JP3030361B2 - Polymer electrolyte ammonium derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymer electrolyte ammonium derivative, and more particularly to a polymer electrolyte ammonium derivative that functions as an actuator by bending and deforming an ion exchange resin molded article.

[0002]

2. Description of the Related Art In the fields of medical equipment, industrial robots, micromachines, and the like, there is an increasing need for small, lightweight, and flexible actuators.

As described above, when the size of the actuator is reduced, the friction and the viscous force become dominant over the inertial force. Therefore, a mechanism that uses an inertial force to convert energy into motion, such as a motor or an engine, has been used for an ultra-small actuator. It was difficult to use as power. For this reason, as the operating principle of the micro actuator, electrostatic attraction type, piezoelectric type, ultrasonic type, shape memory alloy type, polymer expansion / contraction type and the like have been proposed.

An electrostatic attraction type actuator operates by attracting a plate, a rod, or the like serving as an electrode to a counter electrode. For example, a voltage of about 100 V is applied between the counter electrode and the electrode at a distance of several tens μm to bend the electrode. Some things are known. Piezoelectric actuators are operated by applying a voltage of several volts to a ceramic piezoelectric element such as barium titanate to expand and contract the element, and are known to be capable of controlling displacement in nm units. An ultrasonic actuator operates by combining ultrasonic vibration generated by a piezoelectric element or the like with frictional force or by causing a shift. The shape memory alloy type actuator is operated by a temperature change, utilizing the fact that the shape of the shape memory alloy changes greatly with the temperature. The polymer telescopic actuator operates by utilizing the fact that a polymer expands and contracts due to a change in temperature or pH or a change in the concentration of a surrounding chemical substance.

[0005] However, these microminiature actuators have problems such as limitations on the operating environment, insufficient responsiveness, complicated structure and lack of flexibility. was there. For example, to operate a polymer telescoping actuator, the solution in contact with the polymer must be exchanged for a solution containing other salts, making it difficult to use in applications that require a small and fast response. Met.

On the other hand, as a polymer actuator which can be easily miniaturized, has a quick response, and operates with low electric power, it comprises an ion exchange membrane and an electrode joined on the surface of the ion exchange membrane. A polymer actuator that can function as an actuator by applying a potential difference to the ion exchange membrane in a water-containing state to cause the ion exchange membrane to bend and deform has been proposed (see Japanese Patent Application Laid-Open No. 4-275078). .

This polymer actuator comprises an ion exchange resin membrane and a metal electrode joined to the surface of the ion exchange resin membrane in an insulated state.
It is characterized in that by applying a potential difference between the metal electrodes, the ion-exchange resin molded product is bent and deformed.

In such a polymer actuator, electrodes are formed on the surface of the ion-exchange resin molded product by a method such as chemical plating, electroplating, vacuum deposition, sputtering, coating, pressure bonding, or welding.

For example, in chemical plating, an electrode is formed by etching a surface of an ion-exchange membrane, carrying a plating catalyst, and immersing it in a plating bath to perform plating on the surface of the ion-exchange membrane.

[0010]

However, the above-mentioned polymer actuators cannot be said to have a sufficient displacement. Further, for example, N is used as a counter ion as in a polymer actuator described in JP-A-4-75078.
In the case of using a ⁺ and H ⁺ , if the applied voltage between the electrodes is increased in order to increase the displacement amount and enhance the response, the water inside the ion-exchange resin molded product is easily electrolyzed, whereby There is also a problem that air bubbles are easily generated. For this reason, it has been desired to produce a polymer actuator that can generate a larger displacement amount, is less likely to generate bubbles during use, and has good responsiveness.

The present invention is intended to solve the problems associated with the prior art described above, and it is difficult to generate bubbles due to electrolysis of water when a voltage is applied, and the displacement and displacement force are large. It is an object of the present invention to provide a polymer actuator which has a quick response, is flexible, has a simple structure, and is easily miniaturized.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in order to achieve the above-mentioned objects and objects of the prior art, and the polymer electrolyte ammonium derivative according to the present invention is an ion-exchange resin. A molded product, and a metal electrode formed in a mutually insulated state on the surface of the ion exchange resin molded product, wherein the ion exchange resin molded product has a potential difference between the metal electrodes in a water-containing state of an aqueous solution containing an alkylammonium ion. In this case, the ion-exchange resin molded product functions as an actuator by causing the ion-exchange resin molded product to bend and deform.

[0013] By exchanging the counter ion of the ion-exchange resin molded article with a specific alkylammonium ion in this way, the commonly used counter ion becomes Na ⁺ or H 2.
Compared with the ⁺ ion exchange resin, even when a high voltage is applied, generation of bubbles is less likely to occur. Further, in such a polymer electrolyte ammonium derivative, water molecules usually move to the electrode accompanied by ions, the water content increases near the moving side electrode, and the molded product expands by swelling. ,
In the vicinity of the electrode on the side opposite to the moving side, the water content decreases and contracts. Therefore, when the counter ion is exchanged for the above-mentioned alkylammonium ion, the difference in water content between the electrodes is further increased, and the curvature, that is, the displacement is increased.

It is preferable that such an alkylammonium ion contains an alkylammonium ion represented by the following general formula (1). When such an ion is contained, the water content between the electrodes is reduced. The difference can be further increased, and the curvature rate, that is, the displacement amount can be further increased.

