JP2013237757A - Deforming material and actuator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deforming material capable of being widely deformed at a low voltage, and to provide an actuator using the same.SOLUTION: A deforming material comprises: a stimulus-responsive compound whose molecular structure changes by oxidation-reduction reaction; a polymer material; and an electron-conductive substance. It is preferable that the electron-conductive substance is in a particle shape in the deforming material. Moreover, it is preferable that an average particle diameter of the electron-conductive substance is 1 to 10 μm. Furthermore, it is preferable that the electron-conductive substance contains a carbon material.

Description

  The present invention relates to a deformable material and 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 a deformable material that can be largely displaced at a low voltage, and an actuator using the deformable material.

Such an object is achieved by the present invention described below.
The deformable material of the present invention includes a stimulus-responsive compound that changes the molecular structure by a redox reaction,
A polymer material;
And an electronic conductive material.
Thereby, the deformable material which can be largely displaced at a low voltage can be provided.

In the deformable material of the present invention, it is preferable that the electronic conductive substance includes a carbon material.
Thereby, the electron transport function is improved, and the entire deformable material can be greatly displaced at a relatively low voltage.
In the deformable material of the present invention, it is preferable that the electron conductive substance is in the form of particles.
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 deformable material of the present invention, it is preferable that the average particle diameter of the electron conductive substance 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 deformable material of the present invention, the polymer material is one or two selected from the group consisting of a 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 gelatinized more suitably. In addition, the deformable material can be operated more flexibly. 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 deformable material of the present invention, the polymer material preferably includes a liquid crystal polymer.
Thereby, 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 amount of displacement of the entire deformable material can be particularly large.

In the deformable material of the present invention, the liquid crystal polymer is preferably cross-linked by a cross-linking agent.
As a result, the deformable material can be suitably solidified (gelled), and the shape stability and handleability of the deformable material as a whole are particularly excellent. Thereby, the deformable material can more suitably perform anisotropic expansion and contraction.

In the deformable material of the present invention, the stimulus-responsive compound includes a functional group having liquid crystallinity,
The liquid crystal polymer preferably has in its molecule the same functional group as the functional group having the liquid crystal property of the stimulus-responsive compound.
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 more suitably amplified, and the displacement amount of the entire deformable material can be further increased. In addition, the deformable material can be deformed at a lower voltage.

In the deformable material of the present invention, it is preferable that the stimulus-responsive compound has a functional group having liquid crystallinity.
Thereby, 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 amount of displacement of the entire deformable material can be particularly large. In addition, the deformable material can be deformed at a lower voltage.

In the deformable material of the present invention, the stimulus-responsive compound includes a unit A having a bond that functions 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 redox reaction,
It is preferable that the first unit C and the second unit C are functional groups having the liquid crystallinity.
Thereby, the response speed and displacement of the stimulus-responsive compound (deformable material) can be made particularly excellent.

これにより、刺激応答性化合物は、より円滑な変形（変位）が可能となり、変形材料はより低電圧で駆動するものとなる。 In the deformable material of the present invention, the unit A is preferably one type selected from the group consisting of the following formula (1), the following formula (2), and the following formula (3).

As a result, the stimulus-responsive compound can be deformed (displaced) more smoothly, and the deformable material is driven at a lower voltage.

これにより、反応条件を調整することで、ユニットＢ同士の結合状態と非結合状態とを可逆的にかつより容易に進行させることができる。また、反応性が高いため、刺激応答性化合物は、より円滑で、かつより低電圧での変形が可能となる。 In the deformable material of the present invention, the first unit B and the second unit B are 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. In addition, since the reactivity is high, the stimulus-responsive compound can be more smoothly deformed at a lower voltage.

In the deformable material of the present invention, the functional group having liquid crystallinity has a plurality of ring structures,
It is preferable that one or more halogen atoms are bonded to one ring structure of the plurality of ring structures.
Thereby, the movement performance at the time of alignment of the functional group having liquid crystallinity can be made higher, and the speed of transition to alignment becomes faster. As a result, the deformable material can be deformed (displaced) faster and more smoothly, and can be driven at a lower voltage.

The actuator of the present invention is manufactured using the deformable material of the present invention.
Thereby, it is possible to provide an actuator that can be largely displaced at a low voltage.
The actuator of the present invention is formed using the deformable material of the present invention, and a deformable material layer connected to a power source,
A counter electrode connected to the power source;
An electrolyte solution interposed between the deformable material layer and the counter electrode is provided.
Thereby, it is possible to provide an actuator that can be largely displaced at a low voltage.

