JP2015165736A - Actuator and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an actuator excellent in durability and excellent in adhesion between a deformable material and an electrode.SOLUTION: An actuator 100 includes: a conductive films 13, 14 composed of a metal material; and a deformable material layer 15, provided on the conductive films 13, 14, composed of a material containing a stimulant responsive compound that deforms a molecular structure by an oxidation reduction reaction. The metal material and the stimulant responsive compound are bonded by a covalent bond. The conductive films 13, 14 are preferably composed of Au.

Description

  The present invention relates to an actuator and a method for manufacturing the 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 adhesiveness between the deformable material (stimulus responsive compound) that deforms when a voltage is applied and the electrode is insufficient, and along with the deformation of the actuator, the deformable material (stimulus responsive compound) and the electrode There was a problem that peeling occurred between the two. Such a problem occurred more remarkably when the amount of deformation of the actuator was increased.

JP 2011-162473 A

  The object of the present invention is to provide an actuator having excellent adhesion between the deformable material and the electrode and excellent in durability, and producing an actuator excellent in adhesion between the deformable material and the electrode and excellent in durability. An object of the present invention is to provide an actuator manufacturing method that can be manufactured well.

Such an object is achieved by the present invention described below.
The actuator of the present invention includes a conductive film made of a metal material,
A deformable material layer provided on the conductive film and made of a material containing a stimulus-responsive compound whose molecular structure is deformed by an oxidation-reduction reaction;
The metal material and the stimulus-responsive compound are bonded by a covalent bond.

  Thereby, the actuator excellent in the adhesiveness of a deformable material and an electrode (conductive film) and excellent in durability can be provided.

  In the actuator of the present invention, it is preferable that the conductive film is composed of Au.

  Thereby, the conductivity of the conductive film and the adhesion between the deformable material and the conductive film can be made compatible at a higher level. In addition, since Au is a material that is relatively excellent in chemical stability, it can stably maintain excellent electrical conductivity in the actuator for a long period of time, while at the time of manufacturing the actuator, it can be used as a stimulus-responsive compound. It is a material that can be suitably subjected to chemical modification as a pretreatment for forming a covalent bond therebetween. Therefore, it is possible to make the actuator productivity particularly excellent while making the actuator reliability and durability particularly excellent.

  In the actuator of the present invention, it is preferable that the metal material is bonded to the stimulus-responsive compound by a surface treatment with a compound having an alkanethiol structure having a vinyl group at a terminal.

  Thereby, the chemical stability of the conductive film can be made particularly excellent, and the durability of the actuator can be made particularly excellent. In particular, durability against oxygen and water can be made particularly excellent, and the reliability of the actuator can be made particularly excellent. In addition, when manufacturing an actuator, a metal material and a chemical modifier with high reactivity under simple and mild conditions (for example, a condition that a liquid containing a chemical modifier is applied to a conductive film in a room temperature environment). And the actuator productivity can be made particularly excellent.

  In the actuator of the present invention, it is preferable that the metal material and the stimulus-responsive compound are bonded via a chemical structure having a polysiloxane structure.

  This increases the degree of freedom of deformation compared to the case where they are directly bonded without any other chemical structure between the metal material and the stimulus-responsive compound. This is advantageous in realizing smooth deformation. In addition, since the polysiloxane structure is excellent in chemical stability, it is advantageous for improving the reliability and durability of the actuator.

In the actuator of the present invention, the stimulus-responsive compound has a bond that functions as a rotation axis, and a first group located at one end of the bond and a second group located at the other end of the bond. A unit A having
A first unit B disposed at a first binding site of the first group;
A second unit B disposed at a second binding site of the second group;
A first unit C coupled to a reaction part involved in the reaction of formation of the covalent bond;
A second unit C connected to a reaction part involved in the reaction for forming the covalent bond,
It is preferable that the first unit B and the second unit B are bonded by a reduction reaction.

  As a result, faster and smoother deformation (displacement) is possible, and driving is performed at a lower voltage.

  In the actuator of the present invention, it is preferable that the first unit C and the second unit C include a ring structure having aromaticity.

  Thereby, the chemical stability of the stimulus-responsive compound can be further improved. Further, at the time of producing the stimuli-responsive compound, the deformable part (site deformed by the redox reaction) and the reactive part (site involved in the reaction for forming the covalent bond) can be easily combined. In addition, it is possible to more effectively suppress steric hindrance (rotation barrier) during the redox reaction. As a result, the speed of movement of the stimulus-responsive compound is increased.

In the actuator of the present invention, the first unit C is arranged at a third binding site of the first group,
The second unit C is preferably arranged at the fourth binding site of the second group.

  This more effectively prevents the redox reaction of the stimuli-responsive compound from being inhibited by steric hindrance caused by too close proximity between the structure bound by the covalent bond and the unit A and unit B. Can do. As a result, the response speed of the stimulus-responsive compound can be made particularly fast, and the actuator drive voltage can be made lower.

  In the actuator of the present invention, it is preferable that a flexible base material is provided on the surface of the conductive film opposite to the surface facing the deformable material layer.

  As a result, the load bearing characteristics of the actuator can be made particularly excellent, and unintentional buckling of the actuator can be effectively prevented.

  In the actuator of the present invention, it is preferable that the base material is made of a material containing at least one of polyvinylidene fluoride and polyethylene terephthalate.

  Thereby, flexibility can be made particularly excellent and the amount of deformation can be made larger.

  In the actuator of the present invention, it is preferable that the substrate is made of a material containing a liquid crystal elastomer.

  As a result, it is possible to effectively shorten the time required for the actuator to transition from the curved state to the non-curved state, and the operability of the actuator becomes particularly excellent. Further, the deformability in a specific direction (ease of deformation) can be made particularly excellent, and the deformation in an unintended direction can be more effectively prevented.

The actuator manufacturing method of the present invention includes a chemical modification step of chemically modifying a conductive film made of a metal material,
A deformable material applying step of applying a material containing a stimulus-responsive compound whose molecular structure is deformed by an oxidation-reduction reaction on the surface of the conductive film subjected to the chemical modification;
A covalent bond forming step of forming a covalent bond between the metal material and the stimulus responsive compound by reacting the metal material subjected to the chemical modification with the stimulus responsive compound. It is characterized by.

  Thereby, it is possible to provide an actuator manufacturing method capable of manufacturing an actuator excellent in adhesion between the deformable material and the electrode and excellent in durability with high productivity.

  In the actuator manufacturing method of the present invention, it is preferable to use a compound having at least one functional group of a vinyl group and a (meth) acryloyl group as the stimulus-responsive compound.

  Thereby, the chemical stability of the covalent bond can be made particularly excellent, the adhesion between the deformable material layer and the conductive film is made particularly excellent, and the durability and reliability of the actuator are particularly excellent. Can be. In addition, when manufacturing the actuator, the reaction efficiency for forming the covalent bond can be made particularly excellent, the target reaction can be advanced in a short time, and the actuator productivity is excellent. In addition to improving the yield of the reaction product, the adhesion between the deformable material layer and the conductive film is particularly excellent, and the durability and reliability of the actuator are particularly excellent. Can do.

  In the actuator manufacturing method of the present invention, in the chemical modification step, the metal material is preferably treated with a compound having an alkanethiol structure having a vinyl group at the terminal.

  Thereby, the adhesion between the deformable material layer and the conductive film can be made particularly excellent, and the durability of the actuator can be made particularly excellent. In addition, the metal material and the chemical modifier can be reacted with high reactivity under simple and mild conditions (for example, a condition that a liquid containing the chemical modifier is applied to the conductive film in a room temperature environment). . As a result, the productivity of the finally obtained actuator can be made particularly excellent, and the bonding force between the conductive film and the deformable material layer in the actuator can be made particularly excellent.

  In the actuator manufacturing method of the present invention, in the covalent bond forming step, it is preferable that a compound having a polysiloxane bond is reacted with the metal material subjected to the chemical modification together with the stimulus-responsive compound.

  As a result, the metal material and the stimuli-responsive compound can be bonded by a covalent bond through a chemical structure having a polysiloxane structure, and the degree of freedom of deformation is particularly high, and the amount of deformation and the speed of deformation are particularly high. An excellent actuator capable of smoother deformation can be obtained. In addition, since the polysiloxane structure is excellent in chemical stability, it is advantageous for improving the reliability and durability of the actuator. Moreover, although the siloxane compound which does not have a polysiloxane bond can also be used, the productivity of an actuator can be made especially excellent by using the compound which has a polysiloxane bond.

  In the actuator manufacturing method of the present invention, it is preferable to use a polymer containing methylhydrosiloxane as a constituent component as the compound having a polysiloxane bond.

  Thereby, when the stimulus-responsive compound is a compound having at least one functional group of a vinyl group and a (meth) acryloyl group, the vinyl group and the (meth) acryloyl group efficiently react with the SiH group. Accordingly, a strong bond can be formed, and a strong bond can be easily formed between the compound having a polysiloxane bond and the metal material constituting the conductive film. Therefore, the durability of the actuator can be made particularly excellent easily and reliably.

  In the method for producing an actuator of the present invention, it is preferable to use a methylhydrosiloxane homopolymer as the compound having a polysiloxane bond.

