. Thereby, the compatibility of the interface between the intermediate layer 13 and the adjacent first deformable material layer 11 and second deformable material layer 12 is improved. As a result, the adhesion of these layers is improved, and the durability of the actuator 100 is improved.
The solvent content in the intermediate layer 13 is preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 60% by mass or less. Thereby, the actuator 100 can obtain necessary and sufficient flexibility and strength.

<Gelling agent>
Moreover, the intermediate layer 13 can use what contains a gelatinizer. Thereby, the intermediate | middle layer 13 can be adjusted to optimal hardness by selection of the kind, compounding quantity, etc. of a gelatinizer.
Examples of the gelling agent include various resin materials, materials such as agar, gelatin, alginate, gellan gum, etc., but vinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, and organic electrolyte oligomer It is preferable that 1 type or 2 types or more selected from the group which consists of consists of. Thereby, the retention power of the solvent (liquid component) contained in the gel-like intermediate layer 13 can be made excellent. As a result, the intermediate layer 13 can improve the temporal stability. Furthermore, the volume reduction of the actuator 100 over time can be prevented more effectively.

  The gelling agent as a constituent component of the first deformable material layer 11 and the second deformable material layer 12 and the gelling agent as a constituent component of the intermediate layer 13 may be different, but are the same or It is preferable that the same kind of component is included. Thereby, the adhesiveness between the intermediate layer 13 and the first deformable material layer 11 and the second deformable material layer 12 can be made particularly excellent. In addition, the anion can be moved more smoothly between the first deformable material layer 11 and the second deformable material layer 12 via the intermediate layer 13, and the anions in the intermediate layer 13 can be moved. Smooth movement. As a result, the reliability and durability of the actuator 100 can be made particularly excellent.

The content of the gelling agent in the mid layer 13 is preferably 0% by mass to 30% by mass, and more preferably 0% by mass to 10% by mass. Thereby, the intermediate | middle layer 13 can acquire moderate softness | flexibility, and the reliability and durability of the actuator 100 improve.
Further, the intermediate layer 13 may include components other than those described above.
The intermediate layer 13 is preferably in the form of a sheet, and the thickness thereof is not particularly limited, but can be appropriately set according to the shape and size of the actuator 100, and the thickness is 10 μm or more and 500 μm or less. It is preferable that it is 50 μm or more and 250 μm or less. Thereby, the actuator 100 can be made thinner.
The intermediate layer 13 is provided between the first deformable material layer 11 and the second deformable material layer 12 and is in contact with or in close contact with them.

  In FIGS. 1 and 2, the interface between the intermediate layer 13 and the first deformable material layer 11 is clearly shown. However, these clear interfaces may not exist, and in the vicinity of the interface, The material (component) of the first deformable material layer 11 and the intermediate layer 13 may exist in a mixed state. That is, a component (so-called gradient material) in which some of these components are sequentially changed in the thickness direction near the interface between the first deformable material layer 11 and the intermediate layer 13 may be used. Moreover, the unevenness | corrugation which the material of one layer penetrates into the material of the other layer may be provided in these interfaces. Thereby, the adhesiveness between the first deformable material layer and the intermediate layer 13 can be made particularly excellent. Moreover, the movement of ions between the first deformable material layer 11 and the intermediate layer 13 becomes smooth. The same applies to the interface between the second deformable material layer 12 and the intermediate layer 13.

The shape of the actuator 100 is not particularly limited, and includes various shapes such as a fiber shape, a sheet shape, a plate shape, and a rod shape, and the thickness of the deformable material may be relatively large.
Further, the first deformable material layer 11, the second deformable material layer 12, and the intermediate layer 13 may each have a uniform thickness or may partially differ in thickness.
In the structure including the intermediate layer 13 as in the present embodiment, it is possible to move ions between the first deformable material layer 11 and the second deformable material layer 12 via the intermediate layer 13. Therefore, smooth and stable energization is possible. In addition, the adhesion between the intermediate layer 13 and the first deformable material layer 11 and the second deformable material layer 12 is improved.

In particular, since the intermediate layer 13 as described above is present, even if the thicknesses of the first deformable material layer 11 and the second deformable material layer 12 and the actuator 100 are relatively large, The entire deformable material constituting the first deformable material layer 11 and the second deformable material layer 12 can be efficiently deformed. In addition, a sufficiently large amount of displacement can be obtained at a low voltage, and the response speed of the deformable material can be made excellent.
In addition, since the first deformable material layer 11 and the second deformable material layer 12 are provided via the intermediate layer 13 in the three-layer structure, the unidirectional expansion / contraction of the deformable material layer is not achieved. Without reversing the bending / bending.