It is a figure for demonstrating the molecular structure before and behind the oxidation reduction reaction of the stimulus responsive compound which comprises the deformation | transformation material 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 deformation | transformation material 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 deformation | transformation material 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 deformation | transformation material of this invention. It is sectional drawing which shows typically an example of the actuator using the deformable material of this invention. It is sectional drawing which shows an example of the actuator deform | transformed by the voltage application.

Hereinafter, preferred embodiments of the present invention will be described in detail.
<Deformation material>
First, a preferred embodiment of the deformable material of the present invention will be described in detail.
The deformable material of the present invention mainly includes a stimulus-responsive compound, a polymer material, and an electronic conductive substance. Furthermore, the deformable material may contain a solvent, an electrolyte, and the like.

Hereinafter, each component constituting the deformable material of the present invention will be described in detail.
<Stimulus responsive compound>
First, the stimulus-responsive compound will be described.
1, FIG. 2, FIG. 3, and FIG. 4 are diagrams for explaining the molecular structure before and after the oxidation-reduction reaction of the stimulus-responsive compound constituting the deformable material of the present invention. 1 and 2 show a stimulus-responsive compound having no unit D, which will be described in detail later, and FIGS. 3 and 4 show a stimulus-responsive compound having a unit D, which will be described in detail later. 3 corresponds to FIG. 1, and FIG. 4 corresponds to FIG. In FIG. 1, FIG. 2, FIG. 3, and FIG. 4, ◯ 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 may be any compound as long as the molecular structure is changed by the oxidation-reduction reaction, but preferably has a functional group having liquid crystallinity. Thereby, 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 amount of displacement of the entire deformable material can be particularly large. In addition, the deformable material can be deformed at a lower voltage.

  When the stimulus-responsive compound includes a functional group having liquid crystallinity, the functional group having liquid crystallinity has a plurality of ring structures, and a halogen atom is present in one of the plurality of ring structures. It is preferable that one or more of are bonded. Thereby, the movement performance at the time of alignment of the functional group having liquid crystallinity can be made higher, and the speed of transition to alignment becomes faster. As a result, the deformable material can be deformed (displaced) faster and more smoothly, and can be driven at a lower voltage.

  The stimuli-responsive compound shown in FIG. 1A and the like has a unit A having a bond that functions as a rotation axis, and two units bonded to both ends of the unit A (a first binding site and a second binding site). B (first unit B and second unit B) and two units C (first unit C and second unit C), the first unit B and the second unit B binds 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) can be made particularly excellent.

Hereinafter, the stimulus-responsive compound as shown in FIG. 1 will be mainly described.
The unit A constituting the stimulus-responsive compound has a bond that functions as a rotation axis, and is a group (unit) that can rotate around 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 As a result, the stimulus-responsive compound can be deformed (displaced) more smoothly, and the deformable material is driven at a lower voltage.

As shown in FIG. 1A, 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. 1B). 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. Moreover, by stopping the application of voltage, the oxidation-reduction reaction can be stopped, and as a result, the shape of the deformable material can be maintained.

  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. In addition, since the reactivity is high, the stimulus-responsive compound can be more smoothly deformed at a lower voltage.

  Unit C (first unit C and second unit C) is a group having liquid crystallinity. By having liquid crystallinity, when an electric field or magnetic field is applied to the unit C, the unit C is arranged in a predetermined direction. As a result, the stimulus-responsive compound exhibits a predetermined direction for driving. Here, liquid crystallinity means that the orientation direction of molecules can be changed by applying an electric field or a magnetic field.

  The unit C (the first unit C and the second unit C) is not particularly limited as long as it is a group exhibiting liquid crystallinity, and includes a group having a plurality of ring structures, for example, a plurality of aromatic rings (for example, a phenyl group). ) Are linked by an ester group, and aromatic rings (for example, benzene rings) or cyclohexane rings are directly linked. 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.

Further, the unit C (the first unit C and the second unit C) may have a polymerizable functional group. A stimulus-responsive compound having a longer molecular chain can be formed by polymerizing the stimulus-responsive compound by the polymerizable functional group. Further, by elongating the molecular chain in this manner, as described in detail later, the degree of molecular deformation (displacement) can be increased, and it is possible to drive with a stronger force (stress).
Specific examples of the unit C (first unit C and second unit C) include the following.

  The unit C may be bonded to any site in the molecule of the stimulus-responsive compound. For example, the unit C may bind to the unit B, but binds to the unit A. preferable. 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 can be further improved.

  As described above, the stimuli-responsive compound is composed of the unit A capable of rotating the shaft and the two units bonded to both ends (the first binding site and the second binding site) of the unit A, and the redox Unit B (first unit B and second unit B) capable of forming a bond between units by reaction, and two units coupled to unit B (first unit B and second unit B) When the unit has the liquid crystallinity unit C (the first unit C and the second unit C), the unit can be deformed (displaced) with lower electric power, and the displacement Can be made relatively large. This is considered to be due to the following reasons.

