JP2010086864A - Thin-film actuator and touch panel using this - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin-film actuator deformable so as to give a feeling of reactive force to an operator in a short period of time even in an actuator layer with its thickness below 1 mm, and to provide a touch panel using the same. <P>SOLUTION: The thin-film actuator actuated by applying voltage to it has the actuator layer formed of a gel containing a denatured crosslink polyrotaxane with an electrolytic solution impregnated thereinto, and an electrode provided at both sides of the actuator layer with the voltage applied thereto. A denatured crosslink polyrotaxane includes: a first polyrotaxane having a functional group with ion-exchange capability, with a first linear molecule included in a skewered manner at the opening of a first annular molecule; and a second polyrotaxane with a second linear molecule included in the skewered manner at the opening of the second annular molecule. Rings of the first and second annular molecules are substantive, and at least one of the first annular molecules is chemically connected to at least one of the second annular molecules. The touch panel is also provided by using the thin-film actuator. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a thin film actuator that is mechanically driven (curved or deformed) by applying a voltage and thereby generates a reaction force, and a touch panel using the thin film actuator.

  A touch panel display is used as an input device from a user in a small electronic device such as a mobile phone, a digital camera, or a car navigation system display. A touch panel display is a display including an input device that can input a signal to a device by pressing a predetermined portion of the display with a finger or the like. However, in this touch panel type display, the operator has only a method of knowing the confirmation of the input from the sound generated at the same time as the input or the color change in the display screen.

In recent years, even if an operator (for example, a driver who cannot visually recognize a touch panel display during driving, a visually impaired person, or a hearing impaired person) cannot visually recognize the display or confirm the sound, Various devices have been proposed so that the operator feels a reaction force as when the switch is pressed, or the operator is given a degree of reach (achievement) with respect to input.
For example, when a touch panel (switch) is pressed, vibrations due to piezoelectric elements are generated on the touch panel, the touch panel is mechanically or elastically deformed, or a reaction force due to magnetic force is generated on the touch panel. ing. All of these methods use an inorganic material as a main material, and are difficult to apply to a highly flexible device required for downsizing electronic equipment. Furthermore, it is very difficult to reduce the weight as the size is reduced and to give an appropriate feel to the operator who has pressed the switch.

In addition, the organic composition is a material that is rich in flexibility and processability, is lightweight and adaptable to the human body, and it is easy to disperse and mix functional materials such as pigment materials and magnetic materials. Expectation was sent for use.
For example, an input device using a phase change of a polymer gel has been proposed (see, for example, Patent Document 1).

  In recent years, a voltage is applied to a film in which an ion conductive polymer such as an ion exchange resin film or an ionic polymer gel film is laminated on a metal film electrode, thereby enabling ion exchange between the ion conductive polymer and the electrolyte. A potential-responsive polymer actuator that utilizes the resulting volume change has been proposed. The applicant of the present application has previously proposed Patent Document 2 regarding an actuator using a cation exchange resin having anion capturing ability.

  Recently, a supramolecular (crosslinked polyrotaxane) gel called a cyclized gel characterized by free movement of the crosslinking point has been proposed. Supramolecules are attracting attention as polymers having high flexibility, and are expected to be put to practical use in biomaterials such as artificial blood vessels and artificial joints, fibers, cosmetics, and paints (for example, Patent Document 3).

JP-A-5-333171 JP 2008-211938 A International Publication No. 2001/088356 Pamphlet

However, in the case of an input device using a polymer gel, the thickness of the actuator layer cannot be reduced to 1 mm or less (more specifically, if the film thickness is set to 1 mm or less, the swelling required for the polymer gel to form irregularities is required. The liquid cannot be retained.) When the film thickness is increased, the volume change of the polymer gel takes time, and the response speed is so slow that it cannot respond within 1 second.
The problem that the swelling liquid cannot be retained is because the polymer gel forms a three-dimensional structure by physical crosslinking or chemical crosslinking, and therefore cannot have a flexible structure for retaining the swelling liquid. The inventors of the present application thought.
In addition, an actuator using an ion conductive polymer has a problem in practical performance that it does not show a flexible feel and is inferior in reaction force sense when pressed.
As for supramolecular gels, conventional chemical gels and physical gels are irreversible with respect to structural changes. Since the cross-linking point can move freely with respect to shrinkage, stress concentration hardly occurs, and it has excellent flexibility and toughness. In addition, the supramolecular gel can lower the polymer density than the chemical gel or the physical gel, and thus, the supramolecular gel can take in more solvent molecules in the gel than the chemical gel or the physical gel. The inventors have arrived. That is, the inventors have come up with the idea that if a supramolecular gel can be made into a thin film actuator, it can be driven with a film thickness of 1 mm or less, which could not be achieved with conventional gels.
However, since the supramolecular gel does not respond to potential, the conventional supramolecular gel cannot be used for the actuator.

  Therefore, the present invention is a thin film actuator that is driven by applying a voltage, and even when the thickness of the actuator layer is 1 mm or less, for example, when the operator presses a button such as a switch with a finger, the button The thin film actuator is deformed in a short time by pressing and a reaction force feel (reaction force sense, reaction force feel) can be provided to the operator, and a touch panel using this thin film actuator is provided. For the purpose.

The inventors of the present application have conducted intensive studies to achieve the above object,
A thin film actuator that is driven by applying a voltage,
An actuator layer formed of a gel containing a modified crosslinked polyrotaxane impregnated with an electrolyte solution;
An electrode provided along both surfaces of the actuator layer, to which a voltage is applied;
The modified crosslinked polyrotaxane has a functional group having an ion exchange capacity, and the first polyrotaxane formed by including a first linear molecule in a skewered manner in the opening of the first cyclic molecule, and A second polyrotaxane in which a second linear molecule is included in a skewered manner in the opening of the two cyclic molecules, and the rings of the first and second cyclic molecules are substantial rings In the thin film actuator in which at least one of the first cyclic molecules and at least one of the second cyclic molecules are bonded via a chemical bond, even if the thickness of the actuator layer is 1 mm or less, the thin film actuator However, it has been found that it can be deformed in a short time by being pressed, and the reaction force can be felt to the operator (reaction force sense, reaction force feel) by the deformation.
In addition, when the touch panel using the thin film actuator is pressed, the thin film actuator is deformed in a short time, and the deformation gives the operator a reaction force feeling (reaction force feeling, reaction force feeling). I found out that I could perceive that I pressed the button, and completed this application.