Next, the operation of the actuator 100 (drive device 200) will be described based on FIG. 1, FIG. 2, and FIG.
When the stimulus-responsive compound constituting the first deformable material layer 11 and the second deformable material layer 12 is expanded (expanded) by being oxidized and contracted by being reduced (for example, as described above) The actuator 100 (drive device 200) as a whole exhibits the following behavior.

  That is, in the configuration shown in FIG. 1, when the switch 14 is turned on, the first deformable material layer 11 is connected to the positive electrode of the power source 10, and the first deformable material layer 11, the intermediate layer 13, and the second deformable material layer are connected. Electricity is supplied between the material layer 12. In the stimulus-responsive compound constituting the first deformable material layer 11, the molecular chain expands (expands) due to the oxidation reaction, and as a result, the entire first deformable material layer 11 expands (expands). On the other hand, the stimuli-responsive compound constituting the second deformable material layer 12 contracts the molecular chain due to the reduction reaction, and as a result, the entire second deformable material layer 12 contracts. Further, in the intermediate layer 13 of FIG. 1, as shown in FIG. 7B, the anions and water molecules in the anion exchanger contained in the intermediate layer 13 move to the first deformable material layer 11 side. The first deformable material layer 11 side of the intermediate layer 13 swells and the second deformable material layer 12 side contracts. For this reason, the deformation direction of the intermediate layer 13 and the deformation direction of the first deformation material layer and the second deformation material layer are the same direction, that is, the first deformation material layer 11 side (the upper side in the figure). ) To be convex. Further, as shown in FIG. 1 and FIG. 7B, the intermediate layer 13, the first deformable material layer 11, and the second deformable material layer 12 are curved in the same direction as shown in FIGS. The displacement amount of the entire 100 can be increased.

  In the configuration shown in FIG. 2, when the switch 14 is turned on, the polarity is reversed from that in FIG. 1, the first deformable material layer 11 is connected to the negative electrode of the power supply 10, and the first deformable material layer 11, the intermediate layer 13, and the second deformable material layer 12 are energized. In the stimulus-responsive compound constituting the first deformable material layer 11, the molecular chain contracts due to the reduction reaction, and as a result, the entire first deformable material layer 11 contracts. On the other hand, in the stimulus-responsive compound constituting the second deformable material layer 12, the molecular chain expands (expands) due to the oxidation reaction, and as a result, the entire second deformable material layer 12 expands (expands). Further, as shown in FIG. 7C, the intermediate layer 13 in FIG. 2 moves anions and water molecules in the anion exchanger contained in the intermediate layer 13 toward the second deformable material layer 12 side. The second deformable material layer 12 side of the intermediate layer 13 swells and the first deformable material layer 11 side contracts. Therefore, the deformation direction of the intermediate layer 13 and the deformation direction of the first deformation material layer and the second deformation material layer 12 are the same direction, that is, the second deformation material layer 12 side (in the drawing) Curved downward (to the bottom). Moreover, as shown in FIG. 2 and FIG. 7C, the displacement amount of the entire actuator 100 can be increased because the three-layer structure is curved in the same direction.

  In this way, the actuator 100 can change the direction of bending by changing the connection between the positive electrode and the negative electrode. Such an operation is reversible. Further, by reversing the characteristics of the current applied to the actuator 100 continuously or intermittently, the bending direction can be alternately changed repeatedly and can be continuously repeated. Moreover, the reproducibility is also excellent.

  As described above, the actuator 100 including the first deformable material layer 11 and the second deformable material layer 12 and the intermediate layer 13 is in a state in which the molecular chain extends (expands) in one deformable material layer. The other deformable material layer contracts. In this way, the first deformation material layer 11 and the second deformation material layer 12 take opposite states, whereby the deformation rate of the actuator 100 can be increased. In addition, since the first deformable material layer 11 and the second deformable material layer 12 are made of the materials described above, the expansion rate of each deformable material can be increased. Therefore, the deformation rate of the actuator 100 can be further increased by these synergistic effects. Furthermore, combined with the deformation of the intermediate layer 13, the actuator 100 can obtain a sufficiently large displacement force and displacement at a low voltage.

The voltage value applied to the actuator 100 is, for example, preferably from 0.1 V to 10 V, and more preferably from 1 V to 5 V. Thereby, a necessary and sufficient amount of deformation of the actuator 100 can be obtained.
Further, the energization of the actuator 100 is not limited to that using the direct current as described above, but can also use an alternating current or the like. Here, the alternating current refers to a current whose magnitude and direction change periodically with time, such as a sinusoidal alternating current or a pulsed rectangular current.

