WO2008029839A1 - Remplissage d'un actionneur polymère d'une solution électrolytique, choix du module élastique de l'actionneur polymère et production d'un actionneur polymère - Google Patents

Remplissage d'un actionneur polymère d'une solution électrolytique, choix du module élastique de l'actionneur polymère et production d'un actionneur polymère Download PDF

Info

Publication number
WO2008029839A1
WO2008029839A1 PCT/JP2007/067295 JP2007067295W WO2008029839A1 WO 2008029839 A1 WO2008029839 A1 WO 2008029839A1 JP 2007067295 W JP2007067295 W JP 2007067295W WO 2008029839 A1 WO2008029839 A1 WO 2008029839A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
polymer actuator
actuator element
electrolyte
solution
Prior art date
Application number
PCT/JP2007/067295
Other languages
English (en)
Japanese (ja)
Inventor
Kengo Ito
Original Assignee
Eamex Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eamex Corporation filed Critical Eamex Corporation
Publication of WO2008029839A1 publication Critical patent/WO2008029839A1/fr

Links

Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03GSPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
    • F03G7/00Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for
    • F03G7/005Electro-chemical actuators; Actuators having a material for absorbing or desorbing gas, e.g. a metal hydride; Actuators using the difference in osmotic pressure between fluids; Actuators with elements stretchable when contacted with liquid rich in ions, with UV light, with a salt solution
    • HELECTRICITY
    • H02GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02NELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N11/00Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
    • H02N11/006Motors

