CN1742056A - Conductive polymer gel and process for producing the same, actuator, patch label for ion introduction, bioelectrode, toner, conductive functional member, antistatic sheet, printed-circuit member, cond - Google Patents

Abstract

A conductive polymer gel which comprises water as a major component, a conductive conjugated polymer, and a surfactant and/or an alcohol. It may contain an electrolyte. The conductive conjugated polymer may be doped with a dopant. The conductive polymer gel is obtained by adding a surfactant and/or an alcohol to a colloidal dispersion of a conductive conjugated polymer and/or to a solution of a conductive conjugated polymer and allowing the mixture to stand to thereby cause it to gel.

Description

Conductive polymer gel and preparation method thereof, stopper, iontophoretic treatment patch label, biomedical electrode, toning agent, conductive functional, antistatic, printed circuit elements, conduction paste, electrode for fuel cell and fuel cell

Technical field

The present invention relates to a kind of easily by gelationization and have conductive polymer gel of favorable conductive rate and preparation method thereof.More specifically, the present invention relates to a kind of stopper, a kind of iontophoretic treatment patch label and a kind of biomedical electrode, they use conductive polymer gel; A kind of toning agent that uses conductive polymer gel; A kind of conductive functional, a kind of antistatic and a kind of printed circuit elements, they use this toning agent; A kind of conduction of conductive polymer gel of using is stuck with paste; And fuel cell, it uses electrode for fuel cell.

Background technology

As for conductive polymer gel, for example, be known so far below:

(1) Japanese patent application announces for the first time that No.2001-406 (file 1) discloses and is suitable for the conductive polymer gel used that in biomedical electrode this biomedical electrode is used for measuring local bioelectrical signals and is used for electric methods of treatment method.Even wash with water, the bounding force of this conductive polymer gel does not reduce yet, and returns to original level.Conductive polymer gel comprises crosslinked synthetic polymer, water, polyvalent alcohol and electrolyte salt.When crosslinked synthetic polymer ratio was 18 to 25 weight %, the gel that obtains comprised the main polymer chain of suitable proportion and has enough stiffness and strengths.Because can stably keep being sealed in the ionogen in the network of gel, so obtained having the conductive polymer gel of above-mentioned feature.

(2) Synthetic Metals 99 (1999), 53-59 (file 2), and the method by monomeric electrolytic polymerization (electropolymerization) of disclosing obtains the solid film made by the gel Polythiophene with three-dimensional network.According to this method, must in same operation, carry out monomeric polymerization and gelationization.

But conductive polymer gel that obtains by prior art and preparation method thereof has following problem:

Because disclosed conductive polymer gel comprises ionogen in (1), and ionogen has electroconductibility, and it can have unsettled electroconductibility, maybe when in the atmosphere that is exposed to the temperature that is lower than the water zero pour, can not guarantee good electrical conductivity.That is, the conductive polymer gel of prior art is difficult to keep good electrical conductivity in the atmosphere of the temperature that is lower than the water zero pour.

Though disclosed conductive polymer gel has electroconductibility not comprising under the electrolytical condition in (2),, must in same operation, carry out monomeric polymerization and gelationization, and consider controllability, this method is complicated and need high-caliber technology.

As for the toning agent that is used to form circuit card, use comprises the toning agent of the core body of partly being made by metallic particles, insulating resin, the surface of described core body part is insulated resin portion and divides coating, as Japanese patent application, announce for the first time No.2002-151828 (file 3) and Japanese patent application, announce that No.2003-255594 (file 4) is disclosed for the first time.

When use comprises the toning agent of metallic particles in the preparation of printed circuit board (PCB) and electronic unit, be difficult to processing by printed circuit board (PCB) and electronic unit, for example separate the metal-powder that constitutes toning agent the resin part from organic constituent.Therefore, recycling resource difficulty.

Particularly, the toning agent of circuit card formation usefulness comprises the core body part of being made by metallic particles in the prior art, even burn by using the printed circuit board (PCB) and the electronic unit of this toning agent preparation, metal component keeps.

It is for example mixture of metal-powder and resin glue of electro-conductive material that conduction is stuck with paste.Base material for example in resin film or the basic unit coating conduction stick with paste, then by being heating and curing, can give base material electroconductibility thus.Therefore, will conduct electricity to stick with paste and be used for forming printed circuit board (PCB) for example RF-ID (radio frequency-identification) antenna of usefulness, the circuit card of printed circuit board (PCB), the electrode of liquid-crystal display and the film circuit board of keyboard.Except printed circuit board (PCB), conduction stuck with paste the lead-in wire of be used for boning terminals and electronic unit and be used for forming the inner conductive film (interlayer connecting conductive layer) of laminated ceramic compacitor.

Stick with paste as for conduction, Japanese patent application, announce for the first time No.Hei 1-159906 (file 5) and Japanese patent application, announce for the first time that No.Hei 9-306240 (file 6) discloses a kind of conduction and stuck with paste, it comprises as the metal-powder of main ingredient and metal-powder and is dispersed in wherein resin carrier (resin glue).

By using the printed circuit board (PCB) that conduction sticks with paste and the disposal of electronic unit, be difficult to for example separate the resin carrier and constitute the metal-powder that conduction is stuck with paste from organic constituent.Therefore, recycling resource difficulty.

Because comprising as electrolytical solid polymer membrane and under 80 to 100 ℃ low temperature, operates polymer electrolytic fuel battery (hereinafter referred to as PEFC), with all right reduced in size and weight, expect in the special practice as for example power supply use of electromobile of mobile traffic.

An example for the technology of PEFC is disclosed in Japanese patent application, announces among the No.2003-282078 (file 7) for the first time.Figure 22 is the synoptic diagram of battery 3101 of formation power generation part that shows the PEFC of prior art.Fuel electrode (negative potential) 3131 and air electrode (positive electrode) 3132 that battery 3101 comprises polymer electrolyte film 3102 and provides on the two sides of polymer electrolyte film 3102.Fuel electrode 3131 and air electrode 3132 as electrode 3103 are made up of following: as the porousness supporting layer 3161a and the 3161b by carbon tissue (carbon paper) system of running contact, the catalyst layer 3162a and the 3162b that provide on supporting layer 3161a and 3161b are provided with catalyst layer 3162a and 3162b.

Provide fuel electrode 3131 and air electrode 3132 with a kind of like this state on the two sides of polymer electrolyte film 3102: wherein catalyst layer 3162a contacts with polymer electrolyte film 3102 with 3162b.

To fuel electrode 3131 hydrogen supplies, and the catalyst layer 3162a of hydrogen adsorption on fuel electrode 3131, change hydrogen ion and electronics then into.The hydrogen ion that obtains moves to air electrode 3,132 one sides in the polymer electrolyte film 3102 with water, and electronics flows towards air electrode 3132 from the circuit card (not shown) of fuel electrode 3131 by the outside simultaneously.

Supply with oxygen to air electrode 3132, and oxygen is adsorbed in the catalyst layer 3162b on the air electrode 3132, and water is by oxygen molecule, hydrogen ion and move the electronics that comes from fuel electrode 3131 and generate.

As for catalyst layer 3162a and 3162b, mainly use platinum and platinum alloy.Because the platinum costliness, the expense that preparation PEFC needs increases.In order to reduce the platinum amount, various technology have been reported.But because in fuel electrode 3131, activity of such catalysts is subjected to reducing owing to the catalysts influence of the carbon monoxide poisoning that comprises trace in the hydrogen, needs to use a large amount of platinum.Therefore, be difficult to reduce the platinum amount.

In addition, fuel electrode 3131 and air electrode 3132 are respectively by two-layer, and for example supporting layer 3161a and 3161b and catalyst layer 3162a and 3162b make, and every layer thickness is big.Therefore, the minimizing of the thickness of electrode 3103 and fuel cell is restricted.

Summary of the invention

Conductive polymer gel of the present invention comprises water, the conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and/or the alcohol.

Conductive polymer gel of the present invention is by for example polyacetylene, polyphenylene, polypyrrole, Polythiophene, poly-furans or poly-selenophen gelation form and do not comprise as the ionogen of basal component magnesium chloride for example with conjugated conductive polymer.Give electroconductibility because constitute the conjugated conductive polymer of the conductive polymer gel of the conjugated conductive polymer, conjugated conductive polymer, tensio-active agent and/or the alcohol that comprise as the water of main ingredient, even therefore expose to the open air under the atmosphere of the temperature that is lower than the water zero pour, conductive polymer gel also can keep good electrical conductivity.

Therefore, conductive polymer gel of the present invention can be used for the various purposes under really good, promptly need temperature around to be lower than under the rigor condition of water zero pour and have stabilization function, for example have functional (for example, the reaction that electrolysis is stimulated, to the reaction of moisture absorption, thermosensitive response etc.) conducting gelation, the ionogen of battery for example.

Conductive polymer gel can comprise ionogen.Comprise under the electrolytical situation at it, the conductive polymer gel of the electroconductibility with remarkable excellence is provided.

Even do not add ionogen, the conjugated conductive polymer that is included in the conductive polymer gel also shows electroconductibility under mixing without doping agent.Because provide conjugated conductive polymer and the gel that use among the present invention, even, also do not weaken electroconductibility when in the atmosphere that is lower than the water zero pour, exposing to the open air with electricity conduction and ionic conduction.

Conjugated conductive polymer is to be selected from least a in following: polyacetylene, polyphenylene, polypyrrole, Polythiophene, poly-furans, poly-selenophen, polyisothianaphthene, polyphenylene sulfide, polyaniline, polyvinylene benzene, polyvinylene thiophene, poly-perinaphthene, poly-anthracene, poly-naphthalene, poly-pyrene, poly-, and their derivative.In these polymkeric substance, preferably use polypyrrole or Polythiophene, because it has excellent stability, reliability and practicality.

Doping agent comprises and for example is selected from least a in following: iodine, fluoridize arsenic, iron(ic) chloride, perchloric acid, sulfonic acid, perfluorinated sulfonic acid, polystyrolsulfon acid, sulfuric acid, hydrochloric acid, nitric acid, and their derivative.In these doping agents, preferred polystyrolsulfon acid is because can easily regulate high conductivity.

Tensio-active agent comprises and for example is selected from least a in following: the condenses of alkylsurfuric acid or its ester, Voranol EP 2001 sulfuric acid or its ester salt, alkyl benzene sulphonate (ABS) or its salt, alkyl naphthalene sulfonic acid or its salt, alkyl sulfo-succinic acid or its salt, alkyl diphenyl ether disulphonic acid or its salt, naphthene sulfonic acid or its formalin, and their derivative.In these tensio-active agents, the preferred alkyl Phenylsulfonic acid because after gelation its chemical stability.

Alcohol comprises and for example is selected from least a in following: Virahol, butanols, 1,2 ethylene glycol, propylene glycol, glycerol, red bright alcohol, polyoxyethylene glycol, polyvinyl alcohol reach their derivative.In these alcohol, preferably have the monohydroxy-alcohol or the polyvalent alcohol of 3 or above carbon atom, more preferably 1,2 ethylene glycol and polyoxyethylene glycol.

Method according to preparation conductive polymer gel of the present invention, in the solution of conjugated conductive polymer colloidal dispersion and/or conjugated conductive polymer, add tensio-active agent and/or alcohol, place mixture then, make conjugated conductive polymer colloidal dispersion and/or conjugated conductive polymer solution gelization thus.

Because in aforesaid method, use conjugated conductive polymer colloidal dispersion and/or conjugated conductive polymer solution as starting material, do not need as the method for prior art, in same operation, to carry out monomeric polymerization and gelation.Do not form by pouring into conjugated conductive polymer colloidal dispersion and/or conjugated conductive polymer solution and add tensio-active agent and/or alcohol under the condition of bubble.Then, only form three-dimensional network and make the mixture gelation easily: mixture is placed on the scheduled time in open space in the air atmosphere of routine or the seal cavity by following method, therefore, can obtain above-mentioned conductive polymer gel with stable manner, this conductive polymer gel has good electrical conductivity.

Stopper of the present invention comprises the stopper main body made by conductive polymer gel and this conductive polymer gel and comprises water, conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and the alcohol.Though the stopper main body can have Any shape for example strip, spirrillum, ring-type, plate-like, pectination or indefinite shape, preferably it is a strip, because its easy control.Strip is not only to refer to accurate rectangle solid, and its width and thickness can have a little in vertically and changes.

Only water and solvent for example acetone replace dipping solution, form conductive polymer gel reexpansion or contraction in vertically of predetermined shape.Therefore, can use conductive polymer gel as stopper.

The electrode that iontophoretic treatment patch label among the present invention comprises pad and is made up of anode that provides with regular interval on a surface of pad and negative electrode.Contact and between electrode, apply electric current by analyte with another surface of pad, send the healing potion part to analyte.Pad is made by water, conjugated conductive polymer and the tensio-active agent and/or the pure conductive polymer gel that comprise as main ingredient.

In the iontophoretic treatment patch label, because pad is to be made by water, conjugated conductive polymer and the tensio-active agent and/or the pure conductive polymer gel that comprise as main ingredient, electricity conduction in the pad and well balanced being maintained between the ionic conduction.Therefore, can reduce the thickness of the gel coat that constitutes pad, therefore can reduce the thickness of iontophoretic treatment patch label.

Biomedical electrode among the present invention comprises electrode device and element, and this element is with electrode device and analyte electricity and physical connection.Element is made by conductive polymer gel, and conductive polymer gel comprises water, conjugated conductive polymer and tensio-active agent and/or the alcohol as main ingredient.

In biomedical electrode, the element of electrode device and analyte electricity and physical connection is made by conductive polymer gel, conductive polymer gel comprises water, conjugated conductive polymer and tensio-active agent and/or the alcohol as main ingredient, therefore, according to the preparation condition of gel, can select electricity conduction and ionic conduction arbitrarily.Because the gel that provides has electricity conduction and ionic conduction, though when the thickness of the gel coat of composed component little, also can guarantee good electrical conductivity, therefore can measure accurately.In addition, because gel can keep shape steadily in the long term, therefore can be satisfactorily with electrode device and analyte electricity and physical connection.

Toning agent among the present invention comprises core body part and the lip-deep resin part in the core body part, and the core body part is made by water, conjugated conductive polymer and the tensio-active agent and/or the pure conductive polymer gel that comprise as main ingredient.

Distribution in the prior art forms in the toning agent of usefulness, has used metallic particles as the core body part.On the contrary, in the present invention, use conductive polymer gel to replace traditional metallic particles, therefore, compared with prior art, can reduce the content of metal component in the toning agent as the core body part.Preferred core body partly has spherical form.

In toning agent, can also be doped with doping agent by conjugated conductive polymer.Therefore, the concentration of current carrier in the conductive polymer gel can be improved, and electroconductibility can be improved.

The current-carrying part that first kind of conductive functional among the present invention comprises base material and provide at least one surface of base material, current-carrying part is made by toning agent.The resin part that toning agent comprises the core body part and provides on the surface of core body part, this core body part is made by water, conjugated conductive polymer and the tensio-active agent and/or the pure conductive polymer gel that comprise as main ingredient.

Antistatic current-carrying part that comprises base material and provide at least one surface of base material of the present invention, current-carrying part is made by toning agent.Current-carrying part has planeform, comprise the resin part that provides on core body part and the core body part surface with toning agent, this core body part is made by water, conjugated conductive polymer and the tensio-active agent and/or the pure conductive polymer gel that comprise as main ingredient.