That is, a plurality of stimuli-responsive compound molecules can exist in an aligned (aligned) state 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 be connected to each other. Bonds (crosslinks) by redox reaction. Thus, by utilizing the orientation (liquid crystallinity) of unit C and the binding property of unit B by stimulation, the state shown in FIG. 1 (a) can be reliably changed to the state shown in FIG. 1 (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, when the stimulus responsive compound polymerized using the polymerizable functional group of the unit C is used, as described above, further large deformation is possible at a low voltage.

  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.2 (a), it exists in the state which the structural unit extended in the longitudinal direction. Thereby, the three-dimensional structure of the molecule is in an expanded (expanded) state. Then, in the state in which the stimuli-responsive compound is reduced, as shown in FIG. 2B, 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.

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, as a whole stimulus-responsive material, the degree of displacement is larger 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 the respective structural units. It can be.
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 stimuli-responsive compound further includes intramolecular In addition, a unit D including a polyalkylene oxide structure obtained by polymerizing an alkylene oxide having 2 and / or 3 carbon atoms may be included (see FIGS. 3 and 4). Thereby, it can deform | transform suitably with a lower voltage. Further, the flexibility of the deformable material can be further improved. Moreover, crystallization of the deformable material containing the stimulus-responsive compound can be reliably prevented even at a low temperature, and the operability in a low temperature region (for example, −10 ° C. or lower) can be made particularly excellent. Further, since the stimulus-responsive compound contains unit D, the stimulus-responsive compound as a whole can have excellent affinity and compatibility with the salt (electrolyte), and charge transfer in the oxidation-reduction reaction. Will be faster. As a result, the response speed of the deformable material containing the stimulus responsive compound becomes faster.

The stimulus-responsive compound may include one unit D in the molecule, but in the configuration shown in FIG. 3, 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 deformable material and the operability in the low temperature region can be further improved.
The unit D may bind to any site in the molecule of the stimulus-responsive compound. For example, the unit D may bind to the unit B, but binds to the unit A. preferable. 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 deformable material and the operability in the 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 deformable material and the operability in the 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 formed by polymerizing alkylene oxides having 2 and / or 3 carbon atoms.

When the unit D has a structure obtained by polymerizing alkylene oxide (ethylene oxide) having 2 carbon atoms, flexibility of the deformable material, operability in a low temperature region, and the like can be made particularly excellent. Further, the response speed of the deformable material 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 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 is sufficiently excellent, the flexibility of the deformable material, the operability in the low temperature region, etc. can be made particularly excellent, and the response speed of the deformable material is particularly fast. can do.

  As described above, in the present invention, the stimulus-responsive compound is a compound in which the three-dimensional structure of the molecule is changed by a redox reaction. This is easily deformed (displaced) by applying a voltage, and as a result, the entire deformable material can be greatly displaced. As a result, for example, when a deformable material is applied to the actuator, a sufficiently large displacement force and displacement amount can be obtained at a low voltage. Further, the response speed of the deformable material can be made excellent, and the deformation reproducibility is also excellent. Further, the weight of the deformable material and the weight of the actuator to which the deformable material is applied can be reduced.

In addition, the change in the three-dimensional structure of a stimulus-responsive compound due to an oxidation-reduction reaction is reversible. Displacement from a contracted state to an expanded (expanded) state, and displacement from an expanded (expanded) state to a contracted state Can be repeated 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 mainly composed of the stimulus-responsive compound has the same effect. As a result, the entire deformable material can have a large degree of deformation (deformation rate) and can have directionality in the deformation. And the shape of a deformable material can be hold | maintained by stopping the application of a voltage. Therefore, such a deformable material can be suitably used for manufacturing an excellent actuator.
The content of the stimulus-responsive compound in the deformable material is preferably 10% by mass or more and 80% by mass or less, and more preferably 20% by mass or more and 60% by mass or less. Thereby, the effect of the present invention by including a polymer material and an electron conductive substance as described in detail later together with the stimulus-responsive compound as described above is more remarkably exhibited.

<Polymer material>
The deformable material of the present invention includes a polymer material in addition to the stimulus-responsive compound as described above. As a result, the polymer material is also displaced with the deformation of the stimuli-responsive compound due to the redox reaction. As a result, the degree of deformation due to the redox reaction is amplified, and the degree of deformation of the entire deformable material is reduced. Can be big.