The frequency of the alternating current is not particularly limited, and may be determined in consideration of the response of the actuator 100. For example, the frequency of the alternating current may be 0.01 Hz or more and 100 Hz or less. As a result, energization suitable for the responsiveness of the actuator 100 is possible, and smooth continuous reversal motion is possible.
The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above.

For example, in the above-described embodiment, the structural unit of the stimulus-responsive compound includes the unit A, the first unit B, the second unit B, the first unit C, and the second unit C, In the present invention, the stimuli-responsive compound has a polymerizable functional group, and has a redox reaction by means of the case where the unit C and the second unit C have a polymerizable functional group. As long as the molecular structure is changed, the structural unit is not limited to one having all the above units.
In the above-described embodiment, the wiring drawn from the power source 10 has been described as being in contact with the first deformable material layer and the second deformable material layer. For example, the wiring faces the intermediate layer of the deformable material layer. A conductive film (eg, a metal film) may be provided on the surface opposite to the surface. Thereby, the response speed of the actuator can be further improved.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
Example 1
[1] Production of constitutional unit [1.1] Synthesis of unit A Dimerization and bromination using bromothiophene as a raw material using zinc and nickel catalysts, and introduction of aldehyde groups with DMF (formylation) .
Next, acetal protection of the aldehyde group with ethylene glycol was performed, and bromine was further converted into a formyl group. Subsequently, a diol (corresponding to unit A) having two hydroxyl groups in the bithiophene skeleton was obtained by a reduction reaction with NaBF ₄ .

[1.2] Synthesis of Unit C and Unit D First, 2,3-difluorophenylboronic acid was obtained by treating n-butyllithium with 1,2-difluorobenzene and treating with trimethylborate. .
Next, the compound represented by the following formula (16) is obtained by reacting the obtained 2,3-difluorophenylboronic acid with 1-bromo-4- (3-butenyloxy) benzene in the presence of a palladium catalyst. It was.

  Next, n-butyllithium was allowed to act on the obtained compound represented by the following formula (16) and treated with trimethyl borate to obtain a compound represented by the following formula (17). Next, the compound represented by the following formula (17) obtained was subjected to a coupling reaction with 1-bromo-4-iodobenzene, and the resulting compound was treated with n-butyllithium and trimethylborate to give the following: A unit C represented by the formula (18) was obtained.

Next, the obtained unit C represented by the above formula (18) was reacted with oligoethylene glycol having bromine at the end to obtain a liquid crystalline compound having an oligoethylene oxide chain at the end.
Further, by reacting with p-toluenesulfonyl chloride, a liquid crystalline compound having a p-toluenesulfonyl group at the terminal (corresponding to unit C and unit D) was obtained.

[1.3] Production of Structural Unit The diol synthesized in the above [1.1] and the liquid crystalline compound synthesized in the above [1.2] are reacted in dimethylformamide (DMF) in the presence of sodium hydride, Bithiophene derivatives into which liquid crystalline molecules were introduced were obtained.
Thereafter, the above bithiophene derivative is reacted with benzenedithiol in the presence of an acid catalyst, treated with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), boron tetrafluoride is added, unit A, unit B (First unit B, second unit B), unit C (first unit C, second unit C), unit D (first unit D, second unit D) The structural unit (bithiophene derivative) represented by 19) was obtained.
In the formula (19), n is 4.

[2] Production of stimulus-responsive compound The stimulus-responsive polymer was obtained by polymerizing the structural unit produced in [1] above.
[3] Preparation of liquid crystal polymer [3.1] Synthesis of monomer 1- (8-hydroxyoctyl-1-oxy) -4- [2,3-difluoro-4- (4-butoxyphenyl) phenyl] benzene (described below) Formula (20)) and triethylamine were dissolved in THF, cooled to 0 ° C., and acryloyl chloride was added dropwise. After stirring for 4 hours, water was added and the mixture was extracted three times with dichloromethane. The organic layer was washed with water and saturated brine, dried over sodium sulfate, filtered and concentrated. Purification by column chromatography gave the target compound.
In the formula (20), R is C ₄ H ₉ .

As described above, a monomer represented by the above formula (13) (n = 8, R = C ₄ H ₉ ) was obtained.