The current-carrying part that first kind of printed component part of the present invention comprises base material and provide at least one surface of base material, current-carrying part is made by toning agent.Current-carrying part is a planeform, the resin part that toning agent comprises core body part and provides on the surface of core body part, this core body part is by the conductive polymer gel that comprises water, conjugated conductive polymer and tensio-active agent as main ingredient and/or alcohol and make.

The toning agent that forms usefulness with the prior art distribution is compared, and the content of the metal component in the toning agent reduces.Therefore, in first kind of conductive functional, above-mentioned antistatic and first kind of printed component part because current-carrying part is made by toning agent, compared with prior art, can reduce the content of metal component.

Conduction of the present invention is stuck with paste water, conjugated conductive polymer and tensio-active agent and/or the pure conductive polymer gel that comprises as main ingredient; Conductive powder; And resin glue.

Therefore, can reduce and obtain the needed conductive powder of enough electric conductivitys.Conductive polymer gel in conduction is stuck with paste is the polymer compound (organic compound) identical with resin glue, and mixes mutually easily, and has excellent consistency.

Because the formation that this conduction is stuck with paste can also be doped with doping agent by conjugated conductive polymer.Therefore, the concentration of current carrier in the conductive polymer gel can be improved, and electroconductibility can be improved.

The current-carrying part that second kind of conductive functional among the present invention comprises base material and provide at least one surface of base material, current-carrying part is pasted by conduction.Conduction is stuck with paste water, conjugated conductive polymer and tensio-active agent and/or the pure conductive polymer gel that comprises as main ingredient; Conductive powder; And resin glue.

The current-carrying part that second kind of printed component part of the present invention comprises base material and provide at least one surface of base material, current-carrying part is pasted by conduction.Current-carrying part is a planeform, and conduction is stuck with paste water, conjugated conductive polymer and tensio-active agent and/or the pure conductive polymer gel that comprises by comprising as main ingredient; Conductive powder; And resin glue.

Therefore, at second kind of conductive functional and second kind of printed component part, compared with prior art, can reduce obtaining the needed conductive powder content of enough electric conductivitys.

Because the formation of second kind of printed component part, it plays a part to have the antenna of linearity configuration, and the IC chip can be connected with antenna.Therefore, it can also use as non-contact type IC medium.

Electrode for fuel cell in the present invention comprises by water, conjugated conductive polymer and the tensio-active agent and/or the pure conductive polymer gel that comprise as main ingredient.

When using conductive polymer gel to act as a fuel electrode, hydrogen is dissolved in the water that comprises in the conductive polymer gel, can dissociate into hydrogen ion and electronics thus.When using conductive polymer gel as air electrode, oxygen can the combination by being dissolved in the water that comprises in the conducting polymer gel.Therefore, can replace electrode for fuel cell in the prior art by conductive polymer gel, described electrode for fuel cell comprises, the catalyst layer that load is made by platinum on supporting layer.

In electrode for fuel cell, can also be doped with doping agent by conjugated conductive polymer.Therefore, the concentration of current carrier in the conductive polymer gel can be improved, and electroconductibility can be improved.

Fuel cell of the present invention is that this power generation part of fuel cell that comprises power generation part is made by mutual stacked one or more batteries, each battery comprises first and second electrodes, with be clipped in electrode intermediary ionogen, wherein first electrode and/or second electrode comprise, and this conductive polymer gel comprises water, conjugated conductive polymer and tensio-active agent and/or the alcohol as main ingredient.

Therefore, use the situation of supporting layer (load has the catalyst layer that platinum is made on it) to compare, can prepare electrode for fuel cell with low cost, and can reduce the thickness of the generator that uses fuel cell with prior art.

The accompanying drawing summary

Fig. 1 schematically shows the key drawing of poly-(3, the 4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) molecular structure (PEDCT/PSS) of conduction.

Fig. 2 A is the key drawing that schematically shows the aqueous colloidal dispersion of PEDOT/PSS, with Fig. 2 B be the key drawing that schematically shows conductive polymer gel of the present invention, this conductive polymer gel obtains by following: add tensio-active agent in the aqueous colloidal dispersion of the PEDCT/PSS shown in Fig. 2 A, make the aqueous colloidal dispersion gelation thus.

Fig. 3 shows the diagrammatic cross-section that is used for an example of the local iontophoretic treatment patch label that transmits healing potion according to of the present invention.

Fig. 4 shows the diagrammatic cross-section that is used for another example of the local iontophoretic treatment patch label that transmits healing potion according to of the present invention.

Fig. 5 shows the diagrammatic cross-section that is used for another example of the local iontophoretic treatment patch label that transmits healing potion according to of the present invention.

Fig. 6 is the diagrammatic cross-section that shows according to an example of biomedical electrode of the present invention.

Fig. 7 is the diagrammatic cross-section that shows according to another example of biomedical electrode of the present invention.

Fig. 8 is the diagrammatic cross-section that shows according to another example of biomedical electrode of the present invention.

Fig. 9 is the diagrammatic cross-section that shows according to the another one example of biomedical electrode of the present invention.

Figure 10 is the diagrammatic cross-section that shows according to the example of another one again of biomedical electrode of the present invention.

Figure 11 is the diagrammatic cross-section that shows according to an example of toning agent of the present invention.

Figure 12 is the diagrammatic cross-section that shows an example of molecular structure in the conjugated conductive polymer.

Figure 13 A shows that key drawing and Figure 13 B of the aqueous colloidal dispersion of PEDOT/PSS are the key drawings that shows according to an example of conductive polymer gel of the present invention.

Figure 14 is the diagrammatic cross-section that shows an example of antistatic.

Figure 15 is the diagrammatic cross-section that shows an example of sticking with paste according to conduction of the present invention.

Figure 16 shows the diagrammatic cross-section of an example of the molecular structure of conjugated conductive polymer.

Figure 17 A shows that key drawing and Figure 17 B of the aqueous colloidal dispersion of PEDOT/PSS are the key drawings that shows according to an example of conductive polymer gel of the present invention.

Figure 18 is the orthographic plan that shows according to an example of second kind of printed component part of the present invention.

Figure 19 is the synoptic diagram of demonstration according to an example of the battery of fuel cell of the present invention.

Figure 20 is the synoptic diagram of an example that shows the molecular structure of conjugated conductive polymer.

Figure 21 A shows that key drawing and Figure 21 B of the aqueous colloidal dispersion of PEDOT/PSS are the key drawings that shows according to an example of conductive polymer gel of the present invention.

Figure 22 is the synoptic diagram of demonstration according to an example of the battery of the fuel cell of prior art.

Implement best mode of the present invention

By preferred embodiment of the present invention is described with reference to the drawings.The present invention is not subjected to the restriction of following corresponding example and can suitably be used in combination these constitutive characteristics.

In the present invention, in conjugated conductive polymer aqueous colloidal dispersion and/or conjugated conductive polymer solution (hereinafter referred to as the conjugated conductive polymer colloidal dispersion), add tensio-active agent and/or alcohol, or conjugated conductive polymer is doped with the doping agent colloidal dispersion, places mixture then under the condition of gelation.Therefore, with the gelation of conjugated conductive polymer colloidal dispersion, obtain conductive polymer gel.

Disclosed in the example as described below, conductive polymer gel is the gel with electroconductibility, and has those performances that are different from " having high viscosity but the mobile fluid ".For example, even under the situation of the test below carrying out, conductive polymer gel does not emit from beaker: under barometric point, normal temperature from container for example beaker emit conductive polymer gel of the present invention by the inclination beaker or with its upset.

Fig. 1 is the key drawing that schematically shows conduction poly-(3, the 4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) molecular structure (PEDCT/PSS).

Fig. 2 A is the key drawing that schematically shows the aqueous colloidal dispersion of PEDOT/PSS.Fig. 2 B is the key drawing that schematically shows conductive polymer gel of the present invention, this conductive polymer gel obtains by following: add tensio-active agent in the aqueous colloidal dispersion of the PEDCT/PSS shown in Fig. 2 A, make the aqueous colloidal dispersion gelation thus.

Shown in Fig. 2 A, in the aqueous colloidal dispersion 1 of PEDOT/PSS, in water 2, disperse PEDOT/PSS molecule 3.When under the gelation condition, placing when adding tensio-active agent 4 in the aqueous colloidal dispersion 1 of PEDOT/PSS with mixture, shown in Fig. 2 B,, form three-dimensional network by tensio-active agent 4 in the aqueous while of bag, and the easy gelation of mixture obtains conductive polymer gel 5.

Think that by adding tensio-active agent (and/or alcohol) 4 and mixture is placed under the gelation condition in the aqueous colloidal dispersion 1 of PEDOT/PSS, obtain gel, reason is physically or chemically to form three-dimensional network.Think that the gel that obtains has electroconductibility owing to electric electric conductivity and/or ionic conductivity.Certainly, it is not the mode that is intended to this is restricted to this consideration.

In the present invention, do not limit the gelation condition especially.Disclosed in the example as described below, can for example easily obtain gel: under normal atmosphere (atmospheric atom) and normal temperature condition by following method, in the conjugated conductive polymer aqueous colloidal dispersion, add tensio-active agent and/or alcohol, mix them well, and under the preset temperature from the solidification value to the boiling temperature, mixture is placed preset time.

Not restricted gelation still is preferably 5 to 90 ℃ to form the temperature of gel, and more preferably 50 ℃ or higher, so that obtain having the solid gel of high conductivity and excellent handling property.

Time of placing and temperature change according to the kind of conjugated conductive polymer colloidal dispersion and kind, combination and the amount of tensio-active agent and alcohol.Preferably suitably select temperature and time, this temperature and time can make gelation have good efficiency and preparing gel satisfactorily.

Obtain the conjugated conductive polymer colloidal dispersion by following method: disperse at least a in (1) at least a conjugated conductive polymer and (2) conjugated conductive polymer with the colloidal state state in dispersion medium (for example water): conjugated conductive polymer (1) is to be selected from polyacetylene, polyphenylene, polypyrrole, Polythiophene, poly-furans, poly-selenophen, polyisothianaphthene, polyphenylene sulfide, polyaniline, polyvinylene benzene, the polyvinylene thiophene, poly-perinaphthene, poly-anthracene, poly-naphthalene, poly-pyrene, poly-, and their derivative, and conjugated conductive polymer (2) is adulterated with at least a doping agent, this doping agent is selected from iodine, fluoridize arsenic, iron(ic) chloride, perchloric acid, sulfonic acid, perfluorinated sulfonic acid, polystyrolsulfon acid, sulfuric acid, hydrochloric acid, nitric acid, and their derivative.

Its specific examples comprise by catalyzer for example toluenesulphonic acids iron (III) in the presence of, polyase 13,4-Ethylenedioxy Thiophene and the aqueous colloidal dispersion of poly-(3, the 4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) (hereinafter referred to as PEDOT/PSS) of obtaining.Aqueous colloidal dispersion can be purchased, and commodity are called BaytronP ((conductive polymers (concentration of PEDOT/PSS): about 1.3 weight % are prepared by Bayer Co.).

Obtain conjugated conductive polymer solution by dissolving conjugated conductive polymer in water or organic solvent.

Can use conjugated conductive polymer colloidal dispersion and conjugated conductive polymer solution separately, or can be used in combination with arbitrary proportion.

Specifically do not limit the tensio-active agent that the present invention uses, can use at least a tensio-active agent that is selected from following: known cats product, anion surfactant, amphoterics, nonionogenic tenside and their two or more miscellanys.

The example of cats product comprises season alkylammonium salt and halogenated alkyl pyridine.

The example of anion surfactant comprises the condenses of alkylsurfuric acid or its ester salt, Voranol EP 2001 sulfuric acid or its ester salt, alkyl benzene sulphonate (ABS) or its salt, alkyl naphthalene sulfonic acid or its salt, alkyl sulfo-succinic acid or its salt, alkyl diphenyl ether two sulphur sulfuric acid or its salt, lipid acid or its salt, naphthene sulfonic acid or its formalin.

Examples of amphoteric surfactants comprises the collagen of alkyl betaine, amine oxide and hydrolysis.

The example of nonionogenic tenside comprises Voranol EP 2001, polyoxyalkylene alkyl, polyoxyethylene, sorbitan fatty(acid)ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene hardened castor oil, polyoxyethylene alkyl amine, alkyl chain triacontanol acid amides, and their derivative.

In these tensio-active agents, particularly preferably be, can use the alkyl benzene sulphonate (ABS) of long-chain, because the efficient of gelation is improved.

Specifically do not limit the amount of the tensio-active agent that in conductive polymer gel, adds, but, be preferably 0.1 to 30 weight part, more preferably 0.5 to 10 weight part based on the conductive polymers of 1 weight part.When this amount was lower than 0.1 weight part, gelation may not take place.On the other hand, when this amount surpassed 30 weight parts, gelation may not take place yet.

Concrete restriction alcohol can use at least a alcohol in two or more the mixture that is selected from known monohydroxy-alcohol or polyvalent alcohol and they.

The example of monohydroxy-alcohol comprises side chain or straight chain alcohol, for example ethanol, Virahol and butanols; Pure and mild their two or more the mixture of cyclic alcohol, polymkeric substance.

Examples of polyhydric alcohols comprises dibasic alcohol, for example 1,2 ethylene glycol and propylene glycol; The chain polyvalent alcohol is glycerol, red bright alcohol, xylylol (xylytol) and Sorbitol Powder for example; Cyclic polyols is glucose and scroll for example; The polyvalent alcohol of polymer-like is polyoxyethylene glycol and polyvinyl alcohol for example; With their two or more mixture.

In these alcohol, can preferably use Virahol, 1,2 ethylene glycol, polyoxyethylene glycol, because following reason, special preferred polyol is 1,2 ethylene glycol and polyoxyethylene glycol for example.Especially preferably use 1,2 ethylene glycol, even because its performance causes the effect of gelation and also do not have volatility under lower concentration.Specifically do not limit the molecular weight of polyoxyethylene glycol, but be preferably 1000, even, gelation takes place also because be lower than under molecular weight is lower than 400 situation when this amount.

Specifically do not limit the amount of the alcohol in the conductive polymer gel, but be based on the conductive polymers of 1 weight part, be preferably 1 to 70 weight part, more preferably 10 to 50 weight parts.When this amount was lower than 1 weight part, gelation can not take place.It is not preferred that this amount surpasses 70 weight parts, because the viscosity of gel becomes too low and gelation may not take place yet.

Can use tensio-active agent and alcohol separately, or be used in combination with arbitrary proportion.When tensio-active agent and alcohol are used in combination, specifically do not limit its ratio.

Describe the present invention now and prepare two kinds of typical technologies that conductive polymer gel is used.

＜the first kind of technology 〉

First kind of technology is a kind of method of preparation in bottle commonly used, and its program is described below.

(1a) use transfer pipet that Baytron P is dripped in bottle, weigh then.

(1b) similarly, use transfer pipet with additive for example 1,2 ethylene glycol drip in bottle.

(1c) in air, under the room temperature by after closing bottle cap sealing, with the solution in the have gentle hands jog rolling bottle 1 minute.

(1d) in sealing, be to place bottle with stable position in the atmosphere of 10 ℃ (in refrigerators), 25 ℃ (indoor), 50 ℃ (in process furnace) keeping temperature.Under the sort of situation, bottle is exposed in the air in every kind of temperature.

(1e) after about 3 days, confirm gel formation and take out gel.After turning back to about room temperature, in the space of cold-peace dark (temperature is 5 ℃ to 10 ℃), store gel.

To (1e), in bottle, obtain conductive polymer gel by above-mentioned step (1a).