Definitions

  • Electrolytic solution filling method for polymer actuator element elastic modulus control method for polymer actuator element, and method for producing polymer actuator element
  • the present invention relates to a method for filling an electrolyte solution of a polymer actuator element, a method for controlling an elastic modulus of the polymer actuator element, and a method for manufacturing the polymer actuator element. More specifically, the present invention relates to a polymer activator element that functions as an activator element by applying a voltage to a pair of metal electrodes formed so as to be in contact with an electrolyte containing an ion exchange resin. The present invention relates to a method for filling an electrolyte, a method for controlling the elastic modulus of a polymer actuator element, and a method for manufacturing a polymer actuator element.
  • a conventional polymer actuator element an ion exchange resin molded product and a metal electrode formed in a mutually insulated state on the surface of the ion exchange resin molded product, the ion exchange resin molded product is provided.
  • a polymer actuator element that functions as an actuator element by applying a potential difference between the metal electrodes in a water-containing state to cause displacement or deformation of the ion-exchange resin molded product (for example, Patent Documents). 1).
  • polymer actuator elements are lightweight and flexible, they are expected to be suitably used as introduction parts for medical devices such as catheters.
  • the polymer actuator element is light in weight and simple in configuration, it is expected to be applied as various driving devices and pressing devices.
  • the polymer actuator element can drive a large displacement or displacement for a long time by applying a voltage to a pair of metal electrodes. It is. However, in a state where the polymer actuator element is taken out from the aqueous solution and the polymer actuator element is installed in the air, the water as the electrolyte medium evaporates with time, so that the charge carrier over time. Some ions will not move. Thus, water or aqueous solution can be used as an electrolyte medium. It was found that the above-described polymer actuator element used as a device could not maintain the initial driving (displacement amount) for 1 hour when exposed to air without coating!
  • the polymer actuator element is expected to be used in driving devices in various devices in order to bend or displace.
  • the high-molecular-weight actuator element cannot maintain the initial displacement (driving performance) for even 1 hour, so that driving in an environment other than in an aqueous solution is virtually impossible. Still difficult. For this reason, in the case where the polymer actuator element is used in a driving device of various devices, there are still limited applications.
  • the coating layer is cracked by driving the polymer actuator element. If galling occurs, water will also evaporate the polymer actuator element force over time. Therefore, the polymer actuator element can maintain the initial driving performance only for about 20 minutes in the open system at room temperature and normal pressure when the coating layer is not provided, and is provided with the coating layer.
  • repeated driving causes a significant drop from the initial driving performance within a few hours due to cracking and wrinkling of the coating layer. For this reason, even when the polymer actuator element is coated, it must be driven while confirming that there is no cracking or cracking of the coating resin, especially when used for a long period of time. It becomes a problem.
  • an ion exchange resin is generally used for the polymer composite of the polymer actuator element.
  • a cationic compound or the like is preferred over a nonionic compound (nonionic organic compound) that coexists by an ion exchange action.
  • the polymer complex that has previously adsorbed a cation compound or the like significantly impairs the subsequent affinity with other solvents, especially the filling of nonionic components, As a result, it was found that the element film lacks flexibility, and the practical voltage response or environmental response is significantly insufficient.
  • the polymer actuator element is also required to have sufficient material hardness (elastic modulus) and responsiveness for practical use. Yes.
  • the polymer actuator element improves the elastic modulus.
  • the problem is that the responsiveness is inferior. For this reason, for practical use of the actuator element, there is a demand for a method of controlling the material hardness to any desired value without impairing responsiveness in a wider elastic modulus range.
  • Patent Document 1 Japanese Patent No. 2961125
  • an object of the present invention is to provide an electrolyte solution for a polymer activator element that can be easily filled with an electrolyte solution containing a liquid nonionic organic compound at room temperature and normal pressure. It is to provide a filling method.
  • an object of the present invention is to provide an elastic property of a high molecular weight actuator element that can easily adjust the elastic modulus of a high molecular weight element element having an electrolytic solution containing a liquid nonionic organic compound at room temperature and normal pressure. It is to provide a rate control method.
  • an object of the present invention is to provide a simple method for producing a polymer actuator element having an electrolytic solution containing a liquid nonionic organic compound at room temperature and normal pressure. Means for solving the problem
  • the present inventors have intensively investigated the electrolyte solution filling process of the polymer actuator element, and as a result, have used the following electrolyte solution filling method of the polymer actuator element. As a result, the inventors have found that the above problems can be solved, and have completed the present invention.
  • the method for filling an electrolyte solution of a polymer actuator element of the present invention is a method for filling an electrolyte solution of a polymer actuator element including a polymer composite having a metal electrode on a polymer electrolyte,
  • the first step and the second step are included.
  • this method it is possible to easily fill the polymer actuator element with an electrolytic solution containing a liquid nonionic organic compound at normal temperature and pressure.
  • a nonionic component such as the liquid nonionic compound is used.
  • the polymer electrolyte (or polymer composite) that is the base resin have a good balance of affinity and diffusivity, and as a result, nonionic ions such as the above liquid nonionic compounds It is presumed that the inhibition of the filling of the components can be reduced.
  • a nonionic compound particularly a nonionic polymer compound
  • the electrolyte medium has never been used as the electrolyte medium.
  • nonionic compounds are used as a medium (electrolyte medium)
  • the polymer electrolyte which is an ion exchange resin
  • the molecular chain of the polymer compound is entangled with the polymer electrolyte (ion exchange resin), or the movement of ions is hindered by the high molecular weight medium.
  • the electrolytic solution filling method of the present invention the polymer activator element can be easily filled with an electrolytic solution containing a nonionic compound.
  • the present invention preferably includes a step of performing plating using a metal complex solution containing an organic ion compound as a pre-step of the first step.
  • a metal complex solution containing an organic ion compound as a pre-step of the first step.
  • the nonionic organic compound is preferably an organic compound having a boiling point or a decomposition temperature of 180 ° C. or higher.
  • the nonionic organic compound is preferably a polyether compound such as polyethylene glycol, polypropylene glycol, and / or a similar compound thereof.
  • polyether compounds such as polyethylene glycol, polypropylene glycol, and / or a similar compound thereof.
  • the elastic modulus control method for a polymer actuator element of the present invention is a method for controlling the elastic modulus of a polymer actuator element including a polymer composite having a metal electrode on a polymer electrolyte.