[0015]

Embedded image

(Wherein, R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom, a hydrocarbon group, an oxygen-containing hydrocarbon group, or a nitrogen-containing hydrocarbon group;
^At least ^{one of} R ^{1 to} R ⁴ is a group other than a hydrogen atom;
Two or more of ^{1 to} R ⁴ may be linked to form a ring. In the polymer electrolyte ammonium derivative according to the present invention, the alkylammonium ion is preferably the ion itself represented by the above general formula (1), and in particular, CH ₃ N ⁺ H
^{_{3, C 2 H 5 N +}} H 3, (CH 3) 2 N + H 2, (C 2 H 5) 2 N + H 2,
_{(C 4 H 9) 2 N} + H 2, (C 5 H 11) 2 N + H 2, (CH 3) 3 N + H,
_{(C 2 H 5) 3 N} + H, (C 4 H 9) 3 N + H, (C 5 H 11) 3 N + H,
(CH ₃ ) ₄ N ⁺ , (C ₂ H ₅ ) ₄ N ⁺ , (C ₃ H ₇ ) ₄ N ⁺ , (C ₄ H ₉ ) ₄
N ⁺ , H ₃ N ⁺ (CH ₂ ) ₄ N ⁺ H ₃ , H ₂ C = CHCH ₂ N ⁺ HC
H ₃ , H ₃ N ⁺ (CH ₂ ) ₄ N ⁺ H ₂ (CH ₂ ) ₄ N ⁺ H ₃ , HC≡C
CH ₂ N ⁺ H ₂ , CH ₃ CH (OH) CH ₂ N ⁺ H ₃ , H ₃ N ⁺ (C
H ₂ ) ₅ OH, H ₃ N ⁺ CH (CH ₂ OH) ₂ , (HOCH ₂ ) ₂ C
(CH ₂ N ⁺ H ₃ ) ₂ , C ₂ H ₅ OCH ₂ CH ₂ N ⁺ H ₃ or

[0017]

Embedded image

Is preferred. More preferably (C_FourH₉)_ThreeN⁺
H, (C_FiveH₁₁)_ThreeN⁺H, (C_ThreeH₇)_FourN ⁺, (C_FourH₉)_FourN⁺so
is there. Such a polymer electrolyte ammonium derivative of the present invention
The conductor is simple in structure, easy to miniaturize, and high
Even when voltage is applied, water inside the molded product
It is possible to suppress bubbles, and the response is fast and large
It is possible to generate a large displacement amount.

[0019]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 and FIG.
FIG. 2 is a schematic cross-sectional view showing an optimal example of the polymer electrolyte ammonium derivative according to the present invention. In this embodiment, a polymer electrolyte ammonium derivative (polymer actuator) 1 is an elongated rectangular plate-like ion exchange resin molded product 2.
And electrodes 3a and 3b formed on the surface of the ion-exchange resin molded product 2 in a mutually insulated state. And
In the hydrated state of the ion-exchange resin molded product 2, by applying a potential difference between the electrodes, the ion-exchange resin molded product is bent and deformed.

One ends of a pair of lead wires 4a, 4b are electrically connected to the electrodes 3a, 3b, respectively, and the lead wires 4a, 4b are connected to a power supply 5.

The ion-exchange resin molded product 2 includes:
The shape is not limited to the rectangular flat plate shape, but may be a film shape, a columnar shape, a cylindrical shape, or the like. Examples of the ion exchange resin constituting such an ion exchange resin molded article 2 include a cation exchange resin and a both ion exchange resin. Among them, a cation exchange resin is preferably used because the amount of displacement of the polymer electrolyte ammonium derivative can be increased.

Examples of such a cation exchange resin include those in which a functional group such as a sulfonic acid group or a carboxyl group is introduced into polyethylene, polystyrene, fluororesin, or the like. Cation exchange resins into which functional groups such as groups have been introduced are preferred.

The cation exchange resin has an ion exchange capacity of 0.8 to 3.0 meq / g, preferably 1.4 to 3.0 meq / g.
2.0 meq / g is desirable. That is, if a cation exchange resin having such an ion exchange capacity is used, the displacement of the polymer electrolyte ammonium derivative can be further increased.

As the metal constituting the electrodes 3a and 3b,
Gold, platinum, palladium, rhodium, ruthenium and the like. The electrode formed on the surface of the ion-exchange resin molded product is, for example, when the ion-exchange resin molded product to be used has a membrane shape, the thickness of the formed electrode is as shown in FIG. the thickness of the metal electrode formed on the surface of the goods and a _1, the thickness of the ion-exchange resin molded article including the metal electrodes when the b _1, a ₁ / b ₁ is 0.03 to 0. 4
0, preferably in the range of 0.15 to 0.30. With such a ratio, a polymer electrolyte ammonium derivative having a large displacement and a low surface resistance can be obtained.

In the case where the ion-exchange resin molded article has a cylindrical shape, the metal electrode is formed on the surface of the outer tube, the surface of the inner tube, or both surfaces of the outer tube and the inner tube. You may.