  As the polymer material constituting the deformable material of the present invention, various resin materials can be used. However, the deformable material of the present invention includes, as the polymer material, vinylidene fluoride-hexafluoropropylene copolymer, poly ( It is preferable that 1 type (s) or 2 or more types selected from the group which consists of methyl methacrylate and an organic electrolyte oligomer are included. Thereby, the whole deformation | transformation material can be gelatinized more suitably. In addition, the deformable material can be operated more flexibly. 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 particular, when the deformable material of the present invention includes a vinylidene fluoride-hexafluoropropylene copolymer as the polymer material, the deformable material can be made more flexible.
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 (9).

In formula (9), a is preferably from 0.60 to 0.98, and more preferably from 0.75 to 0.95. Thereby, the deformable material can have flexibility more suitable for deformation.
Moreover, when the deformable material of the present invention contains polymethyl methacrylate as the polymer material, it is possible to more reliably prevent cracks and the like from occurring when the deformable material is deformed.
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 (10).

Moreover, when the deformable material of the present invention contains an organic electrolyte oligomer as a polymer material, the organic electrolyte oligomer can also serve as an electrolyte described later.
In addition, as an organic electrolyte oligomer, what is represented by following formula (11) can be used, for example.

（式（１１）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 (11), 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.)

  When the deformable material contains one or more selected from the group consisting of vinylidene fluoride-hexafluoropropylene copolymer, poly (meth) methyl acrylate, and organic electrolyte oligomer, The sum of the content ratios of these compounds in is preferably 5% by mass or more and 50% by mass or less. Thereby, the effects as described above can be more remarkably exhibited while sufficiently exhibiting the functions of the stimulus-responsive compound and the electronic conductive material.

The deformable material of the present invention may contain a liquid crystal polymer as a polymer material. Thereby, 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 amount of displacement of the entire deformable material can be particularly large.
In particular, it is preferable that the liquid crystal polymer has a function to assist so as to be advantageous for deformation of the molecule due to the three-dimensional structure of the stimulus-responsive compound as described above. In particular, when the deformable material includes a stimulus-responsive compound having a functional group having liquid crystallinity, by including a liquid crystal polymer, a functional group having liquid crystallinity (unit) due to a redox reaction of the stimulus-responsive compound With the change in the orientation of (C), the orientation of the liquid crystal polymer also changes favorably for the deformation of the molecule due to the three-dimensional structure of the stimulus-responsive compound as described above. For this reason, the deformation | transformation as the whole deformable material can make the degree larger and the response speed faster. That is, the deformable material 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 methacryl group.
Examples of such a monomer include compounds represented by the following formula (6) or (7).

（式（６）、（７）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 (6) and (7), 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 as a polymer material, the liquid crystal polymer is preferably crosslinked by a crosslinking agent. Thereby, a deformable material can be solidified (gelled) suitably. That is, by including a liquid crystal polymer having a crosslinked structure, a stimulus-responsive compound can be taken into the molecule and the deformable material can be solidified (gelled). As a result, the shape stability and handleability of the deformable material as a whole are particularly excellent. Thereby, the deformable material can more suitably perform anisotropic expansion and contraction. 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 monomers, and any cross-linking agent may be used. By using a cross-linking agent represented by the following formula (8), liquid crystal The stimulus-responsive compound can be easily incorporated into the polymer molecule, and the deformable material can be solidified (gelled) more reliably.

（式（８）中、ｍは４以上の整数を示す。）

(In formula (8), 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 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. 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 entire deformable material can be further increased. In addition, the deformable material 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.
By using the liquid crystal polymer as described above, the response speed of the 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 amount of displacement of the entire deformable material can be particularly large.

The content of the liquid crystal polymer in the deformable material is preferably 3% by mass or more and 40% by mass or less. Thereby, the effects as described above are more remarkably exhibited while sufficiently exhibiting the functions of the stimulus-responsive compound and the electronic conductive material.
Further, the deformable material of the present invention is used as a polymer material with one or more selected from the group consisting of vinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, and organic electrolyte oligomer. When the liquid crystal polymer is included, the above-described effects can be obtained, and these can act synergistically to further improve the strength of the deformable material and to increase the displacement. can do.
The content of the polymer material in the deformable material is preferably 5% by mass or more and 80% by mass or less. Thereby, the effects as described above are more remarkably exhibited.

<Electronic conductive material>
The deformable material of the present invention includes an electron conductive substance having a function of transporting electrons in the deformable material, in addition to the stimulus-responsive compound and the polymer material as described above.
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 are more preferable. Thereby, high electronic conductivity can be provided to the whole deformable material.

  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. Since electrons are transported only on the surface of the particles, the use of carbon nanoparticles having a hollow shell structure further improves the electron transport function. Further, the entire deformable material can be greatly displaced with a relatively low voltage.