  • the elastic modulus of the polymer actuator element can be easily controlled.
  • Power S can be. This makes it possible to easily prepare the electrolytic mass and the amount of the electrolyte contained in the polymer composite (polymer actuator element) by using the filling method including the second step, and as a result, This is presumably because the elastic modulus of the polymer actuator element can be controlled.
  • the method for producing a polymer actuator element of the present invention is a method for producing a polymer actuator element comprising a polymer composite comprising a metal electrode on a polymer electrolyte, the polymer composite comprising: A first step of immersing in a solution containing a liquid nonionic organic compound under normal temperature and pressure, and
  • the polymer complex is included in the polymer complex when immersed in a solution obtained by adding an electrolyte to the solution.
  • the electrolytic mass and the amount of the electrolytic solution may be adjusted.
  • the method for producing a polymer actuator element of the present invention includes the steps as described above, the polymer actuator having an electrolytic solution containing a liquid nonionic organic compound at room temperature and pressure.
  • An eta element can be easily manufactured.
  • a polymer actuator element having a controlled elastic modulus can be easily produced.
  • the polymer actuator element obtained by the above production method can be easily used for a wide variety of practical applications as an actuator element that produces displacement or bending displacement.
  • the polymer actuator element is suitable for applications that require long-term driving.
  • by combining the polymer actuator element with a device that converts a bending motion into a linear motion it is possible to provide an actuator that generates a linear displacement.
  • An actuator that generates a linear displacement or a bending displacement can be used as a drive unit that generates a linear drive force or a drive unit that generates a drive force for moving a track-type track composed of an arcuate portion.
  • the above-described actuator can also be used as a pressing portion that performs a linear operation.
  • a method for filling an electrolyte solution of a polymer actuator element of the present invention includes a method for filling an electrolyte solution of a polymer actuator element including a polymer composite having a metal electrode on a polymer electrolyte.
  • the elastic modulus control method for a polymer actuator element of the present invention is a method for controlling the elastic modulus of a polymer actuator element comprising a polymer composite having a metal electrode on a polymer electrolyte,
  • the polymer actuator element in the present invention is a polymer actuator element including a polymer composite provided with a metal electrode on a polymer electrolyte.
  • a polymer actuator element including a metal electrode and an electrolyte including a polymer electrolyte, wherein the metal electrode is formed so as to form a pair, and the metal electrode is It is in contact with the electrolyte and contains a nonionic organic compound that is liquid at normal temperature and pressure, in particular, a boiling point or decomposition temperature of 180 ° C or higher and a liquid organic compound that is liquid at normal temperature and pressure.
  • a nonionic organic compound that is liquid at normal temperature and pressure
  • a boiling point or decomposition temperature of 180 ° C or higher
  • a liquid organic compound that is liquid at normal temperature and pressure.
  • the polymer actuator element is a nonionic organic compound that is liquid in the electrolyte at room temperature and normal pressure, particularly a liquid organic compound or polysiloxane that has a boiling point or decomposition temperature of 180 ° C or higher at room temperature and normal pressure.
  • the ether compound By including the ether compound, the bending amount or the displacement amount of the actuator element hardly changes over time even in an open system at room temperature and normal pressure. For this reason, the polymer actuator element can be driven outside the solution, that is, in the air as an open system, and since there is almost no evaporation of the electrolyte medium solution, it can be driven for a long period of time. Is preferred.
  • the nonionic organic compound is not particularly limited as long as it has an ionic functional group or an ionic moiety in the molecular structure, and can be used as appropriate.
  • the organic compound may be an organic compound that can serve as a salt solvent containing ions that serve as charge carriers, or an organic compound that can serve as charge carriers.
  • the nonionic organic compound has a boiling point or decomposition temperature of 180 ° C or higher, and is preferably liquid at normal temperature and pressure, and also has a function as a solvent. Further, an organic solvent having a boiling point of 245 ° C. or higher is more preferable. These compounds may be used alone or in admixture of two or more.
  • nonionic organic compound examples include diethylene glycol, glycerin, glycerin carbonate, sulfolane, propylene carbonate, butyrolatatone, and polyether compounds.
  • diethylene glycol, glycerin carbonate, sulfolane, and polyether compounds are preferred. It is particularly preferable to use a monotel compound.
  • the polyether compound is not particularly limited as long as it is liquid at normal temperature and pressure.
  • the above polyether compound also has a function as a solvent.
  • the polyether compound may be any polyether compound that can serve as a salt solvent containing ions that serve as charge carriers, or any polyether compound that can serve as charge carriers. These polyether compounds may be used alone or in admixture of two or more.
  • the polyether compound is not particularly limited as long as it is a compound having an ether structure as a repeating unit, such as an alkylene oxide (oxyalkylene) unit, among which ethylene oxide (oxyethylene) More preferably, it is a compound having a unit or propylene oxide (oxypropylene) as a repeating unit.
  • an alkylene oxide (oxyalkylene) unit among which ethylene oxide (oxyethylene) More preferably, it is a compound having a unit or propylene oxide (oxypropylene) as a repeating unit.
  • polyether compounds examples include those having a structure in which the number of added moles (the number of repeating units) of oxyalkylene units such as alkylene oxide (oxyalkylene) units is repeated by 3 units or more. And homopolymers and copolymers having a high molecular weight in a branched or branched manner, compounds containing these polymer structures, analogs thereof, ether type surfactants, and ether type plasticizers.
  • polyether compound for example, polyethylene glycolate, polypropylene glycolole, polyethylene glycolate and polypropylene glycolole, polyoxyethylene lauryl sulfate triethanolamine, polyoxyethylene Examples include sodium lauryl sulfate, polyoxyethylene methyl darcoside, polyetherol ester, and analogs thereof.
  • polyethylene glycol, polypropylene glycol, and / or their related compounds it is preferable to use polyethylene glycol, polypropylene glycol, and / or their related compounds.
  • examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, and polypropylene glycol copolymers (polyoxyethylene polyoxypropylene glycol).
  • polypropylene glycol polyethylene glycol polypropylene glycol Block copolymer polypropylene Examples thereof include a block copolymer of lenglycol glycol, a polyethylene glycol glycol block copolymer, a polyethylene glycol polypropylene glycol, a block copolymer of polyethylene glycol, and a random copolymer of polypropylene glycol-polyethylene glycol.
  • the end of the glycol chain may be a hydroxyl group or may be substituted with an alkyl group, a phenyl group or the like. These compounds may be used alone or in combination of two or more.
  • ether type surfactant examples include polyoxyalkylene alkyl ether sulfates such as polyethanolamine lauryl sulfate triethanolamine and sodium polyoxyethylene lauryl sulfate. These compounds may be used alone or as a mixture of two or more.