When a metal electrode is formed on the surface of the outer cylindrical portion of the ion-exchange resin molded product as shown in FIG. 2 (b), the thickness of the metal electrode is set to a ₂ and the cylindrical ion including the metal electrode is formed. When the thickness of the tubular portion of the exchange resin molded product is b ₂ , a ₂ /
b ₂ is 0.02 to 0.70, preferably 0.30 to 0.50
Is desirably within the range. With such a ratio,
A polymer electrolyte ammonium derivative having a large displacement and a low surface resistance can be obtained.

When a metal electrode is formed on the surface of the inner cylindrical portion of the ion-exchange resin molded product as shown in FIG. 2C, the thickness of the metal electrode is set to a ₃ and the ion-exchange resin molding including the metal electrode is formed. When the thickness of the cylindrical portion of the product is b ₃ , a ₃ / b ₃ is equal to 0.3.
It is desirably in the range of 02 to 0.70, preferably 0.30 to 0.50. With such a ratio, a polymer electrolyte ammonium derivative having a large displacement and a low surface resistance can be obtained.

As shown in FIG. 2 (d), when metal electrodes are formed on both surfaces of the inner cylindrical portion and the outer cylindrical portion of the ion exchange resin molded product, the cylindrical shape of the ion exchange resin molded product including the metal electrodes the thickness of the part and b _4, the thickness of the cylindrical portion of the ion-exchange resin moldings metal electrode is not formed is taken as C, C
/ B ₄ is 0.20 to 0.95, preferably 0.45 to 0.7
It is desirable to be in the range of 0. Furthermore the thickness of the metal electrode formed on the outer cylinder portion surface and a _4, the thickness of the metal electrode formed on the inner cylindrical portion surface when the a _5, 0.05 to is a ₄ / a ₅ 20.0, preferably in the range of 0.50 to 2.00. With such a ratio, a polymer electrolyte ammonium derivative having a large displacement and a low surface resistance can be obtained.

The polymer electrolyte ammonium derivative according to the present invention is prepared by immersing an ion-exchange resin molded article having metal electrodes formed on the surface thereof in a mutually insulated state in an aqueous solution containing alkylammonium ions to remove counter ions. It can be produced by exchanging with an alkylammonium ion. At this time, the concentration of the alkylammonium salt only needs to include an alkylammonium salt in an amount equal to or more than the functional group of the ion exchange resin.
The amount may be from 0.01 to 10 mol / l, preferably from 0.1 to 1.0 mol / l.

As the alkyl ammonium ion, those containing an alkyl ammonium ion represented by the following general formula (1) are preferable. Further, an alkylammonium ion itself is also preferably an alkylammonium ion represented by the following general formula (1).

[0031]

Embedded image

(Where R¹~ R^FourAre the same as each other
May be different, hydrogen atom, hydrocarbon group, oxygen-containing
A hydrocarbon group or a nitrogen-containing hydrocarbon group;
¹~ R^FourIs a group other than a hydrogen atom, and R
¹~ R^FourTwo or more of which may combine to form a ring
No. ) Such alkyl ammonium ions include CH
_ThreeN⁺H_Three, C_TwoH_FiveN⁺H _Three, (CH_Three)_TwoN⁺H_Two, (C_TwoH_Five)_TwoN
⁺H_Two, (CH_Three)_ThreeN⁺H, (C_TwoH_Five)_ThreeN⁺H, (CH _Three)_FourN⁺,
(C_TwoH_Five)_FourN⁺, (C_ThreeH₇)_FourN⁺, (C_FourH₉)_FourN⁺, H_ThreeN
⁺(CH_Two)_FourN⁺H_Three, H_TwoC = CHCH_TwoN⁺HCH_Three, H_ThreeN
⁺(CH_Two)_FourN⁺H_Two(CH_Two)_FourN⁺H_Three, HC≡CCH_TwoN
⁺H_Two, CH_ThreeCH (OH) CH_TwoN⁺H_Three, H_ThreeN⁺(CH_Two)_FiveO
H, H_ThreeN⁺CH (CH_TwoOH)_Two, (HOCH_Two)_TwoC (CH_TwoN
⁺H_Three)_Two, C_TwoH_FiveOCH_TwoCH_TwoN⁺H_ThreeOr

[0033]

Embedded image

Is preferred. More preferably (C_FourH₉)_ThreeN⁺
H, (C_FiveH₁₁)_ThreeN⁺H, (C_ThreeH₇)_FourN ⁺, (C_FourH₉)_FourN⁺so
is there. These alkyl ammonium ions alone
May be used, or two or more kinds may be used in combination.
No. In the present invention, such an alkyl ammonium is usually used.
Chloride, bromide and iodide of muon are used.

In the polymer electrolyte ammonium derivative according to the present invention, since water molecules move to the electrode accompanying the ions, the water content increases near the moving-side electrode, and swells and expands. In the vicinity of the electrode on the side opposite to the moving side, the water content decreases and contracts. When such a moving ion having a large ion radius such as an alkylammonium ion is used, the difference in water content between the electrodes is further increased, so that the curvature, that is, the displacement is increased. Therefore, the polymer electrolyte ammonium derivative obtained in the present invention has a larger displacement of the element than the conventional polymer electrolyte ammonium derivative. Further, even when a voltage higher than that of Na ⁺ and H ⁺ is applied as in the case of alkylammonium ions, water impregnated in the ion-exchange resin molded article is less likely to be electrolyzed, thereby suppressing the generation of bubbles. be able to. Therefore, the polymer electrolyte ammonium derivative according to the present invention can apply a higher voltage than the conventional polymer electrolyte ammonium derivative, and can improve responsiveness.