That is, this invention provides the following 1-7.
1. A thin film actuator that is driven by applying a voltage,
An actuator layer formed of a gel containing a modified crosslinked polyrotaxane impregnated with an electrolyte solution;
An electrode provided along both surfaces of the actuator layer, to which a voltage is applied;
The modified crosslinked polyrotaxane has a functional group having an ion exchange capacity, and the first polyrotaxane formed by including a first linear molecule in a skewered manner in the opening of the first cyclic molecule, and A second polyrotaxane in which a second linear molecule is included in a skewered manner in the opening of the two cyclic molecules, and the rings of the first and second cyclic molecules are substantial rings A thin film actuator in which at least one of the first cyclic molecules and at least one of the second cyclic molecules are bonded via a chemical bond.
2. 2. The thin film actuator according to 1 above, wherein the functional group is at least one selected from the group consisting of a carboxy group, a sulfo group, an amino group, an amino group having 1 to 3 hydrocarbon groups, and a salt thereof.
3. 3. The thin film actuator according to 1 or 2 above, wherein the functional group is bonded to an end of the first linear molecule and / or the second linear molecule.
4). 4. The thin film actuator according to any one of 1 to 3, wherein the electrolyte solution is an ionic liquid.
5). 5. The thin film actuator according to any one of 1 to 4, wherein the first cyclic molecule and / or the second cyclic molecule is at least one selected from the group consisting of α-cyclodextrin and β-cyclodextrin.
6). The first linear molecule and / or the second linear molecule is selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene. 6. The thin film actuator according to any one of 1 to 5, which is at least one selected.
7). The touch panel using the thin film actuator in any one of said 1-6.

The present invention is characterized in that the cross-linked polyrotaxane (supramolecular gel) in which the cross-linking point moves freely is provided with ion exchange ability (capturing ability for cations or anions), and these are regarded as electrically compatible thin film actuators. It is what you have.
As a result, it has been found that application to a touch-sensitive touch-sensing input device using the thin film actuator is possible.
That is, the thin film actuator of the present invention is an electric response type, and achieves a high response speed within 1 second and a flexible film having a film thickness of 1 mm or less by using a modified crosslinked polyrotaxane.
In addition, the touch panel of the present invention (a touch panel device that performs an input operation by touching an operator) reversibly changes the surface shape of the touch panel to a smooth shape that feels soft to the user, thereby enabling the analog switch to The same reaction force sensation (operation feeling) as when inputting can be transmitted.

In the thin film actuator of the present invention, even if the film thickness of the actuator layer is 1 mm or less, the thin film actuator can be deformed in a short time by being pressed and can give a reaction force to the operator.
In the touch panel of the present invention, even if the thickness of the actuator layer is 1 mm or less, for example, when the operator presses a button such as a switch with a finger, the thin film actuator is deformed in a short time, and the operator feels the reaction force. Can be given.

The present invention will be described in detail below.
The thin film actuator of the present invention is
A thin film actuator that is driven by applying a voltage,
An actuator layer formed of a gel containing a modified crosslinked polyrotaxane impregnated with an electrolyte solution;
An electrode provided along both surfaces of the actuator layer, to which a voltage is applied;
The modified crosslinked polyrotaxane has a functional group having an ion exchange capacity, and the first polyrotaxane formed by including a first linear molecule in a skewered manner in the opening of the first cyclic molecule, and A second polyrotaxane in which a second linear molecule is included in a skewered manner in the opening of the two cyclic molecules, and the rings of the first and second cyclic molecules are substantial rings , Wherein at least one of the first cyclic molecules and at least one of the second cyclic molecules are bonded via a chemical bond.

The thin film actuator of the present invention will be described below with reference to the accompanying drawings. The present invention is not limited to the attached drawings.
FIG. 3 is a schematic cross-sectional view showing an embodiment of the thin film actuator of the present invention.
In FIG. 3, a thin film actuator 10 is provided along an actuator layer 12 formed of a gel containing a modified crosslinked polyrotaxane impregnated with an electrolyte solution, and along both surfaces of the actuator layer 12, and voltage is applied from both sides of the actuator layer 12. , A power source 20 that applies a voltage to the electrode 13, and a controller 22 that controls the application of the voltage.
The power source 20 applies a voltage for giving a predetermined potential difference to the electrode 13. Examples of the power source include a DC power source (direct current power source). The power supply 20 can apply a voltage of −2 to +2 V between the electrodes 13 via the controller 22.
The controller 22 adjusts voltage application according to a control signal from an external device (not shown).

The actuator layer will be described below.
The actuator layer used in the thin film actuator of the present invention is formed of a gel containing a modified crosslinked polyrotaxane impregnated with an electrolyte solution.
In the present invention, the modified crosslinked polyrotaxane contained in the gel has a functional group having an ion exchange ability as a first feature.
The ion exchange capacity may be either anion exchange capacity or cation exchange capacity, or both anion exchange capacity and cation exchange capacity.

In the present invention, examples of the functional group having anion exchange ability include Bronsted bases such as amino groups and amino groups having 1 to 3 hydrocarbon groups, or salts thereof. Specifically, for example, —NH ₂ , —NHR (R: hydrocarbon group, the same applies to functional groups having ion exchange capacity hereinafter), —NR ₂ , —NR ₃ ⁺ , —NH ₃ ⁺ , —NH ₃ ⁺ X ^- (X: ^{_{halogen), - NH 3 + OH -}} , -NR 3 + X - (X: halogen), ^- NR ₃ ⁺ OH - and the like.
The hydrocarbon group that the amino group has is not particularly limited. For example, an alkyl group such as a methyl group or an ethyl group; an aromatic hydrocarbon group; an aralkyl group can be mentioned.
When a functional group having anion exchange ability forms a salt, examples of the anion species forming the salt include a low valence valence such as OH ⁻ , bromine ion, and chlorine ion (ie, ion valence). (With a small radius).

In the present invention, examples of the functional group having a cation exchange ability include Bronsted acids such as a carboxy group and a sulfo group, and salts thereof.
When a functional group having a cation exchange ability forms a salt, examples of the cationic species that form the salt include alkali metal ions such as sodium ion and potassium ion, atomization such as ammonium (NH ₄ ⁺ ), and proton. Those having a low valence and a small number of valence electrons (that is, a small ionic radius) can be mentioned.

The functional groups can be used alone or in combination of two or more.
Functional groups can be attached to cyclic molecules and / or linear molecules. The functional group can be bonded to the side chain and / or the terminal of the linear molecule.
Among them, the functional group is preferably bonded to the ends of the linear molecule from the viewpoint of excellent reaction force feeling, thin film actuators can be made thinner, and excellent transparency. More preferably, it binds to.
The unmodified crosslinked polyrotaxane may be referred to as “crosslinked polyrotaxane” hereinafter.

  In the present invention, the modified crosslinked polyrotaxane has, as a second feature, a first polyrotaxane in which a first linear molecule is skewered in an opening of the first cyclic molecule, and a second A second polyrotaxane in which a second linear molecule is included in a skewered manner in the opening of the cyclic molecule, and the rings of the first and second cyclic molecules are substantial rings, At least one of the first cyclic molecules and at least one of the second cyclic molecules are bonded via a chemical bond.

The modified cross-linked polyrotaxane has two or more polyrotaxane molecules, as described above, in addition to the first feature (modified), and the cyclic molecules of the two or more polyrotaxane molecules are cross-linked through chemical bonds. It is.
In this specification, “polyrotaxane” or “polyrotaxane molecule” includes a cyclic molecule as a “rotor” and a linear molecule as an “axis”, and the opening of the cyclic molecule is skewered. In this way, it is a molecule that is included and integrated non-covalently. The modified crosslinked polyrotaxane includes a compound having the above structure in part.