  • the number of moles of the oxyalkylene unit added (the number of repeating units) of the polyether compound is preferably 3 to 100 force S, more preferably 3 to 30, from the viewpoint of interaction with ions. 10 is more preferred. If the number of moles of oxyalkylene units added is less than 3, it may be difficult to maintain the driving performance over time due to increased volatility of the medium in the electrolyte and reduced hygroscopicity. .
  • the molecular weight of the polyether compound-containing compound is not particularly limited as long as it is liquid at normal temperature and pressure, but those having a number average molecular weight of 1000 or less are suitably used, and those having 200 to 800 are more preferred. 300 to 600 are more preferably used. If the number average molecular weight exceeds 1000, it may be solidified at normal temperature and pressure, which is not preferable.
  • the number average molecular weight is obtained by GPC (gel “permeation” chromatography).
  • the nonionic organic compounds may be used singly or in combination of two or more, but the blending amount is 0.01 to 100 parts by weight of the base polymer. ⁇ ; 10 parts by weight is preferred 0.05 to 5 parts by weight is more preferred 0.;! ⁇ 1 part by weight is even more preferred. If the amount is less than 01 parts by weight, sufficient durability over time may not be obtained, and if it exceeds 10 parts by weight, the nonionic organic compound may bleed. By including the above-mentioned organic compound in the electrolyte, even if the polymer actuator element is not sealed, it can be bent (displacement angle) of 50 ° or more after one day. it can.
  • the above polyether compound when used, the above polyether compound may be used singly or as a mixture of two or more thereof. It is preferably 0.0 to! To 10 parts by weight with respect to 100 parts by weight of the polymer, more preferably 0.05 to 5 parts by weight 0.;! To 1 part by weight Is more preferable. If it is less than 0.01 parts by weight, sufficient durability cannot be obtained, and if it exceeds 10, the polyether compound may bleed. By including the polyether compound in the electrolyte, even in a state where the polymer actuator element is not hermetically sealed, bending (displacement-angle) of 180 ° or more can be performed after one day.
  • the conventional polymer actuator element has a relatively low voltage of 1.2 V.
  • the angle (°) representing the degree of bending or displacement is the angle (displacement angle) formed by the tangential direction of the bending or displacement convex surface at the tip of the polymer actuator element and the direction of gravity. Is required.
  • the polymer actuator element in the present invention includes a metal electrode and a polymer electrolyte, and is formed so that the metal electrode can form a pair, and the metal electrode is in contact with the electrolyte.
  • a molecular actuator element having a structure provided with a plurality of the metal electrodes.
  • the above-mentioned actuator element may be provided with one electrode layer on both sides of the ion exchange resin layer, or may be provided with a plurality of electrode layers on both sides or one side.
  • an actuator element in which a pair of electrode layers forms an electrode pair with an ion exchange resin layer interposed therebetween can be used.
  • a plurality of metal electrodes may be provided on the inner surface.
  • the polymer actuator element in which the electrode layer described above forms an electrode pair with an ion exchange resin interposed therebetween can be obtained by a known method. For example, an electroless plating is performed on an ion exchange resin tangible material having a membrane shape, a plate shape, or a tube shape, thereby forming a metal layer on the inside surface of the ion exchange resin tangible material surface or the ion exchange resin tangible material surface
  • the metal layer metal as an electrode layer, the polymer composite (metal ion exchange resin assembly) can be obtained.
  • the electroless plating for example, it is possible to suitably use the following electroless plating method.
  • an adsorption process for adsorbing a metal complex such as a platinum complex or a gold complex on the ion exchange resin is performed in a state where the ion exchange resin is immersed in water and swollen.
  • a reduction step of reducing the adsorbed metal complex with a reducing agent to deposit a metal may be performed, and a cleaning step of cleaning and removing the reducing agent may be performed as necessary after the reduction step.
  • the ion exchange resin contained in the electrolyte of the polymer actuator element in the present invention is not particularly limited, and a known ion exchange resin can be used.
  • a cation exchange resin is used as the ion exchange resin
  • a resin obtained by introducing a hydrophilic functional group such as a sulfonic acid group or a carboxyl group into polyethylene, polystyrene, fluororesin, or the like can be used.
  • Such resins include perfluorosulfonic acid resin (trade name “Nafion”, manufactured by DuPont), perfluorocarboxylic acid resin (trade name “Flemion”, manufactured by Asahi Glass Co., Ltd.), ACIPLEX (manufactured by Asahi Kasei Kogyo Co., Ltd.). , NEOSEPTA ( Tokuyama Co., Ltd.) can be used. These ion exchange resins may be used alone or in combination of two or more.
  • the ion-exchange resin has a thickness (when swollen) of usually 0 ⁇ ;
  • the thickness of the ion exchange resin is 10 mm or more, the distance between the electrodes may be excessively increased.
  • the metal complex solution used in the above-described electroless plating adsorption step includes any metal complex that can function as an electrode layer.
  • a metal having a low ionization tendency is electrochemically stable, and therefore, a metal complex such as a gold complex, a platinum complex, a radium complex, a rhodium complex, or a ruthenium complex may be used. preferable.
  • a metal complex made of a noble metal with good electrical conductivity and high electrochemical stability is preferred, and a gold complex made of gold that is relatively less susceptible to electrolysis. Is more preferable.
  • the solvent used in the metal complex solution is not particularly limited. However, since the metal salt (metal complex) is easily dissolved and handled, It is preferable that water is a main component. More specifically, the metal complex solution is preferably a metal complex aqueous solution, more preferably a gold complex aqueous solution or a platinum complex aqueous solution, and more preferably a gold complex aqueous solution.
  • the reducing agent used in the above-described electroless plating reduction step is appropriately selected according to the type of metal complex used in the metal complex solution adsorbed on the ion exchange resin. You can power to use.
  • the reducing agent include sodium sulfite, hydrazine, sodium borohydride, phosphorous acid, sodium hypophosphite, and the like. These reducing agents may be used alone or in combination of two or more.
  • the reducing agent may be appropriately selected depending on the metal species to be deposited.
  • the metal deposited by reduction is nickel or cobalt
  • sodium phosphinate, dimethylaminoborane, hydrazine, potassium tetrahydroborate, etc. can be used as the reducing agent.
  • the metal deposited by reduction is palladium
  • the reducing agent For example, sodium phosphinate, sodium phosphonate, potassium tetrahydroborate and the like can be used.
  • the metal to be deposited by reduction is copper, it is possible to use, for example, formalin, sodium phosphonate, potassium tetrahydroborate as the reducing agent.
  • the metal deposited by reduction is silver or gold
  • dimethylolaminoborane, potassium tetrahydroborate and the like can be used as the reducing agent.
  • the metal to be deposited by reduction is platinum, for example, hydrazine, sodium tetrahydroborate, etc. can be used as the reducing agent.
  • the metal to be deposited by reduction is tin, for example, titanium trichloride can be used as the reducing agent.
  • reducing agents are not limited to the above types, but are used with catalysts such as platinum black, non-metallic acids or ions such as HgS, HI and I—, Na (H 3 PO 4) and Na 2 SO Such as
  • Lower oxygenates lower oxides such as CO and SO, Li, Na, Cu, Mg, Zn, Fe, Fe (II),
  • Metals with a high ionization tendency such as Sn (II), Ti (111), Cr (II) or their amalgams and low valent metal salts, such as A1H [(CH 2) CHCH] and lithium aluminum hydride