As a method for forming a metal electrode on the surface of an ion-exchange resin molded product, a conventionally known method can be employed without any particular limitation. In particular, it is desirable to form a metal electrode by the following steps. (i) a step of adsorbing the metal complex on the ion-exchange resin molded article in an aqueous solution (adsorption step), and (ii) the metal complex adsorbed on the ion-exchange resin molded article is reduced by a reducing agent to form the ion-exchange resin molded article. A step of depositing a metal on the surface of the article (precipitation step); and (iii) a step of washing the ion-exchange resin molded article on which the metal has been precipitated with a washing liquid (washing step).

When the metal electrode is formed by the above-described steps, the surface of the ion-exchange resin molded article to be used may be roughened in advance. Examples of the roughening treatment of the film surface include a sandblast treatment and a sandpaper treatment.
The degree of surface roughening may be such that the surface layer is shaved.

By performing such a roughening treatment,
The contact area between the surface of the ion-exchange resin molded article and the electrode formed thereon is increased, and the displacement of the polymer electrolyte ammonium derivative can be increased.

In the present invention, when forming a metal electrode, the following treatment may be applied to an ion exchange resin molded article to be used in advance, alone or in combination. Water treatment: boil the ion-exchange resin molded product in hot water.

Hydrochloric acid treatment: In dilute hydrochloric acid of about 25% by volume,
Holds the ion-exchange resin molded product. NaOH treatment: in about 0.1 sodium hydroxide aqueous solution,
Holds the ion-exchange resin molded product.

Alcohol treatment: The ion-exchange resin molded article is immersed in alcohol such as methanol or ethanol. Autoclave treatment: The ion-exchange resin molded product is heated at 110 to 150 ° C in an autoclave.

As the metal complex used to form the metal electrode, a metal complex such as a gold complex, a platinum complex, a palladium complex, a rhodium complex, and a ruthenium complex can be used. Among them, a gold complex or a platinum complex is preferable, and a gold complex is particularly preferable because the displacement of the polymer electrolyte ammonium derivative can be increased.

The adsorption of these metal complexes to the ion-exchange resin molded article is performed by immersing the ion-exchange resin molded article in an aqueous solution containing the metal complex. Further, such reduction of the metal complex is performed by immersing the ion-exchange resin molded article on which the metal complex is adsorbed in an aqueous solution containing a reducing agent.

The reducing agent depends on the kind of the metal complex to be used, and includes, for example, sodium sulfite, hydrazine,
Potassium borohydride and the like can be used. Further, when reducing the metal complex, an acid or an alkali may be added as necessary.

When the ion-exchange resin molded article having the metal complex adsorbed thereon is reduced, a metal is deposited on the surface of the ion-exchange resin molded article by contact of the metal complex with the reducing agent, and then the metal complex inside the membrane is reduced. Moves to the vicinity of the film surface (toward the deposited metal) and is reduced to deposit the metal. That is, the crystal growth of the metal proceeds from the surface of the ion-exchange resin molded product toward the inside. Therefore, since such a metal precipitates not only on the surface of the ion-exchange resin molded product but also on the inside near the surface, the contact area between the ion-exchange resin molded product and the metal electrode is reduced by the conventional chemical plating. It is larger than the law. For this reason, by repeating such adsorption and precipitation of the metal complex, deposition of the metal further proceeds inside the ion-exchange resin molded product, and the contact area between the ion-exchange resin molded product and the metal electrode further increases. As a result, the number of electrode active sites increases, and the number of ions moving to the electrode also increases.

The metal complex and the reducing agent that have not been deposited are removed from the ion-exchange resin molded product on which the electrodes have been formed in the washing step. It is preferable to use water, an aqueous solution of sodium hydroxide, an aqueous solution of sulfuric acid, or an aqueous solution of hydrochloric acid as the washing liquid. The use of these washing liquids enables efficient removal of unreacted metal complex and reducing agent. The concentration of the aqueous sodium hydroxide solution used at this time is desirably in the range of 0.01 to 5.0 mol / l, preferably in the range of 0.1 to 1 mol / l. The concentration of the aqueous sulfuric acid solution is preferably in the range of 0.01 to 6 mol / l, and more preferably in the range of 0.1 to 6 mol / l. Further, the concentration of the aqueous hydrochloric acid solution is 0.0.
It is desirably in the range of 1 to 6 mol / l, preferably 0.1 to 3 mol / l.

When the metal electrode is formed, the steps of adsorbing, depositing, and washing the metal complex onto the ion-exchange resin molded article are repeated to form the metal electrode on the surface of the ion-exchange resin molded article. Good. By repeating such a process, the amount of displacement of the polymer electrolyte ammonium derivative can be increased.

Insulation between the electrodes thus formed can be performed by cutting the end of the ion-exchange resin molded product on which the metal electrode is formed when the molded product is in the form of a film. When the molded product is cylindrical or columnar, the laser beam is applied to the ion-exchange resin molded product on which the metal electrode is formed, and a part of the metal electrode is shaved to form an insulating band between the electrodes. With the provision, insulation between the electrodes can be performed.