＜the second kind of technology 〉

Second kind of technology is a kind of method for preparing the gel of film like, and its program is described below.

(2a) to by PYREX ^In the glass disc of making, pour the solution that is wherein comprised the 1,2 ethylene glycol of adding in the step (1c) in first kind of technology gently into, obtain (completely) under the bubble and have the solution dish not forming thus.Under the sort of situation, coil in the air that is exposed in every kind of temperature.

(2b) in air, under the normal pressure, at 50 ℃ of (in the process furnace) settling position holding trays.

(2c) after about 3 days, confirm gel formation and take out gel.Place gel and be back to about room temperature up to it.

(2d) use atomizer, on the whole surface of gel, spray distilled water, and in air, at room temperature placed gel about 30 seconds.

(2e) in dish, pour for example acetone of solvent into, cover the surface of gel thus from peripheral portion.

(2f) between bottom of coiling and gel, sandwich for example top of tweezers of sharp anchor clamps, peel off gel then.

(2g) use shear tool for example the blade of razor cut gel at leisure, be cut into piece then with any width and length.

To (2g), obtain the conductive polymer gel of strip by above-mentioned step (2a).

Can determine the electrical property of conductive polymer gel, for example electric conductivity and electromotive force by following method.

The measuring method of＜electric conductivity 〉

(3a) put into the cylindrical battery that comprises unlimited upper bottom portion and the lower bottom part that opens wide in the solution with preparation in the step (1c), to form gel, the interior diameter of cylindrical battery is 5mm and highly is 10mm.

(3b) after forming gel, battery is to comprise in cylinder that wherein the state transitions of gel is in air.

(3c) in air, settle platinum electrode on the whole surface of each exposed portion of gel, it constitutes the upper and lower bottom of cylinder battery, so that cover each exposed portion.

(3d) between platinum electrode, sandwich the gel two ends that comprise in the cylinder battery, measure electric conductivity with two jointing methods.

＜electro-motive force measurement method 〉

(4a) gel that will obtain in step (1e) is transferred in the container of being made by material, and for example beaker inserts copper sheet and the aluminium flake that fixes as electrode by the regular interval with about 1cm then in gel.

(4b) two kinds of sheets as electrode connect with the volt ohm-milliammeter that is connected by the copper lead-in wire, to form the metering circuit plate.

(4c) electromotive force that obtains immediately behind connection metering circuit plate is read by volt ohm-milliammeter.

To (4c), can easily measure the electromotive force in the conductive polymer gel by above-mentioned step (4a).

The embodiment of toning agent

Figure 11 is the diagrammatic cross-section of demonstration according to an example of the toning agent 1001 of embodiment of the present invention.

The resin part 1012 that is generally spheric core body part 1011 and provides on the surface of core body part 1011 is provided toning agent 1001, and core body part 1011 is made by conductive polymer gel 1002.

The particle size of preferred toning agent 1001 is 15 μ m or following, more preferably 8 μ m or following.Therefore, when toning agent 1001 shifts and is fixed on the base material, can realize excellent resolving power and can form pattern distribution with fine linewidth.

Shown in Figure 13 B, conductive polymer gel 1002 comprises water 1021, conjugated conductive polymer 1022 and tensio-active agent 1023 and/or the alcohol as main ingredient.

By using tensio-active agent 1023 and/or alcohol to make conjugated conductive polymer 1022 gelationizations, form conductive polymer gel 1002, and can use those conductive polymer gel that in Japanese patent application No.2003-19120, propose.

Figure 12 is the synoptic diagram of an example that shows the molecular structure of the conjugated conductive polymer 1022 shown in Figure 13 B.Conjugated conductive polymer 1022 is poly-(3, the 4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) (hereinafter referred to as PEDOT/PSS), and be by obtaining as doping agent doping poly-(3, the 4-Ethylenedioxy Thiophene) (hereinafter referred to as PEDOT) with poly-(styrene sulfonic acid) (hereinafter referred to as PSS).

Figure 13 A schematically shows the key drawing of aqueous colloidal dispersion of PEDOT/PSS and Figure 13 B to schematically show the key drawing of the present invention by the conductive polymer gel 1002 that adds tensio-active agent 1023 and gelation mixture obtain in the aqueous colloidal dispersion of the PEDOT/PSS shown in Figure 13 A.

As shown in FIG. 13A, in the aqueous colloidal dispersion of PEDOT/PSS, in water 1021, disperse the PEDOT/PSS molecule.When in the aqueous colloidal dispersion of PEDOT/PSS, adding tensio-active agent 1023, under the gelation condition, place mixture, shown in Figure 13 B, when comprising water 1021 therein, form three-dimensional network by tensio-active agent 1023, and therefore the easy gelation of mixture obtains conductive polymer gel 1002.

Think, by add tensio-active agent 1023 (and/or alcohol) in the aqueous colloidal dispersion of PEDOT/PSS, place mixture under the gelation condition, obtain gel, reason is physically or chemically to form three-dimensional network.Consider that the gel that obtains has electroconductibility owing to electric electroconductibility and/or ionic conductivity.Certainly, it is not the mode that is intended to this is limited this consideration.

Conjugated conductive polymer 1022 comprises and for example is selected from least a in following: polyacetylene, polyphenylene, polypyrrole, Polythiophene, poly-furans, poly-selenophen, polyisothianaphthene, polyphenylene sulfide, polyaniline, polyvinylene benzene, polyvinylene thiophene, poly-perinaphthene, poly-anthracene, poly-naphthalene, poly-pyrene, poly-, and their derivative.In these polymkeric substance, preferably use polypyrrole shown in Figure 12 and Polythiophene, because it has high stability and high reliability, and utilize easily.

Preferred conjugated conductive polymer is doped with doping agent 1022, and the carrier concentration in conductive polymer gel 1002 improves thus, and can improve electroconductibility.

Doping agent comprises and for example is selected from least a in following: iodine, fluoridize arsenic, iron(ic) chloride, perchloric acid, sulfonic acid, perfluorinated sulfonic acid, polystyrolsulfon acid, sulfuric acid, hydrochloric acid, nitric acid, and their derivative.In these doping agents, preferred polystyrolsulfon acid is because can easily regulate high conductivity.

The example of the aqueous colloidal dispersion of conjugated conductive polymer 1022 comprise by catalyzer for example toluenesulphonic acids iron (III) in the presence of, polyase 13,4-Ethylenedioxy Thiophene and gathered the aqueous colloidal dispersion of (3, the 4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) (hereinafter referred to as PEDOT/PSS).Aqueous colloidal dispersion can be purchased, and commodity are Baytron P ((concentration of conductive polymers (PEDOT/PSS) is about 1.3 weight %, by Bayer Co. preparation).

Concrete limiting surface promoting agent 1023 and can using is selected from least a tensio-active agent in following: known cats product, anion surfactant, amphoterics, nonionogenic tenside and two or more miscellanys in them.

The example of cats product comprises season alkylammonium salt and halogenated alkyl pyridine.

The example of anion surfactant comprises the condenses of alkylsurfuric acid or its ester salt, Voranol EP 2001 sulfuric acid or its ester salt, alkyl benzene sulphonate (ABS) or its salt, alkyl naphthalene sulfonic acid or its salt, alkyl sulfo-succinic acid or its salt, alkyl diphenyl ether disulphonic acid or its salt, lipid acid or its salt, naphthene sulfonic acid or its formalin.

Examples of amphoteric surfactants comprises the collagen of alkyl betaine, amine oxide and hydrolysis.

The example of nonionogenic tenside comprises Voranol EP 2001, polyoxyalkylene alkyl, polyoxyethylene, sorbitan fatty(acid)ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene hardened castor oil, polyoxyethylene alkyl amine, alkyl chain triacontanol acid amides, and their derivative.

In these tensio-active agents 1023, especially preferably can use the alkyl benzene sulphonate (ABS) of long-chain, because improved the efficient of gelation.

Specifically do not limit the amount that in conductive polymer gel, adds tensio-active agent 1023, still, based on the conductive polymers of 1 weight part, be preferably 0.1 to 30 weight part, more preferably 0.5 to 10 weight part.When this amount was lower than 0.1 weight part, gelation may not take place.Gelation preferably should amount not surpass 30 weight parts, because may not take place yet.

Concrete restriction alcohol can use at least a alcohol that is selected from two or more the mixture of known monohydroxy-alcohol and polyvalent alcohol and its.

The example of monohydroxy-alcohol comprises side chain or straight chain alcohol, for example ethanol, Virahol and butanols; Pure and mild its two or more the mixture of cyclic alcohol, polymer-like.

Examples of polyhydric alcohols comprises dibasic alcohol for example 1,2 ethylene glycol and propylene glycol; The chain polyvalent alcohol is glycerol, red bright alcohol, xylylol and Sorbitol Powder for example; Cyclic polyols is glucose and scroll for example; The polyvalent alcohol of polymer-like is polyoxyethylene glycol and polyvinyl alcohol for example; With its two or more mixture.

In these alcohol, can preferably use Virahol, 1,2 ethylene glycol, polyoxyethylene glycol, because following reason, special preferred polyol is 1,2 ethylene glycol and polyoxyethylene glycol for example.Especially preferably use 1,2 ethylene glycol, even because its performance causes the effect of gelation and do not have volatility under lower concentration.Specifically do not limit the molecular weight of polyoxyethylene glycol, but be preferably 1000, even, gelation takes place also because be lower than under molecular weight is lower than 400 situation when this amount.

Specifically do not limit the alcohol amount in the conductive polymer gel 1002, but be based on the conductive polymers of 1 weight part, be preferably 1 to 70 weight part, more preferably 10 to 50 weight parts.When this amount was lower than 1 weight part, gelation can not take place.It is not preferred that this amount surpasses 70 weight parts, because the viscosity of gel becomes too low and gelation may not take place yet.

Can use tensio-active agent 1023 and alcohol separately, or be used in combination with arbitrary proportion.When tensio-active agent 1023 and alcohol are used in combination, specifically do not limit its ratio.

By using tensio-active agent 1023 and/or alcohol, make conjugated conductive polymer 1022 gelations in the following method.

By in the colloidal dispersion that in water 1021 and/or conjugated conductive polymer solution, prepares, add as additive tensio-active agent 1023 and/or alcohol not forming under the bubble with colloidal dispersion conjugated conductive polymer 1022.

Then, with vibrational state not, in the open space of common air atmosphere or enclosed space, place the mixture scheduled time.

Therefore, form three-dimensional network and the easy gelation of mixture, therefore, obtain conductive polymer gel 1002 as the composition gel of toning agent 1001 with stable manner.

Obtain conjugated conductive polymer solution by dissolving conjugated conductive polymer 1022 in water or organic solvent.Can use conjugated conductive polymer colloidal dispersion and conjugated conductive polymer solution separately, or also can be used in combination with arbitrary proportion.

The core body that constitutes toning agent 1001 is partly made by conductive polymer gel 1002, specifically do not limit its shape, but core body partly is a particle shape.

Toning agent 1001 based on 100 weight parts, the preferred amount that constitutes the conductive polymer gel of core body part 1011 be 40 weight parts or more than, more preferably 65 weight parts or more than, when toning agent 1001 is transferred on the base material, can give base material enough electroconductibility thus.

Surface with resin part 1012 coating core body portions 1011.Resin part 1012 is made of insulating resin, and insulating resin plays a part tackiness agent, and can apply the known tackiness agent of using as toning agent those.The example comprises can be by adding the resin of heat setting toning agent, for example styrene-propene acid copolymer resin, vibrin and Resins, epoxy; With the resin compound that obtains by adding conductive polymers in resin.

Based on the toning agent 1001 of 100 weight parts, the amount that preferably constitutes the resin of resin part 1012 be 0.1 weight part or more than, 30 weight parts or following more preferably can give toning agent 1001 surfaces enough chargeable property thus.

On the surface of core body part 1022, that is, the interface between core body part 1022 and the resin part 1012 provides by the various insulation components insulated part made of resin for example, improves the chargeable property on toning agent 1001 surfaces and the development property of raising thus.

Apply toning agents 1001 surfaces with charge control agent 1013, thus under the situation of charging toning agent 1001, the polarity (charge polarity) that can regulate toning agent 1001 surfaces of can charging.

As for charge control agent 1013, can use the known charge control agent and the example to comprise quaternary ammonium salt, azo-group metal-containing complex, salicylic acid metal title complex, calixarene and contain amino fluorochemical.According to the charge polarity on toning agent 1001 surfaces, can suitably select and use charge control agent.

Based on the toning agent 1001 of 100 weight parts, the amount of preferred charge control agent 1013 be 0.1 weight part or more than, more preferably 5 weight parts or following can give toning agent 1001 surperficial ideal charge polarities thus.

Apply the surface of toning agent 1001 with releasing agent 1014.As for releasing agent 1014, can use known releasing agent, the example comprises olefinic wax and carnauba wax.

Based on the toning agent 1001 of 100 weight parts, the amount of preferred releasing agent 1014 be 0.1 weight part or more than, more preferably 10 weight parts can obtain enough release properties thus.

For example Ginding process and particle deposition method can prepare toning agent 1001 by known method.For example; conductive polymer gel 1002 fine grindings are become particle; it plays a part core body part 1011; abrasive grains of fine size and mixed with resin with conductive polymer gel 1002; resin plays a part resin part 1012; the granulation mixture obtains toning agent 1001 then, and it comprises the core body part 1011 that resin part 1012 and its surface are partly applied by resin.

Conductive polymer gel 1002, it constitutes the core body part 1011 of toning agent 1001, it is the identical polymer compound (organic compound) of insulating resin (tackiness agent) that constitutes resin part 1012 with conduct, with mixed easily, and have an excellent consistency, therefore can be with the whole surface of resin part 1012 even coating core body portions 1011.

Form in the toning agent of usefulness at existing circuit card by technology, the metallic particles of formation core body part is not easy with the resin that constitutes the resin part mixed, so partly is difficult to the whole surface of coating core body portion with resin.Therefore, core body partly exposes to the open air on toner surface, and the chargeable property deterioration of toning agent, and it is poor to cause problem for example to be developed thus.

On the contrary, according to the present invention, as mentioned above, can realize having the toning agent 1001 of excellent chargeable property thus, and can suppress the development of difference with the whole surface of resin part 1012 even coating core body portions 1011.

Can and be fixed on the base material toning agent 1001 transfer printings by known toning system.The example of printing transferring method comprises for example electrostatic latent image transfer printing of toner image printing transferring method, static corona transfer, the transfer printing of static belt, electrostatic drum transfer printing, adhesive transfer, pressure transfer printing and magnetic printing transferring method.When being used in combination polychrome or multiple toning agent, can use for example multiple development of multiple transferring system, transfer drum, intermediate transfer and series system.

Form in the toning agent of usefulness at existing circuit card by technology, the core body part is made with true density big by metallic particles, so developing process needs the big quantity of electric charge.

On the contrary, according to the present invention, because core body part 1011 is formed from a resin, as the toning agent of PPC (plain paper electrostatic copier (Plain Paper Copier)) usefulness, true density is little, uses traditional duplicating machine, toning agent can be shifted and is fixed on the base material.

First kind of conductive functional, antistatic 1003 and first kind of printed component part of the present invention are described now.

The current-carrying part that first kind of conductive functional of the present invention comprises flat substrates and provide at least one surface of base material, flat substrates is made by resin film or the paper of PET (polyethylene terephthalate), and current-carrying part is made by toning agent.