In the modified crosslinked polyrotaxane, at least one of the first cyclic molecules and at least one of the second cyclic molecules are bonded via a chemical bond. At least one of the first cyclic molecules and at least one of the second cyclic molecules are bonded via a chemical bond to form a crosslinked cyclic molecule (bicyclo molecule). When the modified crosslinked polyrotaxane has a plurality of crosslinked cyclic molecules, the plurality of crosslinked cyclic molecules may be the same or different.
Two or more polyrotaxane molecules may be the same or different. That is, the first polyrotaxane molecule and the second polyrotaxane molecule different from the first polyrotaxane molecule can be bonded or crosslinked. The first polyrotaxane molecule has a first cyclic molecule, and the second polyrotaxane molecule has a second cyclic molecule, where the first cyclic molecule and the second cyclic molecule are the same. Or different.

The modified crosslinked polyrotaxane will be described below with reference to the accompanying drawings.
FIG. 1 is a diagram schematically showing an example of a modified crosslinked polyrotaxane.
In FIG. 1, a modified cross-linked polyrotaxane 100 has a polyrotaxane molecule 1 and a polyrotaxane molecule 2. The polyrotaxane molecule 1 has a cyclic molecule 3 as a “rotor”, and a linear molecule 5 as an “axis” that is included by skewing the opening of the cyclic molecule 3. The polyrotaxane molecule 2 has a cyclic molecule 4 as a “rotor”, and a linear molecule 6 as an “axis” that is included by squeezing the opening of the cyclic molecule 4. The cyclic molecule 3 and the cyclic molecule 4 are bonded or cross-linked at the bonding portion 7 to form a cross-linked cyclic molecule 8. Two or more polyrotaxane molecules (polyrotaxane molecule 1 and polyrotaxane molecule 2 in FIG. 1) are crosslinked by the crosslinked cyclic molecule 8 to form a modified crosslinked polyrotaxane 100. In FIG. 1, functional groups are not shown.
It is preferable that at least two cross-linked cyclic molecules 8 are present on the linear molecule 5 from the viewpoint that the reaction force sensation is superior, the thin film actuator can be made thinner, and the responsiveness is excellent. More preferably. The inclusion amount of the crosslinked cyclic molecule in the polyrotaxane molecule can be confirmed by NMR, light absorption, elemental analysis or the like.

FIG. 2 is a diagram schematically showing an example of a modified crosslinked polyrotaxane.
In FIG. 2A, a modified crosslinked polyrotaxane 200 is formed by a plurality of polyrotaxane molecules 1 having a plurality of crosslinked cyclic molecules 11, a linear molecule 5, and a functional group 9 having ion exchange ability. The functional group 9 is bonded to the end of the linear molecule 5.
The crosslinked cyclic molecule 11 and the linear molecule 5 are in an inclusion state in which they are integrated non-covalently, and the crosslinked cyclic molecule 11 can easily move on the linear molecule 5.
The modified cross-linked polyrotaxane does not use a cyclic molecule or an inclusion compound in which the cross-linked cyclic molecules are closely packed, but the cross-linked cyclic molecule 11 is above the linear molecule 5 like the polyrotaxane molecule 1 shown in FIG. It is preferable that it exists in a sparse state from the viewpoint of being superior in reaction force feeling.
In FIG. 2A, the plurality of polyrotaxane molecules may be different.

The modified cross-linked polyrotaxane does not have a direct cross-linking point between linear molecules, and can be gelled by geometric constraints. That is, the structure is different from that of a conventional physical gel or chemical gel having a direct crosslinking point.
Specifically, when stress is applied to the modified cross-linked polyrotaxane, since there is no direct cross-linking between the polymers, the internal stress in the compound is dispersed, resulting in high strength against fracture. Further, even during swelling, since the linear molecules form a network structure without waste, more uniform and higher swelling characteristics can be provided.

The characteristics of the modified crosslinked polyrotaxane will be described below with reference to the accompanying drawings.
In FIG. 2A, when stress is applied to the modified cross-linked polyrotaxane 200 in the B direction, the cross-linked cyclic molecule 11 or the linear molecule 5 easily moves as shown in FIG. It can be made uniform.
Therefore, the modified cross-linked polyrotaxane has high strength against breakage, and the electrolyte solution can be impregnated in a large amount, for example, in the network structure. Further, the modified crosslinked polyrotaxane can provide a compound having a much higher entropy elasticity than a conventional physical gel due to its structure.
The modified crosslinked polyrotaxane is a material that exhibits high breaking strength, has excellent extensibility, flexibility, transparency, and resilience, and has very high entropy elasticity.

The linear molecule used in the production of the modified crosslinked polyrotaxane is a molecule or substance that can be included in a cyclic molecule and can be integrated non-covalently and is linear, particularly if it is linear. It is not limited.
In the present invention, the “linear molecule” means a molecule including a polymer and all other substances satisfying the above requirements.
Further, “linear” of “linear molecule” means substantially “linear”. That is, the linear molecule may have a branched chain as long as the cyclic molecule that is a rotor is rotatable or the cyclic molecule is slidable or movable on the linear molecule. Further, the length of the “straight chain” is not particularly limited as long as the cyclic molecule can slide or move on the linear molecule.

  Examples of linear molecules that can be used in producing the modified crosslinked polyrotaxane include hydrophilic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, and cellulose resins (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl). Cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethylene imine, casein, gelatin, starch, etc. and / or their co-polymerization Copolymers, etc .; Hydrophobic polymers such as polyethylene, polypropylene, and other copolymer resins with olefinic monomers Polyolefin resins, polyisoprene, polyisobutylene, polybutadiene, polyester resins, polyvinyl chloride resins, polystyrene resins such as polystyrene and acrylonitrile-styrene copolymer resins, polymethyl methacrylate, (meth) acrylic acid ester copolymers, acrylonitrile- Examples thereof include acrylic resins such as methyl acrylate copolymer resins, polycarbonate resins, polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins and the like; and derivatives or modified products thereof.

  Among these, polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetrahydrofuran; polyolefins such as polyethylene and polypropylene are preferable from the viewpoint of excellent reaction force feeling, thin film actuators, and excellent transparency. Polyisoprene, polyisobutylene, polybutadiene; organopolysiloxanes such as polydimethylsiloxane are preferred, and polyethylene glycol and polypropylene glycol are more preferred.

The weight average molecular weight (Mw) of the linear molecule is usually 100 or more, and from the viewpoint of excellent viscoelasticity and responsiveness, the weight average molecular weight (Mw) is preferably 1,000 or more, more preferably 5 1,000 or more.
In the present invention, the weight average molecular weight is measured by standard polystyrene conversion measured by gel permeation chromatography (GPC) using water / acetonitrile as an eluent.
The linear molecules can be used alone or in combination of two or more.

The cyclic molecule that can be used for producing the modified crosslinked polyrotaxane can be any cyclic molecule as long as it is a cyclic molecule that can be included in the linear molecule.
In the present invention, “cyclic molecule” refers to various cyclic substances including cyclic molecules.
A “cyclic molecule” refers to a molecule or substance that is substantially cyclic. That is, “substantially annular” means that the letter “C” is not completely closed, such as the letter “C”, and one end and the other end of the letter “C” are not connected. It is also intended to include those having overlapping spiral structures. Furthermore, the ring of a “bicyclo molecule (bridged cyclic molecule)” described later can be defined in the same manner as “substantially cyclic” of “cyclic molecule”. That is, one or both rings of the “bicyclo molecule” may not be completely closed like the letter “C”, and one end and the other end of the letter “C” are connected to each other. It may have a spiral structure that is not overlapped.