Further, the ion exchange resin molded product after the formation of the electrode may be subjected to the above-mentioned treatments. Furthermore, an additional electrode layer may be provided on the formed electrode. The additional electrode layer can be formed by a method such as chemical plating, electroplating, vacuum deposition, sputtering, coating, pressure bonding, welding, and the like. Such an additional electrode layer may be the same as the metal layer formed on the surface of the ion exchange resin molded product or inside the ion exchange resin molded product,
It may be different. By providing the additional electrode layer in this manner, the displacement force of the polymer electrolyte ammonium derivative can be further increased.

The polymer electrolyte ammonium derivative of the present invention produced by such a method requires that the ion-exchange resin molded product be hydrated during operation. Here, the water-containing state refers to a state in which the inside of the ion-exchange resin molded product is water-containing in an aqueous solution containing an alkylammonium chloride, bromide, iodide, or the like as described above. The polymer electrolyte ammonium derivative according to the present invention can operate even in water or in high humidity atmosphere as long as it contains such an aqueous solution.

The operating principle of such a polymer electrolyte ammonium derivative is that, when a potential difference is applied between the surfaces of the ion-exchange resin molded product in a mutually insulated state, as shown in FIG. Is moved to the cathode side, and water molecules move in the membrane accompanying the + ions, so that a difference in water content occurs between the anode side and the cathode side. That is, the water molecules move along with the + ions, the water content increases on the cathode side, the water content increases, and the water molecules are swollen and expanded, and conversely, the water content decreases on the anode side, so that they shrink, thereby forming the ion exchange resin. This is because the product is curved.

In the polymer electrolyte ammonium derivative according to the present invention, when a DC voltage of 0.1 to 4 V is applied between the electrodes, a displacement of about 1 to 3 times the element length can be obtained within several seconds. . Further, such a polymer electrolyte ammonium derivative can act flexibly. Furthermore, even when a voltage of about 3 V is applied, the electrolysis of water contained in the ion-exchange resin molded product is suppressed, and there is no generation of bubbles associated with this.

An application example using such a polymer electrolyte ammonium derivative is, for example, a derivative shown in FIG. In this application example, a guide wire 11 as a derivative is composed of an elongated linear member 12 made of, for example, a tube made of synthetic resin or stainless steel, and a polymer electrolyte ammonium derivative 13 bonded to the tip of the linear member 12. Have been.

The actuator 13 has a pair of electrodes formed by the method according to the present invention on both surfaces of a slightly elongated rectangular plate-like ion exchange resin molded product 14.
By applying a voltage to a and 15b, the polymer electrolyte ammonium derivative 13 bends in two directions.

The electrodes 15a and 15b have
One ends of the pair of lead wires 16a and 16b are electrically connected to each other. These lead wires 16a, 16b are
The other end of each of the lead wires 16 a and 16 b is connected to the operation control unit 17 while being located inside the linear member 12 and extending over the entire length of the linear member 12.

The operation control unit 17 is provided with an operation lever 18 that can be switched. When the operation lever 18 is operated, a built-in operation lever 18 is built in the operation control unit 17.
The direction of the current flowing from the power supply 20 to the pair of lead wires 16a, 16b can be switched via the pole / double throw switch 19.

That is, in FIG. 5, when the double-pole double-throw switch 19 is at the position shown by the solid line, one lead 16a is connected to the + electrode, and the other lead 16b is connected to the-electrode. When the pole / double-throw switch 19 is switched from the neutral position as shown by a two-dot chain line in accordance with the operation of the operation lever 18 of the operation control unit 17, this time, conversely,
One lead 16a is connected to the negative electrode and the other lead 1
6b is connected to the + electrode.

By switching the anode and the cathode in this manner, the polymer electrolyte ammonium derivative 1
Can be arbitrarily and positively deformed. Further, according to the production method of the present invention, a cylindrical polymer electrolyte ammonium derivative 40 as shown in FIG. 6 can be produced.

In such a cylindrical polymer electrolyte ammonium derivative 40, first, the metal complex is adsorbed on the cylindrical ion exchange resin molded article 41 by the method described above.
The metal complex is reduced by a reducing agent to deposit metal on the surface of the ion-exchange resin molded article 41. The adsorption / reduction of the metal complex and the operation of depositing the metal are repeated to grow the deposited metal, and a metal layer is formed from the surface of the ion exchange resin molded article 41 to the inside.

Next, the surface of the cylindrical ion-exchange resin molded article 41 having the metal layer formed near the outer surface thereof is irradiated with laser light from a laser processing apparatus to remove the irradiated metal layer. A groove-shaped insulating band 42 and a plurality of mutually electrically insulated metal electrodes 43a, 43b,
43c and 43d are formed.

The polyelectrolyte ammonium derivative shown in FIG. 6 has the respective metal electrodes 43a, 43b, 43c and 43d.
And one end of each of the lead wires 44a, 44b, 44c, and 44d is electrically connected to the electrodes 43a and 43c, 43b, and 4
By applying a voltage to 3d, it is possible to bend in four directions, and it is possible to rotate by combining the directions of this bend.

