JPH0984372A - Actuator element manufacturing method - Google Patents

Abstract

(57) Abstract: An electrode body is formed on the surface of a cation exchange resin having a carboxyl group. A method for manufacturing an actuator element (1) in which electrode bodies (3, 4) are bonded to the surface of a water-containing cation exchange resin layer (2) having a carboxyl group, wherein the carboxyl group of the cation exchange resin is COOM group (however,
M is a metal or ammonium ion)
A part of the M ⁺ ions of the —COOM group is exchanged for a metal ion or a metal complex ion forming an electrode, and then a cation exchange resin is brought into contact with a reducing agent solution to form the electrode. Complex ions are reduced to form metal nuclei on the surface of the cation exchange resin, and a growth bath is used to grow a metal layer on the metal nuclei to form an electrode body.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an actuator element, and more particularly to a method for manufacturing an actuator element which is curved and deformed by applying a potential difference to a water-containing ion exchange resin.

[0002]

2. Description of the Related Art Membrane-like cation exchange resin having a sulfone group (Dafon: Nafion (registered trademark) 117)
An actuator element having platinum electrodes formed on both sides is known (Reference: New Actuator Handbook for Precision Control, edited by Japan Society for Industrial Technology, Solid Actuator Study Group, Fuji Techno System, Section 19; Polymer Electrolyte) Membrane Actuators, pages 215-219).

In this actuator element, when a cation exchange resin is made to contain water and a potential difference is applied to both platinum electrodes, the actuator element is instantaneously bent or bent, and the tip (free end) side of the actuator element is displaced toward the anode. To operate.

Such an actuator element can be manufactured by forming platinum electrode layers on both sides of a cation exchange resin by a chemical plating method, particularly an adsorption reduction growth method. This method is used in the fields of fuel cells, water electrolysis, salt electrolysis, hydrochloric acid electrolysis, gas diffusion electrodes, metal salt recovery, etc., and has a strong polymer electrolyte-metal joint (so-called SPE (Solid Polymer Electrolyte). ) Cell) is applied, and these are disclosed in
No. 7471, Japanese Patent Publication No. 56-36873, Japanese Patent Publication No. 60-2394, Japanese Patent Publication No. 59-42078 and the like.

The formation of electrodes by such a chemical plating method is because the cation exchange resin in the actuator element has a sulfonic acid type sulfone group (the cation exchange resin is -SO ₃ H type). It will be possible.

[0006]

However, when a cation exchange resin having a carboxylic acid type carboxyl group (cation exchange resin is -COOH type) is used instead of the cation exchange resin having a sulfone group, In the plating process, it is difficult for the hydrogen ions of the carboxyl group of the cation exchange resin to be exchange-adsorbed with the metal ions or metal complex ions forming the electrode, and therefore the formation of metal nuclei and the growth of the metal layer become insufficient, resulting in It is difficult to form electrodes on the surface of the exchange resin.

It is an object of the present invention to provide a method for manufacturing an actuator element capable of forming an electrode body on the surface of a cation exchange resin having a carboxyl group by a chemical plating method.

[0008]

These objects are achieved by the present invention described in (1) to (7) below.

(1) When an actuator element is manufactured by forming an electrode body on the surface of a cation exchange resin having a --COOM group (where M is a metal or ammonium ion), M ^{+ of the} --COOM group is used ^. A step of converting a part of the ions into a metal ion or a metal complex ion forming an electrode, and reducing the metal ion or a metal complex ion forming the electrode to form an electrode metal nucleus on the surface of the cation exchange resin. A method of manufacturing an actuator element, comprising: a step of forming a metal layer on the electrode metal nucleus by using a growth bath to form the electrode body.