  • Any hydride, diimide, formic acid, aldehyde, saccharide, L-ascorbic acid, etc. may be used as appropriate.
  • the reducing agent can be appropriately selected according to the metal species to be reduced as described above. Further, the growth rate of the metal, the particle size of the deposited metal, and the ion exchange with the metal electrode having a fractal structure. In order to adjust the contact area of the resin, the electrode structure, and the flexibility of the resin after plating, the type of reducing agent can be appropriately selected and used. In addition, the type of the reducing agent may be appropriately selected so that the reducing bath in the reducing step is preferred and has a pH.
  • the concentration of the reducing agent solution is not particularly limited as long as it contains an amount of reducing agent sufficient to obtain the amount of metal to be precipitated by reduction of the metal complex. It is also possible to use a concentration equivalent to that of a metal salt solution used when an electrode is formed by ordinary electroless plating.
  • the reducing agent solution can contain a good solvent for the ion exchange resin.
  • an acid or an alkali may be added as necessary when reducing the metal complex.
  • metal complex solution containing an organic ionic compound As the metal complex solution.
  • a metal complex solution containing an organic ionic compound By using a strong and complex metal complex, it is possible to charge the electrolyte in the second step. In some cases, filling can be performed more effectively.
  • organic ionic compound examples include tetraethylammonium chloride, tetraethylammonium acetate, tetraethylammonium perchlorate, ethylmethylethanolimidazole tetrafluoroborate, ethylmethylimidazolehexafluorolin.
  • examples thereof include acids and ethylmethylimidazole fluorelomethanesulfonimide.
  • the organic ionic compound may be used alone or in combination of two or more.
  • the amount of the organic ionic compound used may be as follows. It is preferred that the compound is 0.;! To 50% by weight; more preferably, it is contained !! to 30% by weight, and more preferably 2 to 20% by weight. 0. If it is less than 1% by weight, the effect of addition may not be sufficiently selected, and if it exceeds 50% by weight, bleeding may occur.
  • the polymer actuator element according to the present invention includes a solvent and a salt inside the electrolyte in contact with the metal electrode formed so as to be able to form a pair.
  • the polymer actuator element is preferably flexible so that the polymer actuator element can be bent or displaced.
  • the degree of swelling is not particularly limited! /
  • the swelling degree of the high molecular weight actuator element is 3 to 200%. S, preferably 5 to 100%, more preferably 10 to 60%.
  • the swelling degree is less than 3%, the displacement bending performance may be inferior.
  • the degree of swelling is greater than 200%, the displacement bending performance may be inferior and the tensile strength may be greatly reduced.
  • the said organic compound is contained in electrolyte, when an electrode layer is a porous electrode, a part of said solvent may be contained in the said metal electrode layer with a salt.
  • the electrolyte is obtained with a force S obtained by using a filling method including the first step and the second step.
  • the electrolytic solution filling method of the polymer actuator element of the present invention includes:
  • the polymer composite is immersed in a solution containing a nonionic organic compound that is liquid at normal temperature and pressure.
  • the first step is a step of immersing the polymer composite in a solution containing a nonionic organic compound that is liquid at normal temperature and pressure (a solution containing a nonionic organic compound).
  • the ion exchange resin layer or the polymer electrolyte is immersed in the liquid of the nonionic organic compound or the nonionic organic compound-containing solution.
  • the ion exchange resin can be swollen by the nonionic organic compound or the like.
  • Examples of the nonionic organic compound-containing solution include a solution obtained by appropriately mixing the nonionic organic compound with another organic solvent or water.
  • the solvent to be mixed with the nonionic organic compound is not particularly limited! /, But if it is used as it is, a solvent that does not easily volatilize over time at normal temperature and pressure is preferable.
  • the organic compound remains as a solvent in the electrolyte even after the solvent such as water volatilizes.
  • the nonionic organic compound in the solution is preferably 1 to 100% by weight, and 10 to 100% by weight. More preferably, it is more preferably 30 to 100% by weight.
  • the polyether compound when used, is preferably 1 to 100% by weight, more preferably 10 to 100% by weight in the solution, More preferably 30 to 100% by weight.
  • a solvent mixed with the nonionic organic compound (or the polyether compound) (hereinafter referred to as a mixed solvent). ) Is not particularly limited as long as it can be mixed with the nonionic organic compound (or the polyether compound).
  • a solvent that can be volatilized selectively by heating or the like after filling into the polymer electrolyte together with the organic compound (or the above polyether compound) is preferable.
  • Examples of the mixed solvent include ethylene carbonate, propylene carbonate, butylene carbonate, glycerin carbonate, alcohols, and water. These mixed solvents may be used alone or as a mixture of two or more.
  • the second step is a step of immersing the polymer composite in a solution obtained by adding an electrolyte to the solution after the first step.
  • an ion exchange resin layer or a polymer electrolyte is immersed in a solution obtained by further adding an electrolyte to the solution in the first step, whereby an ion is obtained.
  • the exchange resin can be swollen by the nonionic organic compound or the like and an ionic electrolyte.
  • the above nonionic compound it has been very difficult to easily and quickly fill the ion exchange resin layer together with the nonionic organic compound and the ionic electrolyte.
  • this electrolyte filling method the filling force can be easily reduced.
  • the salt (electrolyte) contained in the inside of the polymer composite (or polymer electrolyte) is not particularly limited as long as it can be dissolved in the nonionic organic compound or the solution containing the nonionic organic compound). Not limited! /.
  • the polyelectrolyte forms a counter ion with a cation
  • the above cation salt it is more preferable to use an alkylammonium ion having a large ionic radius, since it enables a larger bending or displacement.
  • the salt (electrolyte) is generally used as an electrolyte in the second step and is generally filled in the high molecular complex. In other steps, the salt is appropriately added to the high molecular complex. It may be included.
  • alkyl ammonium ions examples include CH N + CH C H N + H (CH) N +
  • ammonium ions having alicyclic hydrocarbons and alicyclic hydrocarbons examples thereof include ammonium ions having alicyclic hydrocarbons and alicyclic hydrocarbons. These ions may be used alone or in admixture of two or more.
  • the content concentration of the salt is not particularly limited as long as it is contained as a concentration equal to or higher than the functional group of the ion exchange resin, but in order to obtain more sufficient bending or displacement, 0;! To 10 mol / l is preferred 0 ⁇ ;! To 1 ⁇ Omol / 1 is more preferred 0.2 to 1; more preferably Omol / 1. In addition, when using an ionic liquid, the said salt does not need to be used.
  • the electrolyte in the present invention can further include an ionic liquid as the electrolyte in the second step.
  • the ionic liquid is not particularly limited! Among these, the ionizable liquid is an imidazolium ion such as a tetraalkyl ammonium ion, a dialkyl imidazolium ion, a trialkyl imidazolium ion, a villarium ion, a pyrrolium ion, a pyrrolium ion, a pyrrolidinium ion, And at least one cation selected from the group consisting of piperidinium ions, PF-, BF-, A1C1-, CIO-, and
  • ionic liquids composed of a combination with at least one selected from the group consisting of sulfonimmidoanions represented by the following formula (I):
  • ionic liquids may be used alone or in combination of two or more.