Examples of the cyclic molecule that can be used in producing the modified crosslinked polyrotaxane include cyclodextrins (for example, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, dimethylcyclodextrin and glucosylcyclodextrin, these Derivatives, modified products, etc.), crown ethers, benzocrowns, dibenzocrowns, dicyclohexanocrowns, and derivatives or modified products thereof.
The above-mentioned cyclodextrins and crown ethers differ in the size of the opening of the cyclic molecule depending on the type. Therefore, the type of linear molecule to be used, specifically, when the linear molecule to be used is assumed to be cylindrical, the cyclic molecule to be used depends on the diameter of the cross section of the cylinder, the hydrophobicity or hydrophilicity of the linear molecule, etc. Can be selected. When a cyclic molecule having a relatively large opening and a cylindrical linear molecule having a relatively small diameter are used, two or more linear molecules can be included in the opening of the cyclic molecule. .

  Among them, from the viewpoint of excellent reaction force feeling, thin film actuators can be made thinner, and viscoelasticity, the cyclic molecules are α-cyclodextrin (glucose hexamer), β-cyclodextrin (glucose 7 amount). Body).

  Examples of the combination of a cyclic molecule and a linear molecule include a combination of α-cyclodextrin and polyethylene glycol, a combination of α-cyclodextrin and polypropylene glycol, a combination of β-cyclodextrin and polyethylene glycol, β -A combination of cyclodextrin and polypropylene glycol.

The crosslinked cyclic molecule will be described below.
In the modified crosslinked polyrotaxane, the first cyclic molecule and the second cyclic molecule are crosslinked via chemical bonds. In this case, the chemical bond may be a simple bond or a bond via various atoms or molecules.
The cyclic molecule can have a reactive group (for example, a hydroxy group, an amino group, a carboxyl group, a thiol group, or an aldehyde group) outside the ring. A reactive group possessed by a cyclic molecule reacts with a crosslinking agent to crosslink the cyclic molecules to produce a crosslinked cyclic molecule. Examples of the method for producing a crosslinked cyclic molecule include the method described in JP-A-2006-002077.
As the crosslinking agent that can be used in the present invention, conventionally known crosslinking agents can be used. For example, 3,5-dimercaptopyridine, cyanuric chloride, trimesoyl chloride, terephthaloyl chloride, epichlorohydrin, dibromobenzene, glutaraldehyde, phenylene diisocyanate, diisocyanate trilein (for example, 2,4-diisocyanate trilein) 1,1'-carbonyldiimidazole, divinylsulfone and the like. Moreover, various coupling agents, such as a silane coupling agent (for example, various alkoxysilanes) and a titanium coupling agent (for example, various alkoxytitanium), can be mentioned. Furthermore, various photocrosslinking agents used for soft contact lens materials, for example, stilbazolium salt-based photocrosslinking agents such as formylstyrylpyridin (K. Ichimura et al., Journal of polymer science. Polymer chemistry edition 20, 1411- 1432 (1982) (this document is incorporated herein by reference), as well as other photocrosslinkers, such as photodimers by photodimerization, specifically cinnamic acid, anthracene, thymine And the like.

The cross-linking agent preferably has a molecular weight of less than 2,000, preferably less than 1,000, more preferably less than 600, and most preferably less than 400.
When α-cyclodextrin having a reactive group is used as a cyclic molecule and crosslinking is performed using a crosslinking agent, examples of the crosslinking agent include 3,5-dimercaptopyridine, cyanuric chloride, and 2,4-diisocyanic acid. Examples include trilein, 1,1′-carbonyldiimidazole, trimesoyl chloride, terephthaloyl chloride, and alkoxysilanes such as tetramethoxysilane and tetraethoxysilane.

Examples of the crosslinked cyclic molecule include a cyclodextrin dimer. Specific examples include α-cyclodextrin dimer and β-cyclodextrin dimer.
The crosslinked cyclic molecule is preferably an α-cyclodextrin dimer or β-cyclodextrin dimer from the viewpoint of excellent viscoelasticity.
The crosslinked cyclic molecules can be used alone or in combination of two or more.

  As a method for producing a modified crosslinked polyrotaxane, for example, a crosslinked cyclic molecule, that is, a “bicyclo molecule” having a first substantial ring and a second substantial ring (bicyclization step) is produced. A chain molecule is mixed to produce a crosslinked polyrotaxane by sandwiching linear molecules in the first and second rings of the “bicyclo molecule” in a skewered manner (mixing step). A modified crosslinked polyrotaxane can be obtained by introducing a functional group having ion exchange capacity (modification step).

In the bicyclization step, a cyclic molecule having a reactive group and a crosslinking agent are reacted to produce a bicyclo molecule (bridged cyclic molecule) having a first substantial ring and a second substantial ring.
The cyclic molecule having a reactive group and the crosslinking agent are as described above. The cyclic molecules having a reactive group can be used alone or in combination of two or more. The crosslinking agents can be used alone or in combination of two or more.
The amount of the cross-linking agent used is 1 to 10 mol with respect to 100 mol of the cyclic molecule having a reactive group from the viewpoint that the reaction force feel is excellent, the thin film actuator can be made thinner, and the viscoelasticity is excellent. Is preferred.

In the mixing step, the bicyclo molecule and the linear molecule are mixed, and the first and second rings of the bicyclo molecule are included in a skewered manner to produce a crosslinked polyrotaxane.
The bicyclo molecule and the linear molecule are as described above. Bicyclo molecules can be used alone or in combination of two or more. The linear molecules can be used alone or in combination of two or more.
The amount of the bicyclo molecule is 1 to 70 parts by mass with respect to 100 parts by mass of the linear molecule from the viewpoint that the reaction force feeling is excellent, the thin film actuator can be made thinner, and the responsiveness is excellent. Preferably, it is 2-30 mass parts.
Examples of the mixing method in the mixing step include a method of stirring an aqueous solution containing a bicyclo molecule and a linear molecule at room temperature.

  In the modification step, a functional group having ion exchange ability is introduced into the linear molecule and / or crosslinked cyclic molecule of the crosslinked polyrotaxane to obtain a modified crosslinked polyrotaxane.

The method for introducing a functional group having anion exchange ability into the unmodified crosslinked polyrotaxane is not particularly limited.
For example, when an amino group is added as a functional group having an anion exchange ability, a primary alcohol that is a terminal portion of a linear molecule constituting an unmodified crosslinked polyrotaxane is halogenated using oxalyl chloride or phosphorus chloride. Then, an amino group can be introduced into the crosslinked polyrotaxane by reacting with an amine and / or ammonia. The amine used after the halogenation is not particularly limited.
The obtained crosslinked polyrotaxane having an amino group can easily form a salt by reaction with hydrochloric acid. Further, N-alkylation can be achieved by reacting the obtained crosslinked polyrotaxane having an amino group with an alkyl halide. The alkyl halide used in the N-alkylation is not particularly limited.