  Thereby, many reaction points with the stimulus-responsive compound and the metal material exist in the compound having a polysiloxane bond. Therefore, the durability of the actuator can be further improved. In addition, by adjusting the compounding ratio of the stimulus-responsive compound functioning as a crosslinking component, the degree of crosslinking in the polymer containing the stimulus-responsive compound and the compound having a polysiloxane bond (component constituting the main chain) as constituent components Can be adjusted easily and reliably.

  In the method for producing an actuator of the present invention, it is preferable to use a copolymer containing methylhydrosiloxane and dimethylhydrosiloxane as components as the compound having a polysiloxane bond.

  Thereby, the hardness and flexibility of the actuator finally obtained can be optimized. Moreover, it is possible to more reliably prevent the SiH group (reactive functional group) of the compound having a polysiloxane bond from remaining unintentionally after the manufacture of the actuator, and the durability and reliability of the actuator are particularly improved. It can be excellent. Further, after this step, the post-treatment (post-treatment for deactivating highly reactive sites) required when the reactive functional group of the compound having a polysiloxane bond remains unintentionally or Since it can be simplified, the productivity of the actuator can be made particularly excellent.

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 molecular structure before and behind oxidation-reduction reaction about an example of a stimulus responsive compound. It is sectional drawing which shows typically other embodiment of the actuator of this invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

First, the actuator of the present invention will be described.
<Actuator>
By the way, in recent years, the need for a small actuator is increasing 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 realize such a low voltage.

  However, in the conventional actuator, the adhesiveness between the deformable material (stimulus responsive compound) that deforms when a voltage is applied and the electrode is insufficient, and along with the deformation of the actuator, the deformable material (stimulus responsive compound) and the electrode There was a problem that peeling occurred between the two. Such a problem occurred more remarkably when the amount of deformation of the actuator was increased.

  In order to solve such a problem, the present inventor conducted intensive research, and as a result, reached the present invention.

  That is, the actuator of the present invention is composed of a conductive film made of a metal material, and a material (deformable material) including a stimulus-responsive compound that is provided on the conductive film and whose molecular structure is deformed by an oxidation-reduction reaction. And the metal material and the stimulus-responsive compound are bonded by a covalent bond. With such a configuration, it is possible to provide an actuator having excellent durability and excellent adhesion between the deformable material (deformable material layer) and the electrode (conductive film). In the present invention, “the metal material and the stimulus-responsive compound are bound by a covalent bond” refers to the case where the metal material and the stimulus-responsive compound are directly bound by a covalent bond. In addition, it includes a case where another atom or atomic group is interposed between the metal material and the stimulus-responsive compound and these are bonded by a covalent bond as a whole. In other words, even when chemical bonds other than covalent bonds (for example, bonds by intermolecular forces including hydrogen bonds, ionic bonds, etc.) are excluded, at least one is present between the metal material and the stimulus-responsive compound. Regardless of whether other atoms are present or not, it is sufficient that the metal material and the stimulus-responsive compound are bonded by at least one covalent bond formed between the atoms.

  1 and 2 are cross-sectional views schematically showing a preferred embodiment of the actuator of the present invention, and FIG. 3 is a diagram for explaining the molecular structure before and after the oxidation-reduction reaction for an example of a stimulus-responsive compound. It is.

  As shown in FIGS. 1 and 2, the actuator 100 of the present embodiment includes a first base material 11 and a first conductive film (first electrode) provided on the surface of the first base material 11. 13, the second base 12, the second conductive film (second electrode) 14 provided on the surface of the second base 12, the first conductive film 13 and the second conductive And a deformable material layer 15 sandwiched between the conductive films 14. The driving device 200 includes an actuator 100, a DC power supply 22, and a switch 21 that selects energization / cutoff of the actuator 100. The actuator 100 is connected to the power supply 22 via the switch 21. It is connected.

  In the configuration shown in FIG. 1, the first conductive film (first electrode) 13 is connected to the power source 22 via the switch 21 so as to be a positive electrode, and the second conductive film (second electrode) Electrode) 14 is connected to a power source 22 so as to be a negative electrode. On the other hand, in the configuration shown in FIG. 2, the first conductive film (first electrode) 13 is connected to the power source 22 via the switch 21 so as to be a negative electrode, and the second conductive film (first electrode) 2 electrode) 14 is connected to a power source 22 so as to be a positive electrode.

Hereinafter, the configuration of the actuator 100 will be described in detail.
<< Base material (first base material, second base material) >>
The first base material 11 has a function of holding the first conductive film 13. The second substrate 12 has a function of holding the second conductive film 14. Both the first base material 11 and the second base material 12 have flexibility.

  By having such base materials (the first base material 11 and the second base material 12), the load resistance characteristics of the actuator 100 can be made particularly excellent, and the actuator 100 is unwilling to buckle. Can be effectively prevented.

  Especially, when the base material (the first base material 11 and the second base material 12) is made of a material containing at least one of polyvinylidene fluoride and polyethylene terephthalate, the flexibility is particularly excellent. The amount of deformation can be larger. Such an effect is remarkably exhibited when the base material (the first base material 11 and the second base material 12) is made of polyvinylidene fluoride.

  Moreover, when the base material (the first base material 11 and the second base material 12) is made of an elastomer, the time required for the actuator 100 to shift from a curved state to a non-curved state is effectively reduced. Therefore, the operability of the actuator 100 is particularly excellent.

  Further, when the base material (the first base material 11, the second base material 12) is made of a liquid crystal elastomer, the anisotropy of the deformation of the actuator 100 as a whole can be increased, Deformation in a desired direction can be realized more reliably.

  Moreover, a base material (the 1st base material 11 and the 2nd base material 12) may have a uniform composition over the whole, and may have a site | part from which a composition differs. For example, the base material (the first base material 11 and the second base material 12) may be a laminated body having a plurality of layers having different compositions, or is composed of a gradient material whose composition changes in a gradient manner. It may be a thing.

  In the present embodiment, the base material (the first base material 11 and the second base material 12) has a sheet shape (film shape). Thereby, the anisotropy of deformation of the actuator 100 can be made higher.

  The thickness of the base material (the first base material 11 and the second base material 12) is not particularly limited, but is preferably 10 μm or more and 500 μm or less. Thereby, the actuator 100 can be driven at a lower voltage, and the effects as described above can be more remarkably exhibited.

  The first substrate 11 and the second substrate 12 may have the same or different conditions for various conditions such as shape, thickness, and constituent material. .

<< Conductive film (first conductive film, second conductive film) >>
The conductive films (the first conductive film 13 and the second conductive film 14) have a function of applying a voltage to the deformable material layer 15.

  In addition, the conductive films (first conductive film 13 and second conductive film 14) are curved in order to follow the deformation of the deformable material layer 15.

  The conductive films (the first conductive film 13 and the second conductive film 14) are made of a metal material. In general, a metal material has excellent conductivity and durability as compared with a conductive organic material or the like. On the other hand, at the time of manufacturing the actuator, a strong covalent bond with the stimulus-responsive compound can be easily and reliably formed by surface treatment (chemical modification) as described in detail later.

  As a metal material constituting the conductive films (the first conductive film 13 and the second conductive film 14), for example, various single metals, various alloys, and the like can be used.

  In particular, when the conductive films (the first conductive film 13 and the second conductive film 14) are made of Au, the conductive films (the first conductive film 13 and the second conductive film). The conductivity of the film 14) and the adhesion between the deformable material and the conductive film can be made compatible at a higher level. In addition, since Au is a material that is relatively excellent in chemical stability, it can stably maintain excellent electrical conductivity in the actuator for a long period of time, while at the time of manufacturing the actuator, it can be used as a stimulus-responsive compound. It is a material that can be suitably subjected to chemical modification as a pretreatment for forming a covalent bond therebetween. Therefore, it is possible to make the actuator productivity particularly excellent while making the actuator reliability and durability particularly excellent.

  The metal material constituting the conductive films (the first conductive film 13 and the second conductive film 14) has been subjected to chemical modification (surface treatment) with a chemical modifier (surface treatment agent). Also good. Thereby, the adhesiveness between the deformable material and the conductive film can be made particularly excellent, and the reliability and durability of the actuator 100 can be made particularly excellent.

  The surface treatment (chemical modification) of the metal material can be performed by various chemical modifiers (surface treatment agents), but it is preferable to use a compound having an alkanethiol structure having a vinyl group at the terminal.

  Thereby, the chemical stability of the conductive film can be made particularly excellent, and the durability of the actuator 100 can be made particularly excellent. In particular, durability against oxygen or water can be made particularly excellent, and the reliability of the actuator 100 can be made particularly excellent. In addition, when the actuator 100 is manufactured, the metal material is chemically modified with high reactivity under simple and mild conditions (for example, a condition that a liquid containing a chemical modifier is applied to the conductive film in a room temperature environment). Thus, the productivity of the actuator 100 can be made particularly excellent.

  In addition, the conductive films (the first conductive film 13 and the second conductive film 14) may have a uniform composition throughout or may have portions having different compositions. Good. For example, the conductive films (the first conductive film 13 and the second conductive film 14) may be a laminated body having a plurality of layers having different compositions, or may be a gradient material whose composition changes in a gradient manner. It may be configured.

  The thicknesses of the conductive films (the first conductive film 13 and the second conductive film 14) are not particularly limited, but are preferably 10 nm or more and 100 nm or less. As a result, the adhesion between the conductive films (first conductive film 13 and second conductive film 14) and the deformable material layer 15, the conductive films (first conductive film 13 and second conductive film). Film 14) and the substrate (first substrate 11 and second substrate 12), and the conductivity of the conductive film (first conductive film 13 and second conductive film 14). The flexibility of the actuator 100 can be made particularly excellent while sufficiently improving the above.