  • n and m are arbitrary integers. ].
  • Examples of the tetraalkylammonium ion include trimethylpropylammonium, trimethylhexylammonium, tetrapentylammonium, and the like.
  • Examples of the imidazolium cation include dialkyl imidazolium ions and / or trialkyl imidazolium ions. More specifically The imidazolium cation includes 1-ethyl-3-methylimidazolium ion, 1-propyl 3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion, 1-hexylol 3-methylimidazolium ion, 1, 3 —Dimethylimidazolium ion, 1-methyl-3-ethyl imidazolium ion, 1,2,3-trimethylimidazolium ion, 1,2 dimethyl-3-ethylimidazolium ion, 1,2 dimethyl-3-propyrimonium ion , 1-Butyl-2, 3 dimethyl imidazolium ion, etc.
  • alkylpyridinium ion examples include N methylpyridinium ion, N ethylpyridinium ion, N-propylpyridinium ion, N butylpyridinium ion, 1-ethylpyridinium ion, and 1-ethylpyridinium ion. 1-butyl-4 methylpyridinium ion, 1-butyl-2,4 dimethylviridinium ion, etc.
  • Examples of the pyrrolium cation include 1,2 dimethylpyrrolium ion, 1-ethyl-2-methylpyrrolium ion, 1-propyl-2-methylpyrrolium ion, 1-butyl-2-methylpyrrolium ion, and the like. I can give you.
  • Examples of the pyrrolidinium cation include 1,1-dimethylpyrrolidinium ion, 1-ethyl-1 methylpyrrolidinium ion, 1-methyl-1 propylpyrrolidinium ion, 1-butyl-1 methylpyrrolidinium ion, and the like. I can give you.
  • Examples of the piberidinium cation include 1,1-dimethylbiperidinium ion, 1-ethyl-1-methylbiperidinium ion, 1-methyl-1-propylpiperidinium ion, 1-butyl-1-methylbication.
  • Peridinium ions can be listed.
  • the ionic liquid has a particularly limited combination of the anion and the cation.
  • EMITFSI 1-methyl-3-ethylimidazolium trifluoromethansulfimide
  • E MIBF 1-methyl-3-imidazolium tetrafluoroborate
  • EMIPF 1-methyl-3-imidazolium hexafluoroline Acid
  • the polymer electrolyte contains the nonionic organic compound and the ionic liquid, so that the polymer electrolyte is the nonionic organic compound and the ionic liquid. Swelling gel electrolyte can be made force S.
  • the non-ionic organic compound includes a boiling point or decomposition temperature power of 80 ° C or higher and a liquid organic compound or a polyether compound at room temperature and normal pressure
  • the polymer electrolyte can be driven even if it is left for about a month under normal pressure.
  • the gel electrolyte containing the nonionic organic compound and the ionic liquid is flexible and can hold a high concentration of electrolyte, it is suitable as an electrolyte for an actuator element and a capacitor.
  • the production method of the polymer electrolyte (or polymer composite) containing the ion exchange resin and the nonionic organic compound (and the ionic liquid) is not particularly limited.
  • the ion exchange resin is immersed in a mixed solution of 5 to 50% by weight of the ionic liquid in the nonionic organic compound (or nonionic organic compound-containing solution), and the size or weight changes at room temperature. You can easily get it by leaving it until it runs out.
  • the polymer actuator element of the present invention includes a resin or a non-ionic organic compound having a boiling point or decomposition temperature of 180 ° C or higher and a liquid organic compound or a polyether compound at room temperature and normal pressure.
  • the electrolyte S may be coated with a force S that can be driven for a long period of time without being covered with a resin, and further with a flexible resin.
  • the flexible resin is not particularly limited.
  • a urethane resin and / or a silicone resin can be mentioned.
  • thermoplastic polyurethane having high flexibility is particularly preferable because of its high flexibility and good adhesion.
  • the above-mentioned thermoplastic polyurethanes include the product name “Asaflex 825” (flexibility 200%, manufactured by Asahi Kasei), the product name “Pelecene 2363-80A” (flexibility 550%), and “Pelecene 2363-80AE” (flexibility) 650%), “Pelecene 2363-90A” (flexibility: 500%), “Pelecene 2363-90AE” (flexibility: 550%) (above, manufactured by Dow Chemical Co., Ltd.).
  • the above-mentioned silicone resin is particularly preferable because, for example, the resin strength with a flexibility of 50% or more is high and the adhesion is good.
  • the silicone resin for example, “SilaSeal 3FW”, “SilaSeal DC738RTV”, “DC3145”, and “DC3140” (hereinafter, manufactured by Dow Co., Ltd.) can be used.
  • the flexibility in the present invention refers to the tensile elongation at break (Ultimate Elongation%) measured in accordance with ASTM D412.
  • the thickness of the above-mentioned actuator element when swollen is preferably 0.02—2. Omm, which is normally used in 0.01-5. Omm. More preferably, it is more preferably 0.05-0.5 mm. If the thickness of the above-mentioned actuator element is 10 mm or more, the electric field strength between the electrodes may be insufficient and the flexibility may be lost.
  • the elastic modulus control method for a polymer actuator element of the present invention is a method for controlling the elastic modulus of a polymer actuator element including a polymer composite having a metal electrode on a polymer electrolyte,
  • the first step is a step of immersing the polymer composite in a solution (organic compound-containing solution) containing a liquid nonionic organic compound under normal temperature and pressure.
  • a solution organic compound-containing solution
  • a liquid nonionic organic compound under normal temperature and pressure.
  • the ion exchange resin layer or the polymer electrolyte By immersing the ion exchange resin layer or the polymer electrolyte in the first step in the liquid of the nonionic organic compound or the nonionic organic compound-containing solution.
  • the ion exchange resin can be swollen by the nonionic organic compound or the like.
  • the second step includes the step of immersing the polymer composite in a solution obtained by further adding an electrolyte to the solution after performing the first step. This is a step of preparing the amount of electrolyte and the amount of electrolyte.
  • the ion exchange resin layer (or polymer electrolyte) is immersed in a solution obtained by adding an electrolyte to the solution in the first step, and further, the polymer
  • the ion exchange resin should be in a swollen state by controlling the amount of each of the nonionic organic compound and the ionic electrolyte filled. Power S can be.
  • each component in the electrolytic solution filling method can be similarly used.
  • the elastic modulus of the polymer actuator element can be controlled to approximately 5 to 200 MPa.
  • the force S depends on the balance between required characteristics and responsiveness in practical use, generally the elastic modulus is 10 to 150 MPa, preferably 20 to 120 MPa, more preferable to the force S, 30 to 30 ! OOMPa is even more preferred.
  • the responsiveness of the polymer actuator element includes the displacement amount of the polymer actuator element, the period of the displacement motion, and the response speed.
  • ethylene glycol, polypropylene glycol, and / or their related compounds are used as the nonionic organic compound.
  • the control force S can also be increased by increasing the content of the electrolyte (salt) added in the second step.
  • the electrolyte (salt) added in the second step Li +, Na + , Ba + , Al 3+ and the like are particularly preferable because they have a large effect of increasing the modulus of elasticity with respect to the amount added, and can be easily controlled with a small amount.
  • the elastic modulus is 5 to 20 MPa and the displacement amount is 0.05 to 5 mm / Sec . Control becomes possible.
  • the force S depends on the balance between required characteristics and responsiveness in practical applications.
  • the elastic modulus is 20 to;! OOMPa and the displacement is 0 .;! To 4 mm / sec. More preferably, the elastic modulus is 30 to 70 MPa, and the displacement is 1.5 to 3. Omm / sec.
  • the measurement point of the displacement is a point 6 mm from the electrode gripping position.
  • the method for producing a polymer actuator element of the present invention is a method for producing a polymer actuator element comprising a polymer composite comprising a metal electrode on a polymer electrolyte, wherein the polymer composite is A first step of immersing in a solution containing a liquid nonionic organic compound under normal temperature and pressure, and