The method for introducing a functional group having a cation exchange ability into an unmodified crosslinked polyrotaxane is not particularly limited. For example, when a carboxy group is imparted as a functional group having a cation exchange ability, a primary alcohol that is a terminal portion of a linear molecule constituting an unmodified crosslinked polyrotaxane is replaced with a hydrogen peroxide solution or a permanganate. The method of oxidizing is mentioned.
Moreover, a carboxy group can be easily converted into a salt (for example, sodium salt) by reacting the obtained crosslinked polyrotaxane having a carboxy group with, for example, sodium hydroxide.
On the other hand, in the provision of a sulfo group, a primary alcohol, which is a terminal portion of a linear molecule constituting an unmodified crosslinked polyrotaxane, is reacted with thionyl chloride to form sulfonyl chloride, and then metal zinc, followed by hydrochloric acid. Examples thereof include a method of introducing a sulfo group by oxidizing sulfinic acid obtained by the reaction with permanganate or the like.
Further, by reacting the obtained crosslinked polyrotaxane having a sulfo group with, for example, sodium hydroxide, the sulfo group can be easily converted into a salt (for example, a sodium salt).

The crosslinked polyrotaxanes can be used alone or in combination of two or more. The compounds used for introducing the functional group having ion exchange ability may be used alone or in combination of two or more.
The amount of the compound used for introducing the functional group having ion exchange capacity can make the thin film actuator thinner, and from the viewpoint of excellent viscoelasticity and responsiveness, with respect to 100 parts by mass of the crosslinked polyrotaxane, It is preferable that it is 0.01-100 mass parts, and it is more preferable that it is 0.1-10 mass parts.

As a method for introducing a functional group into a crosslinked cyclic molecule, for example, when the crosslinked cyclic molecule is a cyclodextrin, a primary hydroxy group (R—CH ₂ —OH) in a glucose molecule constituting the cyclodextrin is sodium- Examples include CH ₂ —O ⁻ Na ⁺ , conversion to carboxylic acid and derivatives thereof (R—COOH, R—COONa), and sulfonic acid and derivatives thereof (R—SO ₃ H, R—SO ₃ Na). It is done.

Examples of the linear molecule possessed by the modified crosslinked polyrotaxane include a linear polymer having functional groups at both ends. Specific examples include those represented by the following formula.

Examples of the modified cross-linked polyrotaxane include a combination of at least one selected from the group consisting of linear polymers represented by the above formula and a cyclodextrin dimer.
Among them, the modified cross-linked polyrotaxane can have many cyclic molecules (cross-linked cyclic molecules) in one linear molecule, is excellent in reaction force feeling, can make the thin film actuator thinner, and is viscoelastic. From the viewpoint of superiority, the combination of the linear molecule and the cyclic molecule is preferably a combination of polyethylene glycol and α-cyclodextrin dimer, or a combination of polypropylene glycol and β-cyclodextrin dimer.
The modified crosslinked polyrotaxanes can be used alone or in combination of two or more.

The electrolyte solution will be described.
The electrolyte solution used for the thin film actuator of the present invention is not particularly limited as long as it has conductivity (ionic conductivity). Examples thereof include a solution containing an electrolyte and an aqueous solvent, a solution containing an electrolyte and a non-aqueous solvent, and an ionic liquid.
The electrolyte is not particularly limited. Examples thereof include gel electrolyte salts and solid electrolyte salts. Specifically, for example, as the cation species, from the group consisting of lithium ion, sodium ion, dialkylimidazolium ion, tetraalkylammonium ion, trialkylimidazolium ion, piperidinium ion, pyrazolium ion, pyrrolium ion, pyrrolidinium ion As anion species, AlCl ₄ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , OTf ⁻ , sulfonium imide anion [for example, (CF ₃ SO ₂ ) ₂ imide anion: NTf ₂ ^-] combination of those selected from the group consisting of and the like.

As a solvent for dissolving the electrolyte, an aqueous solvent or a non-aqueous solvent can be used.
Water is mentioned as an aqueous solvent.
Examples of the non-aqueous solvent include ethylene glycol, diethylene glycol, glycerin, sulfolane, propylene carbonate, and butylene carbonate.

In the case of using a solvent, the concentration of the electrolyte solution is preferably 1 to 50% by mass from the viewpoint that the reaction force feel is excellent and the responsiveness is excellent.
The solvent is preferably an ionic liquid (ionic liquid) from the viewpoint that it is excellent in reaction force feeling and also has the role of an electrolyte salt.

The ionic liquid is not particularly limited. For example, as a cation, at least one kind selected from the group consisting of lithium ion, dialkylimidazolium ion, tetraalkylammonium ion, trialkylimidazolium ion, piperidinium ion, pyrazolium ion, pyrrolium ion, pyrrolidinium ion, and anion, At least one selected from the group consisting of AlCl ₄ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , OTf ⁻ , sulfonium imide anion [for example, (CF ₃ SO ₂ ) ₂ imide anion: NTf ₂ ⁻ ]. The thing which has these.

From the viewpoint of excellent reaction force feeling and excellent responsiveness, the electrolyte solution preferably contains an ionic liquid and an aqueous solvent, such as a lithium perchlorate aqueous solution, a sodium perchlorate aqueous solution,
Lithium trifluoromethanesulfonate (LiOTf) and lithium bis (trifluoromethanesulfonyl) imide (LiNTf ₂ ) are more preferable.
The electrolyte solutions can be used alone or in combination of two or more.

  The amount of the electrolyte solution used when forming the gel (actuator layer) is 1 to 100 parts by mass with respect to 100 parts by mass of the modified crosslinked polyrotaxane from the viewpoint of being superior in reaction force feeling and excellent in responsiveness. Is preferable, and it is more preferable that it is 10-20 mass parts.

The gel forming the actuator layer used in the thin film actuator of the present invention contains a modified crosslinked polyrotaxane impregnated with an electrolyte solution.
The actuator layer is activated by impregnating the modified crosslinked polyrotaxane with the electrolyte solution and swelling (ion exchange) the modified crosslinked polyrotaxane.
The method for impregnating the modified crosslinked polyrotaxane with the electrolyte solution is not particularly limited. For example, the gel can be formed by uniformly mixing the modified crosslinked polyrotaxane and the electrolyte solution.
Moreover, the composition containing a modified crosslinked polyrotaxane and an electrolyte solution can be dried under conditions of, for example, 50 to 80 ° C., if necessary after mixing.
In the present invention, the gel, that is, the actuator layer is formed as described above.

  The actuator layer used in the thin film actuator of the present invention is preferably 1 mm or less, more preferably 0.1 to 0.5 mm from the viewpoint of light weight, transparency, flexibility, and responsiveness. preferable.

The electrode will be described below.
The electrodes used in the thin film actuator of the present invention are provided along the surfaces on both sides of the actuator layer, and a voltage is applied to the electrodes.
The material for the electrode is not particularly limited. For example, metals such as gold, platinum, palladium, nickel; tin doped indium oxide (ITO), aluminum doped zinc oxide, antimony doped tin oxide (ATO), niobium doped tin oxide, tantalum doped tin oxide, fluorine doped tin oxide Conductive inorganic material; conductive polymer material such as polyethylenedioxythiophene (PEDOT).
Of these, ITO and conductive polymer materials are preferable from the viewpoint of excellent transparency and responsiveness.
The electrode materials can be used alone or in combination of two or more.