  The first conductive film 13 and the second conductive film 14 may have the same or different conditions for various conditions such as thickness and constituent materials. .

  At least a part of the metal material constituting the conductive films (the first conductive film 13 and the second conductive film 14) is covalently bonded to the stimuli-responsive compound constituting the deformable material layer 15. Yes. Thereby, it can be made excellent in the adhesiveness of the deformation material layer 15 and a conductive film (the 1st conductive film 13, the 2nd conductive film 14), and the deformation material layer 15 and a conductive film Unintentional peeling between the first conductive film 13 and the second conductive film 14 can be prevented, and the durability of the actuator 100 as a whole can be made excellent. . The form of the covalent bond that connects the metal material and the stimulus-responsive compound will be described in detail later.

≪Deformable material layer≫
The deformable material layer 15 is composed of a deformable material containing a stimulus-responsive compound whose molecular structure changes due to a redox reaction.

  The deformable material layer 15 may be in any form such as solid, gel (semi-solid), liquid, etc., but is preferably in the form of a gel (semi-solid). 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.

<Stimulus responsive compound>
A stimulus-responsive compound refers to a compound having a function of deforming (displacement) the three-dimensional structure of a molecule by stimulation. The stimulus-responsive compound is a compound that constitutes the actuator drive unit.

  In the present invention, the stimulus-responsive compound has a deformed portion that is deformed by an oxidation-reduction reaction. By having such a deformation part, the three-dimensional structure (conformation) of the molecule of the stimulus-responsive compound as a whole changes due to the redox reaction. As a result, the entire deformable material layer can be easily displaced by applying a voltage, and the displacement amount (deformation amount) of the deformable material layer can be easily adjusted according to the magnitude of the applied 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.

  In the present invention, the stimulus-responsive compound has a reactive group (reaction part) that can form a covalent bond with the metal material constituting the conductive film described above, and is included in the deformable material layer. At least a part of the conductive compound is present in a state of being covalently bonded to the metal material constituting the conductive film. As a result, the adhesiveness between the deformable material layer and the conductive film can be improved, and unintentional peeling between the deformable material layer and the conductive film can be prevented, and the entire actuator can be prevented. As a result, the durability can be improved.

  It should be noted that at least a part of the stimulus-responsive compound contained in the deformable material layer 15 reacts with the metal material at the reactive group (the reaction related to the direct bond between the metal material and the stimulus-responsive compound). In addition, it is necessary to include a reaction involving bonding by a covalent bond between a metal material mediated by other atoms or atomic groups and a stimulus-responsive compound), and a molecule in which the reactive group does not contribute to the reaction. May be included. Further, the reactive group not only contributes to a reaction that forms a covalent bond with the metal material constituting the conductive film, but also, for example, a reaction in which stimuli-responsive compounds (molecules) bind (for example, It may contribute to the polymerization reaction. Thus, the deformable material layer 15 of the actuator 100 includes, for example, a stimulus-responsive compound in a molecular state as described below (a stimulus-responsive compound in a state where the reactive group is not reacted). Alternatively, a polymer in which these molecules react with each other may be included. In the present specification, these are collectively referred to as stimulus-responsive compounds.

  In the following description, for convenience, the stimulus-responsive compound will be mainly described in a state where the reaction part has not reacted.

  In the present invention, the stimulus-responsive compound has a deformed portion that is deformed by an oxidation-reduction reaction and a reactive group (reactive portion) that can form a covalent bond between the metal material constituting the conductive film. Any compound may be used as long as it is a stimulus-responsive compound, for example, a compound having a structure shown in FIG. 3 can be preferably used. In FIG. 3, ◯ and □ mean a functional group (atomic group), and a line means a bond.

The stimulus-responsive compound shown in FIG. 3 has one deformation part and two reaction parts, and the deformation part has a bond that functions as a rotation axis, and is located at one end of the bond. And a unit A having a _second group (A _{2 in the} figure) located at the other end of the bond, and a first binding site of the first group (A _{1 in the} figure) The first unit B (B _{1 in the} figure), the second unit B (B _{2 in the} figure) arranged at the second binding site of the second group, and the second unit B connected to one reaction part 1 unit C (in the figure, C ₁ ) and a second unit C (in the figure, C ₂ ) connected to the other reaction part. When the stimulus-responsive compound has such a configuration, the actuator 100 can be deformed (displaced) faster and more smoothly, and is driven at a lower voltage.

  The unit A has a bond that functions as a rotation axis, and a first group and a second group are bonded to both ends of the bond, respectively. And it can rotate centering on the said connection. 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 By using such a group as the unit A, the stimulus-responsive compound can be more smoothly deformed (displaced) and driven at a lower voltage.

The first unit B is bonded to the first binding site of the first group of unit A. The second unit B is bonded to the second binding site of the second group of the unit A.
Further, the first unit B and the second unit B are groups that form a bond between the units B by a reduction reaction. That is, as shown in FIG. 3B, the first unit B and the second unit B are coupled by receiving (reduced) electrons. Further, as shown in FIG. 3A, the first unit B and the second unit B release the bonds by releasing (oxidizing) electrons. Thus, the three-dimensional structure of the molecule can be changed by the oxidation-reduction reaction. Such a redox reaction can be advanced, for example, by applying a voltage, and the redox reaction can be stopped by stopping the application of the voltage.

  The unit B (the first unit B and the second unit B) is not particularly limited as long as it is a group that forms a bond by a reduction reaction between the units B (the first unit B and the second unit B). However, the unit B (the first unit B and the second unit B) is preferably a group represented by the following formula (4). Thereby, it becomes easy for the first unit B and the second unit B to reversibly form and break bonds by changing the reaction conditions. Moreover, since the reactivity is high, the stimulus-responsive compound can be deformed more smoothly and at a low voltage.

  The unit C has a function of connecting the unit A and the unit B and the reaction part.

  In the present embodiment, the first unit C is bonded to the third binding site of the first group of the unit A. The second unit C is bonded to the fourth binding site of the second group of the unit A. Thereby, the structure (for example, metal material etc.) couple | bonded by the covalent bond, and the redox reaction of a stimulus responsive compound are inhibited by the steric hindrance by unit A and unit B being too close. It can prevent more effectively. As a result, the response speed of the stimulus-responsive compound can be made particularly fast, and the actuator drive voltage can be made lower.

  Moreover, the 1st unit C and the 2nd unit C are respectively couple | bonded with the reaction part in the edge part on the opposite side to the location where the unit A is couple | bonded. Moreover, the 1st unit C and the 2nd unit C are couple | bonded with the different reaction part, respectively.

  The unit C (the first unit C and the second unit C) preferably includes a ring structure. Thereby, the chemical stability of the stimulus-responsive compound can be further improved.

  Examples of the ring structure include an aromatic ring structure and an alicyclic structure having no aromaticity. In addition, a ring structure composed only of hydrocarbons and a heterocyclic structure in which the elements constituting the ring include not only carbon but also different atoms in the ring can be mentioned. Moreover, a monocyclic structure, a condensed ring structure, a bridged ring structure, a spiro ring structure, a ring assembly structure, and the like can be given. Specific examples of such ring structures include cycloparaffins such as cyclopentane and cyclopentane, cycloolefins such as cyclopentene and cyclohexene, benzene, thiophene, pyrrole, thiazole, pyridine, piperidine, tetrahydropyran, and tetrahydrothiopyran. , Biphenyl, p-terphenyl, 2,2-bithiophene, adamantane, indene, naphthalene, tetralin, indole, quinoline and the like.

  Among these, those having an aromatic ring structure are preferable, and those having a monocyclic aromatic ring structure such as benzene, thiophene, pyrrole, thiazole, pyridine and pyridine are preferable, and benzene is preferable. Is more preferable. Thereby, the chemical stability of the stimulus-responsive compound can be further improved. Moreover, at the time of manufacture of a stimulus responsive compound, a deformation | transformation part and a reaction part (site | part involved in reaction of formation of the said covalent bond) can be couple | bonded easily. In addition, it is possible to more effectively suppress steric hindrance (rotation barrier) during the redox reaction. As a result, the speed of movement of the stimulus-responsive compound is increased.

  The unit C (the first unit C and the second unit C) is preferably one that forms a conjugated system by combining the unit A with the unit A. For example, a conjugated double bond A chain structure having a conjugated double bond such as 1,3-butadiene, a chain structure having a conjugated triple bond such as diacetylene, and the like. Thereby, the movement of electrons in the stimulus-responsive compound becomes smoother, so that the three-dimensional structure of the molecule can be changed more easily.

  The unit C preferably contains one or more selected from the group consisting of an ester group, an ether group, an amide group and a urethane group in addition to the ring structure as described above, and contains an ether group. Is more preferable. Thereby, a deformation | transformation part and a reaction part can be couple | bonded easily at the time of manufacture of a stimulus responsive compound.

  The reaction part is a site that contributes to the reaction of binding the metal material constituting the conductive film (the first conductive film 13 and the second conductive film 14) and the stimulus-responsive compound by the covalent bond. is there.

  The reactive group (reactive part) may be any group as long as it can form a covalent bond between the metal material and the stimulus-responsive compound, but from the group consisting of a vinyl group and a (meth) acryloyl group. It is preferable that it is 1 type, or 2 or more types selected.