  When carbon nanoparticles having a hollow shell structure are used as the electron conductive substance, 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. More preferably, it is 60 volume% or more and 80 volume% or less. Thereby, the above effects can be more remarkably exhibited while sufficiently maintaining the shape stability of the carbon nanoparticles (electroconductive substance). As a result, the above effects can be exhibited stably over a long period of time, the uniformity of characteristics among lots of deformable materials, and the characteristics between individuals when the deformable materials are applied to actuators, etc. The uniformity 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, it is possible to uniformly disperse the electron conductive material throughout the deformable material, and it is possible to displace the entire deformable material uniformly and largely at a relatively low voltage.

  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. Moreover, the electron supply efficiency to the stimulus-responsive compound can be made particularly excellent, and a larger displacement force and displacement amount can be obtained. 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 size 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 electronically conductive material as described above, the entire deformable material can be greatly displaced at a relatively low voltage. In addition, the entire deformable material can be efficiently deformed. As a result, for example, when a deformable material is applied to the actuator, a sufficiently large displacement force and displacement amount can be obtained at a low voltage. In addition, when an actuator is manufactured using the deformable material of the present invention, the deformable material (deformable material layer) is displaced sufficiently large without contacting the electrode over a wide area of the deformable material (deformed material layer). Can do. As a result, the actuator can be operated flexibly.

  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. 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 material 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 efficiently deformed.

  As described above, the deformable material of the present invention includes a stimulus-responsive compound whose molecular structure is changed by an oxidation-reduction reaction, a polymer material, and an electron conductive substance. Thereby, the whole deformable material can be largely displaced with a relatively low voltage. In particular, even when the thickness of the deformable material is relatively large, the entire deformable material can be efficiently deformed. As a result, for example, when a deformable material is applied to the actuator, a sufficiently large displacement force and displacement amount can be obtained at a low voltage. Further, the response speed of the deformable material can be made excellent. Further, the weight of the deformable material and the weight of the actuator to which the deformable material is applied can be reduced. In addition, since the deformable material as a whole can be solid or gelled, the deformable material is excellent in handleability (easy to handle) and the application range of the deformable material can be expanded. Further, since the entire deformable material can be in the form of a gel, it can be suitably used for manufacturing an actuator that operates flexibly.

<Solvent>
The deformable material of the present invention may contain a solvent. When the solvent is incorporated into the stimulus-responsive compound or the like, the deformable material is suitably gelled, so that it can be easily solidified and the handleability of the deformable material can be improved.
Examples of the solvent include dimethyl sulfoxide (DMSO), toluene, benzene, dimethylformamide (DMF), dimethylacetamide (DMA), chloroform, dichloromethane, dichloroethane, acetone, propylene carbonate, methylpentanone, ethylpentanone, and acetonitrile. Mention may be made of organic solvents.
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.

<Electrolyte>
Moreover, the deformable material of the present invention may contain 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 inorganic salts such as lithium perchlorate, lithium trifluoromethanesulfonate, and lithium hexafluorophosphate; tetrabutylammonium tetrafluoroboron, 1-butyl-1-methylpyrrolidinium bis (tri Fluoromethylsulfonyl) imide (BMPTFSI), Methyl-trioctylammonium bis (trifluoromethylsulfonyl) imide (MTOATFSI), Triethylsulfonylium bis (trifluoromethylsulfonyl) imide (TESTFSI), 1-ethyl-3-methylimidazolium An organic salt such as trifluoromethane sulfonate (EMICF ₃ SO ₃ ) can be used. The structural formulas of BMPTFSI, MTOATSI, TESTFSI, and EMICF ₃ SO ₃ are represented by the following formula (12), the following formula (13), the following formula (14), and the following formula (15), respectively.

  The deformable material includes, as an electrolyte, one or more selected from the group consisting of lithium perchlorate, lithium trifluoromethanesulfonate, lithium hexafluorophosphate, and tetrabutylammonium tetrafluoroboron. It is preferable that As a result, the response speed of the stimulus-responsive compound (deformable material) can be further effectively improved, and the displacement of the entire deformable material accompanying the expansion and contraction of the stimulus-responsive compound can be further amplified.

  By including the electrolyte as described above, charge transfer to the stimulus-responsive compound can be advanced more rapidly, and the high-speed response of the deformable material can be made particularly excellent. Further, in the actuator as described later, the stimuli-responsive compound constituting the deformable material layer can be efficiently expanded and contracted over the entire deformable material layer (particularly, the entire thickness direction of the deformable material layer). As a result, the expansion / contraction rate of the entire deformable material layer can be made particularly large.

In particular, when the deformable material contains an electrolyte together with a solvent, the response speed of the stimulus-responsive compound (deformable material) can be further effectively improved, and the displacement of the entire deformable material accompanying the expansion and contraction of the stimulus-responsive compound can be reduced. Further amplification is possible.
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.
Moreover, the deformable material of the present invention may contain components other than those described above.
The conductivity of the deformable material is preferably 0.1 S / cm or more, and more preferably 1 S / cm or more. Thereby, it can be suitably applied to an actuator described in detail later, and the actuator can be miniaturized.