  The method for providing an electrode on the actuator layer is not particularly limited. For example, the electrode can be formed on the actuator layer by plating, sputtering, or printing (for example, screen printing). Each processing method is not particularly limited. For example, a conventionally well-known thing is mentioned.

The thin film actuator of the present invention has excellent flexibility, transparency, environmental resistance and chemical stability, and has good adhesiveness, and can be easily processed into a flexible film shape.
The thin film actuator of the present invention is superior in flexibility and workability, is lightweight, has a delicate elasticity close to a finger, and feels like a skin as compared with an inorganic material.
In addition, the thickness of the actuator layer can be reduced to 1 mm or less, and a response speed of 1 second or less can be achieved, compared with a material using an organic composition as a material. be able to.
Compared with a material using an ion exchange resin, it is excellent in flexibility and transparency, is easy to manufacture, and can efficiently impart ion exchange capacity.

The thin film actuator of the present invention can be used as an input device. For example, it can be suitably used for a touch panel that allows an operator to input by touching a button. The thin film actuator of the present invention is applied as an input operation button of a touch panel, and when the operator presses with a finger, the button changes its shape in response to the press, so that a reaction force feel that is soft to the fingertip of the operator is given. be able to.
Since the thin film actuator of the present invention is excellent in flexibility, transparency, environmental resistance, chemical stability, adhesiveness, and workability, the advantage of using the thin film actuator for a touch panel is great.

The deformation mechanism of the thin film actuator of the present invention will be briefly described below.
In the present invention, the reaction force is generated by a physical repulsive force generated when the actuator is dented (by being pressed with a finger) and an electrical deformation of the thin film actuator.
In the thin film actuator of the present invention, the actuator layer is formed of a gel containing a modified crosslinked polyrotaxane impregnated with an electrolyte solution.
Since the actuator layer is formed of a gel, when a person touches the thin film actuator of the present invention with a finger or the like, it can be perceived that the thin film actuator of the present invention has been pushed by the elasticity of the gel.
Further, since the gel contains the modified crosslinked polyrotaxane, it can be perceived that the thin film actuator of the present invention has been pushed by the elasticity of the modified crosslinked polyrotaxane.
Further, in the thin film actuator of the present invention, the modified cross-linked polyrotaxane has a functional group having ion exchange ability, and the modified cross-linked polyrotaxane is impregnated with the electrolyte solution. Untrapped ions can form clusters and ions and / or clusters can migrate to the electrode. As the electrolyte solution moves with the movement of ions and / or clusters, volume fluctuations occur in the thin film actuator, and the thin film actuator deforms (for example, deforms into a dome shape). It is possible to confirm that the thin film actuator (switch) has been pressed reliably.
In addition, when the functional group having ion exchange ability in the modified crosslinked polyrotaxane has anion exchange ability (that is, when the functional group is a cation), a voltage is applied between the electrodes while the modified crosslinked polyrotaxane captures the anion in the gel. As a result, the cation moves to the cathode side, and the solvent molecules of the electrolyte solution also move to the cathode side. As a result, the actuator layer is greatly deformed.
On the other hand, when the functional group having ion exchange ability in the modified crosslinked polyrotaxane has cation exchange ability (that is, when the functional group is an anion), a voltage is applied between the electrodes while the modified crosslinked polyrotaxane captures the cation in the gel. As a result, the anion moves to the anode side, and the solvent molecules of the electrolyte solution also move to the anode side. As a result, the actuator layer is greatly deformed.

Next, the touch panel of the present invention will be described below.
The touch panel of the present invention uses the thin film actuator of the present invention.
The thin film actuator used for the touch panel of the present invention is not particularly limited as long as it is the thin film actuator of the present invention.

The touch panel of the present invention is a touch panel that can be input by being pressed by an operator.
As one of the preferable embodiments of the touch panel of the present invention, for example,
A device body comprising an actuator layer formed of a gel containing a modified crosslinked polyrotaxane impregnated with an electrolyte solution, and electrodes provided along both surfaces of the actuator layer to which a voltage is applied;
A first electrode terminal that is provided on both sides of the device body and applies a voltage to the electrode to drive the device body; and a device that is provided on both sides of the device body and is generated by contact of an operator. One having a second electrode terminal that detects an electromotive force generated in the device main body according to deformation and extracts a potential difference of the electrode can be used.
The modified crosslinked polyrotaxane is the same as described above.

  The touch panel of the present invention will be described below with reference to the accompanying drawings. The present invention is not limited to the drawings.

FIG. 4A is a schematic diagram showing a device configuration of a touch panel (hereinafter referred to as a panel) 40.
In FIG. 4A, the panel 40 is provided with nine buttons 42 in three rows and three rows on the operation surface that the operator presses with a finger. Each of the buttons 42 is configured using a thin film actuator.

FIG. 4B is a cross-sectional view taken along line AA ′ in FIG. 4A when the outer cover is removed. FIG. 4C is a perspective view showing a configuration in which the first electrode terminals 46 and 48 and the second electrode terminals 50 and 52 are provided in the thin film actuator 10.
4B, the thin film actuator 10 (button 42) is configured by separating each button 42 by a separator 44, and first electrode terminals 46, 48 and Second electrode terminals 50 and 52 are provided.
The thin film actuator 10 is provided along an actuator layer 12 formed of a gel containing a modified cross-linked polyrotaxane impregnated with an electrolyte solution, and on both sides of the actuator layer 12, and a voltage is applied from both sides of the actuator layer 12. And a power source 20 for applying a voltage to the electrode 13 and a controller 22 for controlling the application of the voltage.
The device body (not shown) refers to a combination of the actuator layer 12 and the electrode 13.

The first electrode terminals 46 and 48 apply voltage to the electrode 13 from the power source 20 in FIG. 4B according to the control of the controller 22, and are connected to the power source 20 and the controller 22. ing.
On the other hand, the second electrode terminals 50 and 52 are connected to the controller 22, and a potential difference between the electrodes is detected in order to detect an electromotive force generated in the actuator layer 12 according to the deformation of the actuator layer 12 due to the contact of the operator. Is configured to take out. The potential difference extracted from the second electrode terminals 50 and 52 is sent to the controller 22 to detect that the operator has pressed the button 42. That is, the thin film actuator 10 can function as a pressure detection sensor that detects the presence or absence of an operator's press by providing the second electrode terminals 50 and 52.

  The controller 22 is configured to apply a predetermined voltage to the thin film actuator 10 in accordance with the detected operator press. For this reason, in response to the pressing of the button 42 by the operator, the thin film actuator 10 is driven and deformed within the contact time (within 1 second) of the button 42 by the pressing. That is, when the operator presses the button 42, the button 42 reacts instantly. Thereby, the operator can perceive that the input by the button 42 is executed.

By using the thin film actuator of the present invention, the touch panel of the present invention can greatly deform the thin film actuator even when the thickness of the actuator layer is 1 mm or less, and can be perceived by the operator in response to pressing of the button. Can give a great reaction force.
The actuator layer used in the touch panel of the present invention is a material that is lightweight, adaptable to the human body and has functions such as a pigment material and a magnetic material because it is excellent in transparency, flexible and easy to process. Can be dispersed and blended.