Incidentally, such a metal electrode may be provided on the inner peripheral surface of the ion exchange resin molded article, or may be provided on both the inner peripheral surface and the outer peripheral surface.

[0063]

EXAMPLES Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples.

[0064]

[Comparative Example 1] A rectangular ion-exchange ion resin molded product (ion exchange capacity 1.8 meq / g) on which a gold electrode was formed was placed in a 1.0 mm × 2
A test piece cut to a size of 0 mm is 0.1 N NaOH
The test piece was immersed in an aqueous solution for 24 hours, and a voltage was applied (0.1 Hz, 1.5 V square wave) through the front and back electrodes to measure the displacement and the voltage (0.1 Hz square wave).

As shown in FIG. 7, the amount of bending displacement was measured by holding a position 8 mm from one side of the test piece with a platinum plate, holding it in water, extending a lead wire from the platinum plate, and passing the lead wire through a potentiostat. The test was performed by applying the voltage to the gold electrodes at both ends of the test piece. The displacement was measured at a position 10 mm from the fixed end using a laser displacement meter.

Table 1 shows the results.

[0067]

[Embodiment 1] Rectangular ion-exchange ion with gold electrode formed
Resin molded product (ion exchange capacity 1.8 meq / g)
0.5M (C_TwoH
_Five) NH _ThreeA test piece was immersed in a Cl aqueous solution for 24 hours.
Apply voltage through front and back electrodes (0.1Hz, 1.5V square
Wave) to measure displacement and generate bubbles
The voltage (0.1 Hz square wave) was measured.

Table 1 shows the results.

[0069]

Embodiment 2 Rectangular ion-exchange ion with gold electrode formed
Resin molded product (ion exchange capacity 1.8 meq / g)
0.5M (C
H_Three)_TwoNH _TwoWhat was immersed in Cl aqueous solution for 24 hours
And apply voltage through the front and back electrodes (0.1Hz, 1.5V
(Square wave) to measure displacement and generate bubbles
Voltage (square wave of 0.1 Hz) was measured.

Table 1 shows the results.

[0071]

Example 3 A rectangular ion-exchange ion resin molded product (ion-exchange capacity 1.8 meq / g) on which a gold electrode was formed was placed in a 1.0 mm × 2
0.5M (C ₂ H
₅ ) A test piece was immersed in ₃ NHCl aqueous solution for 24 hours.
A voltage was applied (0.1 Hz, 1.5 V square wave) through the front and back electrodes to measure the amount of displacement, and a voltage at which bubbles were generated (0.1 Hz square wave) was measured.

Table 1 shows the results.

[0073]

Example 4 A rectangular ion-exchange ion resin molded article (ion exchange capacity 1.8 meq / g) on which a gold electrode was formed was placed in a 1.0 mm × 2
0.5M (C ₃ H
_{7) 4} NCl aqueous those immersed for 24 hours a test piece, a voltage is applied from the front and back of the electrode (0.1 Hz, with a square wave) to the 1.5V, measuring the displacement amount, bubbles generated Voltage (square wave of 0.1 Hz) was measured.

Table 1 shows the results.

[0075]

Example 5 A rectangular ion-exchange ion resin molded product (ion exchange capacity 1.8 meq / g) on which a gold electrode was formed was placed in a 1.0 mm × 2
0.5M (C ₄ H
₉ ) A test piece was immersed in ₄ NCl aqueous solution for 24 hours, and a voltage was applied (0.1 Hz, 1.5 V square wave) via the front and back electrodes to measure the displacement and generate bubbles. Voltage (square wave of 0.1 Hz) was measured.

Table 1 shows the results.

[0077]

Example 6 A rectangular ion-exchange ion resin molded product (ion exchange capacity 1.8 meq / g) on which a gold electrode was formed was placed in a 1.0 mm × 2
A specimen cut to a size of 0 mm was used as a test piece, and a chloride aqueous solution of an alkylammonium ion shown below (concentration of 0.5
M) was immersed for 24 hours as a test piece, and a voltage was applied (0.1 Hz, 1.5 V square wave) via the front and back electrodes to measure the displacement and the voltage at which bubbles were generated ( 0.1Hz
Square wave) was measured.

[0078]

Embedded image

Table 1 shows the results.

[0080]

Example 7 A rectangular ion-exchange ion resin molded article (ion exchange capacity 1.8 meq / g) on which a gold electrode was formed was placed in a 1.0 mm × 2
A specimen cut to a size of 0 mm was used as a test piece, and a chloride aqueous solution of an alkylammonium ion shown below (concentration of 0.5
M) was immersed for 24 hours as a test piece, and a voltage was applied (0.1 Hz, 1.5 V square wave) via the front and back electrodes to measure the displacement and the voltage at which bubbles were generated ( 0.1Hz
Square wave) was measured.

[0081]

Embedded image

Table 1 shows the results.

[0083]

Example 8 A rectangular ion-exchange ion resin molded article (ion exchange capacity 1.8 meq / g) on which a gold electrode was formed was placed in a 1.0 mm × 2
A specimen cut to a size of 0 mm was used as a test piece, and a chloride aqueous solution of an alkylammonium ion shown below (concentration of 0.5
M) was immersed for 24 hours as a test piece, and a voltage was applied (0.1 Hz, 1.5 V square wave) via the front and back electrodes to measure the displacement and the voltage at which bubbles were generated ( 0.1Hz
Square wave) was measured.