  • the first step and the second step are the same as the first step and the second step in the electrolytic solution filling method described above.
  • the polymer complex is included in the polymer complex when immersed in a solution obtained by adding an electrolyte to the solution.
  • the electrolytic mass and the amount of the electrolytic solution may be adjusted.
  • the method for driving the polymer actuator element is to apply and drive the polymer actuator element described above. Since the polymer actuator element of the present invention has the above-described configuration, bubbles are not generated even when a voltage higher than 3.0 V is applied in order to cause bending or displacement of 160 ° or more. Furthermore, by using, for example, the above-mentioned polyether compound as the electrolyte solution (electrolyte solution), the electrolyte solution is less likely to evaporate. Driving substantially equal to the amount or displacement is possible.
  • the above-described polymer actuator element is normally driven by applying a voltage of 0.5 to 50 V.
  • the opposite voltage is applied to each metal electrode with a period of 0.01 Hz to IKHz. It is more preferable to have a period of 0 ⁇ ;! to 200 Hz, and it is more preferable to have a period of 0 ⁇ 2 to 100 Hz.
  • the polymer actuator element of the present invention is, for example, an OA device, an antenna, a device for placing a person such as a bed chair, a medical device, an engine, an optical device, a fixture, a side trimmer, a vehicle, a lifting machine, food Processing equipment, cleaning equipment, measuring equipment, inspection equipment, control equipment, machine tools, processing equipment, electronic equipment, electron microscope, electric razor, electric toothbrush, manipulator, mast, amusement equipment, amusement equipment, riding simulation equipment, vehicle
  • the driving unit that generates a linear driving force or the driving unit that generates a driving force for moving a track-type track composed of an arcuate portion, a linear It can be suitably used as a pressing portion that performs a simple operation or a curved operation.
  • the polymer actuator element of the present invention is, for example, an OA device or a measuring device. Generates a driving force for moving a track-type orbit made up of a driving part that generates a linear driving force and an arcuate part in valves, brakes, lock devices, etc. used in all machines including the above devices. Use with force S to use as a drive unit or a pressing unit that moves linearly.
  • the positioning device drive unit, the attitude control device drive unit, the lifting device drive unit, the transport device drive unit, the movement It can be suitably used as a drive unit for an apparatus, a drive unit for an adjustment device such as an amount or a direction, a drive unit for an adjustment device such as a shaft, a drive unit for a guidance device, or a pressing unit for a pressing device.
  • the polymer actuator element of the present invention is capable of rotational movement, for example, a drive unit of a switching device, a drive unit of a reversing device such as a conveyed product, a winding device such as a wire It can also be used as a drive unit for a traction device, a drive unit for a traction device, or a drive unit for a swiveling device in the horizontal direction such as swinging.
  • ion exchange resin membrane fluororesin ion exchange resin: perfluorocarboxylic acid resin, manufactured by Asahi Glass Co., Flemion, dry film thickness: 0.2 mm, ion exchange capacity: 1.4 meq / g
  • steps (1) to (3) were repeated 6 cycles to obtain an ion exchange resin membrane (a) having a pair of metal electrodes formed with the ion exchange resin sandwiched therebetween.
  • the ion exchange resin membrane (a) was immersed in a water mixed solution (1) (67% by weight) of glycerin carbonate. Next, the ion exchange resin membrane (a) is immersed in the mixed solution (1) containing 0. Olmol / 1 LiTFSI (trifluoromethanesulfonimide) salt for 3 hours so that the degree of swelling is about 25%.
  • the polymer actuator element of Example 1 was obtained by dipping.
  • the ion exchange resin membrane (a) was immersed in a polyethylene glycol methanol mixed solution (2) (80 wt%). Next, the ion exchange resin membrane (a) is immersed in the mixed solution (2) containing 0.001 mol / l LiTFSI (trifluoromethanesulfonimide) salt so that the degree of swelling becomes about 40%.
  • the polymer actuator element of Example 2 was obtained by immersion for 5 hours.
  • the ion exchange resin membrane (a) was immersed in an ethanol mixed solution (3) (80% by weight) of polyethylene glycol monolaurate. Next, the ion exchange resin membrane (a) was immersed in the mixed solution (3) containing 0.005 mol / l sodium sulfate and immersed for 5 hours so that the degree of swelling was about 20%. Three polymer actuator elements were obtained.
  • the ion exchange resin membrane (a) was immersed in a glycerin carbonate mixed solution (4) (50% by weight) of polyethylene glycol. Next, the ion exchange resin membrane (a) is immersed in the mixed solution (4) containing 0.1 mol / l LiTFSI (trifluoromethanesulfonimide) salt so that the degree of swelling becomes about 30%.
  • the polymer actuator element of Example 4 was obtained by immersion for a period of time.
  • the ion exchange resin membrane (a) is immersed in a methanol mixture of polyethylene glycol (polyethylene glycol: 80% by weight) and immersed for 0.5 hour so that the degree of swelling is about 20%. A molecular actuator element was obtained.
  • the width and thickness of the material are measured, and the force (N / mm 2 ) required to apply a constant deflection by applying a weight in the vertical direction of the material is measured. To calculate the elastic modulus.
  • the responsiveness was evaluated by measuring the displacement per unit time (mm / sec) as follows.
  • evaluation was performed by applying a voltage by a method of obtaining a displacement amount calculated backward from the displacement tracking of the reflected light in lsec by forcing the laser beam at a position 6 mm from the position of the object (electrode). (Applied voltage: 3 Vpp, 0.5 Hz, driven by a rectangular wave).
  • the method for controlling the elastic modulus of the polymer actuator element of the present invention is used.
  • a polymer activator element having an electrolytic solution containing a nonionic compound that is liquid at normal temperature and pressure can be easily obtained using the method for producing a polymer activator element of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Analytical Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemically Coating (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne : un procédé visant à remplir un actionneur polymère d'une solution électrolytique, cet actionneur polymère pouvant être facilement rempli d'une solution électrolytique contenant un composé non ionique liquide à pression et température ordinaires; un procédé permettant de régler le module élastique d'un actionneur polymère, selon lequel le module élastique d'un actionneur polymère rempli d'une solution électrolytique contenant un composé non ionique liquide à pression et température ambiantes peut être facilement contrôlé; et un procédé permettant de produire facilement un actionneur polymère rempli d'une solution électrolytique contenant un composé non ionique liquide à pression et température ordinaires. L'invention concerne plus spécifiquement un procédé de remplissage, par une solution électrolytique, d'un actionneur polymère comprenant un complexe polymère constitué d'un polyélectrolyte et d'électrodes métalliques placées sur le polyélectrolyte. Ce procédé est caractérisé par une première étape consistant à plonger le complexe polymère dans une solution contenant un composé non ionique liquide à pression et température ambiantes, et une seconde étape consistant à plonger ledit complexe polymère dans une solution obtenue par ajout d'un électrolyte à la solution précédente.
PCT/JP2007/067295 2006-09-05 2007-09-05 Remplissage d'un actionneur polymère d'une solution électrolytique, choix du module élastique de l'actionneur polymère et production d'un actionneur polymère WO2008029839A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-240431 2006-09-05
JP2006240431A JP4931521B2 (ja) 2006-09-05 2006-09-05 高分子アクチュエータ素子の電解液充填方法、高分子アクチュエータ素子の弾性率制御方法、および高分子アクチュエータ素子の製造方法