By toning agent is shifted and is fixed on the base material 1001, form current-carrying part.Omit toning agent 1001 and describe in detail, because it as mentioned above.Base material is not restricted to flat substrates, can be to shift on it and fixing any element of toning agent 1001.

As mentioned above, can on base material, shift and fixing toning agent 1001, can form meticulous current-carrying part with high precision by known toning system.

Specifically do not limit the shape of current-carrying part, go up to shift and the fixedly linearity or the plane current-carrying part of toning agent 1001 at least one surface that the example is included in base material.

Linearity configuration is meant the shape of one or more straight lines or curve, and for example, pattern form is waviness, straight line, curve, coil shape for example, and Polygons is shape, letter and the symbol of triangle or tetragon, circle, ellipse and its combination for example.By forming a plurality of linear current-carrying part of distance (at interval) continuously, can form the plane current-carrying part.

The example of plane current-carrying part comprises that one surface has the current-carrying part of following shape, for example for example the shape and the symbol of triangle or tetragon, circle, ellipse and its combination of Polygons.

Current-carrying part is not restricted to those that form on substrate surface, can be by the inside of the bore portion, recessed part or the groove that on base material, provide shift and fixedly toning agent 1001 form those.

Therefore, can be by being used alone or in combination the linear conductance part, forming current-carrying part with one dimension, bidimensional or 3D shape.For example, can use current-carrying part, can use two-dimensional shapes to be pattern distribution, electrode, electromagnetic induction coil and antenna as distribution with one dimension shape.Can use current-carrying part to be through type electrode (through electrode) with 3D shape.

Thickness by suitably selecting current-carrying part, width, length can control group characteristic and electroconductibility and first kind of conductive functional can be used to utilize the various purposes of the electroconductibility of current-carrying part.

Can use first kind of conductive functional to be the distribution substrate, and can for example light emitting devices and IC chip are used for various electronicss by settle various electronic units on base material.It can also use as IC mark and IC tag.

Figure 14 is the diagrammatic cross-section that shows according to an example of the present invention antistatic 1003.Antistatic 1003 is examples of first kind of conductive functional, and the current-carrying part 1032 that provides on flat substrates 1031 has planeform.

In antistatic 1003 of the described example as Figure 14, on the whole surface of base material 1031, provide current-carrying part 1032.

In antistatic 1003, current-carrying part 1032 is given antistatic 1003 surface (surface of base material 1031) electroconductibility, and base material 1031 is not charged.Can on a part at least one surface of base material 1031, provide current-carrying part 1032.

First kind of printed component part of the present invention is an example of first kind of conductive functional, and the current-carrying part that provides on flat substrates has linearity configuration.

Can use the linear conductance part as pattern distribution, electrode, through type electrode, electromagnetic induction coil and antenna.Therefore, can use first printed component part as distribution substrate, IC mark and IC tag.

Because, can form the plane current-carrying part, so current-carrying part can be the plane current-carrying part by forming a plurality of linear current-carrying part of distance (at interval) continuously.

Because the core body part 1011 of toning agent 1001 is made by conductive polymer gel 1002, the toning agent that forms usefulness with distribution in the prior art is compared, and can reduce the content of metal component in the toning agent 1001, and wherein core body is partly made by metallic particles.Therefore, the environmental pressure that can reduce printed circuit board (PCB) or dispose by the electronic unit that toning agent 1001 is made.

In first kind of conductive functional of the present invention, antistatic 1003 and first kind of printed component part, because the current-carrying part 1032 that provides at least one surface of base material 1031 is made by toning agent 1001 of the present invention, the toning agent that forms usefulness with distribution in the prior art is compared, can reduce the content of metal component, and can reduce the environmental pressure of disposal, wherein the core body part is made by metallic particles.

Technical scope of the present invention is not subjected to the restriction of top embodiment and can carries out various modifications not leaving the scope of the invention.

For example, can apply the surface of toning agent 1001 to improve liquidity with the external application additive.As for the external application additive, can use known external application additive, the example comprises fine inorganic particle for example silicon oxide, aluminum oxide and titanium oxide (titanium dioxide); With meticulous resin particle.

Can be with applying agent for example siloxane polymer and fluoropolymer; Surface with carbon black coating toning agent 1001.

According to the transfer and the fixed system (toning system) of toning agent 1001, apply toning agent 1001 with magneticsubstance.

For example, toning agent can comprise magnetic-particle for example iron particle and ferrite particle, or magneticsubstance magnetic-particle for example, its surface partly applies with the resin in core body part 1011 or the resin part 1012 and toning agent can be the toning agent 1001 that the surface applies with magneticsubstance.

According to the toning system of toning agent 1001, toning agent 1001 is mixed with carrier.According to the transfer and the fixed system (toning system) of toning agent 1001, the powder of toning agent 1001 can be mixed with support powder.

As for carrier, can use known carrier, the example comprises meticulous resin particle and magnetic powder.The particle size of carrier is preferably 200 μ m or following, more preferably 100 μ m or following.Therefore, can reach enough resolving power.

Conduction is stuck with paste

Figure 15 shows according to the conduction of one embodiment of the invention to stick with paste 2001 synoptic diagram.Conduction is stuck with paste 2001 and is comprised at least a conductive polymer gel 2002, conductive powder 2003 and resin glue 2004.Conductive polymer gel 2002 and conductive powder 2003 are that conduction is stuck with paste the electro-conductive material in 2001.

Conductive polymer gel 2002 comprises water 2021, conjugated conductive polymer 2022 and tensio-active agent 2023 and/or the alcohol as main ingredient, shown in Figure 17 B described as follows.

Make conjugated conductive polymer 2022 gelations by tensio-active agent 2023 and/or alcohol, form conductive polymer gel 2002, for example, can use those conductive polymer gel that propose among the Japanese patent application No.2003-19120.

Figure 16 is the synoptic diagram of an example that shows the molecular structure of the conjugated conductive polymer 2022 shown in Figure 17 B.Conjugated conductive polymer 2022 is poly-(3, the 4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) (hereinafter referred to as PEDOT/PSS), and be by obtaining as doping agent doping poly-(3, the 4-Ethylenedioxy Thiophene) with styrene sulfonic acid (hereinafter referred to as PSS).

Figure 17 A shows that key drawing and Figure 17 B of the aqueous colloidal dispersion of PEDOT/PSS are the key drawings that shows an example of the conductive polymer gel 2002 that obtains by the aqueous colloidal dispersion gelation that makes the PEDOT/PSS shown in Figure 17 A after adding tensio-active agent 2023.

As shown in Figure 17 A, in the aqueous colloidal dispersion of PEDOT/PSS, in water, disperse the PEDOT/PSS molecule.When in the aqueous colloidal dispersion of PEDOT/PSS, adding tensio-active agent 2023 and under the gelation condition, place mixture, as shown in Figure 17 B, when comprising water 2021 therein, form three-dimensional network by tensio-active agent 2023, and the easy gelation of mixture obtains conductive polymer gel 2002 thus.

Think,, obtain gel, because three-dimensional network physically or chemically forms by in the aqueous colloidal dispersion of PEDOT/PSS, adding tensio-active agent 2023 (and/or alcohol) and under the gelation condition, placing mixture.Think that the gel that obtains has electroconductibility owing to electric electroconductibility and/or ionic conductivity.Certainly, it is not the mode that is intended to it is restricted to this consideration.

Conjugated conductive polymer 2022 comprises and for example is selected from least a in following: polyacetylene, polyphenylene, polypyrrole, Polythiophene, poly-furans, poly-selenophen, polyisothianaphthene, polyphenylene sulfide, polyaniline, polyvinylene benzene, polyvinylene thiophene, poly-perinaphthene, poly-anthracene, poly-naphthalene, poly-pyrene, poly-, and their derivative.In these polymkeric substance, preferred polypyrrole or the Polythiophene that uses as shown in figure 16 is because it has high stability and obtains easily.

Preferred conjugated conductive polymer is doped with doping agent 2022, improves the carrier concentration in conductive polymer gel 2002 thus, and can improve electroconductibility.

Doping agent comprises at least a in for example following: iodine, fluoridize arsenic, iron(ic) chloride, perchloric acid, sulfonic acid, perfluorinated sulfonic acid, polystyrolsulfon acid, sulfuric acid, hydrochloric acid, nitric acid, and their derivative.In these doping agents, preferred polystyrolsulfon acid is because can easily regulate high electric conductivity.

The example of the colloidal dispersion of conjugated conductive polymer 2022 is included in catalyzer for example under the existence of toluenesulphonic acids iron (III), pass through polyase 13,4-Ethylenedioxy Thiophene and the aqueous colloidal dispersion of poly-(3, the 4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) (hereinafter referred to as PEDOT/PSS) of obtaining.Aqueous colloidal dispersion can be purchased, and commodity are called Baytron P ((concentration of conductive polymers (PEDOT/PSS) is about 1.3 weight %, by Bayer Co. preparation).

Specifically do not limit the tensio-active agent 2023 that the present invention uses, can use at least a tensio-active agent that is selected from following: two or more miscellany of known cats product, anion surfactant, amphoterics, nonionogenic tenside and its.

The example of cats product comprises season alkylammonium salt and halogenated alkyl pyridine.

The example of anion surfactant comprises the condenses of alkylsurfuric acid or its ester salt, Voranol EP 2001 sulfuric acid or its ester salt, alkyl benzene sulphonate (ABS) or its salt, alkyl naphthalene sulfonic acid or its salt, alkyl sulfo-succinic acid or its salt, alkyl diphenyl ether disulphonic acid or its salt, lipid acid or its salt, naphthene sulfonic acid or its formalin.

Examples of amphoteric surfactants comprises the collagen of alkyl betaine, amine oxide and hydrolysis.

The example of nonionogenic tenside comprises Voranol EP 2001, polyoxyalkylene alkyl, polyoxyethylene, sorbitan fatty(acid)ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene hardened castor oil, polyoxyethylene alkyl amine, alkyl chain triacontanol acid amides, and their derivative.

In these tensio-active agents 2023, especially preferably use the alkyl benzene sulphonate (ABS) of long-chain, because improve the efficient of gelation.

Specifically do not limit the amount of the tensio-active agent 2023 that in conductive polymer gel, adds, but, be preferably 0.1 to 30 weight part, more preferably 0.5 to 10 weight part based on the conductive polymers of 1 weight part.

When this amount was lower than 0.1 weight part, gelation may not take place.It is not preferred that this amount surpasses 30 weight parts, because gelation may not take place yet.

Concrete restriction alcohol can use at least a alcohol that is selected from two or more the mixture of known monohydroxy-alcohol and polyvalent alcohol and its.

The example of monohydroxy-alcohol comprises side chain or straight chain alcohol, for example ethanol, Virahol and butanols; Pure and mild their two or more the mixture of cyclic alcohol, polymer-like.

Examples of polyhydric alcohols comprises dibasic alcohol for example 1,2 ethylene glycol and propylene glycol; The chain polyvalent alcohol is glycerol, red bright alcohol, xylylol and Sorbitol Powder for example; Cyclic polyols is glucose and scroll for example; The polyvalent alcohol of polymer-like is polyoxyethylene glycol and polyvinyl alcohol for example; With their two or more mixture.

In these alcohol, can preferably use Virahol, 1,2 ethylene glycol, polyoxyethylene glycol, because following reason, special preferred polyol is 1,2 ethylene glycol and polyoxyethylene glycol for example.Especially preferably use 1,2 ethylene glycol, even because its performance causes the effect of gelation and also do not have volatility under lower concentration.Specifically do not limit the molecular weight of polyoxyethylene glycol, but be preferably 1000, even, gelation takes place also because be lower than under molecular weight is lower than 400 situation when this amount.

Specifically do not limit the amount of the alcohol in the conductive polymer gel 2002, but be based on the conductive polymers of 1 weight part, be preferably 1 to 70 weight part, more preferably 10 to 50 weight parts.When this amount was lower than 1 weight part, gelation can not take place.It is not preferred that this amount surpasses 70 weight parts, because the viscosity of gel becomes too low and gelation may not take place yet.

Can use tensio-active agent 2023 and alcohol separately, or be used in combination with arbitrary proportion.

When tensio-active agent 2023 and alcohol are used in combination, specifically do not limit its ratio.

In the following method by using tensio-active agent 1023 and/or alcohol to make conjugated conductive polymer 1022 gelations.By in water 2021 and/or conjugated conductive polymer solution with colloidal dispersion conjugated conductive polymer 2022 in the colloidal dispersion of preparation, do not forming under the bubble tensio-active agent 2023 and/or the alcohol that adds as additive.

Then, with vibrational state not in common air atmosphere open space or seal cavity in place the mixture scheduled time.

Therefore, form three-dimensional network and the easy gelation of mixture, therefore, obtain conductive polymer gel 2002 as the composition gel of toning agent 2001 with stable manner.

Obtain conjugated conductive polymer solution by dissolving conjugated conductive polymer 2022 in water or organic solvent.Can use conjugated conductive polymer colloidal dispersion and conjugated conductive polymer solution separately, or can also be used in combination by arbitrary proportion.

The example of sticking with paste the conductive powder 2003 of 2001 formation component as conduction comprises: conductive carbon and metal-powder.

As for conductive carbon, can use carbon black and acetylene carbon black, the conductive stages conductive carbon that preferred use can be purchased by oven process and channel process preparation.

As for metal-powder, excellent electroconductibility is preferably used and given to silver powder.

In order to control electric conductivity and anti-weld decay, can use by adding the powdered alloy that gold, platinum, palladium or rhodium obtain.

Preferably in advance conductive powder 2003 is carried out surface treatment, improve the dispersiveness of conductive powder 2003 thus.Therefore, conductive powder 2003 is homodisperse in resin glue 2004, can eliminate for example variation of electroconductibility of feature thus.As for the treatment agent of conductive powder 2003, can use traditional tensio-active agent and coupling agent.

Stick with paste 2001 examples that constitute the resin glue 2004 of component as conduction and comprise crosslinkable resin for example phenol resins, melamine resin, urea resin, xylene resin, Synolac, unsaturated polyester resin, acrylic resin, polyimide resin, furane resin, urethane resin and polyisocyanate resin; With thermoplastic resin for example polyethylene, polypropylene, polyester, ABS resin, polymethylmethacrylate, polyvinyl chloride, poly-1,1-vinylidene chloride, polyvinyl acetate, polyvinyl alcohol, poly-acetal, polycarbonate, polyester, polyphenylene oxide, polysulfones, polyimide, polyethersulfone, poly-allylat thing (polyallylate), polyetherketone, tetrafluoroethylene and silicone resin.Can use and be selected from these resin glues one or more.

When using cross-linked resin, can suitably use known solidifying agent and curing catalysts.

Add solvent in 2001 regulating viscosity because stick with paste to conduction usually, can be by the traditional printing technology to the base material solution that obtains of resin film or substrates coated for example.

As for solvent, can use known solvent.Particularly, can preferably use boiling point is 250 ℃ or lower solvent, because when sticking with paste 2001 by the conduction that is heating and curing, solvent almost evaporates under the situation that does not stay resistates.

The example of solvent comprise hydrocarbon solvent for example toluene, hexanaphthene, methylcyclohexane, just-hexane and pentane; Alcohol is Virahol and butanols for example; Ketone is pimelinketone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), diethyl ketone and isophorone for example; Ester is ethyl acetate, propyl acetate and butylacetate for example; Ethylene glycol mono-ether, ethylene glycol monomethyl ether, dihydroxypropane single-ether, diethylene glycol monomethyl ether and acetate (3-methoxyl group-3-methyl butyl) ester, and their acetic ester; With their one or more mixture.