[3.2] Production of liquid crystal polymer The monomer: 100 parts by mass, bisacryloyloxyhexane as a crosslinking agent: 10 parts by mass, and azobisisobutyronitrile as an initiator: 1 part by mass in a Schlenk tube The solution is dissolved in toluene and freeze-deaerated three times to remove dissolved oxygen in the solvent. The mixture was stirred at 95 ° C. for 26 hours under a nitrogen atmosphere. After the solution is cooled, the solvent is distilled off, and then dissolved in a minimum amount of tetrahydrofuran. The solution is dropped into acetone, and the deposited precipitate is filtered and dried under vacuum to obtain a liquid crystal polymer (weight average molecular weight: 30,000). Got.

[4] Manufacture of deformable material The stimulus-responsive compound obtained as described above, a liquid crystalline polymer and polymethyl methacrylate (PMMA), carbon nano-particles having an average particle size of 39.5 nm and a porosity of 60 vol% Particles (manufactured by Lion Corporation, Ketjen Black EC300J), dimethyl sulfoxide (DMSO) as a solvent, and LiCl as an electrolyte were mixed. Then, this mixture was shape | molded using the type | mold of a predetermined shape, and the gel-shaped deformation material was obtained.

[5] Manufacture of Actuator Using the deformable material obtained as described above and the following intermediate layer, an actuator as shown in FIGS. 1 and 2 was prepared.
Aciplex A172 manufactured by Asahi Kasei Corporation as an anion exchange resin obtained by introducing a quaternary ammonium group into a styrene-divinylbenzene copolymer (anion exchange capacity: 0.18 to 0.19 meq / g, length: 2) .2 cm × width: 0.4 cm × thickness: 0.14 mm), and the deformable material obtained as described above is prepared on each of the two surfaces, 2.2 cm × width: 0.2 cm × thickness, respectively. The first deformable material layer and the second deformable material layer were formed by joining the materials cut to a size of 0.05 mm.
Thereafter, LiCl as an electrolyte was dissolved in ion-exchanged water as a polar solvent to obtain a 0.1 M LiCl aqueous solution. It was immersed in this LiCl aqueous solution for 24 hours, the counter ion (anion) of the anion exchange resin was replaced with Cl ion, and an actuator as shown in FIGS. 1 and 2 was manufactured.

(Examples 2 to 7)
An actuator was manufactured in the same manner as in Example 1 except that the configurations of the first deformable material layer, the second deformable material layer, and the intermediate layer were as shown in Tables 1 to 3.
(Comparative Example 1)
An actuator was manufactured in the same manner as in Example 1 except that the first deformable material layer and the second deformable material layer were joined without using an intermediate layer.
(Comparative Example 2)
An actuator was manufactured in the same manner as in Example 1 except that a cation exchange resin obtained by introducing a sulfonic acid group into a styrene-divinylbenzene copolymer was used as the intermediate layer.

  Table 1 shows the composition and conductivity of the deformable material layers (first deformable material layer and second deformable material layer) constituting the actuators of the respective Examples and Comparative Example 2, and Table 2 shows the above-mentioned respective examples. The compositions of the intermediate layers constituting the actuators of Examples and Comparative Example 2 are shown, and Table 3 shows the thickness of each part constituting the actuators of the Examples and Comparative Examples. In the table, the compound (structural unit) represented by the above formula (19) is represented by “A1”, the compound represented by the following formula (21) (structural unit) is represented by “A2”, and the following formula (22). The compound (structural unit) is “A3”, the monomer represented by the above formula (13) is “M1”, the monomer represented by the above formula (14) is “M2”, and bisacryloyloxyhexane as a crosslinking agent is “ B1 ", polymethyl methacrylate (weight average molecular weight: 10,000) as" PMMA ", carbon nanoparticle having an average particle diameter of 39.5 nm as electronic conductive material and porosity of 60 vol% (manufactured by Lion Co., Ltd.) Chain black EC300J) was “C1”, carbon nanoparticle (Ketjen black EC300J, manufactured by Lion Corporation) having an average particle diameter of 34.0 nm and a porosity of 80 vol% as an electronic conductive material was “C2”. The ion exchange water as the solvent is “S1”, the lithium chloride as the electrolyte is “E1”, the styrene-divinylbenzene copolymer “J1” as the resin material constituting the ion exchanger, and the negative ion constituting the ion exchanger. A quaternary ammonium group as an ion exchange group is indicated by “K1”, and a sulfonic acid group as a cation exchange group constituting the ion exchanger is indicated by “K2”. Further, the deformable material layers constituting the actuators of the respective examples and comparative examples are all in a gel form, and the intermediate layers constituting the actuators of the respective examples and comparative examples 2 are both in a gel form. It was what made.