<Actuator>
Next, an actuator using the above-described deformable material of the present invention (the above-described stimulus-responsive compound (including a stimulus-responsive compound polymer), a polymer material, and a deformable material including an electronic conductive substance) will be described in detail. explain.
FIG. 5 is a cross-sectional view schematically showing an example of an actuator using the deformable material of the present invention, and FIG. 6 is a cross-sectional view showing an example of an actuator deformed (contracted) by applying a voltage.

The actuator of the present invention is manufactured using the deformable material of the present invention. Thereby, it is possible to provide an actuator that can be largely displaced at a low voltage.
In particular, as shown in FIG. 5, the actuator 100 of the present embodiment includes a switch 15 that turns on and off the power supply 10, and a deformable material layer 11 that is formed using the deformable material of the present invention and is connected to the power supply 10. , A counter electrode 12 connected to the power source 10, an electrolytic solution 13 interposed between the deformable material layer 11 and the counter electrode 12, and a container 14. The container 14 contains an electrolytic solution 13. Then, the deformable material layer 11 and the counter electrode 12 are spaced apart from each other by a predetermined distance and are immersed in the electrolytic solution 13.

  In the state shown in FIG. 5, the power source 10 is a DC power source, and the deformable material layer 11 is connected to the positive electrode of the power source 10 via the switch 15, and the counter electrode 12 is connected to the negative electrode. When the stimulus-responsive compound constituting the deformable material layer 11 has a structure as shown in FIGS. 1 to 4, energization is performed between the deformable material layer 11 and the counter electrode 12 when the switch 15 is turned on. The stimulus-responsive compound takes a state in which the molecular chain is elongated (expanded) by the oxidation reaction. As a result, the deformable material layer 11 as a whole is in an expanded (expanded) state.

On the other hand, in the state shown in FIG. 6, the deformable material layer 11 is connected to the negative electrode of the power supply 10 via the switch 15, and the counter electrode 12 is connected to the positive electrode. When the stimulus-responsive compound constituting the deformable material layer 11 has a structure as shown in FIGS. 1 to 4, energization is performed between the deformable material layer 11 and the counter electrode 12 when the switch 15 is turned on. The stimulus-responsive compound takes a state in which the molecular chain is contracted by a reduction reaction. As a result, the deformable material layer 11 as a whole is in a contracted state.
The deformable material layer 11 is made of the above-described deformable material, functions as an electrode in the electrolytic solution 13, and is a layer that deforms when a voltage is applied.

  In addition, the shape of the deformable material layer 11 is not particularly limited, and various shapes such as a fiber shape, a sheet shape, a plate shape, and a rod shape may be used, and the thickness of the deformable material may be relatively large. Here, the thickness of the deformable material layer 11 is not particularly limited, but is preferably 0.01 mm or more and 10 mm or less, and more preferably 0.05 mm or more and 2 mm or less. Thereby, a larger displacement force can be obtained while the drive voltage is relatively low. Further, in the conventional small actuator, there is a problem that when the thickness of the deformable material layer 11 is increased, the displacement force and the amount of displacement are rapidly decreased. Even if it is relatively large, the actuator can be suitably driven. That is, when the thickness of the deformable material layer 11 is as described above, the effect of the present invention is more remarkably exhibited.

The counter electrode 12 is made of a conductive material. Examples of the constituent material of the counter electrode 12 include metal materials (including alloys) such as Pt, Al, Cu, and Fe.
The electrolyte solution 13 can be the same as the electrolyte contained in the deformable material as described above, but may be entirely or partially different. The electrolytic solution 13 may be any liquid having electrical conductivity, but a solution in which an ionic substance is dissolved in a solvent can be suitably used.

Examples of the ionic substance include inorganic salts such as sodium chloride, lithium perchlorate, lithium trifluoromethanesulfonate, lithium hexafluorophosphate, and tetrabutylammonium tetrafluoroboron.
As the solvent, for example, propylene carbonate or the like can be used.
Since the deformable material of the present invention contains an electronic conductive substance, even if the deformable material layer 11 is relatively thick, the entire deformable material layer 11 can be efficiently used in the oxidation reaction and the reduction reaction as described above. Since it can be deformed, the deformation amount (displacement amount) of the deformable material layer 11 as a whole can be made sufficiently large, and the displacement force can be made sufficiently large.