  As described above, the thin film actuator and the touch panel using the same according to the present invention have been described in detail. However, the present invention is not limited to the above embodiment, and various modifications and changes may be made without departing from the spirit of the present invention. Of course it is good.

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these.
1. Production of cyclodextrin dimer (1) α-cyclodextrin dimer 16 g of α-cyclodextrin (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 200 mL of anhydrous dimethylformamide (DMF), and sodium hydride (60% in oil, 500 mg). ) And stirred at room temperature for 10 hours. Tosyl chloride (2.9 g) was added to the reaction solution and stirred for 3 hours. The reaction solution was added to acetone, and the white precipitate thus deposited was collected by filtration and purified with a reverse phase silica gel column (40% methanol aqueous solution was used as a developing solvent) to obtain 2-monotosyl-α-cyclodextrin.
Next, 2-monotosyl-α-cyclodextrin (6 g) was added to a 0.2 M aqueous sodium hydroxide solution, stirred at room temperature, neutralized with dilute hydrochloric acid at 0 ° C. after 40 hours, and the reaction solution was added to acetone. 2,3-epoxy-α-cyclodextrin was obtained.
2,3-epoxy-α-cyclodextrin (2 g) was added to DMF (80 mL), sodium hydride (1.2 g) was added, and methyl iodide (4 mL) was added dropwise while maintaining the reaction solution at 0 ° C. And stirred at room temperature for 24 hours after dropping. Methanol (3 mL) was added to the reaction solution, and after deiodination with sodium thiosulfate, the solvent was distilled off to obtain 2,3-epoxy-permethyl-α-cyclodextrin.
2,3-epoxy-permethyl-α-cyclodextrin (1 g) was added to a 0.1M NaHCO ₃ aqueous solution, 3,5-dimercaptomethylpyridine (50 mg) was added, and the mixture was heated to reflux for 24 hours. An α-cyclodextrin dimer crosslinked with mercaptomethylpyridine was obtained. Identification was performed by FAB-MASS.
The obtained α-cyclodextrin dimer is referred to as α-cyclodextrin dimer.

The structure of the α-cyclodextrin dimer is represented by the following formula (1).
In the formula (1), m is 1 and n is 1.

(2) β-cyclodextrin dimer Using 17 g of β-cyclodextrin (manufactured by Tokyo Chemical Industry Co., Ltd.) according to the above method, a β-cyclodextrin dimer crosslinked with 3,5-dimercaptomethylpyridine is obtained. It was.

The structure of the β-cyclodextrin dimer is represented by the following formula (1).
In formula (1), m is 1 and n is 2, respectively.

2. Production of cross-linked polyrotaxane (1) Cross-linked polyrotaxane 1
Α-Cyclodextrin dimer (1 g) crosslinked with 3,5-dimercaptomethylpyridine and polyethylene glycol (weight average molecular weight: 1,500, manufactured by Sigma-Aldrich) (5 mg) were added to water (10 ml). The mixture was mixed at room temperature while irradiating with ultrasonic waves. After 2 hours, a crosslinked polyrotaxane with α-cyclodextrin dimer was obtained as a precipitate. The obtained crosslinked polyrotaxane is designated as crosslinked polyrotaxane 1.

(2) Cross-linked polyrotaxane 2
The α-cyclodextrin dimer crosslinked with 3,5-dimercaptomethylpyridine is replaced with the β-cyclodextrin dimer crosslinked with 3,5-dimercaptomethylpyridine, and polyethylene glycol is replaced with polypropylene glycol (weight average). A crosslinked polyrotaxane by β-cyclodextrin dimer was obtained in the same manner as the crosslinked polyrotaxane 1 except that the molecular weight was 1,000 (manufactured by Sigma-Aldrich). The obtained crosslinked polyrotaxane is designated as crosslinked polyrotaxane 2.

(3) Cross-linked polyrotaxane 3
An experiment was conducted in the same manner as the crosslinked polyrotaxane 1 except that polyethylene glycol having a weight average molecular weight of 1,000 (manufactured by Sigma-Aldrich) was used to obtain a crosslinked polyrotaxane by an α-cyclodextrin dimer. The obtained crosslinked polyrotaxane is designated as crosslinked polyrotaxane 3.

About the obtained bridge | crosslinking polyrotaxane, the ratio (yield) of the inclusion crosslinked cyclic molecule was calculated | required as follows. The results are shown in Table 1.
The cyclodextrin dimer obtained as described above was used in the above amounts.
The filtrate obtained by filtering the crosslinked polyrotaxane with a glass filter is dried, the amount of the cyclodextrin dimer remaining in the filtrate is measured, and the obtained number is applied to the following formula to include the crosslinked cyclic The percentage of molecules was determined.
Proportion of cross-linked cyclic molecules included (mass%) = (A−B) / A × 100
A: Amount of the cyclodextrin dimer used in producing the crosslinked polyrotaxane B: Amount of the cyclodextrin dimer remaining in the filtrate “L” when the yield is less than 30% by mass, 30% by mass The case of less than 60% by mass is “M” and the case of 60 to 100% by mass is “H”.

3. Production of modified crosslinked polyrotaxane (introduction of functional group to crosslinked polyrotaxane)
(1) Modified cross-linked polyrotaxane 1
The resulting crosslinked polyrotaxane (1: 1 g) and hydrogen peroxide solution (10 mL) are mixed and reacted under the conditions of 0 ° C. to oxidize the terminal hydroxy group of polyethylene glycol to a carboxy group, and then carboxy group and sodium hydroxide The carboxy group was converted to a sodium salt by reacting with carboxylic acid to obtain a crosslinked polyrotaxane modified with a carboxylic acid sodium salt. The obtained crosslinked polyrotaxane is referred to as a modified crosslinked polyrotaxane 1.

(2) Modified crosslinked polyrotaxane 2
The obtained crosslinked polyrotaxane (2: 1 g) and hydrogen peroxide solution (10 mL) were mixed and reacted under the condition of 0 ° C. to oxidize the terminal hydroxy group of polyethylene glycol to a carboxy group, and modified with carboxylic acid. Got. The obtained crosslinked polyrotaxane is referred to as a modified crosslinked polyrotaxane 2.

(3) Methoxylated crosslinked polyrotaxane 3: 1 g of the obtained crosslinked polyrotaxane and 0.1 g of methyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and reacted under the condition of 0 ° C., and one end of polyethylene glycol was methoxy grouped. As a result, a crosslinked polyrotaxane having a methoxy group was obtained. The obtained crosslinked polyrotaxane is referred to as a methoxylated crosslinked polyrotaxane.

The structure of the modified linear polymer constituting the modified crosslinked polyrotaxane 1-2, the methoxylated crosslinked polyrotaxane, and the crosslinked polyrotaxane 2 is as follows.
The modified linear polymer constituting the modified crosslinked polyrotaxane 1 is represented by the following formula (I).
The modified linear polymer constituting the modified crosslinked polyrotaxane 2 is represented by the following formula (II).
The linear polymer constituting the methoxylated crosslinked polyrotaxane is represented by the following formula (III).
The linear polymer constituting the crosslinked polyrotaxane 2 is represented by the following formula (IV).