Comprising under thermoset cross-linked resin and thermoplastic resin the situation as resin glue 2004, can be by coming curing conductive to stick with paste 2001 to base material coating post-heating.As for heating means, can use the heating means of well heater separately, or with use infrared rays or high-frequency method is used in combination.

Comprising under the situation of photocurable cross-linked resin as resin glue 2004, can come curing conductive to stick with paste 2001, hertzian wave such as microwave, infrared rays, visible light, UV-light, vacuum-ultraviolet light, X ray or electron beam by after applying, using electromagnetic wave radiation to base material.

In the same manner as described above, can stick with paste 2001 to form distribution by curing conductive.

By using known agitator, mixed formation component is conductive polymer gel 2002, conductive powder 2003 and resin glue 2004 for example, prepares conduction and sticks with paste 2001.

For example, can use for example high speed agitator of agitator, stir mixed conduction and stick with paste 2001 formation component, and use kneader for example three-roller type kneader or kneader mediate the mixture that obtains, disperse more equably thus to constitute component, obtain conduction and stick with paste 2001.

In order disperse to constitute component equably, can mixed constitute component in, use ultrasonic wave or high frequency, or mixed the time, exert pressure in agitator or the kneader and change applied pressure.

Comprise for example metal-powder and of conductive powder 2003 because conduction sticks with paste 2001, compared with prior art, can reduce obtaining the conductive powder 2003 that enough electric conductivitys need as the conductive polymer gel 2002 of electro-conductive material.Because compared with prior art, can reduce the content of metal component (conductive powder 2003), when the disposal of printed circuit board (PCB) that uses conduction paste 2001 and electronic unit, can reduce environmental pressure.

Carbon component (the C of content of conductive polymer gel 2002 (G) and conductive powder 2003 _p) summation (G+C of content _p) stick with paste the ratio of summation (G+P) of the content (P) of the content (G) of the conductive polymer gel 2002 in 2001 and conductive powder 2003 with conduction: ((G+C _p)/(G+P)) be preferably 0.07 or more than, more preferably 0.13 to 0.24, and most preferably be 0.5 or more than.

((G+C _p)/(G+P)) be illustrated in the organic compound component except that metal component in the electro-conductive material for example carbon ratio and can by control this ratio be 0.07 or more than, to reduce environmental pressure.

The ratio of the summation (P+G) of the content (P) of content of conductive polymer gel 2002 (G) and conductive powder 2003 and the content B of resin glue 2004: ((G+P)/B) is preferably 3/7 to 9/1, and more preferably 4 to 6.

(G+P)/B represents the ratio of electro-conductive material and resin glue 2004.When (G+P)/B is 3/7 or when higher, reach conduction and stick with paste 2001 needed electroconductibility, and can form distribution and electrode by using conduction to stick with paste 2001 with enough electroconductibility, can also carry out being connected of lead-in wire of terminals and electronic unit.

When the ratio of (G+P)/B less than 9/1 or when lower, can reach enough globalities, and can use conduction to stick with paste 2001 to form distribution and electrodes, its more difficult being stripped from.

Conductive powder 2003 usually by mineral compound for example metal-powder make, and poor with the consistency of resin glue (organic compound) 2004.Therefore, when conductive powder 2003 content in the conduction paste 2001 were big, as the content of resin glue 2004 of the prior art, conductive powder 2003 mixed mutually with resin glue 2004 hardly, cause thus being separated, therefore the globality and the flexible rapid deterioration of conduction paste 2001 and base material.Therefore, by stick with paste to the base material coated with conductive 2001 and curing conductive stick with paste and form under the situation of distribution, distribution and base material are peeled off.Also flexible owing to what differ from, when base material was crooked, distribution was in the curved part fracture of base material.

On the contrary, according to the present invention, because conductive polymer gel 2002 is polymkeric substance, as resin glue 2004, the surface entanglement of its molecule and conductive powder 2003 keeps conductive powder 2003 thus.As mentioned above, because conductive polymer gel 2002 plays a part electro-conductive material, can reduce the content of conductive powder 2003 by the amount of conductive polymer gel 2002.

Therefore, compared with prior art, can suppress being separated between conductive powder 2003 and the resin glue 2004, can improve thus conduction stick with paste 2001 with the globality of base material and flexible.Therefore, the distributions and the base material that use conduction to stick with paste 2001 formation have excellent globality, and more difficult peeling off.Also because excellent flexible, when base material was crooked, the more difficult curved part at base material of distribution ruptured.

In addition, because compared with prior art, the content in the metal component (conductive powder 2003) is low, so can reduce the environmental pressure that printed circuit board (PCB) is disposed.

Conductive polymer gel 2002 is polymkeric substance (organic compound) identical with resin glue 2004 and mixed easily, and has excellent consistency.Therefore, can evenly mix conductive polymer gel 2002 and resin glue 2004, stick with paste 2001 easily to obtain conduction.

Technical scope of the present invention is not subjected to the restriction of top embodiment, can carry out various modifications not leaving the scope of the invention.

According to purpose, conduction is stuck with paste 2001 and is not comprised conductive powder 2003 and can be made by conductive polymer gel 2002 and resin glue 2004.Even, also give electroconductibility because the electro-conductive material that conduction is stuck with paste in 2001 only is a conductive polymer gel 2002, can lead to the base material coated with conductive and stick with paste 2001 and stick with paste formation with the conduction that is heating and curing, come the pattern distribution.

Conduction sticks with paste 2001 can comprise filler for example silicon oxide, aluminum oxide, mica and carbon dust; Tinting material is pigment and dyestuff for example; Auxiliary material is polymerization retarder, antioxidant, thickening material, thixotropic agent, suspension agent and dispersion agent for example.

The content of every kind of filler, based on the total amount of conductive polymer gel 2002, conductive powder 2003 and resin glue 2004, preferred tinting material and auxiliary material are 35 weight % or following.Therefore, top-operation of the present invention and effect are not subjected to negative impact.

[second kind conductive functional, second printed component part]

Describe according to the second kind of conductive functional of the present invention and second printed component part 2005 now.

The current-carrying part that second kind of conductive functional of the present invention comprises flat substrates and provide at least one surface of base material, flat substrates is to be made by the resin film of PET (polyethylene terephthalate) or paper, and current-carrying part is pasted by conduction.

By on base material, shifting and fixing conduction paste 2001 formation current-carrying parts.Omit the detailed description of conduction paste 2001, because it is as described above.

The method that current-carrying part forms comprises, for example, a kind of like this method, by known printing technology for example silk screen printing on base material, applies conduction of the present invention and sticks with paste 2001, solidified heats or simultaneously with hertzian wave photoirradiation for example.

Base material is not restricted to flat substrates, can be can apply thereon to stick with paste any element of 2001 with curing conductive.

As mentioned above, can form meticulous current-carrying part in high precision ground by known printing technology coated with conductive paste 2001 and curing on base material.

Specifically do not limit the shape of current-carrying part, the example is included at least one surface of base material and goes up coating and solidified linearity or plane conduction paste 2001.

Linearity configuration is meant the shape of one or more straight line or curve, and for example, pattern form is wave-like, straight line, curve, coil shape for example, and Polygons is shape, letter and the symbol of triangle or tetragon, circle, ellipse and its combination for example.By forming a plurality of linear current-carrying part of distance (at interval) continuously, can form the plane current-carrying part.

The example of plane current-carrying part comprises that one surface has following shape current-carrying part, for example for example the shape and the symbol of triangle or tetragon, circle, ellipse and its combination of Polygons.

Current-carrying part is not restricted to those that form on substrate surface, can be internal coat by the bore portion, recessed part or the groove that on base material, provide and curing conductive stick with paste 2001 form those.

Therefore, can by be used alone or in combination linear conductance part form have one dimension, the current-carrying part of bidimensional or 3D shape.For example, can use current-carrying part, can use the current-carrying part of two-dimensional shapes to be pattern distribution, electrode, electromagnetic induction coil and antenna as distribution with one dimension shape.Can use current-carrying part to be the through type electrode with 3D shape.

By thickness, width, the length of suitably selecting current-carrying part, can control group characteristic and electroconductibility and second kind of conductive functional can be used to utilize the various purposes of the electroconductibility of current-carrying part.

Can use second kind of conductive functional as the distribution substrate, and can for example light emitting devices and IC chip are used for various electronicss by settle various electronic units on base material.It can also use as IC mark and IC tag.

Conduction is stuck with paste 2001 and is comprised conductive polymer gel 2002, and conductive polymer gel 2002 is polymkeric substance (organic compound) identical with resin glue 2004, and mix mutually easily, and also have excellent consistency, therefore can evenly mix conductive polymer gel 2002 and resin glue 2004 and stick with paste 2001 to obtain conduction.

Constitute conduction that component obtains and stick with paste 2001 and have almost constant viscosity by evenly mixed,, can form pattern distribution easily with uniform thickness and even live width therefore when when the base material coated with conductive sticks with paste 2001.Therefore, in to realize having second kind of conductive functional of current-carrying part, the electrical property of second kind of conductive functional for example impedance characteristic still less changes.

Current-carrying parts and the base material of sticking with paste 2001 formation by curing conductive have excellent globality and more difficult peeling off.Also because excellent flexible, when base material was crooked, distribution seldom may be in the curved part fracture of base material.

Second kind of printed component part of the present invention is an example of second kind of conductive functional, and the current-carrying part that provides on flat substrates has linearity configuration.

Linear conductance is partly used Prime Computer Inc case distribution, electrode, through type electrode, electromagnetic induction coil and antenna.Therefore, second kind of printed component part can be used as distribution substrate, IC mark and IC tag use.

As mentioned above, have the flexible of excellence because stick with paste 2001 current-carrying parts that form by curing conductive, even comprise the base material of making by the flexible resin(a) sheet at second kind of printed component part, the flexible resin(a) sheet is made by the PET base material, film circuit board as keyboard, under its situation about using by curved substrates, distribution is also more difficult to rupture at the base material curved part.Therefore, can preferably use it.

Figure 18 is the orthographic plan of demonstration as the non-contact type IC medium of an example of second kind of printed component part.

Non-contact type IC medium (below use the reference symbol 2005 identical to represent) with second kind of printed component part comprise base material 2006 and the RF-ID module 2007 that on base material 2006, provides (RF-ID: radio frequency-identification), base material 2006 is made by resin film or the paper of PET (polyethylene terephthalate).

RF-ID module 2007 comprises aerial coil 2071 and the IC chip 2072 that is connected with aerial coil 2071, aerial coil 2071 is made by pattern distribution (linear conductance part), and the pattern distribution is to form by twine one or many with the shape of planar coil on base material 2006.

Pattern distribution (current-carrying part), it plays a part aerial coil 2071, by forming to base material coated with conductive paste 2001 and curing conductive paste.

The formation method of aerial coil 2071 for example comprises, a kind of like this method, by for example silk screen printing of known printing technology, on base material 2006, apply conduction paste 2001 of the present invention and play the predetermined pattern that aerial coil 2071 acts on formation, with solidified simultaneously, heating or with hertzian wave photoirradiation for example.

Can carry out wireless communication with aerial coil 2071.For example, store the data that receive in IC chip 2072, the data that will store in IC chip 2072 can be transferred in the susceptor of outside reader/writer.

Aerial coil 2071 is not restricted to by the aerial coil formed of as shown in Figure 18 planar coil for example of the linear conductance part with two-dimensional shape, and the aerial coil that can be made up of the linear conductance of 3D shape, 3D shape are for example by the inside of the through hole that provides on base material and two spirals that the surface forms of base material 2006.

Antenna is not restricted to the antenna of coil shape, can be any antenna of partly being made by linear conductance, and linear conductance partly has the shape that can accept and transmit the electric wave with preset frequency.The example comprises by having for example dipole antenna partly made of the linear conductance of triangle of one dimension shape such as linearity configuration or Polygons, or the antenna of making by the plane current-carrying part, the plane current-carrying part is partly not form by forming not continuously apart from a plurality of linear conductances of (at interval).

The example of non-contact type IC medium 2005 comprises non-contact type IC mark 5, it comprises flaky base material 2006 for example card, label, postcard or envelope, with the RF-ID module 2007 that on base material, provides, and comprise for example those of those and the RF-ID module 2007 that at least one surface of base material, provides of IC tag or waved plate of base material 2006.

The embodiment of fuel cell

Fuel cell comprises power generation part, power generation part is made up of mutual stacked one or more batteries, and each battery (single battery or elementary cell) comprises first electrode (hereinafter referred to as fuel electrode), second electrode (hereinafter referred to as air electrode) at least and is clipped in its ionogen between the electrode.

Power generation part provides gas supply device and connection portion, gas supply device hydrogen supply and in air electrode, supply with oxygen in fuel electrode, the connection portion is electrically connected with fuel electrode and air electrode,, and power generation part is connected with the circuit card of outside.

Figure 19 is the synoptic diagram that shows according to fuel cell 3001 of the present invention.Fuel cell is polymer electrolytic fuel battery (below be also referred to as PEFC), the fuel electrode (negative potential 3031) that fuel cell 3001 comprises polymer electrolyte film 3002, provides on the two sides of polymer dielectric 3002, and air electrode (positive electrode) 3032.

In fuel electrode 3031 and air electrode 3032, face the outside (in two main planes, another main plane is facing to a main plane that is connected with polymer electrolyte film 3002) each face provide dividing plate (channel separation plate) 3004 and polymer dielectric 3002, fuel electrode 3031 and air electrode 3032 are clipped between a pair of dividing plate 3004.

Hydrogen supply between the dividing plate 3041 of fuel electrode side and fuel electrode 3031 provides oxygen simultaneously between the dividing plate 3042 of air electrode side and air electrode 3032.On the surface of dividing plate 3004, the groove (not shown) is provided, it plays a part gas passage.

Polymer dielectric 3002 is proton conducting solid polymeric films, and the example comprises for example perfluorinated sulfonic acid film (by Dupont preparation, trade(brand)name Nafion) of proton conductive ion exchange membrane.

Shown in Figure 21 B as described below, fuel electrode 3031 and air electrode 3032 comprise water 3051, conjugated conductive polymer 3052 and tensio-active agent 3053 and/or the pure conductive polymer gel 3005 as main ingredient.

Conductive polymer gel 3005 can be used those of Japanese patent application No.2003-19120 proposition by with tensio-active agent 3053 and/or alcohol conjugated conductive polymer 3052 gelations being formed.Conductive polymer gel 3005 is the gels with electroconductibility, but and has and have those different performances of high viscosity mobile fluidic.In addition, conductive polymer gel has suitable intensity and can keep its shape, after forming flaky material or very thin film, can also use as electrode 3003.

In fuel electrode 3031 and air electrode 3032, have only electrode 3003 to form by conductive polymer gel 3005.

Figure 20 is the synoptic diagram of an example that shows the molecular structure of the conjugated conductive polymer 3005 as shown in Figure 21 B.Conjugated conductive polymer 3052 is poly-(3, the 4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) (hereinafter referred to as PEDOT/PSS), and be by obtaining as doping agent doping poly-(3, the 4-Ethylenedioxy Thiophene) with styrene sulfonic acid (hereinafter referred to as PSS).

Figure 21 A is the key drawing that schematically shows the aqueous colloidal dispersion of PEDOT/PSS, with Figure 21 B be the key drawing that shows according to an example of conductive polymer gel 3005 of the present invention, conductive polymer gel 3005 is by adding tensio-active agent 3053 and the mixture gelation is obtained in the aqueous colloidal dispersion of the PEDOT/PSS shown in Figure 21 A.

As shown in Figure 21 A, in the aqueous colloidal dispersion of PEDOT/PSS, in water 3051, disperse the PEDOT/PSS molecule.When in the aqueous colloidal dispersion of PEDOT/PSS, adding tensio-active agent 3053 and under the gelation condition, place mixture, shown in Figure 21 B, when comprising water 3051 therein, form three-dimensional network and gelation easily by tensio-active agent 3053, therefore obtain conductive polymer gel 3005.

Think that by adding tensio-active agent 3053 (and/or alcohol) and place mixture in the aqueous colloidal dispersion of PEDOT/PSS under the gelation condition, obtain gel, reason is physically or chemically to form three-dimensional network.Think that the gel that obtains has electroconductibility owing to electric electroconductibility and/or ionic conductivity.Certainly, it is not the mode that is intended to it is limited this consideration.

Conjugated conductive polymer 3052 comprises and for example is selected from least a in following: polyacetylene, polyphenylene, polypyrrole, Polythiophene, poly-furans, poly-selenophen, polyisothianaphthene, polyphenylene sulfide, polyaniline, polyvinylene benzene, polyvinylene thiophene, poly-perinaphthene, poly-anthracene, poly-naphthalene, poly-pyrene, poly-, and their derivative.In these polymkeric substance, preferred polypyrrole or the Polythiophene that uses as shown in figure 20 because it has high stability and high reliability, and obtains easily.

Doping agent comprises and for example is selected from least a in following at least: iodine, fluoridize arsenic, iron(ic) chloride, perchloric acid, sulfonic acid, perfluorinated sulfonic acid, polystyrolsulfon acid, sulfuric acid, hydrochloric acid, nitric acid, and their derivative.In these doping agents, preferred polystyrolsulfon acid is because can easily regulate high conductivity.

The example of the colloidal dispersion of conjugated conductive polymer 3052 comprise by catalyzer for example toluenesulphonic acids iron (III) in the presence of, polyase 13,4-Ethylenedioxy Thiophene and the aqueous colloidal dispersion of poly-(3, the 4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) (hereinafter referred to as PEDOT/PSS) of obtaining.Aqueous colloidal dispersion can be purchased, and commodity are called Baytron P ((concentration of conductive polymers (PEDOT/PSS) is about 1.3 weight %, by Bayer Co. preparation).

Specifically do not limit the tensio-active agent 3053 that the present invention uses, can use at least a tensio-active agent that is selected from following: known cats product, anion surfactant, amphoterics, nonionogenic tenside and its two or more miscellanys.

The example of cats product comprises season alkylammonium salt and halogenated alkyl pyridine.

The example of anion surfactant comprises the condenses of alkylsurfuric acid or its ester salt, Voranol EP 2001 sulfuric acid or its ester salt, alkyl benzene sulphonate (ABS) or its salt, alkyl naphthalene sulfonic acid or its salt, alkyl sulfo-succinic acid or its salt, alkyl diphenyl ether disulphonic acid or its salt, lipid acid or its salt, naphthene sulfonic acid or its formalin.

Examples of amphoteric surfactants comprises the collagen of alkyl betaine, amine oxide and hydrolysis.

The example of nonionogenic tenside comprises Voranol EP 2001, polyoxyalkylene alkyl, polyoxyethylene, sorbitan fatty(acid)ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene hardened castor oil, polyoxyethylene alkyl amine, alkyl chain triacontanol acid amides, and their derivative.

In these tensio-active agents 3053, especially preferably can use the alkyl benzene sulphonate (ABS) of long-chain, because improved the efficient of gelation.

Specifically do not limit the amount of the tensio-active agent 3053 that in conductive polymer gel, adds, but, be preferably 0.1 to 30 weight part, more preferably 0.5 to 10 weight part based on the conductive polymers of 1 weight part.When this amount was lower than 0.1 weight part, gelation may not take place.On the other hand, it is not preferred that this amount surpasses 30 weight parts, and gelation may not take place yet.

Concrete restriction alcohol can use at least a alcohol that is selected from two or more the mixture of known monohydroxy-alcohol and polyvalent alcohol and its.

The example of monohydroxy-alcohol comprises side chain or straight chain alcohol, for example ethanol, Virahol and butanols; Pure and mild its two or more the mixture of cyclic alcohol, polymer-like.

Examples of polyhydric alcohols comprises dibasic alcohol for example 1,2 ethylene glycol and propylene glycol; The chain polyvalent alcohol is glycerol, red bright alcohol, xylylol and Sorbitol Powder for example; Cyclic polyols is glucose and scroll for example; The polyvalent alcohol of polymer-like is polyoxyethylene glycol and polyvinyl alcohol for example; With its two or more mixture.

In these alcohol, can preferably use Virahol, 1,2 ethylene glycol, polyoxyethylene glycol, because following reason, special preferred polyol is 1,2 ethylene glycol and polyoxyethylene glycol for example.Especially preferably use 1,2 ethylene glycol, even because its performance causes the effect of gelation and also do not have volatility under lower concentration.Specifically do not limit the molecular weight of polyoxyethylene glycol, but be preferably 1000, even because be lower than under 400 the situation when this amount is lower than molecular weight, gelation also takes place.

Specifically do not limit the amount of the alcohol in the conductive polymer gel 3005, but be based on the conductive polymers of 1 weight part, be preferably 1 to 70 weight part, more preferably 10 to 50 weight parts.When this amount was lower than 1 weight part, gelation can not take place.It is not preferred that this amount surpasses 70 weight parts, because the viscosity of gel becomes too low and gelation may not take place yet.

Can use tensio-active agent 3053 and alcohol separately, or be used in combination with arbitrary proportion.

When tensio-active agent uses combination with alcohol, specifically do not limit its ratio.

In the following method by using tensio-active agent 3053 and/or alcohol to make conjugated conductive polymer 3052 gelations.By in water 3051 and/or conjugated conductive polymer solution with colloidal dispersion conjugated conductive polymer 3052 in the colloidal dispersion of preparation, do not forming under the bubble tensio-active agent 2023 and/or the alcohol that adds as additive.

Then, with non-volatile state in common air atmosphere open space and seal cavity in place the mixture scheduled time.

Therefore, form three-dimensional network and the easy gelation of mixture, therefore, obtain conductive polymer gel 3005 with stable manner.

Obtain conjugated conductive polymer 3052 solution by dissolving conjugated conductive polymer 3052 in water or organic solvent.Can use conjugated conductive polymer colloidal dispersion and conjugated conductive polymer solution separately, or can also be used in combination by arbitrary proportion.

Comprise by the method for using conductive polymer gel 3005 to form fuel electrode 3031 and air electrode 3032, for example, a kind of like this method, conductive polymer gel 3005 is formed sheet by above-mentioned method with pre-determined thickness, provide this sheet at the two ends of polymer electrolyte film 3002, to form fuel electrode 3031 and air electrode 3032.

In the fuel electrode of being made up of conductive polymer gel 3,005 3031, the hydrogen of supply dissolves and is attached in the water 3051 that comprises in conductive polymer gel 3005.According to reaction scheme (X), dissolved hydrogen (molecule) is electrolytically dissociated in the water 3051 of conductive polymer gel 3005, generates hydrogen ion and electronics.

(X)

The electronics that generates by the hydrogen disassociation spreads by the conjugated conductive polymer in the conductive polymer gel 3,005 3052, and flows through the circuits outside plate (not shown) that is connected with battery 3001, arrives the air electrode 3032 in the battery 3001.

Move towards polymer electrolyte film 3002 in the water 3051 that the hydrogen ion that produces by the hydrogen disassociation comprises in conductive polymer gel 3005.Hydrogen ion moves towards air electrode 3032 in polymer electrolyte film 3002 with water.

In the air electrode of forming by conductive polymer gel 3,005 3032, the oxygen dissolution of supply and being attached in the water 3051 that in conductive polymer gel 3005, comprises.

The electronics that generates in fuel electrode 3031 is mobile to the circuits outside plate (not shown) of air electrode 3032 by the fuel electrode 3031 from battery 3001, and by 3052 diffusions of the conjugated conductive polymer in the conductive polymer gel 3005.Move in the water 3051 of hydrogen ion in conductive polymer gel 3005.

In the conductive polymer gel in air electrode 3032, oxygen (molecule), hydrogen ion and electronics react to each other according to following reaction scheme (Y), generate water.

As mentioned above, carry out electron exchange in fuel electrode 3031 and air electrode 3032, thus, electric current is emitted from battery 3001.

(Y)

Because fuel electrode 3031 comprises conductive polymer gel 3005 at least, can hydrogen be dissociated into hydrogen ion and electronics by dissolving in the water 3051 that in conductive polymer gel 3005, comprises.Therefore, need be as prior art by not using the catalyst layer of making by platinum or platinum alloy with hydrogen disassociation becoming hydrogen ion.

Because air electrode 3032 comprises conductive polymer gel 3005 at least, can and be combined in the water 3051 that comprises in the conductive polymer gel 3005 oxygen dissolution.

Therefore, need not use the catalyst layer of making by platinum or platinum alloy to come adsorption of oxygen as prior art.

As mentioned above, need not use the catalyst layer of making by platinum or platinum alloy, therefore can realize cheap electrode 3003, and can reduce the production cost of fuel cell by using electrode 3003 as prior art.

Because conductive polymer gel 3005 has suitable intensity and also has electroconductibility, therefore need be as prior art, fuel electrode 3031 and air electrode 3032 have the double-layer structure of supporting layer and catalyst layer, and electrode can only be formed by conductive polymer gel 3005.

Normally, the power generation part of battery has the stepped construction that is obtained by stacked a plurality of batteries 3001, obtains high electromotive force thus.Therefore, in the time can reducing the thickness of fuel electrode 3031 and air electrode 3032, can significantly reduce the thickness of power generation part, therefore can reduce the thickness and the size of fuel cell.

The very thin film thickness that constitutes the conductive polymer gel 3005 of electrode 3003 is preferably 0.01 to 50 μ m, and the very thin film of conductive polymer gel 3005 has suitable intensity thus, and can keep shape.Therefore, the abundant contact between the water 3051 that can guarantee to comprise in hydrogen or oxygen and the conductive polymer gel 3005 is with the dissolving of hydrogen or oxygen be combined in the water 3051.

Because electrode 3003 is made by conductive polymer gel 3005, can not take place as the problem of the double-layer structure of the catalyst layer of prior art and supporting layer two separate for example, so can obtain excellent permanent stability.

In addition, the situation as the catalyst layer of being made by platinum or platinum alloy that uses prior art does not have to reduce sparking voltage and current value owing to the influence of carbon monoxide, can stably obtain about fixed voltage and current value.

Though hydrogen ion moves in the water 3051 of conductive polymer gel 3005, compare with the solid catalyst layer of making by palladium or palldium alloy of prior art, the ionic conductivity excellence of water, so can carry out hydrionic quick travel (diffusion).

Therefore, the reduction reaction of the oxidizing reaction of fuel electrode 3031 and air electrode 3032 can be carried out with high reaction rate, thus, can reduce the power loss of battery 3001, and can obtain high sparking voltage (electromotive force).

Embodiment

Describe the present invention in detail by the following examples and comparative example.But the present invention is not subjected to these

The restriction of embodiment.

＜by adding the gelation of tensio-active agent (placing)〉with closed state

Embodiment 1 to 4 and comparative example 1 to 2 have been described after adding tensio-active agent and have been placed the situation of carrying out gelation with open state.

Embodiment 1

In this embodiment, the conjugated conductive polymer colloidal dispersion PEDOT/PSS (aqueous colloidal dispersion of the conductive polymers (PEDOT/PSS) of the about 1.3 weight % of B with 100 weight parts, Bayer Co. preparation, trade(brand)name: Baytron P) with the Witco 1298 Soft Acid (C of 0.7 weight part as additive ₁₂H ₂₅C ₆H ₄SO ₃H) (below be also referred to as DBS) is mixed, and stir about was placed mixture 1 day with closed state at 10 ℃, 25 ℃, 50 ℃ laying temperature after 10 minutes, obtained the sample of gelation under different laying temperatures.

As for the sample that under every kind of laying temperature, obtains, detect degree of gelation.By three kinds of following grade standards (by symbol zero, △, * expression) the assessment degree of gelation.

Zero: solidify the gel that obtains supporting oneself

△: do not solidify, but high viscosity

*: do not meet top two kinds of standards (zero, △)

Obtaining meeting under the situation of the gel of representing by symbol zero, be 50 ℃ of samples that obtain by the use laying temperature, detect the electric conductivity of gel.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 1.In table 1, symbol "-" expression electric conductivity is less than the measurement limit value, and the situation of electric conductivity is not measured in symbol "+" expression because gelation does not have generation.

Embodiment 2

In this embodiment, except changing into 1.0 weight parts as the amount of the mixed DBS of additive, operate in the mode identical with embodiment 1, place mixture 1 day with closed state at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 1.

Embodiment 3

In this embodiment, except changing into 2.0 weight parts as the amount of the mixed DBS of additive, operate in the mode identical with embodiment 1, place mixture 1 day with closed state at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 1.

Embodiment 4

In this embodiment, except changing into 10 weight parts as the amount of the mixed DBS of additive, operate in the mode identical with embodiment 1, place mixture 1 day with closed state at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 1.

Comparative example 1

In this embodiment, except will not mixing DBS (amount of DBS=0 weight part) as additive, operate in the mode identical with embodiment 1, place mixture 1 day with closed state at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 1.

Comparative example 2

In this embodiment, except changing into 0.5 weight part as the amount of the mixed DBS of additive, operate in the mode identical with embodiment 1, place mixture 1 day with closed state at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 1.

Table 1

	Additive (weight part)	The assessment result of degree of gelation			Conductivity measurement result (mS/cm)
						Laying temperature (℃)
		DBS	10	25					50
	Embodiment 1					0.7	×	×		○	0.5
Embodiment 2		1.0	△	△	○				1.5
	Embodiment 3					2.0	○	○		○	20
Embodiment 4		10.0	○	○	○				98
	Comparative example 1					0.0	×	×		×	*
Comparative example 2		0.5	×	×	△				-

From table 1, the following fact becomes clear.

(1) adding of DBS can gelation.

(2) under laying temperature is 50 ℃ condition, when this amount is 0.5 weight part, does not solidify and take place, but can obtain having full-bodied gel.But the electric conductivity of the gel that obtains is very low.

(3) when this amount be 0.7 weight part or when above, mixture solidified obtains the gel of supporting oneself.Along with the increase of this amount, electric conductivity improves rapidly.

(4) when the amount of DBS is 2.0 weight parts, can gelation, and irrelevant with laying temperature.

Be apparent that from top result, when the amount of DBS is 0.7 to 1.0 weight part, only under laying temperature is 50 ℃ condition, can make its gelation.On the other hand, when the amount of DBS is 2.0 weight parts or can makes its gelation when above, and irrelevant with laying temperature.

Be apparent that from the measuring result of embodiment 1 to 4 along with the amount increase of DES, electric conductivity trends towards bringing up to 98 (mS/cm) from 0.5.

＜by adding the gelation of alcohol (placing)〉with closed state

Embodiment 5 to 9 and comparative example 3 to 9 have been described and have been added the situation that gelation is carried out with the closed state placement in the alcohol back.

Embodiment 5

In this embodiment, except being used as the mixed ethanol of additive: C ₂H ₅OH (being designated hereinafter simply as EtOH) replaces DBS, its add-on is changed into 30 weight parts, also changed into outside 1 week with the time of placing from 1 day with closed state, operate in the mode identical with embodiment 1, place mixture with closed state at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 2.

Embodiment 6

In this embodiment, except being used as the mixed Virahol of additive: (CH ₃) ₂CHOH (being designated hereinafter simply as IPA) replaces EtOH, its add-on is changed into outside 30 weight parts, operate in the mode identical, place mixture with closed state at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures with embodiment 5.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 2.

Embodiment 7

In this embodiment, be 1000 polyoxyethylene glycol [(CH except being used as the mixed molecular weight of additive ₂) ₂O] _n(being designated hereinafter simply as PEG) replaces EtOH, its add-on is changed into outside 10 weight parts, operate in the mode identical, place mixture with closed state at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures with embodiment 5.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 2.

Embodiment 8

In this embodiment, except using molecular weight as additive is that 1000 PEG replaces EtOH, its add-on is changed into outside 30 weight parts, operate in the mode identical with embodiment 5, place mixture at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 2.

Embodiment 9

In this embodiment, except using molecular weight as additive is that 1000 PEG replaces EtOH, its add-on is changed into outside 50 weight parts, operate in the mode identical with embodiment 5, place mixture at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 2.

Comparative example 3

In this embodiment, except using methyl alcohol: CH ₃OH (being designated hereinafter simply as MeOH) replaces EtOH as additive, its add-on is changed into outside 30 weight parts, operate in the mode identical, place mixture at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures with embodiment 5.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 2.

Comparative example 4

In this embodiment, except using EtOH as mixed additive, its add-on is changed into outside 10 weight parts, operates in the mode identical with embodiment 5, place mixture at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 2.

Comparative example 5

In this embodiment, except using EtOH as mixed additive, its add-on is changed into outside 50 weight parts, operates in the mode identical with embodiment 5, place mixture at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 2.

Comparative example 6

In this embodiment, except the Virahol (being designated hereinafter simply as IPA) that is used as additive replaces EtOH, its add-on is changed into outside 10 weight parts, operate in the mode identical with embodiment 5, place mixture at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 2.

Comparative example 7

In this embodiment, except the Virahol (being designated hereinafter simply as IPA) that is used as additive replaces EtOH, its add-on is changed into outside 50 weight parts, operate in the mode identical with embodiment 5, place mixture at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 2.

Comparative example 8

In this embodiment, except being used as the 1,2 ethylene glycol that additive uses: (CH ₂OH) ₂(being designated hereinafter simply as EG) replaces EtOH, and its add-on is changed into outside 30 weight parts, operates in the mode identical with embodiment 5, places mixture at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtains the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 2.

Comparative example 9

In this embodiment, except being used as polyoxyethylene glycol (being designated hereinafter simply as PEG) the replacement EtOH that additive uses, its add-on is changed into 70 weight parts, operate in the mode identical with embodiment 5, place mixture at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 2.

Table 2

	Additive (weight part)					The assessment result of degree of gelation			The measuring result of electric conductivity (mS/cm)
										Laying temperature (℃)
						MeOH	EtOH	IPA					EG	PEG		10	25	50
	Embodiment 5		30								×	×							○	0.5
Embodiment 6								30						×	△	○	1.0
	Embodiment 7									10	×	×						○	0.5
Embodiment 8													30	×	×	○	0.2
	Embodiment 9									50	×	○						○	0.05
Comparative example 3						30								×	×	△	-
	Comparative example 4		10								×	×						×	*
Comparative example 5							50							×	△	△	-
	Comparative example 6			10							×	×						△	-
Comparative example 7								50						×	△	△	-
	Comparative example 8				30						×	×						×	*
Comparative example 9													70	×	△	△	-

From table 2, the following fact becomes clear.

(1) under laying temperature is 10 ℃ condition, all can not gelation by mixed any additives.

(2) under laying temperature is 25 ℃ condition, have only when adding the PEG (embodiment 9) of 50 weight parts, mixture solidified obtains the gel of supporting oneself.In embodiment 6 and comparative example 5,7 and 9, do not solidify and take place, but can confirm to have full-bodied gel.

(3) can be that the additive that solidifies the gel that obtains supporting oneself under 50 ℃ the condition comprises three kinds at laying temperature, as EtOH, IPA and PEG (embodiment 5 to 9).

(4) have only when adding the EtOH (embodiment 5) of 30 weight parts, mixture solidified obtains the gel of supporting oneself.When this amount was 10 or 50 weight parts (comparative example 4,5), gelation did not take place, even or gelation generation, confirmation curing yet.

(5) have only when adding the IPA (embodiment 6) of 30 weight parts, mixture solidified obtains the gel of supporting oneself.When this amount is 10 or 50 weight parts (comparative example 6,7),, do not confirm to solidify even gelation takes place.

(6) when adding the PEG (embodiment 7 to 9) of 10 to 50 weight parts, mixture solidified obtains the gel of supporting oneself.When this amount was 70 weight parts (comparative example 9), gelation did not take place, even or gelation take place, confirm to solidify.

Being apparent that from top result, when using alcohol as additive under the condition of placing with closed state, can be that about 30 weight % come gelation by manipulated variable.

Be apparent that from the measuring result of the electric conductivity of embodiment 5 to 9 gel that obtains has almost in the identical electric conductivity of 0.05 to 1.0 (mS/cm) and irrelevant with the kind of additive.

＜by adding the gelation of alcohol (placing)〉with opening-wide state

Embodiment 10 to 12 and comparative example 10 to 11 are described in the situation that gelation is carried out with the opening-wide state placement in the alcohol back that adds.

Embodiment 10

In this embodiment, except being used as the 1,2 ethylene glycol that additive uses: (CH ₂OH) ₂(being designated hereinafter simply as EG) replaces DBS, its add-on is changed into outside 10 weight parts, operate in the mode identical with embodiment 5, the laying temperature at 10 ℃, 25 ℃, 50 ℃ is placed mixture under opening-wide state then, obtains the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 3.

Embodiment 11

In this embodiment, except changing into 30 weight parts as the amount of the mixed EG of additive, operate in the mode identical, place mixture at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures with embodiment 10.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 3.

Embodiment 12

In this embodiment, except changing into 50 weight parts as the amount of the mixed EG of additive, operate in the mode identical, place mixture at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures with embodiment 10.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 3.

Comparative example 10

In this embodiment, except changing into 5 weight parts as the amount of the mixed EG of additive, operate in the mode identical, place mixture at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures with embodiment 10.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 3.

Comparative example 11

In this embodiment, except changing into 70 weight parts as the amount of the mixed EG of additive, operate in the mode identical, place mixture at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures with embodiment 10.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result and the conductivity measurement of degree of gelation the results are shown in the table 3.

Table 3

	Additive (weight part)	The assessment result of degree of gelation			The measuring result of electric conductivity (mS/cm)
						Laying temperature (℃)
		EG	10	25					50
	Embodiment 10					10	×	×		○	1.0
Embodiment 11		30	×	×	○				3.0
	Embodiment 12					50	×	×		○	5.0
Comparative example 10		5	×	×	△				*
	Comparative example 11					70	×	×		△	*

The fact below table 3 becomes clear.

(1) be under the condition of 10 ℃ and 25 ℃ at laying temperature, all can not gelation by the additive that uses any amount.

(2) under laying temperature is 50 ℃ condition, can gelation.Particularly, when this amount was 10 to 50 weight parts, mixture solidified obtained the gel of supporting oneself.When this amount is 5 to 70 weight parts (comparative examples 10 to 11),, also confirm not solidify even gelation takes place.

Being apparent that from top result, when using 1,2 ethylene glycol (EG) as additive under the condition of placing with opening-wide state, is 10 to 50 weight part gelations stably by controlling this amount.

Be apparent that from the measuring result of the electric conductivity of embodiment 10 to 12 along with the amount of EG increases, electric conductivity is tended to marginal increase.

＜by adding the gelation of ionogen (placing)〉with opening-wide state

Embodiment 13 to 16 has described by place the situation of carrying out gelation in the mode of opening wide after adding tensio-active agent, pure and mild ionogen.

Embodiment 13

This embodiment described use alcohol for example EG be 30 weight parts and also add electrolytical situation as additive and its usage quantity.Except using trifluoromethayl sulfonic acid lithium salts: CF ₃SO ₃Li (being designated hereinafter simply as TFMS-Li) is adjusted into outside 5 weight parts as ionogen and its usage quantity, operate in the mode identical with embodiment 10, place mixture with opening-wide state at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result of degree of gelation and potential difference measuring result are shown in Table 4.

Embodiment 14

In this embodiment, except using trifluoro-methane sulfonic acid silver salt: CF ₃SO ₃Li (being designated hereinafter simply as TFMS-Ag) changes into outside 5 weight parts as ionogen and its usage quantity, operate in the mode identical with embodiment 13, place mixture with opening-wide state at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result of degree of gelation and the measuring result of potential difference are shown in Table 4.

Embodiment 15

This embodiment described the use tensio-active agent for example DBS be 2 weight parts and also add electrolytical situation as additive and its usage quantity.Except using TFMS-Li to change into 5 weight parts as ionogen and its usage quantity, operate in the mode identical with embodiment 13, place mixture with opening-wide state at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electric conductivity in the mode identical with embodiment 1.The assessment result of degree of gelation and the measuring result of potential difference are shown in Table 4.

Embodiment 16

In this embodiment, except using TFMS-Ag to replace TFMS-Li to change into 5 weight parts as ionogen and its usage quantity, operate in the mode identical with embodiment 15, place mixture with opening-wide state at 10 ℃, 25 ℃, 50 ℃ laying temperature then, obtain the sample of gelation under different laying temperatures.

As for the respective sample that obtains in this embodiment, assess degree of gelation and measure electromotive force in the same manner described above in the mode identical with embodiment 1.The assessment result of degree of gelation and the measuring result of potential difference are shown in Table 4.Measure potential difference by identical measuring method.The result is that it is 100mV.

Table 4

	Additive (weight part)				The assessment result of degree of gelation			The measuring result of potential difference (mV)
									Laying temperature (℃)
					EG	DBS	TFMS-Li					TFMS-Ag	10	25	50
	Embodiment 13	30	0	5					0	×	×					○	100
Embodiment 14					30	0	0	5				×	×	○	300
	Embodiment 15	0	2	5					0	×	×					○	150
Embodiment 16					0	2	0	5				×	×	○	400

The fact below from table 4 becomes clear.

(1) be under the condition of 10 ℃ and 25 ℃ at laying temperature, all can not gelation by the additive that uses any amount.

(2) under laying temperature is 50 ℃ condition, can gelation in any embodiment (embodiment 13 to 16) and curing mixture obtain the gel of supporting oneself.

(3) in that for example the potential difference under the situation of the gel that obtains of TFMS-Li is identical with the situation of distilled water by for example add ionogen among the EG (embodiment 13) to additive.But, improved 3 times by the potential difference of using TFMS-Ag (embodiment 14) to obtain as ionogen under the situation of gel.

(4) obtaining by for example add TFMS-Li among the DBS (embodiment 15) to additive that potential difference has improved about 50% under the situation of gel.When using TFMS-Ag as ionogen, potential difference has obviously improved 4 times.

Be apparent that from top result, when using tensio-active agent for example EG or DBS and ionogen when for example TFMS-Li or TFMS-Ag are as additive, gelation stably under the condition of placing with opening-wide state.Confirm electrolytical adding improved potential difference and by ionogen for example the adding of TFMS-Ag produced significant effect.

Embodiment 17

In the PEDOT/PSS aqueous solution (concentration is: about 1.3%, by Bayer Co. preparation, Baytron P), add 5% 1,2 ethylene glycol, this solution of diffusion in experiment plate.Experiment plate is put into thermostatic bath, and placed 12 hours down, obtain the gel film of PEDOT/PSS at 50 ℃.

After in experiment plate, adding a spot of distilled water, add a large amount of acetone in the experiment plate, remove the gel film of PEDOT/PSS thus from the inner bottom surface of experiment plate.

Between filter paper, sandwich the gel film that obtains,, obtain the gel film of this embodiment then at the following heat drying of atmosphere (80 ℃ to 100 ℃ temperature).

It is that 5cm, width are that 5mm and thickness are that the bar of 15 μ m is to obtain sample a that gel film is cut into length.Alternating impregnating sample in water (distilled water) and in the acetone, the volume change of observation sample a.

Behind the dipping, the length of sample a is changed into 5.7cm from 5cm in distilled water, and promptly sample has expanded about 14%.Think and the reasons are as follows: promptly, the result that it is water molecules in the three dimensional gel network that produces by hydration that hydrophilic sample a expands.Suppose isotropically to expand, then with respect to the dry weight of sample a, moisture content is 48%.Then, when the sample a behind the dipping in distilled water flooded in acetone, sample shrank rapidly, and length is reduced to 5.25cm.Think that reason is that the dehydration of sample a is owing to acetone is that poor solvent causes.Confirm that also volume change takes place repeatedly by alternating impregnating sample a in water/acetone.

Be apparent that from top result the sample a that is made by conductive polymer gel according to present embodiment is suitable as the function that stopper uses because its above-mentioned behavior has.

Comparative example 12

Except not using the 1,2 ethylene glycol,, make bar shaped sample β by the gel film that the mode identical with embodiment 17 obtains in the mode identical with embodiment 17.

Sample β keeps bar shaped in air, still swelling when dipping in distilled water.Along with the loss of time, swelling capacity further enlarges, and sample breakage becomes fragment then.Thinking that the fracture of sample β is because it is not crosslinked with 1,2 ethylene glycol, therefore is dynamically frangible.

Be apparent that from the result of embodiment 17 and comparative example 12 when forming bar, conductive polymer gel of the present invention is suitable as stopper and uses.

Embodiment 18

Present embodiment has been described such embodiment, and wherein with above-mentioned conductive polymer gel, for example the gel coating that obtains in embodiment 3 is used for the local iontophoretic treatment patch label that transmits healing potion, with reference to figure 3 to Fig. 5.

Fig. 3 shows the diagrammatic cross-section that is used for an embodiment of iontophoretic treatment patch label according to the present invention.Fig. 4 and Fig. 5 be show respectively according to the present invention local transmit healing potion the diagrammatic cross-section of another embodiment of iontophoretic treatment patch label.

Any iontophoretic treatment patch label that is used for local transmission healing potion that shows among Fig. 3 to Fig. 5 is a kind of like this iontophoretic treatment patch label, the electrode of forming by anode and negative electrode that it comprises pad, provides with regular interval on a surface of pad, its another surface by pad contacts and applies electric current between electrode with analyte, come to the local healing potion that transmits of analyte.This pad is to be made by water, conjugated conductive polymer and the tensio-active agent and/or the pure conductive polymer gel that comprise as main ingredient.

The local iontophoretic treatment patch label 100 that transmits healing potion that is used for shown in Fig. 3 comprises as anodic electrode 101 and the pad 103 made as another electrode 102 and the conductive polymer gel of the present invention of negative electrode, settles pad 103 so that extend on two electrodes.Between electrode, insulating material 104 prevents that electrode from contacting with each other, and power supply 105 is connected with electrode.Be used for the local iontophoretic treatment patch label 100 that transmits healing potion and comprise flat substrates 106 for example paper or plastics, the predetermined position of these parts on base material is stacked.

Healing potion (does not show, for example pharmaceutical chemicals, makeup etc.) prepare in advance on the surface of analyte 10 for example on the skin, by between electrode 101 and 102, applying weak current from power supply 105, the ionization healing potion, infiltrate through in the local organization by analyte 10 thus, can transmit healing potion effectively thus.