  As a result, the chemical stability of the covalent bond formed can be made particularly excellent, the adhesion between the deformable material layer and the conductive film can be made particularly excellent, and the durability and reliability of the actuator can be improved. It can be made particularly excellent. In addition, when manufacturing the actuator, the reaction efficiency for forming the covalent bond can be made particularly excellent, the target reaction can be advanced in a short time, and the actuator productivity is excellent. In addition to improving the yield of the reaction product, the adhesion between the deformable material layer and the conductive film is particularly excellent, and the durability and reliability of the actuator are particularly excellent. Can do.

  In particular, the unit A is one group selected from the group consisting of the above formula (1), the above formula (2), and the above formula (3), and the unit B (the first unit B and the second unit B). ) Is the above formula (4), the unit C (the first unit C and the second unit C) has a benzene ring and an ether group, and the reaction part is composed of a vinyl group and a (meth) acryloyl group. When the stimulus-responsive compound is one or more selected from the group, the adhesion between the deformable material layer and the conductive film is particularly excellent, and the three-dimensional structure of the molecule of the stimulus-responsive compound is improved. It can be changed more easily and greatly, the entire stimulus-responsive compound can be deformed more efficiently, and the deformable material layer can be displaced more greatly at a low voltage. Further, the response speed of the actuator can be made particularly excellent, and the reproducibility of deformation is also excellent. In addition, the weight of the actuator can be reduced.

  Specific examples of the stimulus responsive compound include a compound represented by the following formula (5) (reduced state). By using such a compound, the effects as described above can be exhibited more remarkably.

（式（５）中、ｍ、ｎは、それぞれ独立に、１以上８以下の整数であり、Ｒ^１、Ｒ^２は、それぞれ独立に、水素原子またはＣＯＯＲ^３であり、Ｒ^３は、炭素数が１以上４以下の炭化水素基である。）

(In formula (5), m and n are each independently an integer of 1 to 8, R ¹ and R ² are each independently a hydrogen atom or COOR ³ , and R ³ is the number of carbon atoms. Is 1 or more and 4 or less hydrocarbon group.)

  The deformable material layer 15 may include a stimulus-responsive compound as a constituent component of a polymer (for example, a monomer component, a crosslinking component, etc.). Thereby, the durability of the actuator 100 can be made particularly excellent.

  When the deformable material layer 15 includes a polymer as described above, the weight-average molecular weight of the stimulus-responsive compound is preferably 5000 or more and 100,000 or less, and more preferably 10,000 or more and 50000 or less. Thereby, the durability of the actuator 100 can be made particularly excellent while the flexibility of the deformable material layer 15 is particularly excellent.

  When the deformable material layer 15 includes a polymer as described above, the polymer includes a stimulus-responsive compound (a compound in a state before polymerization as described above) and other components, The other components are preferably included as a polymer monomer component. Thereby, it can prevent more effectively that the oxidation-reduction reaction of a stimulus responsive compound is inhibited by the steric hindrance by a some deformation | transformation part approaching too much. As a result, the response speed of the stimulus-responsive compound can be made particularly fast, and the drive voltage of the actuator 100 can be made lower.

  In addition, when the deformable material layer 15 includes a polymer as described above, the polymer preferably includes a stimulus-responsive compound as a crosslinking component.

  Thereby, the effect that it deform | transforms spontaneously by irritation | stimulation is obtained, having elasticity like rubber | gum.

  As described above, in the present invention, the metal material constituting the conductive film and the stimulus-responsive compound constituting the deformable material layer may be directly bonded by a covalent bond, or the metal constituting the conductive film. Other atoms or atomic groups are interposed between the material and the stimulus-responsive compound constituting the deformable material layer, and these may be bonded by a covalent bond as a whole, but the metal material and the stimulus response The active compound is preferably bonded via a chemical structure having a polysiloxane structure. This increases the degree of freedom of deformation compared to the case where they are directly bonded without any other chemical structure between the metal material and the stimulus-responsive compound. This is advantageous in realizing smooth deformation. In addition, since the polysiloxane structure is excellent in chemical stability, it is advantageous in improving the reliability and durability of the actuator 100.

  Examples of the constituent component (monomer component) of the polysiloxane structure include dimethylsiloxane, methylhydrosiloxane, and dihydrosiloxane.

  In particular, when the polysiloxane structure contains methylhydrosiloxane as a constituent component, an effect that the glass transition temperature is low and flexibility is maintained at room temperature can be obtained. When the polysiloxane structure contains methylhydrosiloxane as a constituent component, the SiH group possessed by methylhydrosiloxane as a compound reacts with other chemical structures in the deformable material layer 15 of the actuator 100. As a result, it may disappear.

  Further, when the polysiloxane structure contains dimethylsiloxane as a constituent component, the effect of increasing the solubility in an organic solvent and facilitating processing can be obtained.

  When the polymer is a copolymer of a stimulus-responsive compound (a compound in a state before polymerization as described above) and another monomer component, the other monomer component is represented by the following formula ( It may be represented by B).

（式（Ｂ）中、Ｒ^１は、水素原子またはメチル基、Ｒ^２は、炭素数が１以上４以下の炭化水素基である。）

(In Formula (B), R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrocarbon group having 1 to 4 carbon atoms.)

  Thereby, it can prevent more effectively that the oxidation-reduction reaction of a stimulus responsive compound is inhibited by the steric hindrance by a some deformation | transformation part being too close. As a result, the response speed of the stimulus-responsive compound can be further increased, and the drive voltage of the actuator 100 can be further decreased. Further, the flexibility of the deformable material layer 15 can be made particularly excellent.

  In such a case, the content ratio of the stimulus-responsive compound (the compound in the state before polymerization as described above) contained in the deformable material layer 15 and the other monomer component is a molar ratio of 1 : It is preferable that it is 20 or more and 1: 5 or less, and it is more preferable that it is 1:20 or more and 1:10 or less. By satisfying such a relationship, the response speed of the stimulus-responsive compound is further increased, the driving voltage of the actuator 100 is further decreased, and the deformation amount and the deformation force of the actuator 100 are increased. Can do.

  The content of the stimuli-responsive compound in the deformable material layer 15 (in the case of containing a polymer as described above, the compound before polymerization as described above) is 10% by mass or more and 80% by mass or less. Is preferable, and it is more preferable that it is 20 mass% or more and 60 mass% or less. Thereby, sufficient deformation amount and deformation force can be obtained at a lower voltage.

<Polymer material>
The deformable material constituting the deformable material layer 15 may include a polymer material in addition to the stimulus-responsive compound as described above. As a result, the polymer material is also displaced along 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 as a whole of the deformable material layer 15 is increased. Can be larger. As a result, the degree of deformation of the actuator 100 as a whole can be increased.

  As the polymer material, any material may be used, but a gelling agent, a liquid crystal polymer and the like as described below can be suitably used.

(Gelling agent)
The gelling agent as the polymer material is a material that can gel the entire deformable material. By including such a gelling agent, the entire deformable material can be more suitably adjusted to an optimal hardness by selecting the type and blending amount of the gelling agent.

  In particular, even when the stimulus-responsive compound is difficult to gel, by including the gelling agent, the entire deformable material can be more suitably adjusted to the optimum hardness. 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, agar, gelatin, alginate, gellan gum and the like, but the deformable material is a vinylidene fluoride-propylene hexafluoride as a gelling agent. It is preferable to include one or more selected from the group consisting of a copolymer, methyl (meth) acrylate, and an organic electrolyte oligomer. Thereby, the whole deformation | transformation material can be more appropriately adjusted to optimal hardness by selection of the kind, compounding quantity, etc. of a gelatinizer. Further, the deformable material can be deformed more flexibly and operate smoothly.

  In particular, when the deformable material contains 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 prevented more effectively.

  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. Thereby, 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 (6).

  In formula (6), a may satisfy the condition of 0 <a <1, but is preferably 0.60 or more and 0.98 or less, and is 0.75 or more and 0.95 or less. Is more preferable. Thereby, the deformable material can have flexibility more suitable for deformation.

  In addition, when the deformable material contains poly (meth) acrylate, 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 methyl poly (meth) acrylate 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.

  In addition, the chemical structure of poly (meth) acrylate methyl can be represented by the following formula (7), for example.

  Further, when the deformable material contains an organic electrolyte oligomer, the organic electrolyte oligomer can also function as an electrolyte described later.

  In addition, as an organic electrolyte oligomer, what is represented by following formula (8) can be used, for example.

（式（８）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 (8), 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 effects as described above can be exhibited more significantly while the functions of the stimulus-responsive compound and the like are sufficiently exhibited.

(Liquid crystal polymer)
The deformable material may include a liquid crystal polymer.

  The liquid crystal polymer preferably has an assisting function so as to be advantageous for deformation of the molecule due to the three-dimensional structure of the stimulus-responsive compound as described above.

  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 crystalline functional group and an acryloyl group (acrylic group), and a monomer having a liquid crystalline functional group and a methacryloyl group (methacrylic group). .

  Examples of such a monomer include compounds represented by the following formula (9) or formula (10).

（式（９）、（１０）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 (9) and (10), 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, a deformable material can be adjusted to optimal hardness more suitably. 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, but by using a cross-linking agent represented by the following formula (11), The deformable material can be reliably gelled.

（式（１１）中、ｍは４以上の整数を示す。）

(In formula (11), 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.