(2) A method for producing an actuator element comprising a cation exchange resin in a water-containing state having a -COOM group (M is a metal or ammonium ion) and an electrode body bonded to the cation exchange resin. And
A step of converting at least a part of the carboxyl group of the cation exchange resin into a —COOM group (where M is a metal or an ammonium ion), and a part of M ⁺ ion of the —COOM group to form an electrode. Converting into metal ions or metal complex ions, reducing the metal ions or metal complex ions forming the electrode to form electrode metal nuclei on the surface of the cation exchange resin, and using a growth bath to A step of forming a metal layer on an electrode metal nucleus to form the electrode body, and a method of manufacturing an actuator element.

(3) A method for manufacturing an actuator element comprising a cation exchange resin in a water-containing state having a -COOM group (M is a metal or ammonium ion) and an electrode body bonded to the cation exchange resin. And
A step of roughening the surface of the cation exchange resin on which the electrode body is formed;
Is a metal or ammonium ion), a step of converting a part of the M ⁺ ions of the —COOM group into a metal ion or a metal complex ion forming an electrode, and a metal ion or a metal forming the electrode. A step of reducing complex ions to form an electrode metal nucleus on the surface of the cation exchange resin, and a step of forming a metal layer on the electrode metal nucleus using a growth bath to form the electrode body. A method for manufacturing an actuator element, comprising:

(4) A method of manufacturing an actuator element comprising a cation exchange resin in a water-containing state having a —COOM group (where M is a metal or ammonium ion) and an electrode body bonded to the cation exchange resin. And
A step of roughening the surface of the cation exchange resin forming the electrode body; a step of pickling the roughened surface; and a step of removing at least a part of the carboxyl groups of the cation exchange resin by -COOM. Group (where M is a metal or ammonium ion), and M of the --COOM group
⁺ A step of converting a part of ions into a metal ion or a metal complex ion forming an electrode, and reducing the metal ion or a metal complex ion forming the electrode to form an electrode metal nucleus on the surface of the cation exchange resin. And a step of forming the electrode body by growing a metal layer on the electrode metal nuclei using a growth bath.

(5) The reduction of the metal ion or metal complex ion forming the electrode is carried out by bringing the cation exchange resin into contact with a reducing agent solution, according to any one of the above (2) to (4). Actuator element manufacturing method.

(6) The method for manufacturing an actuator element according to any one of the above (2) to (5), wherein the growth bath contains a metal salt, a reducing agent and a stabilizer.

(7) The method for manufacturing an actuator element according to any one of (1) to (6) above, wherein the M ⁺ ion of the —COOM group is a metal ion of an alkali metal or an alkaline earth metal.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION A method for manufacturing an actuator element of the present invention will be described in detail below. FIG. 1 is a perspective view showing a configuration example of an actuator element manufactured according to the present invention, and FIG. 2 is a sectional view taken along line II-II in FIG. As shown in these drawings, the actuator element 1 includes a cation exchange resin layer 2 and a pair (one set) of electrode bodies 3 arranged so as to face each other with the cation exchange resin layer 2 interposed therebetween.
4. Needless to say, the shape of the cation exchange resin layer, the number of electrode bodies installed, the arrangement, etc. are not limited to those shown in the drawings.

In such an actuator element, the carboxyl group of the cation exchange resin is -COOM (M
Is a metal or ammonium ion),
It is manufactured by forming an electrode body on the surface of this cation exchange resin by a chemical plating method, particularly an adsorption reduction growth method.

The cation exchange resin is a cation exchange resin having a carboxyl group (having a carboxyl group as a main dissociating group). In this case, as the cation-exchange resin having a carboxyl group that can be used, it is preferable to use a fluorine-based cation-exchange resin from the viewpoint that the deformability of the actuator element 1 is excellent.

The cation exchange resin having such a carboxyl group is in a water containing state at least when the actuator element 1 is used. As a result, the actuator element 1 is deformed by applying the potential difference.
Here, the "water-containing state" means that the cation exchange resin contains a little water. That is, in addition to the case where the cation-exchange resin contains water in advance, the cation-exchange resin is in a water-containing state when it is placed in a water atmosphere, for example, in water or in a high-humidity atmosphere.

The equivalent weight number (EW value) of the carboxyl group in the cation exchange resin is preferably about 450 to 1700, and more preferably about 550 to 1100.

The method of manufacturing an actuator element according to the present invention comprises a first step of roughening the surface of the cation exchange resin forming the electrode body, and a second step of pickling the roughened surface.
A third step of converting at least a part of the carboxyl group of the cation exchange resin into a -COOM group (where M is a metal or ammonium ion), and a part of M ⁺ ion of the -COOM group to form an electrode. A fourth step of exchanging a metal ion or a metal complex ion with a metal ion or a metal complex ion, a fifth step of reducing the metal ion or the metal complex ion to form a metal nucleus (electrode metal nucleus) on the surface of the cation exchange resin, and a growth bath And a sixth step of forming an electrode body by growing a metal layer on the metal nuclei. Hereinafter, each step will be sequentially described.

[First Step] The surface of the cation exchange resin forming the electrode body, that is, both surfaces of the cation exchange resin layer 2 is roughened. Thereby, the electrode body can be easily formed by the chemical plating method, and the adhesion of the electrode body to the cation exchange resin is improved. The method of surface roughening is not particularly limited, and examples thereof include sandblasting, polishing with water-resistant abrasive paper, and low-temperature plasma treatment.

[Second Step] The surface of the roughened cation exchange resin is pickled. This pickling can be performed by, for example, immersing the cation exchange resin in a solution of strong acid or weak acid such as hydrochloric acid or sulfuric acid, or spraying the same solution on the surface of the cation exchange resin.

By carrying out such pickling, foreign substances such as metal powder generated in the roughening step can be dissolved and removed, and the electrode body can be formed favorably in the subsequent step.
After the pickling, it is preferable to wash with pure water or the like (at this time, the carboxyl group in the cation exchange resin is H type due to the pickling). In addition, ultrasonic cleaning may be performed prior to pickling.

[Third Step] At least a part of the hydrogen ions of the carboxyl group in the cation exchange resin, preferably 5
0% or more, more preferably 65% or more, is converted to a -COOM group (where M is a metal or ammonium ion).

[0026] Such a process is carried out by, for example, lithium ion
The cation exchange resin is immersed at room temperature or under heating in a solution in which a monovalent cation such as sodium ion, potassium ion, rubidium ion, cesium ion, or ammonium ion or a divalent cation such as strontium ion exists. It is done by The valence of the metal ion is not limited to monovalent or divalent, and may be multivalent.

The metal ion forming M of the --COOM group contained in the cation exchange resin is particularly an alkali metal (Li,
Na, K, Rb, Cs) or alkaline earth metal (B
e, Mg, Ca, Sr, Ba) metal ions, preferably Li, K, Rb, Cs, Be, Mg, Ca,
The metal ions of Sr and Ba are particularly preferable.

Among these, the actuator element 1
Of the potassium ion, rubidium ion, cesium ion, calcium ion, strontium ion, and barium ion, the retention of the deformed state (hereinafter referred to as “shape retention”) when a potential difference is continuously applied is particularly excellent. At least one type is preferable.

[Fourth Step] For example, by immersing the cation exchange resin in a solution containing metal ions or metal complex ions forming an electrode at room temperature or under heating, the cation exchange resin has --COOM. Part of the M ⁺ ions of the group is exchange-adsorbed to the metal ion or metal complex ion forming the electrode (adsorption process).

The metal ion or metal complex ion forming the electrode that is exchange-adsorbed with the M ⁺ ion of the --COOM group is a metal ion or metal complex ion which can be obtained by reducing the salt thereof to obtain a metal nucleus and a metal layer forming the electrode. Any metal complex ion may be used, and all those used in the chemical plating (electroless plating) method, which is an adsorptive reduction growth method, can be used.

Preference is given to platinum (Pt), ruthenium (R) because of their corrosion resistance and catalytic activity.
u), rhodium (Rh), palladium (Pd), osmium (Os), or iridium (Ir), which is a metal ion or a metal complex ion belonging to the platinum group element.

Particularly preferred are [Pt] because of the ease of exchange adsorption with M ⁺ ions and the stability of the metal ion form or metal complex ion form of the electrode.
(NH ₃ ) ₄ ] ²⁺ , [PtCl (NH ₃ ) ₃ ] ³⁺ , [P
It is a platinum ammine complex ion form such as t (NH ₃ ) ₆ ] ⁴⁺ .

The temperature of the immersion liquid containing metal ions or metal complex ions forming the electrodes is preferably about room temperature to 90 ° C. After exchanging a part of the M ⁺ ions of the —COOM group possessed by the cation exchange resin to the metal ions or metal complex ions forming the electrode in this way, washing with pure water or the like is carried out if necessary.

[Fifth Step] The metal ions or metal complex ions forming the electrode in the cation exchange resin are reduced to deposit metal nuclei on the surface of the cation exchange resin. The reduction of the metal ion or metal complex ion is preferably carried out by a method such as immersing the cation exchange resin in a reducing agent solution or spraying the reducing agent solution.

For example, the washed cation exchange resin was immersed in an aqueous solution of sodium borohydride, so that it was adsorbed in the cation exchange resin [Pt (NH ₃ ).
₆ ] ⁴⁺ is reduced, the surface of the cation exchange resin turns black, and platinum nuclei precipitate (reduction process).

As the reducing agent in the reducing agent solution, all the reducing agents used in the chemical plating (electroless plating) method, which is an adsorptive reduction growth method, can be used.
Dialkylaminoboranes such as dimethylaminoborane and diethylaminoborane, alkali borohydride salts such as sodium borohydride, hydrazine hydrate, hydrochlorides or sulfates, and the like, and one or more of these may be used. Can be used.

If necessary, the reducing agent solution may include
Additives such as stabilizers (pH adjusters) can be added. The portion of the cation exchange resin where the electrode body is not formed can be masked in advance.

[Sixth step] A cation exchange resin having metal nuclei deposited on the surface is immersed in a growth bath to grow a metal layer on the metal nuclei to form an electrode body.

The bath composition of the growth bath includes a solution in which a metal salt, in particular, a metal ion or a metal complex ion forming the electrode used in the fourth step is present, and a reducing agent as an additive is added to the solution. And a stabilizer (pH adjusting agent) are added as necessary.

In this case, the reducing agent may be one or more of the above-mentioned reducing agents. Further, the pH of the growth bath is adjusted to a desired level by adding a stabilizer (pH adjuster) (preferably pH = 7-1).
0), a metal ion form or a metal complex ion form can be stably present. As such a stabilizer, any of those used in the chemical plating (electroless plating) method which is an adsorption reduction growth method can be used, and a typical example thereof is hydroxylammonium hydrochloride.

For example, a cation exchange resin having platinum nuclei deposited on its surface is immersed in a hexaammine chloride platinum salt aqueous solution as a growth bath, and a predetermined amount of a reducing agent and a pH adjusting agent is added to the platinum nuclei deposited during the reduction process. The platinum layer grows and is formed on the surface of the cation exchange resin by the autocatalytic action of (the growth process). This platinum layer (metal layer) serves as an electrode body of the actuator element.

In the present invention, arbitrary steps may be added before and after each of the first to sixth steps. For example, after the sixth step, a step (seventh step) of exchanging cations other than hydrogen ions in the cation exchange resin for other cations may be added.

Further, after the sixth step or the seventh step, a step (seventh step or eighth step) of connecting lead wires 14 and 15 described later to the electrode bodies 3 and 4, respectively, may be added. .

Also, after the 7'th step or the 8th step,
A step (8'th step or 9th step) of forming a coating layer made of a water-impermeable material on the surface of the actuator element may be added, whereby ion exchange in the cation exchange resin is prevented, The performance of the cation exchange resin as an actuator can be stably maintained regardless of the environment in which the actuator element is used. In the present invention, of the first to sixth steps, for example, the second step may be omitted, or the first step and the second step may be omitted.

The actuator element 1 is manufactured through the above steps. Electric power is supplied to the electrode bodies 3 and 4 of the actuator element 1 by the power supply means 11, and a potential difference is given. That is, the lead wires (conductors) 14 and 15 are connected to the electrode bodies 3 and 4, respectively. In this case, whether the electrode bodies 3, 4 and the lead wires (conductors) 14, 15 from the power source 16 are fixed by a laser welding method, an ultrasonic welding method, a high frequency welding method, or the like,
It is preferable that they are fixed by an adhesive fixing or a brazing method via conductive materials 12 and 13 such as a conductive adhesive.
This allows the actuator element 1 to exhibit more reproducible and stable deformation performance. The power supply 16 may be a DC power supply or an AC power supply.

When a potential difference (a low voltage that does not cause electrolysis of water, for example, 1.5 V or less) is applied between the electrode bodies 3 and 4 by the power supply means 11, the actuator element 1 moves to the electrode body 3. It is curved and deformed so as to project to the anode side of 4. Due to the above-described configuration of the cation exchange resin, the deformed state of the actuator element 1 is maintained while the potential difference is continuously applied. The degree of holding this deformed state is, for example, at least 5 seconds or more after the actuator element 1 is deformed in the anode direction and reaches the maximum value when a potential difference is applied between the electrode bodies 3 and 4. 90
It is only to keep the deformation of%. In addition, the electrode body 3,
When the potential difference to 4 is set to 0, the actuator element 1 becomes
Immediately returns to its original shape.

[0047]

EXAMPLES The present invention will now be described in more detail with reference to specific examples.

(Example 1) Membrane-like fluorine-based cation exchange resin having mainly -COOH group as a carboxyl group (Flemion C-800 (registered trademark), manufactured by Asahi Glass Co., Ltd., E
Glass powder GP of Sahara (made by Sekisui Chemical Co., Ltd.) as a sand blaster and a mean particle size of about 200 μm as a sand blaster on both surfaces of W value = 800, film thickness when wet 100 μm)
Injection pressure 2 using 105A (manufactured by Toshiba Ballotini)
Blasting was performed under the conditions of kg / cm ² and an injection distance of 10 cm to roughen the surface.

Next, the glass beads adhering to the ion exchange resin were removed by ultrasonic cleaning and immersed in 1N hydrochloric acid to remove the metal powder generated from the inner wall of the sand blaster, and this was further washed with pure water. .

The cation exchange resin thus obtained was immersed in a 1N aqueous solution of lithium hydroxide for 15 hours at room temperature, and then sufficiently washed with pure water until it became neutral to remove the carboxyl group of the cation exchange resin. Almost all of -COOLi
Converted to the base.

Further, this cation-exchange resin was immersed in an aqueous solution of hexaammine chloride platinum salt for electroless plating (Pt: 2 mg / ml, manufactured by Ishifuku Metal Industry Co., Ltd.) at 60 ° C. for 15 hours, so that a part of lithium ions was It was exchange-adsorbed with a tetravalent hexaammine platinum complex ion ([Pt (NH ₃ ) ₆ ] ⁴⁺ ).

The cation exchange resin was thoroughly washed with pure water and then immersed in an aqueous sodium borohydride solution at 40 to 60 ° C. As a result, the tetravalent hexaammine platinum complex ion ([Pt
(NH ₃ ) ₆ ] ⁴⁺ ) was reduced, and both surfaces of the cation exchange resin became black, and it was confirmed that platinum nuclei were deposited.

Subsequently, this cation exchange resin was mixed with 40 to 6
The solution was immersed in the same hexaammine chloride platinum salt aqueous solution as described above at 0 ° C., and a hydroxylammonium chloride aqueous solution as a pH adjusting agent and a hydrazine aqueous solution as a reducing agent were respectively added. As a result, a platinum layer of about 3 mg / cm ² was grown on the platinum nuclei deposited in the reduction process by its autocatalytic action, and an electrode body was formed.

By the above adsorption reduction growth method, -COOL
The actuator element 1 including the cation exchange resin layer 2 having an i group and the electrode bodies 3 and 4 bonded to the surface of the cation exchange resin layer 2 could be manufactured.

Example 2 Instead of immersing the membranous cation exchange resin in Example 1 in a 1N aqueous solution of lithium hydroxide, it is immersed in a 1N aqueous solution of sodium hydroxide,
Almost all of the carboxyl groups in the cation exchange resin layer-
Example 1 except that the operation was changed to COONa.
An actuator element was manufactured in the same manner as in.

In this production method, both surfaces of the cation exchange resin became black in the reduction process, and precipitation of platinum nuclei was confirmed, and in the subsequent growth process, about 3 mg / cm ² of platinum nuclei was deposited on the platinum nuclei. The platinum layer grew and the electrode body was formed.

(Example 3) Instead of immersing the membrane cation exchange resin in Example 1 in a 1N aqueous solution of lithium hydroxide, the cation exchange resin layer was immersed in a 1N aqueous solution of potassium hydroxide. Almost all of the carboxyl groups of -C
An actuator element was manufactured in the same manner as in Example 1 except that the operation was changed to an OOK group.

In this production method, both surfaces of the cation exchange resin became black in the reduction process, and precipitation of platinum nuclei was confirmed. Further, in the subsequent growth process, about 3 mg / cm ² of platinum nuclei was deposited on the platinum nuclei. The platinum layer grew and the electrode body was formed.

Example 4 Instead of immersing the membranous cation exchange resin in Example 1 in a 1N aqueous solution of lithium hydroxide, the cation exchange resin was immersed in a 0.5N aqueous solution of rubidium hydroxide. An actuator element was manufactured in the same manner as in Example 1 except that almost all of the carboxyl groups in the layer were converted to --COORb groups.

In this production method, both surfaces of the cation exchange resin turned black during the reduction process, and precipitation of platinum nuclei was confirmed. In the subsequent growth process, about 3 mg / cm ² of platinum nuclei were deposited on the platinum nuclei. The platinum layer grew and the electrode body was formed.

Example 5 Instead of immersing the membranous cation exchange resin in Example 1 in a 1N aqueous solution of lithium hydroxide, the cation exchange resin was immersed in a 0.5N aqueous solution of cesium hydroxide. An actuator element was manufactured in the same manner as in Example 1 except that almost all of the carboxyl groups in the layer were converted to —COOCs groups.

In this production method, both surfaces of the cation exchange resin turned black during the reduction process, and precipitation of platinum nuclei was confirmed. Further, in the subsequent growth process, about 3 mg / cm ² of platinum nuclei were deposited on the platinum nuclei. The platinum layer grew and the electrode body was formed.

(Example 6) Instead of immersing the membranous cation exchange resin in Example 1 in a 1N aqueous lithium hydroxide solution, the membrane cation exchange resin was immersed in a saturated strontium hydroxide aqueous solution to form a cation exchange resin layer. An actuator element was produced in the same manner as in Example 1 except that almost all of the carboxyl groups were changed to-(COO) ₂ Sr groups.

In this production method, both surfaces of the cation exchange resin turned black during the reduction process, and precipitation of platinum nuclei was confirmed. Further, in the subsequent growth process, about 3 mg / cm ² of platinum nuclei were deposited on the platinum nuclei. The platinum layer grew and the electrode body was formed.

(Example 7) Instead of immersing the membranous cation exchange resin in Example 1 in a 1N aqueous lithium hydroxide solution, immersing it in saturated aqueous ammonia (28% aqueous ammonia) to perform cation exchange. An actuator element was manufactured in the same manner as in Example 1 except that almost all of the carboxyl groups in the resin layer were converted into —COONH ₄ groups.

In this production method, both surfaces of the cation exchange resin turned black during the reduction process, and precipitation of platinum nuclei was confirmed. Further, in the subsequent growth process, about 3 mg / cm ² of platinum nuclei were deposited on the platinum nuclei. The platinum layer grew and the electrode body was formed.

(Examples 8 to 14) A film-type fluorine-based cation exchange resin having a carboxyl group (Flemion C-690 (registered trademark) manufactured by Asahi Glass Co., Ltd., EW value = 690, film thickness 130 μm in wet condition) was used. Except for the above, the actuator elements corresponding to these were manufactured in the same manner as in Examples 1 to 7.

In each of the production methods of Examples 8 to 14, both surfaces of the cation exchange resin turned black during the reduction process, and the precipitation of platinum nuclei was confirmed. A platinum layer of about 3 mg / cm ² was grown on the nuclei to form an electrode body.

<Experiment> An experiment for examining the deformation characteristics of each actuator element obtained in Examples 1 to 14 was conducted.

When a square wave voltage of 1 V was applied between both electrodes of each actuator element according to the displacement measuring method described below,
It was deformed by about 0.7 to 2.0 mm in the direction of the anode, and the deformed state was maintained in place. Further, the deformed state was maintained even when 1 V was continuously applied for 24 hours. When the applied voltage was set to 0V, it returned to the original position. Even when the same operation was repeated several times to several tens of times, the same deformed state was maintained, and reproducibility of shape retention was also confirmed.

(Method of measuring displacement of actuator element) Width 1
mm-length, 15 mm-long strip-shaped actuator element with 3 mm on one end sandwiched by a platinum block that is a power supply and hung and held in pure water at 37 ° C.
(Toho Giken Co., Ltd.) and a function generator (arbitrary function generator) FG-02 (Toho Giken Co., Ltd.) are used to apply a square wave voltage to bend and deform the actuator element, and 10 mm from the fixed end of the actuator element. The displacement of the position of the position in the direction of the anode is a laser reflection type displacement meter LC210.
0 (manufactured by Keyence Corporation), and the applied voltage, current and displacement were simultaneously monitored by a digital oscilloscope DL2240 (manufactured by Yokogawa Electric Corporation).

(Comparative Example 1) The film-shaped cation exchange resin in Example 1 was immersed in 1N hydrochloric acid instead of being immersed in 1N lithium hydroxide aqueous solution to obtain a carboxyl group in the cation exchange resin layer. An actuator element was manufactured in the same manner as in Example 1 except that all of the above were converted to —COOH groups.

In this production method, the surface of the cation exchange resin did not become black in the reduction process, and the precipitation of platinum nuclei was not confirmed. Also, in the subsequent growth process, the platinum layer could not be formed on the surface of the cation exchange resin. From the above, the electrode body could not be formed on the surface of the cation exchange resin having a carboxyl group.

Comparative Example 2 Other than using a film-form fluorine-based cation exchange resin having a carboxyl group (Flemion C-690 (registered trademark), manufactured by Asahi Glass Co., Ltd., EW value = 690, wet film thickness 130 μm) In the same manner as in Comparative Example 1,
The actuator element was manufactured.

In this production method, the surface of the cation exchange resin did not become black in the reduction process, and the precipitation of platinum nuclei was not confirmed. Also, in the subsequent growth process, the platinum layer could not be formed on the surface of the cation exchange resin. From the above, the electrode body could not be formed on the surface of the cation exchange resin having a carboxyl group.

[0076]

As described above, according to the method for manufacturing an actuator element of the present invention, an electrode body is formed on the surface of a cation exchange resin having a carboxyl group by a chemical plating method, particularly an adsorption reduction growth method. be able to. Therefore, it is possible to easily manufacture the actuator element having the characteristic that the deformed state can be maintained when the same potential difference is continuously applied.

[Brief description of drawings]

FIG. 1 is a perspective view showing a configuration example of an actuator element of the present invention.

FIG. 2 is a sectional view taken along line II-II in FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Actuator element 2 Cation exchange resin layer 3, 4 Electrode body 11 Power supply means 12, 13 Conductive material 14, 15 Lead wire 16 Power supply

Claims (7)

[Claims] 1. When manufacturing an actuator element by forming an electrode body on the surface of a cation exchange resin having a —COOM group (where M is a metal or ammonium ion), M ⁺ ion of the —COOM group is used. Of a part of the metal ion or metal complex ion forming an electrode, and a step of reducing the metal ion or metal complex ion forming the electrode to form an electrode metal nucleus on the surface of the cation exchange resin. And a step of forming the electrode body by growing a metal layer on the electrode metal nuclei using a growth bath. 2. A method of manufacturing an actuator element, comprising: a cation exchange resin having a —COOM group (where M is a metal or ammonium ion) in a water-containing state, and an electrode body bonded to the cation exchange resin. A step of converting at least a part of the carboxyl group of the cation exchange resin into a —COOM group (where M is a metal or an ammonium ion); and a part of M ⁺ ion of the —COOM group as an electrode Forming a metal ion or a metal complex ion forming the electrode, a step of reducing the metal ion or the metal complex ion forming the electrode to form an electrode metal nucleus on the surface of the cation exchange resin, and a growth bath. And a step of forming the electrode body by growing a metal layer on the electrode metal nucleus by using the actuator element. Build method. 3. A method for producing an actuator element, comprising: a cation exchange resin having a —COOM group (where M is a metal or ammonium ion) in a water-containing state, and an electrode body bonded to the cation exchange resin. And a step of roughening a surface of the cation exchange resin on which the electrode body is formed, and at least a part of a carboxyl group of the cation exchange resin is a -COOM group (where M is a metal or ammonium). An ion), a step of converting a part of the M ⁺ ions of the —COOM group into a metal ion or a metal complex ion forming an electrode, and reducing the metal ion or a metal complex ion forming the electrode. And forming an electrode metal nucleus on the surface of the cation exchange resin by using a growth bath to grow a metal layer on the electrode metal nucleus. Method of manufacturing an actuator device characterized by a step of forming the body. 4. A method for manufacturing an actuator element, comprising: a cation exchange resin having a —COOM group (where M is a metal or ammonium ion) in a water-containing state, and an electrode body bonded to the cation exchange resin. And a step of roughening the surface of the cation exchange resin on which the electrode body is formed, a step of pickling the roughened surface, and at least a part of a carboxyl group of the cation exchange resin To a -COOM group (where M is a metal or ammonium ion), and a step of converting a part of M ⁺ ions of the -COOM group into a metal ion or a metal complex ion forming an electrode, Reducing metal ions or metal complex ions forming an electrode to form an electrode metal nucleus on the surface of the cation exchange resin; and using a growth bath, gold on the electrode metal nucleus. Method of manufacturing an actuator device characterized by a step of forming the electrode body by growing layers. 5. The production of the actuator element according to claim 2, wherein the reduction of the metal ion or metal complex ion forming the electrode is performed by bringing the cation exchange resin into contact with a reducing agent solution. Method. 6. The method for manufacturing an actuator element according to claim 2, wherein the growth bath contains a metal salt, a reducing agent and a stabilizer. 7. The method for manufacturing an actuator element according to claim 1, wherein the M ⁺ ion of the —COOM group is a metal ion of an alkali metal or an alkaline earth metal.