[0084]

Embedded image

Table 1 shows the results.

[0086]

Embodiment 9 A rectangular ion-exchange ion resin molded product (ion exchange capacity 1.8 meq / g) on which a gold electrode was formed was placed in a 1.0 mm × 2
H ₂ C = C
A test piece was immersed in a chloride aqueous solution of HCH ₂ N ⁺ H ₂ CH ₃ (concentration: 0.5 M) for 24 hours, and a voltage was applied (0.1 Hz, 1.5 V square wave) through the front and back electrodes. To measure the displacement and the voltage at which bubbles are generated (0.1Hz square wave)
Was measured.

Table 1 shows the results.

[0088]

Embodiment 10 A rectangular ion-exchange ion resin molded product (ion exchange capacity 1.8 meq / g) on which a gold electrode was formed was 1.0 mm
× what was cut into a size of 20mm as a test piece, CH ₃
A test piece was immersed in a CH (OH) CH ₂ N ⁺ H ₃ chloride aqueous solution (concentration: 0.5 M) for 24 hours, and a voltage was applied through the front and back electrodes (0.1 Hz, 1.5 V square wave). ), The displacement was measured, and the voltage (0.1 Hz square wave) at which bubbles were generated was measured.

Table 1 shows the results.

[0090]

Embodiment 11 A rectangular ion-exchange ion resin molded product (ion-exchange capacity 1.8 meq / g) on which a gold electrode was formed was 1.0 mm
A specimen cut into a size of × 20 mm was used as a test piece, and H ₃ N ⁺
A test piece was immersed in a CH (CH ₂ OH) ₂ chloride aqueous solution (concentration: 0.5 M) for 24 hours, and a voltage was applied (0.1 Hz, 1.5 V square wave) through the front and back electrodes. Measures the amount of displacement and the voltage at which bubbles are generated (0.1Hz square wave)
Was measured.

The results are shown in Table 1.

[0092]

Embodiment 12 A rectangular ion-exchange ion resin molded article (ion exchange capacity 1.8 meq / g) on which a gold electrode was formed was placed on a 1.0 mm
A specimen cut to a size of × 20 mm was used as a test piece, and C ₂ H ₅
A test piece was immersed in a chloride aqueous solution of OCH ₂ CH ₂ N ⁺ H ₃ (concentration: 0.5 M) for 24 hours, and a voltage was applied (0.1 Hz, 1.5 V square wave) through the front and back electrodes. To measure the displacement and the voltage at which bubbles are generated (0.1Hz square wave)
Was measured.

Table 1 shows the results.

[0094]

[Table 1]

From the above results, the polymer electrolyte ammonium derivative obtained by exchanging the counter ion of the ion-exchange resin for the ammonium ion represented by the above general formula (1) was used as in Comparative Example 1 to obtain a conventional Na ion. It was found that the displacement was larger and the voltage at which bubbles were generated was higher than that of the polymer electrolyte ammonium derivative having ⁺ as a counter ion.

[0096]

According to the polymer electrolyte ammonium derivative of the present invention, the counter ion of the ion-exchange resin molded product is exchanged for a specific alkyl ammonium ion. For this reason,
Compared with a commonly used ion exchange resin in which the counter ion is Na ⁺ or H ⁺ , even if a high voltage is applied between the electrodes of the polymer electrolyte ammonium derivative, the electrolysis of water inside the molded article is less likely to occur, The generation of bubbles is suppressed. For this reason, the polymer electrolyte ammonium derivative according to the present invention,
Compared with the conventional polymer electrolyte ammonium derivative, a higher voltage can be applied, and the response is improved.

Further, in such a polymer electrolyte ammonium derivative, water molecules move to the electrode accompanying the ions, the water content increases near the moving side electrode, and the molded product expands due to swelling. On the other hand, in the vicinity of the electrode on the side opposite to the moving side, the water content decreases and contracts. For this reason, when the counter ion is exchanged for an alkylammonium ion as described above, the number of water molecules moving to the electrode accompanying this ion increases, and the difference in water content between the electrodes further increases, and the curvature, that is, the displacement, The amount increases.

Therefore, since the present invention has the above-described structure, it is possible to obtain a polymer electrolyte ammonium derivative which has a simple structure, can be easily miniaturized, has a fast response, and has a large displacement.

Therefore, when the polyelectrolyte ammonium derivative according to the present invention is joined to the tip of the guide member main body of the microdevice, the operation by the operation control unit causes
Since it can be arbitrarily and positively bent (deformed), scissors, forceps,
It can improve the guidance performance of microsurgery medical instruments such as snares, laser scalpels, and spatula, various sensors, and microdevices such as tools, so that it can be directed in any direction to the target site and its operation can be performed. It can be carried out quickly and easily without skill.

Accordingly, such a micro device and a micro machine provided with the micro device can be used, for example, in eye surgery,
Apply to medical instruments such as tweezers, scissors, forceps, snares, laser scalpels, spatulaes, clips, etc. in microsurgery technologies such as laparoscopic surgery and microvascular suture surgery to minimize the pain given to patients during examination and treatment. Thus, the physical and mental burden on the patient can be reduced.