Publications (1)

Publication Number Publication Date
WO2008029839A1 true WO2008029839A1 (fr) 2008-03-13

Family

ID=39157265

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/067295 WO2008029839A1 (fr) 2006-09-05 2007-09-05 Remplissage d'un actionneur polymère d'une solution électrolytique, choix du module élastique de l'actionneur polymère et production d'un actionneur polymère

Country Status (2)

Country Link
JP (1) JP4931521B2 (fr)
WO (1) WO2008029839A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5243118B2 (ja) * 2008-07-03 2013-07-24 アルプス電気株式会社 高分子アクチュエータ及びその製造方法
JP5463482B2 (ja) * 2008-08-07 2014-04-09 イーメックス株式会社 高分子アクチュエータ素子およびその駆動方法
JP5604737B2 (ja) * 2008-08-07 2014-10-15 イーメックス株式会社 高分子アクチュエータ素子およびその駆動方法
JP5584896B2 (ja) * 2009-10-14 2014-09-10 イーメックス株式会社 高分子アクチュエータ素子及びこれを用いた高分子センサ

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004260995A (ja) * 2003-02-07 2004-09-16 Eamex Co アクチュエータの駆動方法及び水槽
JP2006081374A (ja) * 2004-09-13 2006-03-23 Eamex Co 空中駆動高分子アクチュエータ素子

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004260995A (ja) * 2003-02-07 2004-09-16 Eamex Co アクチュエータの駆動方法及び水槽
JP2006081374A (ja) * 2004-09-13 2006-03-23 Eamex Co 空中駆動高分子アクチュエータ素子

Also Published As

Publication number Publication date
JP2008067444A (ja) 2008-03-21
JP4931521B2 (ja) 2012-05-16

Similar Documents

Publication Publication Date Title
US20090032394A1 (en) Ionic polymer devices and methods of fabricating the same
EP0943402B1 (fr) Actionneur en matériau polymère, et son procédé de fabrication
JP4871225B2 (ja) 高イオン伝導性固体電解質及びその製造方法並びに該固体電解質を使用した電気化学システム
Oguro et al. Polymer electrolyte actuator with gold electrodes
US8172998B2 (en) Ionic solvents used in ionic polymer transducers, sensors and actuators
JP2005071760A (ja) 固体高分子型燃料電池
JP4711765B2 (ja) 直動駆動型高分子アクチュエータ装置
US20090301875A1 (en) Ionic polymer devices and methods of fabricating the same
JP4931521B2 (ja) 高分子アクチュエータ素子の電解液充填方法、高分子アクチュエータ素子の弾性率制御方法、および高分子アクチュエータ素子の製造方法
JP5310972B2 (ja) 高分子アクチュエータ素子およびその駆動方法
JP4717400B2 (ja) 空中駆動高分子アクチュエータ素子
US7917027B2 (en) Actuator body and throttle mechanism
JP2003170400A (ja) アクチュエータ素子の製造方法
JP5584896B2 (ja) 高分子アクチュエータ素子及びこれを用いた高分子センサ
Guo et al. Guiding principles for the design of artificial interface layer for zinc metal anode
JP5447791B2 (ja) 固体高分子型燃料電池の製造方法
JP5463482B2 (ja) 高分子アクチュエータ素子およびその駆動方法
JP5604737B2 (ja) 高分子アクチュエータ素子およびその駆動方法
Zimmermann et al. Ionic Polymer-Metal Composite Coated with Polyaniline Film by Electrodeposition: A Promising IPMC/PANI Junction for Applications in Robotics and Bioengineering
WO2007069310A1 (fr) Élément activateur polymère activable dans l’air
JP2005033991A (ja) 高分子アクチュエータ素子
JPH0979129A (ja) アクチュエータ素子
JP4575750B2 (ja) 高分子アクチュエータ素子の処理方法
JP2011034739A (ja) 固体高分子型燃料電池及びその製造方法
JP2006158797A (ja) 高分子アクチュエータ素子

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07806738

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07806738

Country of ref document: EP

Kind code of ref document: A1