  The liquid crystal polymer preferably has the same functional group as the liquid crystalline functional group of the stimulus-responsive compound in the molecule. Thereby, the response speed of a 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. Thereby, 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.

  In addition, when the deformable material includes a liquid crystal polymer together with the gelling agent, the above-described effects can be obtained, and these can act synergistically to further improve the strength of the deformable material. In addition, the displacement can be made larger.

  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 significantly exhibited while sufficiently exhibiting the functions of the stimulus-responsive compound and the like as described above.

<Electrolyte>
The deformable material constituting the deformable material layer 15 may include 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), triethylsulfonium bis (trifluoromethylsulfonyl) imide (TESTFSI), 1-ethyl-3-methylimidazo An organic salt such as lithium trifluoromethanesulfonate (EMICF ₃ SO ₃ ) can be used. The structural formulas of BMPTFSI, MTO ATFSI, 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, 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 source 22 is possible. Moreover, the charge delivery to the stimulus-responsive compound can be advanced more quickly, and the high-speed response of the deformable material layer 15 can be made particularly excellent. Further, the stimuli-responsive compound constituting the deformable material layer 15 can be efficiently expanded and contracted over the entire deformable material layer 15 (particularly, the entire thickness direction of the deformable material layer 15). 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>
Moreover, the deformable material constituting the deformable material layer 15 may include an electron conductive substance 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 are more preferable. Thereby, the electron transport function is improved, and the deformable material layer 15 (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 carbon nanoparticles having a hollow shell-like structure 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. More preferably, 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.).

  By including the electronic conductive material as described above, the entire deformable material layer 15 can be greatly displaced at a relatively low voltage. In particular, even when the thickness of the deformable material layer 15 is relatively large, the entire deformable material layer 15 can be efficiently deformed. As a result, a larger displacement force and displacement amount can be obtained at a low voltage. 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>
The deformable material constituting the deformable material layer 15 may include a solvent. When the solvent is taken into the polymer material, the deformable material is suitably gelled, so that it can be easily solidified and the handleability of the deformable material can be improved. Furthermore, the deformable material layer 15 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 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.

  Further, the deformable material constituting the deformable material layer 15 may include components other than those described above.

  The conductivity of the deformable material layer 15 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 deformable material layer 15 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 15 contains an electronic conductive material, 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, the deformation force of the actuator 100 can be increased.

  The application of the actuator of the present invention is not particularly limited, and for example, it can be used for medical equipment such as a rehabilitation assisting glove, various industrial equipment such as an actuator for a micropump, a voltage detection sensor, and the like.

  Next, based on FIG. 1, FIG. 2, the action | operation of the actuator 100 (drive device 200) is demonstrated.

  When the stimulus-responsive compound constituting the deformable material layer 15 is expanded (expanded) by being oxidized and contracted by being reduced, the actuator 100 (drive device 200) as a whole exhibits the following behavior. Show.

  That is, in the configuration shown in FIG. 1, the first electrode 13 is connected to the positive electrode of the power source 22, and when the switch 21 is turned on, the first electrode 13, the deformable material layer 15, and the second electrode 14 Energization is performed between them. When energization is performed, on the side of the deformable material layer 15 in contact with the first electrode 13, the stimulus-responsive compound delivers electrons to the first electrode 13 and enters an oxidized state. Oxidation of the stimulus-responsive compound causes the molecular chain of the stimulus-responsive compound to expand (swell). As a result, the deformable material on the side in contact with the first electrode 13 expands (expands). On the other hand, on the side of the deformable material layer 15 that is in contact with the second electrode 14, the stimulus-responsive compound receives electrons from the second electrode 14 and enters a reduced state. Reduction of the stimulus-responsive compound causes the molecular chain of the stimulus-responsive compound to contract. As a result, the deformable material on the side in contact with the second electrode 14 contracts. For this reason, the entire actuator 100 is curved to be convex toward the first electrode 13 (upper side in FIG. 1).

  In the configuration shown in FIG. 2, the polarity is reversed from that in FIG. 1, the first electrode 13 is connected to the negative electrode of the power source 22, and when the switch 21 is turned on, the first electrode 13 and the deformable material are turned on. Energization is performed between the layer 15 and the second electrode 14. When energization is performed, on the side of the deformable material layer 15 in contact with the first electrode 13, the stimulus-responsive compound is reduced, so that the molecular chain of the stimulus-responsive compound contracts. As a result, the deformable material on the side in contact with the first electrode 13 contracts. On the other hand, on the side of the deformable material layer 15 in contact with the second electrode 14, the stimulus-responsive compound is oxidized, so that the molecular chain of the stimulus-responsive compound is expanded (expanded). As a result, the deformable material on the side in contact with the second electrode 14 expands (expands). For this reason, the entire actuator 100 is curved to be convex toward the second electrode 14 (lower side in FIG. 2).

  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.

  In addition, since the adhesion between the electrodes (the first electrode 13 and the second electrode 14) and the deformable material layer 15 is excellent, the electrode (the first electrode) can be used even when the bending direction is changed alternately. The electrode 13, the second electrode 14) and the deformable material layer 15 can be suitably maintained, and the reproducibility of the bending operation is excellent. In addition, even when the deformation amount is increased, the close contact state between the electrodes (first electrode 13 and second electrode 14) and the deformable material layer 15 can be suitably maintained. Large actuators can be realized.

  Moreover, as a voltage value applied to the actuator 100, it is preferable that it is 0.1V or more and 10V or less, for example, and it is more preferable that it is 1V or more and 5V or less. As a result, a better deformation amount 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.

《Actuator manufacturing method》
Next, the manufacturing method of the actuator of this invention is demonstrated.

  The actuator manufacturing method of the present embodiment includes a conductive film (first conductive material) made of a metal material on the surface of a flexible base material (first base material 11 and second base material 12). Conductive film forming step (1a) for forming conductive film 13 and second conductive film 14), and conductive films made of metal material (first conductive film 13 and second conductive film 14). The first conductive film 13 and the second conductive film 13 that have been chemically modified with a chemical modification step (1b) that chemically modifies the material) and a deformable material that includes a stimulus-responsive compound whose molecular structure is deformed by an oxidation-reduction reaction. The deformable material applying step (1c) to be applied to the surface of the conductive film 14 and the metal material subjected to chemical modification and the stimulus-responsive compound are reacted to form a conductive film (first conductive film 13). And the metal material constituting the second conductive film 14) and the stimulus response A covalent bond forming step (1d) for forming a covalent bond with the compound, and a bonding step for bonding the deformable material on the first conductive film 13 and the deformable material on the second conductive film 14 ( 1e). Thereby, it is possible to manufacture the actuator 100 having excellent adhesion and excellent durability between the deformable material layer 15 and the conductive films (the first conductive film 13 and the second conductive film 14) with high productivity. it can.

≪Conductive film formation process≫
In this step, the first conductive film 13 is formed on the surface of the first base material 11, and the second conductive film 14 is formed on the surface of the second base material 12 (1a).

  The first conductive film 13 and the second conductive film 14 are preferably formed by a vapor deposition method such as vacuum deposition or sputtering, a wet plating method such as electrolytic plating or electroless plating, or a method such as thermal spraying. Can be formed.

  In addition, the base material (first base material 11 and second base material 12) may be subjected to a surface treatment for the purpose of improving adhesion before film formation.

  It should be noted that the first conductive film 13 and the second conductive film 14 may have the same formation method or formation conditions, or may be different.

≪Chemical modification process≫
In this step, the first conductive film 13 and the second conductive film 14 are chemically modified (1b). Thereby, the functional group by chemical modification is introduced into the metal material constituting the surface (surface opposite to the surface facing the base material) of the first conductive film 13 and the second conductive film 14. The

  Thereby, a covalent bond can be formed between the metal material and the stimulus-responsive compound in the covalent bond forming step described in detail later. Moreover, generally the surface of a conductive film becomes hydrophobic (lipophilic) by the chemical modification performed at this process. On the other hand, the stimulus-responsive compound contained in the deformable material applied in the subsequent deformable material applying step is generally hydrophobic (lipophilic). For this reason, by chemically modifying the conductive film in this step, the affinity between the conductive film and the deformable material is improved, and the working efficiency of the deformable material applying step described in detail later is improved. Moreover, aggregation of the stimulus responsive compound on the surface of the conductive film can be effectively prevented, and the deformable material can be applied uniformly. As a result, it is possible to effectively prevent undesired variations in characteristics at each part of the deformable material layer to be finally formed.

  Substances (chemical modifiers) that can be used for chemical modification differ depending on the constituent material of the conductive film, the functional group of the stimulus-responsive compound to be reacted in a later step, and the like.

  For example, the conductive film is made of a material containing Au, and a compound having at least one functional group of a vinyl group and a (meth) acryloyl group as a reactive group is used as the stimulus-responsive compound. In some cases, a compound having an alkanethiol structure having a vinyl group at the terminal, a compound having an acryloyl group, a compound having a methacryloyl group, or the like can be used as the chemical modifier.

  In particular, the conductive film is made of a material containing Au, and a compound having at least one functional group of a vinyl group and a (meth) acryloyl group as a reactive group is used as the stimulus-responsive compound. In this case, as the chemical modifier, a compound having an alkanethiol structure having a vinyl group at the terminal can be particularly preferably used.

  Thereby, the adhesion between the deformable material layer 15 and the conductive film (the first conductive film 13 and the second conductive film 14) is particularly excellent, and the durability of the actuator 100 is particularly excellent. can do. In addition, the metal material and the chemical modifier can be reacted with high reactivity under simple and mild conditions (for example, a condition that a liquid containing the chemical modifier is applied to the conductive film in a room temperature environment). . As a result, the productivity of the actuator 100 finally obtained can be made particularly excellent, and the bonding force between the conductive film and the deformable material layer in the actuator 100 can be made particularly excellent.

As the compound having an alkanethiol structure having a vinyl group at the terminal, for example, a compound represented by the following formula (50) can be used.
CH ₂ = CH (CH ₂ ) _n SH (50)
(In formula (50), n is an integer of 1 or more and 20 or less.)

  In formula (50), n may be an integer of 1 or more and 20 or less, preferably 2 or more and 16 or less, and more preferably 4 or more and 12 or less. Thereby, the efficiency of chemical modification by the chemical modifier can be made particularly excellent, and the productivity of the actuator 100 can be made particularly excellent. Further, since the degree of freedom of deformation can be made particularly high, it is advantageous for further improving the deformation amount and the deformation speed and realizing smoother deformation.

In this step, when the compound represented by the above formula (50) is used as the chemical modifier, the metal material on the surface of the conductive film (the first conductive film 13 and the second conductive film 14). Has a structure represented by the following formula (51).
_{-S (CH 2) n CH =} CH 2 (51)
Moreover, in this process, you may perform reaction of two steps or more.

≪Deformation material application process≫
In this step, a deformable material containing a stimulus-responsive compound whose molecular structure is deformed by an oxidation-reduction reaction is applied to the surfaces of the first conductive film 13 and the second conductive film 14 that have been chemically modified ( 1c).

  The method for applying the deformable material in this step is not particularly limited. For example, when the deformable material has fluidity, various coating methods such as brush coating, various printing methods such as an ink jet method, dipping, etc. Can be adopted. Further, in this step, a deformable material containing a stimulus-responsive compound is previously formed into a predetermined shape such as a sheet shape, and this is formed into a conductive film (first conductive film 13, second conductive material). It may be carried out by contacting (mounting, bonding) with the film 14). Moreover, you may carry out combining these methods.

  Further, the method for applying the deformable material to the first conductive film 13 and the method for applying the deformable material to the second conductive film 14 may be the same or different.

  In this step, the deformable material applied on the first conductive film 13 and the deformable material applied on the second conductive film 14 may have the same composition, It may be different. Further, the amount of deformation material applied to the first conductive film 13 and the amount of deformation material applied to the second conductive film 14 may have the same composition or different. May be.

  In this step, for example, a material having a composition different from that of the deformable material layer 15 constituting the final actuator 100 is used for the purpose of adjusting the viscosity of the deformable material including the stimulus-responsive compound (improving the coating property). May be.

  For example, the deformable material used in this step may include a liquid component (such as a solvent) from which at least a part is removed after this step.

  Further, the deformable material used in this step may be a component that contributes to the reaction in the subsequent covalent bond forming step, and may include a component (for example, a catalyst) that is removed by washing or the like thereafter.

  In addition, the stimulus-responsive compound included in the deformable material used in this step may have a structure different from that of the stimulus-responsive compound included in the final actuator 100. For example, when the stimulus-responsive compound contained in the final actuator 100 is a polymer, the stimulus-responsive compound contained in the deformable material used in this step is the stimulus-responsive compound contained in the final actuator 100. The degree of polymerization may be lower than that.

  Further, when manufacturing the actuator 100 having a configuration in which the metal material and the stimulus-responsive compound are bonded via a chemical structure having a polysiloxane structure, in this step, the polysiloxane is combined with the stimulus-responsive compound. A compound having a bond may be used.

  As the compound having a polysiloxane bond, for example, a polymer containing methylhydrosiloxane as a constituent component can be used.

  Thereby, when the stimulus-responsive compound is a compound having at least one functional group of a vinyl group and a (meth) acryloyl group, the vinyl group and the (meth) acryloyl group efficiently react with the SiH group. Accordingly, a strong bond can be formed, and a strong bond can be easily formed between the compound having a polysiloxane bond and the metal material constituting the conductive film. Therefore, the durability and the like of the actuator 100 can be made particularly excellent easily and reliably.

  In addition, a homopolymer of methylhydrosiloxane can be used as the compound having a polysiloxane bond.

  Thereby, many reaction points with the stimulus-responsive compound and the metal material exist in the compound having a polysiloxane bond. Therefore, the durability of the actuator 100 can be further improved. In addition, by adjusting the compounding ratio of the stimulus-responsive compound functioning as a crosslinking component, the degree of crosslinking in the polymer containing the stimulus-responsive compound and the compound having a polysiloxane bond (component constituting the main chain) as constituent components Can be adjusted easily and reliably.

  In addition, as a compound having a polysiloxane bond, a copolymer containing methylhydrosiloxane and dimethylhydrosiloxane as constituent components can be used.

  Thereby, the hardness and flexibility of the actuator 100 finally obtained can be optimized. In addition, it is possible to more reliably prevent the SiH group (reactive functional group) of the compound having a polysiloxane bond from remaining unintentionally after the actuator 100 is manufactured, and thus the durability and reliability of the actuator 100 can be prevented. Can be made particularly excellent. Further, after this step, the post-treatment (post-treatment for deactivating highly reactive sites) required when the reactive functional group of the compound having a polysiloxane bond remains unintentionally or Since it can be simplified, the productivity of the actuator 100 can be made particularly excellent.

≪Covalent bond formation process≫
In this step, the metal material constituting the conductive film (the first conductive film 13 and the second conductive film 14) is reacted with the stimulus-responsive compound and the metal material subjected to chemical modification; A covalent bond is formed with the stimulus-responsive compound (1d). Thereby, it can be made excellent in the adhesiveness of the deformation material layer 15 and a conductive film (the 1st conductive film 13, the 2nd conductive film 14), and the deformation material layer 15 and a conductive film Unintentional peeling between the first conductive film 13 and the second conductive film 14 can be prevented, and the durability of the actuator 100 as a whole can be made excellent. .

Moreover, in this process, you may perform reaction to which components other than a stimulus responsive compound contribute.
For example, in this step, a compound having a polysiloxane bond may be reacted with a metal material subjected to chemical modification together with a stimulus-responsive compound.

  As a result, the metal material and the stimuli-responsive compound can be bonded by a covalent bond through a chemical structure having a polysiloxane structure, and the degree of freedom of deformation is particularly high, and the amount of deformation and the speed of deformation are particularly high. The actuator 100 which is excellent and can be deformed more smoothly can be obtained. In addition, since the polysiloxane structure is excellent in chemical stability, it is advantageous in improving the reliability and durability of the actuator 100. Moreover, although the siloxane compound which does not have a polysiloxane bond can also be used, the productivity of the actuator 100 can be made especially excellent by using the compound which has a polysiloxane bond.

  The reaction conditions in this step vary depending on the combination of the reactive group of the stimulus-responsive compound and the chemical modifier, but generally a covalent bond is formed between the metal material and the stimulus-responsive compound by heating. The reaction can proceed suitably.

  When this step is performed by heating, the heating temperature is preferably 50 ° C. or higher and 200 ° C. or lower, more preferably 60 ° C. or higher and 150 ° C. or lower, and further preferably 70 ° C. or higher and 130 ° C. or lower. As a result, the reaction rate of the intended reaction can be made faster while more effectively preventing undesired modification / deterioration of the constituent components of the actuator 100 and the progression of undesirable side reactions.

  When this step is performed by heating, the heating time is preferably from 30 minutes to 48 hours, more preferably from 1 hour to 42 hours, and even more preferably from 4 hours to 36 hours. Thereby, while making the productivity of the actuator 100 sufficiently high, it is possible to more effectively prevent harmful effects caused by the target reaction not proceeding sufficiently, and the deformable material layer 15 and the conductive film (first film). The adhesion between the first conductive film 13 and the second conductive film 14) can be made particularly excellent, and the reliability of the actuator 100 can be made particularly excellent.

  The reaction conditions for the deformable material applied on the first conductive film 13 and the reaction conditions for the deformable material applied on the second conductive film 14 may be the same or different. It may be a thing.

  In this step, at least a reaction for forming a covalent bond between the metal material and the stimulus-responsive compound may proceed, but in addition to this reaction, another reaction may proceed. For example, in this step, a reaction in which molecules of the stimulus-responsive compound contained in the deformable material applied in the deformable material applying step polymerize may proceed.

  For example, the reactive group of the stimulus-responsive compound is a functional group of at least one of a vinyl group and a (meth) acryloyl group, and the chemical modifier used in the chemical modification step is 3- (2-bromoisobutyryl). ) In the case of propyldimethylchlorosilane, in this step, a reaction that forms a covalent bond between the metal material and the stimulus-responsive compound proceeds, and a reaction in which molecules of the stimulus-responsive compound polymerize. proceed. Such a reaction is called ATRP (Atom Transfer Radical Polymerization). In such a reaction, a polymer having a sharp molecular weight distribution and a uniform chain length is obtained. As a result, it is possible to effectively prevent the occurrence of unintended variation in characteristics at each part of the deformable material layer.

≪Lamination process≫
In this step, the deformable material on the first conductive film 13 and the deformable material on the second conductive film 14 are bonded together (1e). Thereby, the first base material 11, the second base material 12, the first conductive film (first electrode) 13, the second conductive film (second electrode) 14, and the deformation The actuator 100 having the material layer 15 is obtained.

  The bonding of the deformable material on the first conductive film 13 and the deformable material on the second conductive film 14 may be performed so that they are in direct contact with each other, but the first conductive film At least one of the surface of the deformable material on 13 and the surface of the deformable material on the second conductive film 14 is provided with a solvent (for example, at least a part of the constituent material of the deformable material is a soluble solvent, stimulus responsiveness) You may give the solvent which can gelatinize a compound, the liquid substance (electrolyte solution, liquid polymer electrolyte, etc.) containing an electrolyte, etc. Thereby, for example, the bonding strength between the deformable material on the first conductive film 13 and the deformable material on the second conductive film 14 can be made particularly excellent, and the durability and reliability of the actuator 100 can be improved. The property can be made particularly excellent.

  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 drive device has been described as including an actuator having a structure in which a deformable material layer is sandwiched between two electrodes. However, the present invention is not limited to this, and each unit constituting the drive device includes: It can be replaced with any structure capable of performing the same function. For example, the drive device may have a structure as shown in FIG. That is, as shown in FIG. 4, the driving device 200 is in close contact with the power source 22, the switch 21 for turning on / off the power source 22, the first electrode 13 connected to the power source 22, and the first electrode 13. An actuator 100 including the deformable material layer 15, a counter electrode 23 connected to the power source 22, an electrolytic solution 24 interposed between the deformable material layer 15 and the counter electrode 23, and a container 25. It may be. Thus, in the present invention, the actuator may have only one conductive film. Moreover, you may have three or more electroconductive films.

  In the above-described embodiment, the stimulus-responsive compound mainly includes the unit A, the first unit B, the second unit B, the first unit C, and the second unit C. As described above, 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, and is not limited to, for example, a compound including all the units described above. Further, the stimulus-responsive compound may have a unit other than the units A, B, and C as described above.

  In the above-described embodiment, the reaction unit has been described as being coupled to the end of the unit C (the first unit C and the second unit C) opposite to the unit A. The joining location is not limited to this.

  In the above-described embodiment, the reaction unit is described as being coupled to the first unit C and the second unit C one by one. However, the number of reaction units is 1 in the stimulus-responsive compound. There may be one, or three or more.

  In the above-described embodiment, the case where the polysiloxane structure is contained as the other component in the polymer has been mainly described. However, the polysiloxane structure may be in another form, for example, in the polymer. In, it may be included as a crosslinking component.

  Further, the actuator of the present invention may not be manufactured using the method described above. For example, a method in which the order of the steps is different from the method described above, such as a covalent bond forming step after the bonding step, may be used. In the above-described embodiment, the deformation material is applied to both the first conductive film and the second conductive film. However, the first conductive film and the second conductive film are used. The deformation material may be applied to only one of the films. Alternatively, a method may be employed in which the first conductive film and the second conductive film face each other with a predetermined distance therebetween, and in this state, a deformable material is injected between them ( It is not necessary to have a bonding step).

  Moreover, the manufacturing method of this invention may have other processes (a pre-processing process, an intermediate process, a post-processing process, etc.) in addition to the process mentioned above.

  In addition, the shape of the deformable material layer 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.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

[1] Manufacture of actuator and drive device (Example 1)
(Conductive film forming process)
As a flexible substrate, a polyvinylidene fluoride (PVdF) filter (film thickness: 0.1 mm, pore size: 0.45 μm) manufactured by Millipore was prepared, and after forming a through hole for wiring connection, An Au film (conductive film) having a thickness of 40 nm was formed on one surface of the substrate by sputtering.

  Next, the base material on which the Au film (conductive film) was formed was mixed with ultrapure water (MilliQ water): 25 mL, 28 mass% ammonia water: 2 mL, 35 mass% hydrogen peroxide solution: 2 mL. Then, it was heated at 85 ° C., then washed successively with ultrapure water (MilliQ water) and methanol, and dried at room temperature.

(Chemical modification process)
The base material on which the conductive film is formed is put in a glass tube, and here, toluene: 10 mL, a compound represented by the above formula (50) as a chemical modifier (provided that n in the formula (50) is 9) A certain compound): 30 mg was added, and left at room temperature for 20 hours. Thereby, a structure represented by Au—S— (CH ₂ ) ₉ —CH═CH ₂ was introduced on the surface of the conductive film.
Thereafter, the substrate subjected to the chemical modification as described above was washed with dichloromethane and dried.

(Deformation material application process)
About the base material subjected to the chemical modification step, the compound represented by the following formula (17) (stimulation responsive compound): 7.93 mmol, methyl acrylate: 24 mmol, ethyl 2-bromoisobutyrate: 0.25 mmol, copolymer of methylhydrosiloxane and dimethylhydrosiloxane: 2 mmol, and N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine: 0.25 mmol Anisole: A solution (deformable material) dissolved in 2.5 mL was applied by an inkjet method.

  As the compound (stimulus responsive compound) represented by the above formula (17), a compound synthesized as follows was used.

First, a mixture of a compound represented by the following formula (18) and Pd (PPh ₃ ) ₄ was stirred in toluene, and an ethanol solution of 4-tert-butyldimethylsilyloxyphenylboronic acid and 2.3M carbonic acid were added. A potassium aqueous solution was added, and the mixture was heated to reflux for 17.5 hours. The reaction solution was cooled to room temperature, the organic layer was separated, and the aqueous layer was extracted with dichloromethane. The collected organic layer was washed with water and saturated brine, dried over sodium sulfate, filtered and concentrated. Then, it refine | purified by column chromatography and the compound represented by following formula (19) was obtained.

Next, the compound represented by the above formula (19) was dissolved in THF, and a THF solution (1 M) of tetrabutylammonium fluoride was added. The reaction solution was stirred for 2 hours, then quenched with hydrochloric acid, extracted with dichloromethane, dried over sodium sulfate, filtered and concentrated. To the obtained solid, DMF, potassium carbonate, and a compound represented by the following formula (20) were added, and the mixture was heated and stirred at 80 ° C. The reaction solution was extracted with dichloromethane, washed with water and saturated brine, dehydrated with sodium sulfate, and purified by column chromatography to obtain a compound represented by the following formula (21). In formula (21), CH ₂ = CH— (CH ₂ ) ₄ — (part excluding OTs in the structure represented by formula (20)) is represented by R (formula (22) and formula shown later). The same applies to (23).

  Next, the compound represented by the above formula (21), p-toluenesulfonic acid, and 1,2-benzenedithiol were heated to reflux in benzene. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution, extracted with dichloromethane, and dried over sodium sulfate. Sodium sulfate was filtered and concentrated, and then purified by column chromatography to obtain a compound represented by the following formula (22).

Next, a compound represented by the formula (22) was dissolved in dichloromethane _and stirred with _{(BrC 6 H 4) 3 NSbCl} 6. 250 mL of diethyl ether was added to the reaction solution, and the precipitated solid was filtered, dissolved in a mixed solvent of dichloromethane, acetonitrile, and THF, added with zinc powder, and stirred at room temperature. The zinc powder was removed by filtration and concentrated. Then, it refine | purified by column chromatography and the compound represented by following formula (23) was obtained.

  Further, as the copolymer of methylhydrosiloxane and dimethylhydrosiloxane, a copolymer having a molar ratio of methylhydrosiloxane to dimethylhydrosiloxane in the copolymer of 1: 2 was used.

(Covalent bond formation process)
The substrate provided with the solution was heated at 100 ° C. for 24 hours. As a result, the polymerization reaction progressed, and Au (metal material) constituting the conductive film and the stimulus-responsive compound were bonded by a covalent bond (covalent bond via a polysiloxane structure).
Thereafter, it was washed with dichloromethane and dried.

(Lamination process)
After that, the base material subjected to the covalent bond forming step is cut into a strip of 5 mm × 2 cm, the two pieces are immersed in the electrolyte solution, and bonded so that the deformable materials are in contact with each other and the base material faces outward. The actuator was obtained. As the electrolyte solution, an acetonitrile solution of tetrabutylammonium tetrafluoroboric acid adjusted to 0.1M was used.

  Then, wiring was connected to each conductive film through the through-hole provided in the base material, and the drive device as shown in FIG. 1 and FIG. 2 was obtained. The thickness of the deformable material layer was 0.1 mm.

(Example 2)
In the deformable material application step, the compound (stimulation responsive compound) represented by the following formula (17) on the conductive film subjected to the chemical modification with respect to the base material subjected to the chemical modification step: 7. 93 mmol, methyl acrylate: 24 mmol, ethyl 2-bromoisobutyrate: 0.25 mmol, homopolymer of methylhydrosiloxane (weight average molecular weight: 2000): 0.6 mmol, and N, N, N ′, N ″, An actuator and a driving device were manufactured in the same manner as in Example 1 except that a solution (deformable material) obtained by dissolving N ″ -pentamethyldiethylenetriamine: 0.25 mmol in anisole: 2.5 mL was applied by the inkjet method. .

(Example 3)
An actuator and a driving device were manufactured in the same manner as in Example 1 except that a sheet material made of polyethylene terephthalate (manufactured by Teijin DuPont) having a thickness of 0.1 mm was used as the flexible substrate.

Example 4
The actuator and drive device were the same as in Example 1 except that a sheet material made of an elastomer (Aron Kasei Co., Ltd., AR-760) having a thickness of 0.1 mm was used as the flexible substrate. Manufactured.

(Example 5)
An actuator and a driving device were manufactured in the same manner as in Example 1 except that a compound represented by the following formula (32) was used as the stimulus responsive compound.

(Example 6)
An actuator and a driving device were manufactured in the same manner as in Example 1 except that the compound represented by the following formula (33) was used as the stimulus responsive compound.

(Example 7)
Except for using the compound represented by the above formula (50) as a compound (chemical modifier) used for the chemical modification of the conductive film (wherein n in the formula (50) is 15), Actuators and drive devices were manufactured in the same manner as in Example 1.

(Example 8)
An actuator and a driving device were manufactured in the same manner as in Example 1 except that methyl methacrylate was used instead of methyl acrylate as a component of the deformable material layer.

Example 9
An actuator and a driving device were manufactured in the same manner as in Example 1 except that isopropyl acrylate was used instead of methyl acrylate as a component of the deformable material layer.

(Comparative Example 1)
Actuator and drive in the same manner as in Example 1 except that the chemical modification step is omitted and there is no covalent bond between Au (metal material) constituting the conductive film and the stimulus-responsive compound. The device was manufactured.

  Table 1 summarizes the configurations of the actuators of the examples and comparative examples. In Table 1, the polyvinylidene fluoride is “PVdF”, the polyethylene terephthalate is “PET”, the elastomer (AR-760 manufactured by Aron Kasei Co., Ltd.) is “AR760”, and is represented by the above formula (50) as a chemical modifier. A compound represented by the above formula (50) as a chemical modifier (provided that n in the formula (50) is 15). (50), the stimuli-responsive compound represented by the above formula (17) is “C17”, the homopolymer of methylhydrosiloxane is “PS1”, and the copolymer of methylhydrosiloxane and dimethylhydrosiloxane is “ PS2 ”, the stimulus-responsive compound represented by the above formula (32) is“ C32 ”, the stimulus-responsive compound represented by the above formula (33) is“ C33 ”, Le "MA", methyl methacrylate "MMA" showed isopropyl acrylate with "IPA". Moreover, in the table | surface, the component (component) used for superposition | polymerization was shown in the column of the constituent material about a deformation | transformation material layer, and these compounding ratios were shown in the column of content rate. In the actuators of the above examples, the weight average molecular weight of the stimulus-responsive compound (compound after polymerization) constituting the deformable material layer was a value in the range of 3000 or more and 10,000 or less. In the actuators of the above examples, the conductivity of the deformable material layer was 1 S / cm or more.

[2] Actuator evaluation [2.1] Deformation amount In the environment of 25 ° C., the energization direction is reversed as shown in FIG. 2 from the state shown in FIG. Observe the displacement in the actuator bending direction (vertical direction in FIGS. 1 and 2) at a location 2 mm away from the end of the actuator (a location 8 mm away from the center of the actuator in the right direction in the figure). evaluated. The applied voltage was 3V.

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.

[2.2] Evaluation of Adhesiveness between Conductive Film and Deformable Material Layer For the actuators of Examples and Comparative Examples, a voltage was applied under the conditions of an applied voltage of 10 V and a frequency of 10 Hz in an environment of 25 ° C. The bending motion was repeated for 30 minutes continuously.

  Thereafter, the interface between the conductive film and the deformable material layer was observed with a scanning electron microscope (SEM), and the adhesion between the conductive film and the deformable material layer was evaluated according to the following criteria.

A: The conductive film and the deformable material layer are in close contact with each other, and no floating or peeling is observed.
B: The conductive film and the deformable material layer are in close contact with each other, and there is almost no floating / peeling.
C: Slight floating / peeling is observed between the conductive film and the deformable material layer.
D: Floating / peeling is clearly observed between the conductive film and the deformable material layer.
E: Remarkable floating / peeling is recognized between the conductive film and the deformable material layer.
These results are summarized in Table 2.

  As is apparent from Table 2, the actuator of the present invention has a sufficiently large amount of deformation when a low voltage is applied, and has excellent adhesion between the conductive film and the deformable material layer, resulting in durability and reliability. It was highly probable.

  In particular, in examples using a methylhydrosiloxane homopolymer as a compound having a polysiloxane bond, the number of reaction points with a stimulus-responsive compound or a metal material in the compound having a polysiloxane bond should be increased. The durability of the actuator can be further improved. In addition, by adjusting the compounding ratio of the stimulus-responsive compound functioning as a crosslinking component, the degree of crosslinking in the polymer containing the stimulus-responsive compound and the compound having a polysiloxane bond (component constituting the main chain) as constituent components Can be adjusted easily and reliably.

  Further, in the example using a copolymer containing methylhydrosiloxane and dimethylhydrosiloxane as constituents as the compound having a polysiloxane bond, the hardness and flexibility of the actuator could be optimized.

  Moreover, in the Example using a polyvinylidene fluoride and a polyethylene terephthalate as a base material, the softness | flexibility was made especially excellent and the deformation amount could be made larger. Such an effect was more remarkably exhibited in Examples in which the base material was composed of polyvinylidene fluoride.

Further, in the embodiment using the material made of elastomer as the base material, it is possible to more effectively shorten the time for the actuator to move from the curved state to the non-curved state, and the operability of the actuator is particularly good. It was excellent. In addition, the deformability in a specific direction (ease of deformation) can be made particularly excellent, and the deformation in an unintended direction can be more effectively prevented.
On the other hand, in the comparative example, a satisfactory result was not obtained.

A ₁ ... first group A ₂ ... second group B ₁ ... first unit B B ₂ ... second unit B C ₁ ... first unit C C ₂ ... second unit C 200 ... drive unit DESCRIPTION OF SYMBOLS 100 ... Actuator 11 ... 1st base material 12 ... 2nd base material 13 ... 1st electroconductive film | membrane (1st electrode) 14 ... 2nd electroconductive film | membrane (2nd electrode) 15 ... Deformation material layer 21 ... Switch 22 ... Power supply 23 ... Counter electrode 24 ... Electrolyte solution 25 ... Container

Claims (17)

A conductive film made of a metal material;
A deformable material layer provided on the conductive film and made of a material containing a stimulus-responsive compound whose molecular structure is deformed by an oxidation-reduction reaction;
An actuator, wherein the metal material and the stimulus-responsive compound are bonded by a covalent bond.   The actuator according to claim 1, wherein the conductive film is made of Au.   The actuator according to claim 1 or 2, wherein the metal material is bonded to the stimulus-responsive compound by a surface treatment with a compound having an alkanethiol structure having a vinyl group at a terminal.   The actuator according to any one of claims 1 to 3, wherein the metal material and the stimulus-responsive compound are bonded via a chemical structure having a polysiloxane structure. The stimulus-responsive compound has a bond that functions as a rotation axis, and a unit A having a first group located at one end of the bond and a second group located at the other end of the bond; ,
A first unit B disposed at a first binding site of the first group;
A second unit B disposed at a second binding site of the second group;
A first unit C coupled to a reaction part involved in the reaction of formation of the covalent bond;
A second unit C connected to a reaction part involved in the reaction for forming the covalent bond,
The actuator according to any one of claims 1 to 4, wherein the first unit B and the second unit B are coupled by a reduction reaction.   The actuator according to claim 5, wherein the first unit C and the second unit C include a ring structure having aromaticity. The first unit C is arranged at a third binding site of the first group,
The actuator according to claim 5 or 6, wherein the second unit C is disposed at a fourth binding site of the second group.   The actuator according to any one of claims 1 to 7, wherein a base material having flexibility is provided on a surface opposite to the surface facing the deformable material layer of the conductive film.   The actuator according to claim 8, wherein the base material is made of a material containing at least one of polyvinylidene fluoride and polyethylene terephthalate.   The actuator according to claim 8 or 9, wherein the substrate is made of a material containing a liquid crystal elastomer. A chemical modification step for chemically modifying a conductive film made of a metal material;
A deformable material applying step of applying a material containing a stimulus-responsive compound whose molecular structure is deformed by an oxidation-reduction reaction on the surface of the conductive film subjected to the chemical modification;
A covalent bond forming step of forming a covalent bond between the metal material and the stimulus responsive compound by reacting the metal material subjected to the chemical modification with the stimulus responsive compound. An actuator manufacturing method characterized by the above.   The method for manufacturing an actuator according to claim 11, wherein a compound having at least one functional group of a vinyl group and a (meth) acryloyl group is used as the stimulus-responsive compound.   The method for manufacturing an actuator according to claim 12, wherein in the chemical modification step, the metal material is treated with a compound having an alkanethiol structure having a vinyl group at a terminal.   The method for manufacturing an actuator according to claim 12 or 13, wherein in the covalent bond forming step, a compound having a polysiloxane bond is reacted with the metal material subjected to the chemical modification together with the stimulus-responsive compound.   The method for manufacturing an actuator according to claim 14, wherein a polymer containing methylhydrosiloxane as a constituent component is used as the compound having a polysiloxane bond.   The method for manufacturing an actuator according to claim 14, wherein a homopolymer of methylhydrosiloxane is used as the compound having a polysiloxane bond.   The method for manufacturing an actuator according to any one of claims 14 to 16, wherein a copolymer containing methylhydrosiloxane and dimethylhydrosiloxane as constituent components is used as the compound having a polysiloxane bond.

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