Further, such a micro device and a micro machine provided with the micro device can be used for various sensors for inspecting and repairing a piping system of a mechanical system such as an airplane engine and an engine, etc. If the present invention is applied to a tool or the like, the repair work can be reliably performed without requiring labor and time.

In addition to the above, the polyelectrolyte ammonium derivative according to the present invention may be used in addition to the above, such as a micropump by high-frequency vibration, a health appliance such as an auxiliary power massager for rehabilitation, a hygrometer, a hygrometer controller, a soft manipulator, It can also be suitably used for industrial equipment such as underwater valves and soft transporters, underwater mobiles such as goldfish and seaweed, and hobby supplies such as moving fishing baits and propulsion fins.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a polymer electrolyte ammonium derivative according to the present invention in a state where no voltage is applied.

FIG. 2 is a schematic view showing one embodiment of a polymer electrolyte ammonium derivative according to the present invention.

FIG. 3 is a schematic cross-sectional view of the polymer electrolyte ammonium derivative according to the present invention in a voltage applied state.

FIG. 4 is a schematic diagram showing an application example of the polymer electrolyte ammonium derivative according to the present invention.

FIG. 5 is an enlarged schematic view showing a main part of FIG. 4;

FIG. 6 is a schematic view showing an example of still another polyelectrolyte ammonium derivative according to the present invention.

FIG. 7 is a schematic diagram showing the principle of measuring the amount of displacement measured in Examples 1 to 5 and Comparative Example.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Polymer electrolyte ammonium derivative 2 Ion exchange resin molded article 3, 3a, 3b Electrode 4 4a, 4b Lead wire 5 Power supply 6 Ion

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tatsuhiro Okada 1-1, Higashi, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor, Kazuo Onishi Higashi, Musashino, Hyogo 1-26-10- 304 (72) Inventor Shingo Seka 2806-4 Inoguchi, Nakai-cho, Ashigara-gun, Kanagawa Prefecture Examiner Hiroshi Kamemaru (56) References JP-A-9-84372 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) F03G 7/00 H02N 11/00

Claims (4)

(57) [Claims] 1. An ion-exchange resin molded article, and a metal electrode formed on a surface of the ion-exchange resin molded article in a mutually insulated state, wherein the ion-exchange resin molded article is in a water-containing state of an aqueous solution containing an alkylammonium ion. , A polymer electrolyte ammonium derivative that functions as an actuator by causing a potential difference between the metal electrodes to cause the ion-exchange resin molded product to bend and deform. 2. The polymer electrolyte ammonium derivative according to claim 1, wherein the alkyl ammonium ion is an alkyl ammonium ion containing at least an ion represented by the following general formula (1). Embedded image (Wherein, R ^{1 to} R ⁴ may be the same or different from each other, and represent a hydrogen atom, a hydrocarbon group, an oxygen-containing hydrocarbon group,
Or a nitrogen-containing hydrocarbon group, and at least one of R ¹ to R ⁴ is a group other than a hydrogen atom, it may form a ring more than is linked among R ¹ to R ^4. ) 3. The polymer electrolyte ammonium derivative according to claim 1, wherein the alkyl ammonium ion is an ion represented by the following general formula (1). Embedded image (Wherein, R ^{1 to} R ⁴ may be the same or different from each other, and represent a hydrogen atom, a hydrocarbon group, an oxygen-containing hydrocarbon group,
Or a nitrogen-containing hydrocarbon group, and at least one of R ¹ to R ⁴ is a group other than a hydrogen atom, it may form a ring more than is linked among R ¹ to R ^4. ) 4. An ion represented by the general formula (1) is CH _{3
^{N + H 3, C 2 H}} 5 N + H 3, (CH 3) 2 N + H 2, (C 2 H 5) 2 N +
H ₂ , (C ₄ H ₉ ) ₂ N ⁺ H ₂ , (C ₅ H ₁₁ ) ₂ N ⁺ H ₂ , (CH ₃ ) ₃ N
_{^{+ H, (C 2 H 5}} ) 3 N + H, (C 4 H 9) 3 N + H, (C 5 H 11) 3 N +
H, (CH ₃ ) ₄ N ⁺ , (C ₂ H ₅ ) ₄ N ⁺ , (C ₃ H ₇ ) ₄ N ⁺ , (C ₄
H ₉ ) ₄ N ⁺ , H ₃ N ⁺ (CH ₂ ) ₄ N ⁺ H ₃ , H ₂ C = CHCH ₂ N
⁺ HCH ₃ , H ₃ N ⁺ (CH ₂ ) ₄ N ⁺ H ₂ (CH ₂ ) ₄ N ⁺ H ₃ , HC
≡CCH ₂ N ⁺ H ₂ , CH ₃ CH (OH) CH ₂ N ⁺ H ₃ , H ₃ N
⁺ (CH ₂ ) ₅ OH, H ₃ N ⁺ CH (CH ₂ OH) ₂ , (HOCH ₂ )
₂ C (CH ₂ N ⁺ H ₃ ) ₂ , C ₂ H ₅ OCH ₂ CH ₂ N ⁺ H ₃ or The polymer electrolyte ammonium derivative according to claim 2, wherein: