JP4323308B2 - Manufacturing method of laminate - Google Patents

Description

  The present invention relates to an electroless plating method for forming a dense metal layer having a large surface area on a polymer electrolyte, and a laminate comprising the metal layer and the polymer electrolyte layer.

  The electroless plating method includes a metal layer and a polymer electrolyte layer as a laminate that can be used as a bendable actuator because a metal layer can be easily formed on the polymer electrolyte. This is useful because a laminate can be obtained.

  Bendable actuators, particularly polymer actuators, have been attracting particular attention in recent years because they can be used as a drive unit such as a catheter due to their flexibility. As the actuator, for example, a laminated body of an ion exchange resin film that is a polymer electrolyte and a metal electrode bonded to the surface thereof is applied with a potential difference between the metal electrodes in the water-containing state of the ion exchange resin film. Thus, the ion-exchange resin molded product can be used as an actuator by bending or deforming the ion-exchange resin molded product (see, for example, Patent Document 1).

As a manufacturing method of a laminate as such an actuator, after performing a roughening treatment, the ion exchange resin film that is a polymer electrolyte is swollen by being immersed in water, and the ion exchange resin film swollen with water An electrode is formed by electroless plating, in which a metal complex such as a platinum complex or gold complex is adsorbed in an aqueous solution, and the metal complex adsorbed with the reducing agent is deposited, and this adsorption / reduction process is performed. Repeatedly done. Repeating the adsorption / reduction process is repeated 6 times or more in order to ensure the amount of metal on the polymer electrolyte that can be displaced such as bending as an actuator. In the laminate of the polymer electrolyte and the electrode layer thus obtained, a metal layer is grown in the inner direction of the polymer electrolyte to form an electrode, and at the interface between the polymer electrolyte and the electrode layer, The cross section of the electrode layer forms a fractal structure (see, for example, Non-Patent Document 1). With this fractal-like structure, an electric double layer can be formed at the interface between the metal layer and the polymer electrolyte layer, and favorable displacement such as bending can be obtained.
Japanese Patent No. 2961125 (pages 1-9) Edited by Yoshihito Nagata, “Biomimetics Handbook”, first edition, NTS, Inc., September 13, 2000, P932-938

  However, with regard to polymer actuators in recent years, application to a wide range of uses for artificial muscles and various devices has been studied, and application to applications that require a larger swing width than actuators used for catheters is desired, such as bending Is required to be larger than the laminate obtained by the electroless plating method. In addition, it is desired to use an actuator with a larger displacement amount for the catheter due to operability.

  In order to obtain a laminate that can obtain a larger amount of bending than the conventional actuator, the amount of metal deposited on the polymer electrolyte can be increased by increasing the number of repetitions of the adsorption / reduction process by the electroless plating method. It is also possible. However, in the method of increasing the number of repetitions of the adsorption / reduction process, the amount of deposited metal is limited, and it is difficult to further improve the bending amount of the laminate obtained by the electroless plating method.

  An object of the present invention is an electroless plating method capable of obtaining a laminate of a metal layer and a polymer electrolyte layer, which can be used in applications requiring a larger bend than a conventional bend. Is to provide.

As a result of intensive studies, the present inventors have, as a pretreatment step for electroless plating on a polymer electrolyte, a swelling step in which a good solvent or a mixed solvent containing a good solvent is permeated to swell the polymer electrolyte, An adsorption step of adsorbing a metal complex to the swollen polymer electrolyte; and a reduction step of forming a metal layer with the polymer electrolyte by bringing a reducing agent solution into contact with the polymer electrolyte adsorbed with the metal complex. And the polymer electrolyte in the swelling step has a predetermined shape, and the thickness of the polymer electrolyte in a swollen state is the polymer electrolyte. 110% or more of the thickness in a dry state, the polymer electrolyte is an ion exchange resin, and the good solvent is methanol, ethanol, propanol, hexafluoro 2-propanol, dimethyl sulfoxide, N- methylpyrrolidone, dimethylformamide, ethylene glycol, diethylene glycol, using the manufacturing method of the actuator element for laminate characterized in that it contains at least one member selected from the group consisting of glycerol As a result, it has been found that a laminate that can be bent more than before can be obtained, and the present invention has been achieved.
In the present invention, the thickness of the polymer electrolyte in a swollen state is preferably 110 to 240% with respect to the thickness of the polymer electrolyte in a dried state.
Further, in the present invention, in the swelling step, the good solvent or a mixed solvent containing the good solvent is permeated into the polymer electrolyte, thereby reducing the crystallinity of the polymer electrolyte. It is preferable to reduce the entanglement of the side chain having at least a functional group in the constituting polymer.
In the present invention, the good solvent preferably contains at least one selected from the group consisting of methanol, ethanol, and propanol, more preferably contains methanol, and the good solvent further includes It is preferable to contain a basic salt.
In the present invention, the electric double layer capacity measured by the cyclic voltammetry method at the interface between the metal layer and the polymer electrolyte layer is 3 mF / as a value when the dry film thickness of the polymer electrolyte is converted to 170 μm. preferably cm ² or more, also, the electric double layer capacity by constant current discharge method of the interface between the metal layer and the polymer electrolyte layer is preferably 2.0 F / cm ³ or more.

Since the electroless plating method of the present invention performs a swelling process as a pretreatment process, the electroless plating method is a laminate including a metal layer and a polymer electrolyte layer, and has a large displacement (bending) when driven as an actuator. Can be obtained. In addition, the laminate can be used as a drive unit for applications that require bending beyond the conventional bending. In the laminate of the present invention, the electric double layer capacity at the interface between the electrode layer and the polymer electrolyte layer is 3.0 mF / cm as a value when the dry thickness of the polymer electrolyte is converted to 170 μm. ² or more, or because the electric double layer capacity by the constant current discharge method is 2.0 F / cm ³ or more, the actuator has a large displacement such as bending, and mechanical energy similar to the conventional one with a low applied voltage. Therefore, it is possible to greatly reduce the energy cost.

  The present invention is a swelling step of swelling a polymer electrolyte by impregnating a good solvent or a mixed solvent containing a good solvent as a pretreatment step for electroless plating on the polymer electrolyte, The molecular electrolyte has a predetermined shape, and a swelling process is performed in which the thickness of the polymer electrolyte in a swollen state is 110% or more with respect to the thickness of the polymer electrolyte in a dried state An electroless plating method for polymer electrolyte. After the swelling process, which is a pretreatment process, is performed, an adsorption process for adsorbing the metal complex to the polymer electrolyte as a metal layer formation by an electroless plating method, and the adsorbed metal complex is reduced with a reducing agent solution. Then, a reduction process for depositing the metal is performed. After the reduction step, it is preferable to perform a washing step of washing the polymer electrolyte on which the metal has been deposited in order to easily remove the reducing agent and perform the step performed after the reduction step.

(Swelling process)
The electroless plating method of the present invention is a swelling step in which a polymer solvent is swollen by infiltrating a good solvent or a mixed solvent containing a good solvent as a pretreatment, and the swollen polymer electrolyte has a predetermined shape. And a swelling step in which the thickness of the polymer electrolyte in a swollen state is 110% or more with respect to the thickness of the polymer electrolyte in a dried state. The good solvent is used according to the composition of the polymer electrolyte. The swelling step causes the polymer electrolyte to swell by allowing the good solvent to permeate the polymer electrolyte. By using a good solvent or a mixed solvent containing a good solvent in the swelling step, the polymer electrolyte swells larger than that of the poor solvent. Due to this swelling, the polymer electrolyte formed into a film shape or a columnar shape, when not subjected to special processing such as coating, increases the overall size while maintaining almost the same shape, When special processing such as coating is performed, a portion not subjected to special processing becomes large and deformation such as bending may occur. In the swelling step, when the polymer electrolyte does not have a shape in a swollen state, it is difficult to form a metal layer in a later step. Therefore, the polymer electrolyte is mixed with a good solvent or a good solvent. Due to the permeation of the solvent, it is necessary to swell in a state having a predetermined shape such as substantially the same shape as before swelling or a deformed shape such as a curve. In the swelling step, the thickness of the polymer electrolyte with respect to the surface on which the metal layer is formed varies depending on the type of the polymer electrolyte. It is preferable that the polymer electrolyte is 110 to 3000% with respect to the thickness in a dry state in order to easily perform operations such as the transition to the adsorption step and the reduction step performed, and the polymer More preferably, the electrolyte is 120 to 1000% of the thickness in a dry state. Further, when the good solvent reacts with the metal complex used in the adsorption step to inhibit the formation of the metal layer, the thickness of the polymer electrolyte in a swollen state is the state where the polymer electrolyte is dried. The thickness is preferably 120 to 300%. In addition, the ratio of the thickness of the polymer electrolyte in the swollen state with respect to the dry state of the polymer electrolyte can be indicated by how much the polymer electrolyte is swollen from the dry state. This is hereinafter referred to as the degree of swelling. For example, when the thickness of the swollen polymer electrolyte is 110% with respect to the thickness in the dry state, the degree of swelling is 10%.

  The polymer electrolyte is not particularly limited as long as it is an electrolyte mainly formed of a polymer, but an ion exchange resin is preferable in order to sufficiently adsorb the metal complex. The ion exchange resin is not particularly limited, and a known resin can be used, and one obtained by introducing a hydrophilic functional group such as a sulfonic acid group or a carboxyl group into polyethylene, polystyrene, fluororesin or the like is used. Can do. In particular, a cation exchange resin in which a sulfonic acid group and / or a carboxyl group is introduced into a fluororesin is used as the ion exchange resin. The rigidity is moderate, the ion exchange amount is large, chemical resistance, and durability against repeated bending. It is preferable as a polymer actuator because of its good properties. Specific examples of the ion exchange resin include perfluorocarboxylic acid resin and perfluorosulfonic acid resin. For example, Nafion resin (perfluorosulfonic acid resin, manufactured by DuPont), Flemion (perfluorocarboxylic acid resin or Perfluorosulfonic acid resin (Asahi Glass Co., Ltd.) can be used. As the polymer electrolyte, a polymer electrolyte molded product having a shape suitable for the shape can be used as a laminate obtained by an electroless plating method, and a film shape, a plate shape, a cylindrical shape, a columnar shape, a tubular shape, or the like can be used. Can be used.

  In the swelling step, the polymer electrolyte swollen has a predetermined shape by infiltrating the polymer electrolyte with a good solvent or a mixed solvent containing a good solvent, and the polymer electrolyte is swollen. Swelling is performed so that the thickness in the dried state is 110% or more with respect to the dry thickness of the polymer electrolyte. The resin component that forms the polymer electrolyte has a functional group by swelling the thickness of the polymer electrolyte in a swollen state to 110% or more of the thickness of the polymer electrolyte in a dried state Increased freedom of segmental motion for the side chain. This increase in the degree of freedom makes it easier for the metal complex to be adsorbed from the surface of the polymer electrolyte in the adsorption step of the electroless plating method, and the reducing agent in the reducing agent solution also becomes a polymer electrolyte in the reduction step. It is considered that the metal complex and the reducing agent are easily moved in the Brownian motion inside the polymer electrolyte.

  In addition, the laminate in which the metal layer is formed on the polymer electrolyte layer obtained by the electroless plating method in which the swelling process has been performed has a higher electrode layer than the conventional one when the metal layer is used as the electrode layer. Large electric double layer capacity. In the metal layer of the laminate obtained by the electroless plating method, a structure in which the cross section of the metal layer is more uneven than the conventional fractal structure is formed at the interface between the polymer electrolyte layer and the metal layer. Even after the body is obtained, even when the polymer electrolyte contracts, it is considered that the fractal structure formed at the time of swelling retains its shape.

  The good solvent is a solvent that can swell the polymer well, and varies depending on the type of polymer constituting the polymer electrolyte. Accordingly, as the good solvent, a suitable solvent species can be used according to the composition of the polymer electrolyte employed depending on the use of the laminate finally obtained by the electroless plating method. The good solvent may be a mixture of a plurality of good solvents. As the good solvent, for example, methanol, dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide, ethylene glycol, diethylene glycol, glycerin and the like can be used. When the polymer electrolyte is a perfluorocarboxylic acid resin or a perfluorosulfonic acid resin, methanol, ethanol, propanol, hexafluoro-2-propanol, diethylene glycol, and glycerin can be used. In particular, in the swelling step, when the polymer electrolyte is a perfluorocarboxylic acid resin or a perfluorosulfonic acid resin, methanol or a solvent containing methanol is infiltrated to swell the polymer electrolyte in a swollen state. It is preferable that the thickness swells to 110% or more with respect to the thickness of the polymer electrolyte in a dry state. This is because methanol is easy to swell and is easy to handle, and therefore has good workability.

  In the swelling step, if the thickness of the polymer electrolyte in a swollen state can be 110% or more with respect to the thickness of the polymer electrolyte in a dried state, the polymer electrolyte can be obtained using only a good solvent. The electrolyte may be swollen or a mixed solvent containing a good solvent may be used. By swelling the polyelectrolyte, the crystallinity of the polyelectrolyte is lowered, in particular, the entanglement of the side chain having a functional group is alleviated, and the degree of freedom of segment movement with respect to the side chain is increased. For this reason, a laminate including a metal layer and a polymer electrolyte layer obtained by an electroless plating method using the swelling step as a pretreatment step can move ions more efficiently and obtain a large displacement. It is considered possible.

  The mixed solvent containing a good solvent for the polymer electrolyte is a mixed solvent in which a good solvent is mixed with another solvent at an arbitrary ratio, and the thickness of the polymer electrolyte in a swollen state is set as the polymer solvent. The mixing ratio of the good solvent and the other solvent is not particularly limited as long as it can be 110% or more with respect to the thickness of the electrolyte in a dry state. When the swollen polymer electrolyte is less than 110% of the thickness of the polymer electrolyte in the dry state, the laminate obtained by the electroless plating method is driven as an actuator. This is because the amount of displacement (the amount of bending) decreases when it is applied. The other solvent is a solvent different from the good solvent of the polymer electrolyte to be used, and may be water or an organic solvent as long as it can maintain a stable mixed state with the good solvent. When the process is performed in an aqueous metal complex solution, water is preferably used as the other solvent because there is no inhibition of the adsorption of the metal complex such as precipitation of the metal complex. When the polymer electrolyte is a perfluorocarboxylic acid resin or a perfluorosulfonic acid resin, a good solvent that is a swelling solvent for swelling the polymer electrolyte or a mixed solvent containing the good solvent is methanol and In the case of a mixed solvent with water, since it can easily swell, it is preferable that methanol is contained in the swelling solvent in an amount of 5 to 100% by weight. In the case where the ion exchange capacity is 1.8 meq / g, it is more preferable that methanol is contained in the swelling solvent in an amount of 5 to 40 wt% because large swelling can be easily obtained. Alternatively, when the ion exchange capacity of the perfluorosulfonic acid resin is 1.4 meq / g, methanol swells. More preferably it contained 100 wt% to use a solvent. When only the good solvent is used as the swelling solvent instead of the mixed solvent, the polymer electrolyte can be swollen appropriately in a preferable temperature range, although it varies depending on the kind of the good solvent. It is preferable to immerse the polymer electrolyte in a good solvent at a temperature at which it does not gel. When methanol is used as the swelling solvent, the swelling step is preferably performed at room temperature.

  In the pretreatment step, the swollen polymer electrolyte has a predetermined shape, and the thickness of the polymer electrolyte in a swollen state is 110% of the thickness of the polymer electrolyte in a dried state. As long as it can be swollen as described above, the means for penetrating the polymer electrolyte with the good solvent or the mixed solvent containing the good solvent is not particularly limited. For example, as the means, a method of immersing the polymer electrolyte in a good solvent or a mixed solvent containing a good solvent may be used, or a method of applying a good solvent or a mixed solvent containing a good solvent to the surface of the polymer electrolyte is used. May be. As the means, it is preferable to use a method of immersing the polymer electrolyte in a good solvent or a mixed solvent containing a good solvent because workability is easy.

  The swelling step can also be performed using a mixture of the good solvent and a basic salt in an amount of 1 to 30% by weight, preferably 1 to 10% by weight. Or the process of swelling the basic salt aqueous solution of the said ratio with a solvent can also be provided in the process before or after the swelling process by the said good solvent. When the swelling step is performed with a solvent containing such a basic salt, the degree of swelling of the polymer electrolyte can be increased as compared with the case where the swelling step is performed using only a good solvent. This is because a good solvent relaxes the entanglement of the side chain of the polymer electrolyte and swells the polymer electrolyte, whereas an ionic substance produced by dissolving a basic salt in a solvent is a polymer electrolyte. This is because it is considered that the entanglement of the functional group of the polymer is eased to swell the polymer electrolyte. That is, the entanglement of the functional group portion of the polymer electrolyte that could not be swollen by the good solvent alone is also alleviated by the basic salt, and thus the polymer electrolyte can achieve a large degree of swelling synergistically.

  The basic salt can be used without limitation as long as it is soluble in a good solvent or water. As described above, the basic salt can obtain the effects of the present invention by separately adding a swelling step with an aqueous basic salt solution. Specific examples of these basic salts include LiOH, NaOH, aqueous ammonia, tetramethylammonium hydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH), tetrapropylammonium hydroxide (TPAOH), and tetrabutylammonium hydroxide. (TBAOH). Among such basic salts, an optimal ionic solvent or salt can be selected according to the polymer electrolyte used. For example, when the polymer electrolyte is a perfluorocarboxylic acid resin or a perfluorosulfonic acid resin, it is preferably swollen with a basic salt such as TEAOH, TPAOH, or TBAOH. Even if the polymer electrolyte has the same component, the optimum basic salt is different if the ion exchange capacity is different. For example, when the trade name “Flemion” (manufactured by Asahi Glass Co., Ltd.), which is a perfluorocarboxylic acid resin, is used for the polymer electrolyte, TEAOH and TPAOH are suitable for the ion exchange capacity of 1.4 meq / g type, whereas ions TBAOH is appropriate if the exchange capacity is 1.8 meq / g. This is considered to be because the cluster size of the ion exchange resin matches the size of the basic salt according to such a combination.

  The basic salt is not particularly limited as long as it is a salt that can swell the polymer electrolyte. For example, when the basic salt is a salt containing a polyvalent ion such as a copper ion or an iron ion, a cation of the polyvalent ion is complexed by using a molecule containing a polycycle as a ligand. Thus, the basic salt can be used in the present invention. However, if the cation in the solution is monovalent, it is not necessary to coordinate a huge ligand to the central atom as described above, so the basic salt is preferably a monovalent salt. . As described above, as a pretreatment step for electroless plating on a polymer electrolyte, the salt is infiltrated with an aqueous salt solution to swell the polymer electrolyte, and the salt is an ion-exchange resin constituting the polymer electrolyte. A swelling step, which is a salt containing an ion that can exchange ions with an exchange group, can be performed. For example, in the case where the polymer electrolyte is a cation exchange resin, as described above, ions that can be exchanged with sulfo groups or carboxyl groups that are exchange groups are tetramethylammonium ions, tetraethylammonium ions, and the like. When the polymer electrolyte is an anion exchange resin, the salt aqueous solution to be permeated into the polymer electrolyte may be a salt containing an ion exchangeable with the exchange group of the anion exchange resin.

  As described above, when the swelling step is performed with a basic salt-containing solvent, the degree of swelling of the polymer electrolyte is larger than that of the good solvent alone, so the number of repetitions of the adsorption step and the reduction step by the subsequent electroless plating method Can be reduced. In other words, in the case where the expansion process is performed with a good solvent alone, in order to form a good metal layer on the polymer electrolyte, the adsorption step and the reduction step are repeated a plurality of times, particularly 4 times or more, and more preferably 6 times or more. It is preferable. However, when the swelling step is carried out with a solvent containing a basic salt, the degree of swelling of the polymer electrolyte is large, so even if this is not repeated, an equivalent metal layer can be reduced by one adsorption step and each reduction step. It can be formed in a process. This is thought to be because the entanglement between the side chain and the functional group of the polymer electrolyte is released and the degree of expansion increases, so that the metal adsorption to the polymer electrolyte is facilitated. In other words, even if the adsorption step and the reduction step are performed only once, a sufficient amount of the metal complex is adsorbed to the polymer electrolyte, and the metal complex is reduced to form a metal layer. Even if it performs once, it is thought that the metal layer equivalent to the case where an adsorption process and a reduction process are performed repeatedly is obtained.

(Electroless plating method)
After the above swelling process is performed, the polymer electrolyte in which the thickness in the swollen state of the polymer electrolyte is swollen to 110% or more with respect to the thickness in the dry state of the polymer electrolyte is swollen. In this state, an adsorption step of adsorbing the metal complex to the polymer electrolyte is performed, and then a reduction step of bringing the reducing agent solution into contact with the polymer electrolyte adsorbed with the metal complex is performed. By performing the reduction step after the adsorption step, the metal complex is reduced and deposited as a metal on the polymer electrolyte, and a metal layer is formed to obtain a laminate. By performing the electroless plating method on the polymer electrolyte after the swelling step, as a pretreatment step for the method of manufacturing a laminate of the present invention, that is, electroless plating on the polymer electrolyte, a good solvent or The polymer electrolyte is infiltrated with a mixed solvent containing a good solvent, the swollen polymer electrolyte has a predetermined shape, and the thickness of the swollen state of the polymer electrolyte is the dried state of the polymer electrolyte An adsorption step for adsorbing a metal complex to a polymer electrolyte after performing a swelling step for swelling to 110% or more with respect to the thickness of the metal, and a reduction step for bringing a reducing agent solution into contact with the polymer electrolyte adsorbed with the metal complex The metal layer is formed by performing a method for producing a laminate including a metal layer and a polymer electrolyte layer.

(Adsorption process)
In the adsorption step in the method for producing a laminate of the present invention, the swollen polymer electrolyte has a predetermined shape, and the thickness of the swollen state of the polymer electrolyte is determined in the dry state of the polymer electrolyte. There is no particular limitation as long as it is a step of adsorbing the metal complex to the polymer electrolyte swollen to 110% or more with respect to the thickness. In the adsorption step, the metal complex solution may be applied to the polymer electrolyte, but the polymer electrolyte having a film thickness swollen to 110 to 300% by the swelling process is immersed in the metal complex solution. This is preferable because the operation is easy.

  The metal complex solution in the adsorption step is not particularly limited as long as the metal layer formed by reduction contains a metal complex that can function as an electrode layer. The metal complex is preferably a metal complex such as a gold complex, a platinum complex, a palladium complex, a rhodium complex, or a ruthenium complex because a metal having a small ionization tendency is electrochemically stable. Therefore, a metal complex composed of a noble metal having good electrical conductivity and high electrochemical stability is preferable, and a gold complex composed of gold which is relatively difficult to undergo electrolysis is preferable. In the metal salt solution, the solvent is not particularly limited. However, since the metal salt is easily dissolved and easy to handle, it is preferable that the solvent contains water as a main component. A metal salt aqueous solution is preferred. Therefore, the metal complex solution is preferably a metal complex aqueous solution, particularly preferably a gold complex aqueous solution or a platinum complex aqueous solution, and more preferably a gold complex aqueous solution.

  The adsorption step is a step of adsorbing a metal complex to a polymer electrolyte swollen to 110% or more of the thickness of the polymer electrolyte in a swollen state relative to the thickness of the polymer electrolyte in a dry state. If there are, conditions such as temperature and immersion time are not particularly limited, but a temperature of 20 ° C. or higher is preferable for efficient swelling. In the adsorption step, the metal complex solution may contain a good solvent for the polymer electrolyte so that the metal complex is easily adsorbed into the polymer electrolyte.

(Reduction process)
The reducing agent solution used in the present invention is not particularly limited as long as the reducing agent is dissolved regardless of the shape of the polymer electrolyte. The reducing agent can be used by appropriately selecting the type according to the type of metal complex used in the metal complex solution adsorbed on the polymer electrolyte, such as sodium sulfite, hydrazine, sodium borohydride. Etc. can be used. In addition, when reducing a metal complex, you may add an acid or an alkali as needed. The concentration of the reducing agent solution is not particularly limited as long as it contains a sufficient amount of reducing agent to obtain the amount of metal to be deposited by reduction of the metal complex. It is also possible to use a concentration equivalent to the metal salt solution used when forming the electrode by plating. Further, the reducing agent solution can contain a good solvent for the polymer electrolyte.

  In the method for producing a laminate of the present invention, a laminate comprising a metal layer and a polymer electrolyte layer can be obtained by performing the adsorption step and the reduction step once, but the adsorption step and the reduction step are performed. By further repeating the process, the displacement amount (bending amount) when driven as an actuator and the electric double layer capacity at the interface between the metal layer and the polymer electrolyte layer can be made larger than the conventional values. it can. When the adsorption step and the reduction step are repeated, it is preferable to perform a washing step after the reduction step in order to easily remove the reducing agent from the polymer electrolyte and perform the adsorption step. The washing step is not particularly limited, and the reducing agent may be removed by washing with water.

(Laminate)
The laminate obtained by the method for producing a laminate of the present invention was obtained by forming a structure in which the cross section of the metal layer was more uneven than the conventional fractal structure at the interface between the polymer electrolyte layer and the metal layer. When a metal layer formed on the polymer electrolyte layer is used as an electrode layer, a large electric double layer capacity can be obtained. That is, the obtained laminate is a laminate of the present invention, and includes an electrode layer and a polymer electrolyte layer, and has an electric double layer capacity at the interface between the electrode layer and the polymer electrolyte layer. The laminate has a value of 3 mF / cm ² or more as a value when the thickness of the laminate is converted to 170 μm. Or it is a laminated body of this invention, Comprising: The electrical double layer capacity | capacitance by a constant current discharge method is a laminated body which is 2.0 F / cm < ³ > or more. In addition, the laminated body of this invention does not specifically limit the thickness as a laminated body.

  When the reduction process is performed through the swelling process, the metal complex enters the polymer electrolyte as described above, and becomes a particulate metal by the reduction process, and these particulate metals are connected to each other, so that the metal component is on the electrolyte. Is formed. Since the metal layer is formed on the polymer electrolyte through such a process, in the laminate of the present invention, the interface between the metal layer and the electrolyte layer is not always clear, and is near the outside of the polymer electrolyte. There may be a structure in which there is a region where the metal component is rich, and the electrolyte component gradually becomes richer toward the center of the electrolyte. That is, the metal layer referred to in the laminate of the present invention does not require a clear metal component as a layer on the electrolyte layer, and at least the metal components present near the outside of the electrolyte are electrically connected to each other. Therefore, it is sufficient that a portion having good conductivity is formed.

The laminate of the present invention has an electric double layer capacity of 3 mF / cm ² or more when the thickness of the laminate is converted to 170 μm. The upper limit is not limited. The larger the electric double layer capacity value of the electrode layer (metal layer) of the laminate, the easier the movement of ions contained in the polymer electrolyte occurs when a voltage is applied to the electrode layer. As a result, the bending (displacement) becomes larger, the bending reactivity becomes faster, and it is suitable for practical use requiring a large bending. The electric double layer capacitance, it is possible to obtain a larger bending, more preferably 5mF / cm ² or more, further preferably 10 mF / cm ² or more. In addition, since the laminate of the present invention can obtain a conventional displacement amount with a low applied voltage, it is also energy efficient. When the electric double layer capacity value obtained by converting the thickness of the laminate to 170 μm is obtained, the electric double layer capacity value used in the measurement (d) is added to the value of the electric double layer actually obtained by the measurement. It can be obtained by multiplying the value (170 / d) obtained by dividing [μm] by 170 μm. The actual measured value of the electric double layer capacity of the laminate can be measured by a known cyclic voltammetry method using a known apparatus.

Moreover, the laminated body of this invention can also evaluate electric double layer capacity | capacitance by the constant current discharge method separately from evaluation by the electric double layer capacity | capacitance by the said cyclic voltammetry method. Here, the electric double layer capacity by the constant current discharge method referred to in the present invention is the Japan Electronic Industry Association standard published by the Japan Electronic Machinery Manufacturers Association, standard number EIAJ RC-2377 (established in April 2000, electric double layer capacitor This is a value measured in accordance with the test method (3.3.1 Constant current discharge method) and corresponds to a value called capacitance in a capacitor. The laminate of the present invention, an electric double layer capacitor according to the constant current discharge method has a feature that is 2.0 F / cm ³ or more, in order to obtain a larger bending, 3.0F / cm ³ or more Is preferably 4.0 F / cm ³ or more.

  The laminate of the present invention is suitable as an actuator because the electrode layer has an interface with the polymer electrolyte layer. In particular, the laminate is preferably a joined body of an electrode and a polymer electrolyte because peeling at the interface between the electrode and the polymer electrolyte hardly occurs. The laminate may be a laminate having a two-layer structure in which the electrode layer is formed of a metal layer, and the electrode layer and the polymer electrolyte layer are one layer each. A three-layer structure may be used. In addition, the actuator of the present invention can be formed into a film shape, a plate shape, a cylindrical shape, a columnar shape, a tubular shape, or the like.

(Use)
By using the above electroless plating method, it is possible to obtain a laminate that exhibits a large bend as an actuator when a voltage is applied to the electrode layer. Since the laminated body bends greatly, it is particularly suitable for applications that require larger mechanical energy. That is, the laminate can be suitably used for actuators for applications that require large mechanical energy including micromachines and artificial muscles. Moreover, even if it is a conventional use, it can drive with a low applied voltage. The actuator can have a known structure. The laminated body of the present invention, for example, an actuator described in JP-A-8-10336, the pair of electrodes are arranged on the inner peripheral surface or outer periphery of the cylindrical polymer electrolyte so that the polymer electrolyte is sandwiched between them. The actuator can be formed on the surface and deformed (bent) by applying a voltage to the electrode.

  The laminate can be suitably applied to medical instruments such as tweezers, scissors, forceps, snares, laser scalpels, spatulas, and clips in micromachines and microsurgery techniques that use actuators as drive units. In addition, the laminated body includes various sensors or repair tools for inspection and repair, health appliances, hygrometers, hygrometer control devices, soft manipulators, submersible valves, soft transport devices, and other industrial equipment, goldfish, etc. In an article used underwater such as an underwater mobile or a hobby article such as a moving fishing bait or a propeller fin, it can also be suitably used for a mechanical device using an actuator as a drive unit.

  The laminate obtained by the electroless plating method of the present invention and the laminate of the present invention are laminates that can be driven as actuators, and can be used as actuators that cause bending displacement. Further, by combining the laminated body with a device that converts a bending motion into a linear motion, an actuator that generates a linear displacement can be obtained. An actuator that generates a linear displacement or a bending displacement can be used as a driving unit that generates a linear driving force or a driving unit that generates a driving force for moving a track-type orbit made of an arc portion. . Further, the actuator can be used as a pressing portion that performs a linear operation.

  That is, the actuator element is an OA device, an antenna, a device on which a person such as a bed or a chair is placed, a medical device, an engine, an optical device, a fixture, a side trimmer, a vehicle, a lifting device, a food processing device, a cleaning device, or a measuring device. , Inspection equipment, control equipment, machine tools, processing machines, electronic equipment, electron microscopes, electric razors, electric toothbrushes, manipulators, masts, amusement equipment, amusement equipment, vehicle simulation equipment, vehicle occupant restraining devices, and aircraft accessories In a stretching device, a driving unit that generates a linear driving force or a driving unit that generates a driving force for moving a track-type track composed of an arcuate portion, or a pressing unit that performs a linear operation or a curved operation Can be suitably used. The actuator element is, for example, a track type composed of a drive unit or a circular arc part that generates a linear drive force in valves, brakes, and lock devices used in all machines including the above-mentioned equipment such as OA equipment and measurement equipment. It can be used as a driving unit that generates a driving force for moving the track, or a pressing unit that performs a linear operation. In addition to the above-mentioned devices, devices, instruments, etc., in general mechanical devices, a positioning device drive unit, a posture control device drive unit, a lifting device drive unit, a transport device drive unit, and a movement device drive unit It can be suitably used as a drive unit for an adjustment device such as an amount and a direction, a drive unit for an adjustment device such as a shaft, a drive unit for a guidance device, and a pressing unit for a pressing device. In addition, since the actuator element can perform a rotational movement, the drive unit of the switching device, the drive unit of the reversing device such as the conveyed product, the drive unit of the winding device such as a wire, the drive unit of the traction device It can also be used as a drive unit for a swiveling device in the left-right direction such as swinging.

  The actuator element includes, for example, a drive unit of an inkjet part in an inkjet printer such as a CAD printer, a drive unit that displaces the optical axis direction of the light beam of the printer, a head drive unit of a disk drive device such as an external storage device, and the like. It can be suitably used as a drive unit for a paper pressing contact force adjusting means in a paper feeding device of an image forming apparatus including a printer, a copying machine, and a fax machine.

  The actuator element includes, for example, a measurement unit for moving a high frequency power supply unit such as a frequency sharing antenna for radio astronomy to the second focal point, a drive unit for a drive mechanism for moving the power supply unit, and a vehicle mounted pneumatic operation It can be suitably used for a drive part of a lift mechanism in a mast such as a telescopic mast (telescoping mast) or an antenna.

  The actuator element includes, for example, a massage unit driving unit of a chair-shaped massage machine, a nursing or medical bed driving unit, a driving unit of a posture control device for an electric reclining chair, a reclining used for a massage machine or an easy chair, etc. Backrest of chair / Extension rod drive that allows ottoman to move up and down, chair backrest, legrest, etc. It can be suitably used for a drive unit used for turning the bed bed or the like and a drive unit for controlling the posture of the standing chair.

  The actuator element is, for example, a driving unit of a testing device, a driving unit of a pressure measuring device such as a blood pressure used in an extracorporeal blood treatment device, a driving unit of a catheter, an endoscope device, forceps, or the like, and an ultrasonic wave. Drive unit of a cataract surgery device, a drive unit of an exercise device such as a jaw movement device, a drive unit of a means for relatively expanding and contracting a chassis member of a hoist for sick people, and raising / lowering, moving and posture control of a care bed It can use suitably for the drive part for etc.

  The actuator element includes, for example, a vibration isolator driving unit that attenuates vibration transmitted from a vibration generating unit such as an engine to a vibration receiving unit such as a frame, and a valve operating unit driving unit for an intake and exhaust valve of an internal combustion engine. It can be suitably used as a drive unit for an engine fuel control device and a drive unit for an engine fuel supply device such as a diesel engine.

  The actuator element drives, for example, a driving unit of a calibration device of an imaging apparatus with a camera shake correction function, a driving unit of a lens driving mechanism such as a home video camera lens, and a moving lens group of an optical device such as a still camera or a video camera. Drive unit of mechanism, drive unit of camera autofocus unit, drive unit of lens barrel used in imaging device such as camera, video camera, drive unit of auto guider that captures light of optical telescope, stereoscopic camera, binoculars, etc. A lens drive mechanism or lens barrel drive unit of an optical device having two optical systems, a drive unit or a pressing unit that applies a compressive force to a wavelength conversion fiber of a fiber-type wavelength tunable filter used for optical communication, optical information processing, optical measurement, or the like It can be suitably used for a driving unit of a camera unit, an optical axis alignment device driving unit, and a shutter mechanism of a camera.

  The actuator element can be suitably used, for example, for a pressing portion of a fixture such as caulking and fixing a hose fitting to a hose body.

  The actuator element includes, for example, a driving unit such as a winding spring of an automobile suspension, a driving unit of a fuel filler lid opener for unlocking a fuel filler lid of a vehicle, a driving unit for driving the extension and retraction of a bulldozer blade, and a transmission for an automobile. It can be suitably used for a drive unit of a drive device for automatically switching the gear ratio of the machine or for automatically connecting and disconnecting the clutch.

  The actuator element includes, for example, a driving unit of a lifting device of a wheelchair with a seat plate lifting device, a driving unit of a lifting machine for level difference, a driving unit of a lifting / lowering transfer device, a medical bed, an electric bed, an electric table, an electric chair, a nursing care Bed, elevating table, CT scanner, truck cabin tilt device, lifter, etc., and elevating drive unit for various elevating machine devices, and drive unit for heavy vehicle transport special vehicle unloading device. .

  The actuator element can be suitably used for, for example, a drive unit of a discharge amount adjusting mechanism such as a food material discharge nozzle device of a food processing apparatus.

  For example, the actuator element can be suitably used in a drive unit such as a carriage or a cleaning unit of a cleaning device.

  The actuator element is, for example, a driving unit of a measuring unit of a three-dimensional measuring apparatus that measures the shape of a surface, a driving unit of a stage device, a driving unit of a sensor part such as a detection system for tire operating characteristics, and an impact response of a force sensor. The drive unit of the device that gives the initial speed of the evaluation device, the drive unit of the piston drive device of the piston cylinder of the device including the in-hole water permeability test device, the drive unit for moving in the elevation angle direction of the concentrating tracking power generation device, the gas concentration XYθ table when alignment is required in the driving unit of the tuning mirror vibration device of the sapphire laser oscillation wavelength switching mechanism of the measuring device including the measuring device, the inspection device of the printed circuit board, and the inspection device of the flat panel display such as liquid crystal and PDP Drive unit, electron beam (E beam) system or focused ion beam (FIB) system Adjustable aperture device drive unit used in charged particle beam systems, etc., etc., flatness measuring device support device or detection unit drive unit, as well as assembly of fine devices, semiconductor exposure devices and semiconductors It can be suitably used for a driving unit of a precision positioning device such as an inspection device or a three-dimensional shape measuring device.

  The actuator element can be suitably used for, for example, an electric razor drive unit and an electric toothbrush drive unit.

  The actuator element, for example, a three-dimensional object imaging device or a drive unit of a focal depth adjustment device of a CD / DVD shared readout optical system, and a plurality of actuator elements to change the shape of the surface to be driven as an active curved surface. The drive unit of the variable mirror that can form the desired curved surface approximately and easily change the focal position, and the drive unit of the disk device that can linearly move the moving unit having at least one of the magnetic heads such as an optical pickup , Magnetic tape head actuator element assembly head drive mechanism drive unit for linear tape storage system, etc., drive unit for image forming apparatus applied to electrophotographic copying machine, printer, facsimile, etc., mounting member such as magnetic head member Light that controls the drive of the focusing lens group in the optical axis direction Drive unit of disk master exposure device, drive unit of head drive means for driving optical head, drive unit of information recording / reproducing device for recording information on recording medium or reproducing information recorded on recording medium, and circuit cutoff It can be suitably used for a drive unit for opening / closing operation of a power supply (circuit breaker for power distribution).

  The actuator element includes, for example, a drive unit of a rubber composition press molding vulcanizing device, a driving unit of a component aligning device that aligns a transferred component into a single row / single layer and a predetermined posture, and a compression molding device. Drive unit, welding device holding mechanism drive unit, bag making and filling machine drive unit, machine tool such as machining center, drive unit such as injection molding machine and press machine, etc., printing device, coating device and lacquer Drive unit for fluid application device such as spraying device, drive unit for manufacturing device for manufacturing camshaft, etc., drive unit for lifting device for lining material, drive device for tufted ear regulating body in non-woven loom, tufting machine Needle drive system, looper drive system, drive unit such as knife drive system, drive unit of polishing device that polishes parts such as cam grinder and ultra-precision machined parts, brake device for hook frame in loom Of a moving part, a driving part of an opening device for forming an opening part of a warp for inserting a weft in a loom, a driving part of a protective sheet peeling device such as a semiconductor substrate, a driving part of a threading device, and an assembly device of an electron gun for CRT Drive unit of shifter fork drive selection linear control device and drive of horizontal movement mechanism of annealing window drive device in torsion race machine for manufacturing torsion race with application to drive unit, clothing decoration, table cloth and seat cover etc. , Glass melting furnace fore Haas support arm drive unit, drive unit for moving the rack of the exposure device such as the fluorescent screen forming method of the color picture tube, the drive unit of the torch arm of the ball bonding apparatus, the XY direction of the bonding head Drive of components, mounting of chip components and driving of components in measurement using probes, etc. Moving part, raising / lowering driving part of the cleaning tool support of the substrate cleaning apparatus, driving part for moving the detection head scanned on the glass substrate forward / backward, driving part of the positioning apparatus of the exposure apparatus for transferring the pattern onto the substrate, precision processing, etc. Used when manufacturing circuit devices such as conductor circuit elements and liquid crystal display devices in the sub-micron order in the field, driving units for micro-positioning devices, positioning units for chemical mechanical polishing tool measuring devices, and conductor circuit elements and liquid crystal display elements. A drive unit for positioning a stage device suitable for an exposure apparatus and a scanning exposure apparatus, a drive unit for means for conveying or positioning a workpiece, etc., a drive unit for positioning and conveying a reticle stage, a wafer stage, etc., a chamber In precision positioning stage device, workpiece in chemical mechanical polishing system Or a drive unit for semiconductor wafer positioning device, a drive unit for semiconductor stepper device, a drive unit for device that accurately positions in the processing machine introduction station, a machine tool such as NC machine or machining center, or a stepper in the IC industry. The reference grating plate of the light beam scanning device in the drive unit of the passive vibration isolation device for various representative devices and the vibration isolation device for active vibration isolation, the exposure device used in the lithography process for manufacturing semiconductor elements and liquid crystal display elements, etc. It can be suitably used for a drive unit that displaces the light beam in the optical axis direction, and a drive unit for a transfer device that transfers the light beam into the article processing unit in the transverse direction of the conveyor.

  The actuator element can be suitably used for, for example, a drive unit for a probe positioning device of a scanning probe microscope such as an electron microscope and a drive unit for positioning an electron microscope sample fine movement device.

  The actuator element is, for example, an automatic welding robot, a robot including an industrial robot or a nursing robot, or a joint mechanism represented by a wrist of a robot arm in a manipulator, a joint drive other than a direct drive type, a robot To operate a minute object in an arbitrary state in the movement part of a slide opening and closing type chuck device used as a hand of a robot or the like, a micro-manipulation operation of a cell or a micro part It can be suitably used for a driving unit of a micromanipulator, a driving unit of a prosthesis such as an electric prosthesis having a plurality of fingers that can be opened and closed, a driving unit of a handling robot, a driving unit of a prosthesis, and a driving unit of a power suit.

  The actuator element can be suitably used for, for example, a pressing portion of a device that presses an upper rotary blade or a lower rotary blade of a side trimmer.

  The actuator element is preferably used for, for example, a driving unit for an accessory in a game device such as a pachinko machine, a driving unit for an amusement device such as a doll or a pet robot, and a driving unit for a simulation device of a boarding simulation device. it can.

  The actuator element can be used, for example, in a valve drive unit used in general machines including the above-described devices. For example, a valve drive unit of an evaporative helium gas reliquefaction device, a bellows pressure-sensitive control valve A drive unit, a drive unit of an opening device that drives the frame, a drive unit of a vacuum gate valve, a drive unit of a solenoid-operated control valve for a hydraulic system, a drive unit of a valve incorporating a motion transmission device using a pivot lever, It can be suitably used for the drive unit of the rocket movable nozzle valve, the drive unit of the suck back valve, and the drive unit of the pressure regulating valve unit.

  The actuator element can be used, for example, as a pressing portion of a brake used in all machines including the above devices. For example, braking suitable for use in an emergency brake, a safety brake, an elevator brake, or an elevator brake. It can be used suitably for the pressing part of the device and the pressing part of the brake structure or brake system.

  The actuator element can be used, for example, as a pressing portion of a locking device used in all machines including the above devices, etc., for example, a pressing portion of a mechanical locking device, a pressing portion of a vehicle steering lock device, and a load It can be suitably used for a pressing portion of a power transmission device having both a limiting mechanism and a coupling release mechanism.

  Hereinafter, although the Example and comparative example of this invention are shown, this invention is not limited to these.

Example 1
(Swelling process)
A membrane polymer electrolyte (fluorine resin-based ion exchange resin: perfluorocarboxylic acid resin, trade name “Flemion”, manufactured by Asahi Glass Co., Ltd., ion exchange capacity 1.4 meq / g) having a film thickness of 170 μm at the time of drying is a swelling solvent. It was immersed in methanol at 20 ° C. for 1 hour or longer. The film thickness of the swollen membrane-shaped polymer electrolyte was measured, and the ratio [swelling degree (%)] of the film thickness after swelling to the dry film thickness was calculated. The membrane polymer electrolyte was immersed in a swelling solvent so that the value (50%) was obtained.

(Electroless plating process)
After the membrane polymer electrolyte was swollen with a swelling solvent, the following steps (1) to (3) were repeated 6 times to obtain a polymer electrolyte (laminate) having a metal layer formed thereon. (1) Adsorption step: Immerse in dichlorophenanthroline gold chloride aqueous solution for 12 hours to adsorb dichlorophenanthroline gold complex in the molded product, (2) Reduction step: Adsorbed dichlorophenanthroline gold complex in aqueous solution containing sodium sulfite And a gold electrode was formed on the membrane polymer electrolyte. At this time, the temperature of the aqueous solution was set to 60 to 80 ° C., and the dichlorophenanthrine gold complex was reduced for 6 hours while gradually adding sodium sulfite. Next, (3) washing step: The membrane polymer electrolyte having a gold electrode formed on the surface was taken out and washed with water at 70 ° C. for 1 hour. The polymer electrolyte on which the metal layer was formed was cut into a size of 1 mm × 20 mm to obtain a laminate of Example 1.

(Example 2)
A laminate of Example 2 was obtained in the same manner as in Example 1 except that the dipping time was shortened to set the degree of swelling to 40%.

(Example 3)
As a membrane polymer electrolyte, a membrane polymer electrolyte with a film thickness of 170 μm (fluorine resin-based ion exchange resin: perfluorocarboxylic acid resin, trade name “Flemion”, manufactured by Asahi Glass Co., Ltd., ion exchange capacity 1.8 meq / g) A laminate of Example 3 was obtained in the same manner as in Example 1 except that a methanol-water mixed solvent (methanol: water = 3: 7) was used as the swelling solvent.

(Example 4)
As a membrane polymer electrolyte, a membrane polymer electrolyte with a film thickness of 170 μm (fluorine resin-based ion exchange resin: perfluorocarboxylic acid resin, trade name “Flemion”, manufactured by Asahi Glass Co., Ltd., ion exchange capacity 1.8 meq / g) A laminate of Example 4 was obtained in the same manner as in Example 1 except that a methanol-water mixed solvent (methanol: water = 4: 6) was used as the swelling solvent.

(Examples 5 and 6)
In the same manner as in Example 1 except that dimethyl sulfoxide (DMSO) (Example 5) or N-methylpyrrolidone (NMP) (Example 6) was used instead of methanol as the swelling solvent. A laminate or a laminate of Example 6 was obtained.

(Example 7)
A laminate of Example 7 was obtained in the same manner as in Example 1 except that the steps (1) to (3) of Example 1 were performed for 4 cycles.

(Example 8)
Instead of a membrane polymer electrolyte with an ion exchange capacity of 1.4 meq / g, a membrane polymer electrolyte with an ion exchange capacity of 1.1 meq / g (perfluorocarboxylic acid resin, trade name “Flemion”, manufactured by Asahi Glass Co., Ltd.) A laminate of Example 8 was obtained in the same manner as in Example 1 except that it was used.

Example 9
The same as in Example 1 except that the dipping time was increased and the swelling degree was adjusted to 80%, and instead the process cycles of (1) to (3) in Example 1 were reduced to one time. The laminate of Example 9 was obtained by the method.

(Example 10)
Prior to immersion in methanol, a step of immersing in a 10% aqueous solution of TEAOH at 20 ° C. for about 2 hours was performed, and the process cycles (1) to (3) of Example 1 were performed once. A laminated body of Example 10 was obtained in the same manner as in Example 1 except that.

Example 11
As a swelling solvent, the polymer electrolyte was immersed in the swelling solvent using a 10% methanol mixed solution of TEAOH so that the swelling degree was 120%, and the process cycle of (1) to (3) of Example 1 A laminate of Example 11 was obtained in the same manner as in Example 1 except that the number of times was set to 1.

Example 12
As a swelling solvent, a 10% methanol mixed solution of tetrapropylammonium hydroxide was used to immerse the polymer electrolyte in the swelling solvent so that the degree of swelling was 140%, and (1) to (3) of Example 1 A laminate of Example 12 was obtained in the same manner as in Example 1 except that the number of process cycles was set to 1.

(Example 13)
Except that the polymer electrolyte was immersed in the swelling solution using a 10% aqueous solution of tetraethylammonium hydroxide (TEAOH) instead of methanol as the swelling solvent so that the degree of swelling was 30%, the same method as in Example 1 was used. And the laminated body of Example 13 was obtained.

(Comparative Examples 1-3)
(Electroless plating process)
Unlike the Example, the electroless plating process was performed without passing through the swelling process. The membrane-like polymer electrolyte (fluorine resin ion exchange resin: perfluorocarboxylic acid resin, trade name “Flemion”, manufactured by Asahi Glass Co., Ltd., ion exchange capacity: listed in Table 3) having a thickness of 170 μm at the time of drying is as follows ( The steps 1) to (3) were repeated 6 cycles to obtain a polymer electrolyte having a metal layer formed thereon. (1) Adsorption step: Immerse in dichlorophenanthroline gold chloride aqueous solution for 12 hours to adsorb dichlorophenanthroline gold complex in the molded product, (2) Reduction step: Adsorbed dichlorophenanthroline gold complex in aqueous solution containing sodium sulfite Was reduced to form a gold electrode on the membranous polymer electrolyte. At this time, the temperature of the aqueous solution was set to 60 to 80 ° C., and the dichlorophenanthrine gold complex was reduced for 6 hours while gradually adding sodium sulfite. Next, (3) washing step: The membrane polymer electrolyte having a gold electrode formed on the surface was taken out and washed with water at 70 ° C. for 1 hour. The polymer electrolyte on which the metal layer was formed was cut into a size of 1 mm × 20 mm to obtain a laminate of each comparative example. The laminates of Comparative Examples 1 to 3 are shown in Table 3. In addition, as a swelling degree of the comparative example in Table 3, the swelling degree was measured after immersing in a dichlorophenanthroline gold chloride aqueous solution for 12 hours in the first adsorption step.

(Comparative Example 4)
In the swelling process described in Example 1, when the polymer electrolyte was immersed in a methanol single solvent at 60 ° C. until the degree of swelling became 120%, the laminate of Comparative Example 4 was prepared. Gelation occurred during methanol immersion.

[Evaluation]
(Displacement distance)
The laminates of Examples 1 to 12 and Comparative Examples 1 to 3 and 5 were each used as a working electrode, and a platinum plate was used as a counter electrode. Hold each working electrode and counter electrode in water, connect each electrode end to a power source via a lead, apply voltage (1Hz, 2.0V rectangular wave), and measure the amount of bending displacement did. In addition, the displacement amount was fixed at a position of 18 mm from one end of Examples 1 to 12 and Comparative Examples 1 to 3 and 5, and the displacement amount of the tip was measured from the fixed position when a voltage was applied. The results are shown in Tables 1-3.

(Electric double layer capacity)
The electric double layer capacity (measurement method A) was measured under the measurement conditions of 0.1 mV / sec and ± 0.5 V using a known cyclic voltammetry method. As an actual measurement value of the electric double layer capacity of the cyclic voltammetry method, a trade name “Potentio Galvanostat Model 263A” (manufactured by Princeton Applied Research) was used. On the other hand, the measured value of the electric double layer capacity (measurement method B) by the constant current discharge method is measured in accordance with the standard number EIAJ RC-2377 using the trade name “HJ-201B” (made by Hokuto Denko). It is the value. In Examples 1 to 12 and Comparative Examples 1 to 3 and 5, the constituent ions of the laminated body element in the electric double layer capacity measurement are sodium ions. The obtained measurement results are shown in Tables 1-3.

  Moreover, about the laminated body of Example 1, and the laminated body of the comparative example 1, when applied voltage (V) is set to +/- 2.0, +/- 1.5, and +/- 1.0, it is displaced by said method, respectively. The amount was measured. The results are shown in Table 4.

  The laminates of Examples 1 and 2 obtained by the electroless plating method of the present invention had a swelling degree of 50% and 40% in the swelling step, that is, the thickness of the used polymer electrolyte in the swollen state (swelling) The film thickness of the membrane-shaped polymer electrolyte was 150% and 140% of the thickness of the polymer electrolyte in a dried state (dry film thickness), and the displacement was 25 mm. And 24 mm. On the other hand, the laminate of Comparative Example 1, which is a laminate obtained by the conventional electroless plating method, has a swelling degree of 5%, that is, the thickness (swelling) of the used polymer electrolyte in the swelling process. Film thickness of the polymer electrolyte) was 105% of the dry thickness of the polymer electrolyte (dry film thickness), and the displacement was 11 mm. . When the laminates of Examples 1 and 2 were driven as actuators, the displacement amount was more than twice that of the laminate obtained by the conventional method.

  The laminates of Examples 3 and 4 are cases where a mixed solvent containing a good solvent is used as a swelling solvent in the swelling step, and the degree of swelling is 30%, that is, the thickness of the used polymer electrolyte in the swollen state. This is a case where (the film thickness of the swollen membrane-like polymer electrolyte) was 130% of the thickness of the polymer electrolyte in a dried state (dry film thickness), and the displacement was 21 mm and It was 20 mm. On the other hand, the laminate of Comparative Example 2 in which the ion exchange resin having the same ion exchange capacity as that of the laminates of Examples 2 and 3 was used had a swelling degree of 5%, that is, the polymer used. The thickness of the electrolyte in the swollen state (film thickness of the swollen membrane-shaped polymer electrolyte) was 105% of the thickness of the polymer electrolyte in the dried state (dry film thickness). The displacement amount was 11 mm. When the laminates of Examples 3 and 4 were driven as actuators, the displacements were more than twice as good as the laminates obtained by the conventional method.

  Similarly, the laminates of Examples 5 and 6 are cases where a good solvent other than methanol was used as the swelling solvent, and the laminate of Comparative Example 3 using an ion exchange resin having the same ion exchange capacity of 1.1 meq / g. The displacement amount was more than twice that of the body.

  When the laminate of Example 7 is driven as an actuator, the laminate has a displacement equivalent to that of the laminate of Comparative Example 1. By using the electroless plating method of the present invention, the adsorption step, It can be obtained by repeating the cycle of the reduction process and the cleaning process four times, and can shorten the process by 1/3 compared with the conventional electroless plating method. Since the cycle of the adsorption process, the reduction process and the cleaning process takes one day all night, it takes at least 6 days to obtain a laminate by the conventional electroless plating method, whereas in the electroless plating method of the present invention, Even if one day is required for the swelling process, it takes 5 days, so the laminate can be produced as a daily production work form, and the production workability as an industry is good.

  Furthermore, as in Examples 10 to 12, the polymer electrolyte can be swollen so as to be gelled with a good solvent alone by passing through a swelling step using a basic salt. For this reason, even when the number of cycles of the electroless plating method is reduced to one by sufficiently increasing the degree of swelling of the polymer electrolyte using a basic salt in the swelling step, the lamination of Examples 10-12 Like the body, a layered body having the same performance as the layered body shown in the other examples produced with the good solvent alone can be obtained. That is, instead of the good solvent only swelling step, a swelling step using a basic salt-containing good solvent is used, or in an aqueous solution in which the basic salt is dissolved in the previous or subsequent step in the good solvent only swelling step. Since the time in the subsequent electroless plating step can be shortened by providing the swelling step, the production efficiency as a whole can be further improved in the production of the laminate of the present invention.

  The laminate of Example 13 was prepared by electroless plating after swelling a polymer electrolyte using a 10% aqueous solution of tetraethylammonium hydroxide as an aqueous solution of a salt containing ions exchangeable with exchange groups of the ion exchange resin. It is the laminated body which has a metal electrode on the polymer electrolyte obtained by performing. This laminate also showed excellent displacement.

  Further, as shown in Table 4, the laminate of Example 1 obtained by the electroless plating method of the present invention has a larger difference in displacement than the laminate of Comparative Example 1 as the applied voltage is lowered. The displacement amount of the laminate of Example 1 when the applied voltage is ± 1.0 (V) is 6 times or more that of Comparative Example 1, and the displacement amount is almost equivalent to the applied voltage ± 2.0 (V). It is. In other words, when the laminate obtained by the electroless plating method of the present invention is used for an actuator for a use in which the displacement amount by driving is the same as the conventional displacement amount, the laminate obtained by the conventional electroless plating method is used. Compared with the above, the energy efficiency is good and the applied voltage can be reduced, so that the energy consumption can be greatly reduced. This is considered to be due to the fact that the electric double layer capacity of the laminate obtained by the electroless plating method of the present invention is larger than the electric double layer capacity of the laminate obtained by the conventional electroless plating method. .

The electroless plating method of the present invention can be used for producing the laminate of the present invention in which a metal layer is formed on a polymer electrolyte. Since the laminate of the present invention has a property of bending when a voltage is applied to a metal layer, for example, it can be used as an actuator. Specifically, a positioning device, a posture control device, a lifting device, a transport device, a moving device, an adjusting device, an adjusting device, a guiding device, a joint device, a switching device, a reversing device, using the laminate of the present invention as a drive unit, The present invention can be used for a winding device, a traction device, a turning device, etc., a pressing device using a laminated body as a pressing portion, and the like. In addition, since the laminate of the present invention forms an electric double layer between the metal layer and the polymer electrolyte, it can also be used as an electric double layer capacitor.

Claims (8)

As a pretreatment step for electroless plating on the polymer electrolyte, a swelling step of allowing the polymer electrolyte to swell by infiltrating a good solvent or a mixed solvent containing a good solvent, and
An adsorption step of adsorbing a metal complex to the swollen polymer electrolyte;
A reduction step of forming a metal layer with the polymer electrolyte by bringing a reducing agent solution into contact with the polymer electrolyte to which the metal complex is adsorbed, and a method for producing a laminate for an actuator element,
The polymer electrolyte in the swelling step has a predetermined shape,
The thickness of a state swollen in the polymer electrolyte, the thickness in dry state of the polymer electrolyte state, and are more than 110%,
The polymer electrolyte is an ion exchange resin;
The good solvent contains at least one selected from the group consisting of methanol, ethanol, propanol, hexafluoro-2-propanol, dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide, ethylene glycol, diethylene glycol, and glycerin. A method for manufacturing a laminate for an actuator element. 2. The actuator element according to claim 1, wherein a thickness of the polymer electrolyte in a swollen state is 110 to 240% with respect to a thickness of the polymer electrolyte in a dried state . A manufacturing method of a layered product. The swelling step reduces the crystallinity of the polymer electrolyte by penetrating the good solvent or a mixed solvent containing the good solvent into the polymer electrolyte, and at least in the polymer constituting the polymer electrolyte. The method for producing a laminate for an actuator element according to claim 1 or 2, wherein the entanglement of the side chain having a functional group is relaxed . The said good solvent contains at least 1 sort (s) selected from the group which consists of methanol, ethanol, and a propanol , The manufacturing method of the laminated body for actuator elements in any one of Claims 1-3 characterized by the above-mentioned . The good solvent is, the manufacturing method of the actuator element for laminate according to claim 1, characterized in that it contains methanol. The method for producing a laminate for an actuator element according to claim 1, wherein the good solvent further contains a basic salt . The electric double layer capacity measured by the cyclic voltammetry method at the interface between the metal layer and the polymer electrolyte layer is 3 mF / cm ² or more when the dry film thickness of the polymer electrolyte is converted to 170 μm. The method for producing a laminated body for an actuator element according to any one of claims 1 to 6, wherein: Electric double layer capacitor according to a constant current discharge method of the interface between the polymer electrolyte layer and the metal layer is, actuator according to any one of claims 1 to 7, characterized in that 2.0 F / cm ³ or more A method for producing a laminated body for an element .