The combinations of the linear polymer and the cyclodextrin dimer constituting the modified crosslinked polyrotaxane 1-2, the methoxylated crosslinked polyrotaxane, and the crosslinked polyrotaxane 2 are as shown in Table 1 below.
CD means “cyclodextrin”.

4). Production of Gel of Modified Crosslinked Polyrotaxane Using the components shown in Table 2 in the amounts (parts by mass) shown in the same table, the mixture was stirred and mixed uniformly to obtain a modified crosslinked polyrotaxane composition.
Thereafter, the modified crosslinked polyrotaxane composition was dried in a petri dish at 50 ° C. for 2 hours to produce a modified crosslinked polyrotaxane gel having a thickness of 1 mm or less. Note that the above drying is not performed when an ionic liquid is used as the electrolyte solution. The obtained gel was used as actuator layers 1 to 10 in the production of the next thin film actuator.

5). Manufacture of thin film actuators Using the sputtering layers for the obtained actuator layers 1 to 10 (thickness of 1 mm or less), ITO is used as a metal target, argon gas, nitrogen gas, and oxygen gas are used, and -100 V at room temperature. Sputtering was performed under the conditions described above to provide ITO layers (electrodes) on both surfaces of each actuator layer. The thin film actuator obtained from the actuator layer 1 is referred to as a thin film actuator 1. Similarly, the thin film actuators obtained from the actuator layers 2 to 10 are referred to as thin film actuators 2 to 10, respectively.

Details of the components shown in Table 2 are as follows.
Modified crosslinked polyrotaxane 1-2: Modified crosslinked polyrotaxane 1-2 produced as described above
Methoxylated cross-linked polyrotaxane: methoxylated cross-linked polyrotaxane produced as described above Cross-linked polyrotaxane 2: Cross-linked polyrotaxane 2 produced as described above
-Electrolyte solution 1: 1 mol / L lithium perchlorate aqueous solution-Electrolyte solution 2: 1 mol / L sodium perchlorate aqueous solution-Electrolyte solution 3: Lithium trifluoromethanesulfonate (LiOTf), manufactured by Sigma-Aldrich

7). Manufacture of touch panel (1) Example 7
A touch panel was manufactured using the thin film actuator 1 as the button 42 of the touch panel 40 shown in FIG.
(2) Example 8
A touch panel was manufactured in the same manner as in Example 1 except that the thin film actuator 1 was replaced with the thin film actuator 2.
(3) Example 9
A touch panel was manufactured in the same manner as in Example 1 except that the thin film actuator 1 was replaced with the thin film actuator 3.
(4) Comparative Example 5
A touch panel was manufactured in the same manner as in Example 1 except that the thin film actuator 1 was replaced with the thin film actuator 4.
(5) Comparative Example 6
A touch panel was manufactured in the same manner as in Example 1 except that the thin film actuator 1 was replaced with the thin film actuator 5.
(6) Example 10
A touch panel was manufactured in the same manner as in Example 1 except that the thin film actuator 1 was replaced with the thin film actuator 6.
(7) Example 11
A touch panel was manufactured in the same manner as in Example 1 except that the thin film actuator 1 was replaced with the thin film actuator 7.
(8) Example 12
A touch panel was manufactured in the same manner as in Example 1 except that the thin film actuator 1 was replaced with the thin film actuator 8.
(9) Comparative Example 7
A touch panel was manufactured in the same manner as in Example 1 except that the thin film actuator 1 was replaced with the thin film actuator 9.
(10) Comparative Example 8
A touch panel was manufactured in the same manner as in Example 1 except that the thin film actuator 1 was replaced with the thin film actuator 10.

8). Evaluation of Touch Panel Using the obtained touch panel, a DC power source was used as the power source 20 and a voltage of −2 to +2 V was applied to the electrodes to evaluate the responsiveness of the thin film actuator.
As an evaluation standard, whether or not the thin film actuator was deformed into a dome shape within 1 second after the button was pressed with a finger was confirmed by touch and visual observation.

As a result, in the touch panels of Examples 7 to 12, the thin film actuator is deformed into a smooth dome shape within one second after being pressed with a finger, even though the film thickness of the actuator layer of the thin film actuator is 1 mm or less. It was confirmed.
On the other hand, the touch panels of Comparative Examples 5 to 8 using the crosslinked polyrotaxane having no functional group having ion exchange ability confirm the remarkable operation on the thin film actuator even when a voltage is applied in the same manner as in the examples. I couldn't.

FIG. 1 is a diagram schematically showing an example of a modified crosslinked polyrotaxane. FIG. 2 is a diagram schematically showing an example of a modified crosslinked polyrotaxane. FIG. 3 is a schematic cross-sectional view showing an embodiment of the thin film actuator of the present invention. FIG. 4A is a schematic diagram showing a device configuration of one embodiment of the touch panel of the present invention, and FIG. 4B is a cross-sectional view taken along line AA ′ in FIG. FIG. 4 (c) is a perspective view showing a configuration in which a first electrode terminal and a second electrode terminal are provided in the thin film actuator.

Explanation of symbols

100, 200 Modified cross-linked polyrotaxane 1, 2 Polyrotaxane molecule 3, 4 Cyclic molecule 5, 6 Linear molecule 7 Bonding portion 8, 11 Cross-linked cyclic molecule 9 Functional group 10 Thin film actuator 12 Actuator layer 13 Electrode 20 Power supply 22 Controller 40 Touch panel ( panel)
42 Button 44 Separator 46, 48 First electrode terminal 50, 52 Second electrode terminal

Claims (7)

A thin film actuator that is driven by applying a voltage,
An actuator layer formed of a gel containing a modified crosslinked polyrotaxane impregnated with an electrolyte solution;
An electrode provided along both surfaces of the actuator layer, to which a voltage is applied;
The modified crosslinked polyrotaxane has a functional group having an ion exchange capacity, and the first polyrotaxane formed by including a first linear molecule in a skewered manner in the opening of the first cyclic molecule, and A second polyrotaxane in which a second linear molecule is included in a skewered manner in the opening of the two cyclic molecules, and the rings of the first and second cyclic molecules are substantial rings A thin film actuator in which at least one of the first cyclic molecules and at least one of the second cyclic molecules are bonded via a chemical bond.   2. The thin film actuator according to claim 1, wherein the functional group is at least one selected from the group consisting of a carboxy group, a sulfo group, an amino group, an amino group having 1 to 3 hydrocarbon groups, and a salt thereof.   The thin film actuator according to claim 1, wherein the functional group is bonded to an end of the first linear molecule and / or the second linear molecule.   The thin film actuator according to claim 1, wherein the electrolyte solution is an ionic liquid.   5. The thin film actuator according to claim 1, wherein the first cyclic molecule and / or the second cyclic molecule is at least one selected from the group consisting of α-cyclodextrin and β-cyclodextrin. .   The first linear molecule and / or the second linear molecule is selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene. The thin film actuator according to claim 1, which is at least one selected.   A touch panel using the thin film actuator according to claim 1.