  The conductivity of the first deformable material layer obtained in each example was in the range of 0.1 S / cm or more and 50 S / cm or less. Also. The conductivity of the second deformable material layer was in the range of 0.1 S / cm to 50 S / cm. Further, the anion exchange capacity of the intermediate layer of each example was in the range of 0.18 meq / g or more and 0.19 meq / g or less.

[6] Actuator evaluation [6.1] Deformation amount With the temperature of the electrolyte at 25 ° C., the energization direction is reversed from the state shown in FIG. 1 as shown in FIG. Displacement in the bending direction (vertical direction in FIGS. 1 and 2) at a location 10 mm from the contact point between the actuator and the external electrode (location indicated by X in FIGS. 1 and 2) was evaluated and evaluated according to the following criteria. . The applied voltage was 2V.
A: The displacement is 10 mm or more.

B: Displacement amount is 5 mm or more and less than 10 mm.
C: The displacement is 3 mm or more and less than 5 mm.
D: The displacement is 1 mm or more and less than 3 mm.
E: The displacement is less than 1 mm.
These results are shown in Table 4.

  As apparent from Table 4, in the present invention, the actuator can be greatly displaced at a relatively low voltage, and the entire deformable material layer can be efficiently removed even when the thickness of the deformable material layer is relatively large. It could be deformed, and a sufficiently large displacement force and displacement amount could be obtained at a low voltage. In the present invention, the response speed of the actuator was also excellent. Moreover, in this invention, it was excellent also in the operativity and durability in a low temperature area | region. On the other hand, in the comparative example, satisfactory results were not obtained.

  A ... Unit A B ... Unit B C ... Unit C D ... Unit D 200 ... Driving device 100 ... Actuator 10 ... Power supply 11 ... First deformable material layer 12 ... Second deformable material layer 12a ... Anion 12b ... Solvent molecule 13 ... Middle layer 14 ... Switch

Claims (15)

A first deformable material layer;
A second deformable material layer;
An intermediate layer provided between the first deformable material layer and the second deformable material layer;
The first deformable material layer includes a first deformable material including a first stimulus-responsive compound whose molecular structure is changed by a redox reaction,
The second deformable material layer includes a second deformable material including a second stimulus-responsive compound whose molecular structure is changed by a redox reaction,
The first stimulus responsive compound and / or the second stimulus responsive compound is a polymer in which a structural unit having a polymerizable functional group is polymerized,
The actuator according to claim 1, wherein the intermediate layer includes an ion exchanger for exchanging anions.   The actuator according to claim 1, wherein the deformable material is a gel.   3. The actuator according to claim 1, wherein the first deformable material layer and / or the second deformable material layer includes an electron conductive substance.   The actuator according to claim 3, wherein the electronically conductive substance contains carbon.   The actuator according to claim 3 or 4, wherein the electron conductive substance is a particle.   The actuator according to claim 5, wherein an average particle diameter of the electronic conductive material is 1 nm or more and 10 μm or less.   The actuator according to claim 1, wherein the structural unit includes a functional group having liquid crystallinity.   The actuator according to any one of claims 1 to 7, wherein in the structural unit, the functional group having liquid crystallinity and the polymerizable functional group are arranged via a linking group.   The actuator according to any one of claims 1 to 8, wherein the structural unit includes a polyalkylene oxide structure in which an alkylene oxide having 2 and / or 3 carbon atoms is polymerized. The structural unit includes a unit A having a coupling functioning as a rotation axis;
A first unit B disposed at a first binding site of the unit A;
A second unit B disposed at a second binding site of the unit A;
A first unit C;
A second unit C,
The first unit B and the second unit B are combined by a reduction reaction,
The actuator according to any one of claims 1 to 9, wherein the first unit C and the second unit C have the polymerizable functional group.   The actuator according to claim 10, wherein the unit C has the functional group having the liquid crystallinity.   The deformable material further includes one or more selected from the group consisting of a vinylidene fluoride-hexafluoropropylene copolymer, poly (meth) methyl acrylate, and an organic electrolyte oligomer. The actuator according to any one of 1 to 11.   The actuator according to any one of claims 1 to 12, wherein the ion exchanger is composed of an anion exchange resin and / or an ion exchange resin.   The actuator according to claim 1, wherein the ion exchanger has a quaternary ammonium group.   The actuator according to claim 1, wherein the first deformable material layer and / or the second deformable material layer includes an electrolyte.

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