As described above, the deformable material of the present invention can be expanded and contracted a plurality of times by repeating expansion (expansion) and contraction, and is excellent in reproducibility. Therefore, in the actuator of the present invention, not only the direct current structure as described above but also an alternating current structure can be adopted, and the actuator can be repeatedly expanded and contracted.
Thereby, while being able to provide the actuator which can be displaced largely with a low voltage, the deformable material layer 11 comprised with the deformable material of this invention can be operated by a more flexible motion.
As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.

  For example, in the above-described embodiment, the stimulus-responsive compound mainly includes a unit A, a first unit B, a second unit B, a first unit C, and a second unit C. As described above, in the present invention, the stimulus-responsive compound may be any compound that changes its molecular structure due to the oxidation-reduction reaction, and is not limited to one having all of the above units.

  Further, the actuator of the present invention may be any one as long as it is manufactured using the deformable material of the present invention, and has the structure shown in FIGS. The present invention is not limited to a material that is formed using a material and includes a deformable material layer connected to a power source, a counter electrode connected to the power source, and an electrolytic solution interposed between the deformable material layer and the counter electrode. .

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 stimuli-responsive compound [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) went.
Next, acetal protection of the aldehyde group with ethylene glycol was performed, and bromine was further converted into a formyl group. Subsequently, a diol having two hydroxyl groups on the bithiophene skeleton was obtained by a reduction reaction with NaBF ₄ .

[1.2] Synthesis of Unit C and Unit D First, 2,3-difluoroboronic acid was obtained by allowing n-butyllithium to act on 2,3-difluorobenzene and treating with trimethyl borate.
Next, 4- (1-alkoxyphenyl) -2,3-difluorobenzene was obtained by reacting the obtained 2,3-difluoroboronic acid with 4-alkoxy 1-bromobenzene in the presence of a palladium catalyst.
Next, n-butyllithium is allowed to act on the obtained 4- (4-alkoxyphenyl) -2,3-difluorobenzene and treated with trimethyl borate to give 4- (4-alkoxyphenyl) -2, 3-Difluoroboronic acid was obtained.

Next, 4-bromophenol was reacted with the obtained 4- (4-alkoxyphenyl) -2,3-difluoroboronic acid in the presence of palladium to give 1-hydroxy-4- [4- (4-alkoxyphenyl- 2,3-Difluorophenyl] benzene was obtained.
Next, the obtained 1-hydroxy-4- [4- (4-alkoxyphenyl-2,3-difluorophenyl] benzene is reacted with oligoethylene glycol having a terminal bromine, and a liquid crystal having an oligoethylene chain at the terminal. Further, by reacting with paratoluenesulfonyl chloride, a liquid crystalline compound having a paratoluenesulfonyl group at the terminal was obtained.

[1.3] Production of stimuli-responsive compound The diol synthesized in [1.1] and the liquid crystalline compound synthesized in [1.2] are reacted in dimethylformamide (DMF) in the presence of sodium hydride. Thus, a bithiophene derivative having liquid crystal molecules introduced therein was 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 stimulus-responsive compound (bithiophene derivative) represented by 17) was obtained.
In the formula (17), n is 4.

[2] Preparation of polymer material [2.1] Synthesis of monomer 1- (8-hydroxyoctyl-1-oxy) -4- [2,3-difluoro-4- (4-butoxyphenyl) phenyl] benzene ( The following formula (18)) 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 (18), R is C ₄ H ₉ .

As described above, a monomer represented by the above formula (6) (n = 8, R = C ₄ H ₉ ) was obtained.

[2.2] 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.

[2.3] Mixing of liquid crystal polymer and vinylidene fluoride-hexafluoropropylene copolymer Thereafter, liquid crystal polymer obtained as described above: 1 part by weight, and vinylidene fluoride-hexafluoropropylene copolymer Combined (weight average molecular weight: 150,000): 2 parts by weight were mixed.
[3] Manufacture of deformable material The stimuli-responsive compound obtained as described above, a liquid crystalline polymer and a vinylidene fluoride-hexafluoropropylene copolymer, an average particle size: 39.5 nm, and having continuous pores Porosity as a porous body: 60% by volume of carbon nanoparticles (manufactured by Lion Corporation, Ketjen Black EC300J), propylene carbonate as a solvent, and lithium hexafluorophosphate 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.

[4] Manufacture of Actuator Using the deformable material obtained as described above, an actuator as shown in FIG. 5 was created.
The deformable material obtained as described above is cut into a size of length: 20 cm × width: 0.3 cm × thickness: 0.05 mm, and this is used as a deformable material layer to form an actuator as shown in FIG. Manufactured. A plate material made of platinum (Pt) was used as the counter electrode, and a 1M lithium hexafluorophosphate propylene carbonate solution was used as the electrolyte.

(Examples 2 to 6)
A deformable material and an actuator were manufactured in the same manner as in Example 1 except that the configuration of the deformable material was as shown in Table 1.
(Comparative Example 1)
A deformable material and an actuator were manufactured in the same manner as in Example 1 except that no electronic conductive material was used.

  For each of the above Examples and Comparative Examples, the composition of the deformable material and the like are shown together in Table 1. In the table, the compound represented by the above formula (17) (stimulus responsive compound) is “A1”, the compound represented by the following formula (19) (stimulus responsive compound) is “A2”, and the following formula ( The compound represented by 20) (stimulus responsive compound) is “A3”, the compound represented by the following formula (21) (stimulus responsive compound) is “A4”, and the monomer represented by the above formula (6) is represented by “M1”, “M2” as the monomer represented by the above formula (7), “B1” as bisacryloyloxyhexane as a crosslinking agent, and a vinylidene fluoride-hexafluoropropylene copolymer (weight average molecular weight: 150, 000) is “PVdF”, the average particle size as an electronically conductive material is 39.5 nm, and the porosity is 60 vol% (Lion Corporation, Ketjen Black EC300J) is “C1”, the electronically conductive material. Average grain : Carbon nanoparticle (34.0 nm, porosity: 80 vol%, Ketjen Black EC300J) “C2”, propylene carbonate “S1” as solvent, lithium hexafluorophosphate as electrolyte “ E1 ". Further, the deformable materials of the respective Examples and Comparative Example 1 were all in a gel form.

[5] Actuator evaluation [5.1] Deformation amount With the temperature of the electrolyte set at 25 ° C., the energization direction is reversed as shown in FIG. Directional displacement was observed and evaluated according to the following criteria. The applied voltage was 5V.

A: The displacement is 12 mm or more.
B: The displacement is 10 mm or more and less than 12 mm.
C: The displacement is 8 mm or more and less than 10 mm.
D: The displacement is 6 mm or more and less than 8 mm.
E: The displacement is less than 6 mm.

  As is apparent from Table 2, in the present invention, the entire deformable material can be greatly displaced at a relatively low voltage, and the entire deformable material can be efficiently deformed even when the thickness of the deformable material is relatively large. It was possible to obtain a sufficiently large displacement force and displacement at a low voltage. In the present invention, the response speed of the deformable material 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, a satisfactory result was not obtained.

  A ... Unit A B ... Unit B C ... Unit C D ... Unit D 100 ... Actuator 10 ... Power supply 11 ... Deformable material layer 12 ... Counter electrode 13 ... Electrolyte solution 14 ... Container 15 ... Switch

Claims (15)

A stimulus-responsive compound that changes the molecular structure by a redox reaction;
A polymer material;
An electronically conductive material;
A deformable material comprising:   The deformable material according to claim 1, wherein the electronically conductive substance includes a carbon material.   The deformable material according to claim 1, wherein the electron conductive substance is in the form of particles.   The deformable material according to claim 3, wherein an average particle diameter of the electron conductive substance is 1 nm or more and 10 μm or less.   2. The polymer material includes one or more selected from the group consisting of vinylidene fluoride-hexafluoropropylene copolymer, poly (meth) methyl acrylate, and an organic electrolyte oligomer. 5. The deformable material according to any one of items 4 to 4.   The deformable material according to any one of claims 1 to 5, wherein the polymer material includes a liquid crystal polymer.   The deformable material according to claim 6, wherein the liquid crystal polymer is crosslinked with a crosslinking agent. The stimulus responsive compound has a functional group having liquid crystallinity,
The deformable material according to claim 6 or 7, wherein the liquid crystal polymer has in its molecule the same functional group as the functional group having the liquid crystal property of the stimulus-responsive compound.   The deformable material according to any one of claims 1 to 8, wherein the stimulus-responsive compound includes a functional group having liquid crystallinity. The stimulus-responsive compound includes a unit A having a bond that functions 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 redox reaction,
The deformable material according to claim 8 or 9, wherein the first unit C and the second unit C are functional groups having the liquid crystallinity. The deformable material according to claim 10, wherein the unit A is one selected from the group consisting of the following formula (1), the following formula (2), and the following formula (3).

The deformable material according to claim 10 or 11, wherein the first unit B and the second unit B are groups represented by the following formula (4).

The functional group having liquid crystallinity has a plurality of ring structures,
The deformable material according to claim 8, wherein one or more halogen atoms are bonded to one of the plurality of ring structures.   An actuator manufactured using the deformable material according to any one of claims 1 to 13. A deformable material layer formed using the deformable material according to any one of claims 1 to 13 and connected to a power source;
A counter electrode connected to the power source;
An actuator comprising: an electrolyte solution interposed between the deformable material layer and the counter electrode.

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