In Fig. 4, thereafter two with Fig. 3 in reference symbol in back two identical reference symbols represent identical parts.Shown in Figure 4ly be used for the local iontophoretic treatment patch label 200 that transmits healing potion and be that with the local difference that transmits the iontophoretic treatment patch label 100 of healing potion that is used for shown in Figure 3 healing potion 207 is included in the pad of being made by conductive polymer gel 203 in advance.

Be used for the local iontophoretic treatment patch label 200 that transmits healing potion because healing potion 207 is included in advance, so it in use has excellent handling property or convenient because need be on the surface of analyte 10 administering therapeutic medicament in advance.

In Fig. 5, thereafter two with Fig. 3 in reference symbol in back two identical reference symbols represent identical parts.The iontophoretic treatment patch label 300 that is used for local transmission healing potion shown in Figure 5 is with iontophoretic treatment patch label 100 differences that are used for local transmission healing potion shown in Figure 3, the many micropores 309 that provide thereon are provided the box-like base material that is made of plastics, and the container 310 that comprises healing potion 307 is positioned on the base material 308.

Under the situation of the iontophoretic treatment patch label 300 that is used for local transmission healing potion, in the direction shown in the head, the healing potion 307 that comprises in container 310 is supplied in the gel 303 of filling in base material 308 by hole 309.Healing potion can be by external power supply (not shown) coercively fed, or supplies with naturally by gravity or adsorptive power.This plenum system can transmit healing potion to the surface of analyte, therefore can improve preferred patch label for a long time.

Embodiment 19

Present embodiment has been described such embodiment, wherein with top conductive polymer gel, for example the gel coating that in embodiment 3, obtains on biomedical electrode, with reference to figure 6 to Figure 10.

Fig. 6 is the diagrammatic cross-section that shows according to an example of biomedical electrode of the present invention.Fig. 7 to Figure 10 is the diagrammatic cross-section that shows respectively according to another example of biomedical electrode of the present invention.

Any biomedical electrode shown in Fig. 6 to Figure 10 is the biomedical electrode that comprises electrode device and element, this element is with analyte and electrode device electricity or physically be connected, wherein element is made by conductive polymer gel, and this conductive polymer gel is as water, conjugated conductive polymer and tensio-active agent and/or the alcohol of main ingredient.

In the biomedical electrode shown in Fig. 6 400, the element of being made by conductive polymer gel of the present invention 401 is included in 402, container is carried out siloxane treated, but but giving, and also use by sheet lid 403 sealings that element 401 shown bounding forces and dielectric polypropylene, polyethylene terephthalate, polyethylene or polyvinyl chloride are made by the vessel surface release property made of polypropylene or polyethylene terephthalate or paper for example of the plastics with excellent release property.Lid 403 is equipped with electrode device 404, so that be electroconductibility by an end of lid to element 401.The other end 405 of electrode device 404 plays a part terminals, and it is connected with the lead-in wire that extends out from electrocardiograph.

Under the situation of using biomedical electrode 400 recording ecgs, the lead-in wire of electrocardiograph is connected with the other end 405 of electrode device 404, container 402 separates with lid 403, places the element of being made by conductive polymer gel 401 in the predetermined position of human body (analyte) then.

In Fig. 7, thereafter two with Fig. 6 in reference symbol in back two identical reference symbols represent identical parts.Biomedical electrode shown in Figure 7 400 is with the difference of biomedical electrode 400 shown in Figure 6, provides binder layer 506 along the internal layer of container 502, and container 502 comprises the element of being made by the conductor polymer gel 501.

When container 502 separated with lid 503, binder layer 506 moved towards the side of element 501.Therefore, placing under the situation of the element of making by conductive polymer gel 501 on the predetermined position of human body (analyte) skin surface, improving the bounding force of skin surface by the effect of binder layer 506.Preferably provide binder layer 506 in advance, but and container 502 inside are carried out that the demoulding is handled so that improve release property to container 502 in container 502 inside.

In Fig. 8, thereafter two with Fig. 6 in reference symbol in back two identical reference symbols represent identical parts.Biomedical electrode 600 shown in Figure 8 is with the difference of biomedical electrode 400 shown in Figure 6, use planar electrode arrangements 604 to replace stereo electrod device 404, planar electrode arrangements 604 by on lid 503 at predetermined position pattern printing conductive inks or place tinsel and form, lid 503 is made by plastics film.

Because planar electrode arrangements 604 can provide flat outer surface to biomedical electrode 600, the skin of human body (analyte) can not come to harm, and can improve the security between the usage period.

In Fig. 9, thereafter two with Fig. 6 in reference symbol in back two identical reference symbols represent identical parts.Biomedical electrode 700 shown in Figure 9 is with the difference of biomedical electrode 400 shown in Figure 6, in lid, arrange electrode device 705a and 705b at interval with fixed, each electrode deployment has element 701a and the 701b that is made by conductive polymer gel.

Use biomedical electrode 700 measure or the situation of treatment under, the lead-in wire of external device (ED) is connected with 705b with electrode device 705a, and the element 701a that will be made by conductive polymer gel and the 701b predetermined position that is placed on human body (analyte).

In Figure 10, thereafter two with Fig. 6 in reference symbol in back two identical reference symbols represent identical parts.Biomedical electrode 800 shown in Figure 10 is with the difference of biomedical electrode 400 shown in Figure 6, the element 801a and the 801b that are made by conductive polymer gel are arranged on two surfaces of the base material of being made by nonwoven fabric 810, in addition, provide dividing plate 811a and 811b, with relative with 801b with base material 810 by element 801a.Figure 10 shows such example, and acrylic, rubber-based, siloxanes or vinyl ether group binder layer 806 wherein are provided on the side of element 801a.As for dividing plate 811a and 811b, preferably plastics film or the paper that uses is discharged processing by coating silicone resin or fluoro-resin on its one or two surface.

Prepare biomedical electrode 800 by following method: use tackiness agent, the dividing plate 811b that will provide binder layer 806 in the predetermined position is fixed on the lower surface of base material 810, peace is disposed the framework (not shown) on the predetermined position of base material 810 upper surfaces, but fills framework with containing water, conjugated conductive polymer and tensio-active agent as main ingredient and/or the flow composition of alcohol.Therefore, but opening or the slit of flow composition by base material 810 leach downwards.When but but the flow composition in framework and the flow composition former state that leaches are downwards placed, but two kinds of flow composition gelations form conductive polymer gel 801a and 801b on two surfaces of base material 810.Then, remove framework and settle dividing plate 811a, so that contact, to obtain biomedical electrode 800 with polymer gel 811.

After removing dividing plate 811b,, use biomedical electrode 800 by conductive polymer gel 801b being placed on the predetermined position of human body (analyte).Because the binder layer 806 that provides in the outside of conductive polymer gel 801b is used for improving the bounding force of conductive polymer gel 801b and human body (analyte), so the stability can guarantee to measure the time.

Embodiment 20 to 23

Conductive polymer gel 2002 shown in Figure 17 B is to prepare by following method:

With the PEDOT/PSS colloidal dispersion (aqueous colloidal dispersion of about 1.3% conductive polymers (PEDOT/PSS) of 100 weight parts as conjugated conductive polymer 2022, by Bayer Co. preparation, trade(brand)name: Baytron P) with the Witco 1298 Soft Acid (C of 1 weight part as tensio-active agent 2023 ₁₂H ₂₅C ₆H ₄SO ₃H) (the following DBS that also is called) is mixed, after 10 minutes, places mixture 1 day with closed state at stir about under 50 ℃ laying temperature, obtains conductive polymer gel 2002.

According to the prescription shown in the table 5, mixed conductive polymer gel 2002, the conductive powder 2003 as silver powder, resin glue 200 and solvent obtain conduction and stick with paste 2001.

In table 5, the total amount of conductive polymer gel 2002, the conductive powder 2003 as silver powder, resin glue 200 and solvent is 100 weight parts.

Conductive powder 2003 as silver powder is that silver powder is (by TOKURIKI HONTEN CO., LTD. preparation, commodity are called SILVEST E-20) and silver powder (by TOKURIKI HONTEN CO., LTD. preparation, commodity are called SILVEST E-20) with weight ratio be 8: 2 mixture.

As for resin glue 2004, use polyester (by TOYOBO CO., LTD. prepares, and commodity are called VYLON 500).

Table 5

	Silver powder	Resin glue	Solvent		Conductive polymer gel
						Butyl cellosolve acetate	Isophorone
			Embodiment 20	61.9				14.3	17.1	1.9	4.8
Embodiment 21	59.1	13.6			16.4	1.8	9.1
			Embodiment 22	56.5				13.0	15.7	1.7	13.0
Embodiment 23	54.2	12.5			15.0	1.7	16.7
			Comparative example 13	70.0				15.0	13.0	2.0	0

By silk screen print method, stick with paste 2001 to PET film (by Toray Industries preparation, commodity are called Lumirror S) coated with conductive, the PET film is to be made with the form of plane coiled material by base material 2006.

Stick with paste 2001 PET film to be placed on internal temperature be in 150 ℃ the hotblast stove 30 minutes being coated with conduction, curing conductive sticks with paste 2001 thus, therefore forms aerial coil 2071.

Then,, IC chip 2072 (by Philips preparation, commodity are called Mifare) is installed on the base material 2006, so that gold-plated is electrically connected with two terminals of aerial coil 2071 by NCP (nonconductive resin paste) technology.

As mentioned above, as shown in figure 18, prepared untouchable IC medium 2005, it comprises by sticking with paste the RF-ID module 2007 that 3001 aerial coils that form 2071 are formed by curing conductive, with the IC chip 2072 that is connected with aerial coil 2071.

Comparative example 13

Except using the conduction paste that does not comprise conductive polymer gel but comprise silver powder, resin glue and solvent, outside content is as shown in table 5,, prepare untouchable IC medium in the mode identical with top embodiment.

Measure the resistance of the aerial coil 2071 of each untouchable IC medium 2005.The untouchable IC medium 2005 of IC chip 2072 will be installed, promptly, comprise base material 2006 and by coated with conductive on base material 2006 stick with paste 2001 and curing conductive stick with paste the IC medium of the aerial coil 2071 that forms, the amount of the metal residuum after solidifying is measured in roasting then.The resistance that obtains is shown in Table 6 with the amount of the metal residuum that obtains.

Table 6

	(G+C p)/(G+P)	(G+P)/B	Sheet resistance	Metal residuum after the roasting
					Embodiment 20	0.0714	4.67	2.7	68% or below
Embodiment 21	0.133	5.00	4.9	60% or below
					Embodiment 22	0.188	5.33	6.8	58% or below
Embodiment 23	0.235	5.67	10.3	56% or below
					Comparative example 13	0	4.67	1.0	70% or more than

Resistance increases along with the increase of conductive polymer gel 2002 content.As embodiment, when ratio (G+P)/when B was 4 to 6, resistance was 11O/ or following, and can reach the enough electric conductivitys that are suitable for distribution, the product that obtains can be used as aerial coil 2071.

By improving the content of conductive polymer gel 2002, can reduce the content of silver powder and can suppress environmental pressure.Particularly, as ratio (G+C _p)/(G+P) is 0.07 or when above, the quantitative change of the metal residuum after the curing be 68% or below, compare with comparative example 13, can suppress environmental pressure effectively.

As ratio (G+C _p)/(G+P) is 0.13 or when above, the quantitative change of the metal residuum after the curing be 60% or below, compare with comparative example 13, can significantly suppress environmental pressure.

As for each untouchable IC medium 2005, use reader/writer (by the Philips preparation) to carry out data transmission and reception.Confirm that any untouchable IC medium 2005 can or receive data with IC chip 2072 transmission data.

Embodiment 24

Prepare the conductive polymer gel 3005 shown in Figure 21 B by following method.

With the colloidal dispersion (aqueous colloidal dispersion of about 1.3% conductive polymers (PEDOT/PSS) of 100 weight parts as conjugated conductive polymer 3052, by Bayer Co. preparation, commodity are called Baytron P) PEDOT/PSS and 1 weight part as the Witco 1298 Soft Acid (C of tensio-active agent 3053 ₁₂H ₂₅C ₆H ₄SO ₃H) (the following DBS that also is called) is mixed, after 10 minutes, places mixture 1 day with closed state at stir about under 50 ℃ laying temperature, obtains conductive polymer gel 3005.

Use the perfluorinated sulfonic acid film (to prepare by Dupont, commodity are called Nafion, thickness: 150 μ m) as polymer electrolyte film 3002, polymer electrolyte film 3002 is arranged between a pair of dividing plate 3004, conductive polymer gel 3005 (2cm * 2cm, thickness are 15 μ m) contacts with two surfaces of polymer electrolyte film simultaneously.Polymer electrolyte film 3002 and conductive polymer gel 3005 are clipped between the dividing plate 3004, obtain battery 3001, as shown in Figure 19.

On the surface of dividing plate 3004, the groove that plays the gas passage effect is provided, therefore can hydrogen supply or oxygen between dividing plate 3004 and conductive polymer gel 3005.

In the conductive polymer gel 3005 that provides on two surfaces of polymer electrolyte film 3002, a conductive polymer gel 3005 plays a part fuel electrode 3031, and another conductive polymer gel 3005 plays a part air electrode 3032 simultaneously.

Under 80 ℃ service temperature, when hydrogen supply between the dividing plate 3041 of fuel electrode side and fuel electrode 3031, and when supplying with oxygen between the dividing plate 3042 of air electrode side and air electrode 3032, electric current is emitted from battery 3001, therefore reaches the electromotive force of 0.905V.

Comparative example 14

Carbon paper 3161a and 3161b (2cm * 2cm that platinum catalyst 3162a and 3162b are arranged except working load, thickness is 300 to 500 μ m) act as a fuel electrode 3131 and air electrode 3132 replace outside the conductive polymer gel 3005, in the mode identical with embodiment 24, the battery 3101 shown in preparation Figure 22.

Under 80 ℃ service temperature, when hydrogen supply between the dividing plate 3141 of fuel electrode side and fuel electrode 3131, and when supplying with oxygen between the dividing plate 3142 of air electrode side and air electrode 3132, electric current is emitted from battery 3001, therefore reaches the electromotive force of 0.945V.

In comparative example 14, the thickness of fuel electrode 3131 and air electrode 3132 is 300 to 500 μ m, and in embodiment 24, the thickness of fuel electrode 3131 and air electrode 3132 is 15 μ m, and can reduce thickness is about 1/20 to 1/30.In embodiment 24, can reach high electromotive force, its almost with comparative example 14 in identical.

Different with comparative example 14 is not use platinum in embodiment 24, and can prepare electrode for fuel cell at low cost.

Industrial usability

The invention provides a kind of conductive polymer gel, even when exposing to the open air in the air that is lower than the water freezing point, it also can keep good electric conductivity. Conductive polymer gel can be used for various purposes, for example brake, iontophoretic treatment patch label, biomedical electrode, toner, conductive functional, antistatic sheet, printed circuit elements, electroconductive paste, electrode for fuel cell and fuel cell. Conductive polymer gel also helps the output stability of equipment, and described equipment needs environment around to be lower than under the rigor condition of water freezing point to have stable function.

Claims (24)

1. conductive polymer gel, it comprises water, conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and/or the alcohol.

2. according to the conductive polymer gel of claim 1, it also comprises ionogen.

3. according to the conductive polymer gel of claim 1, wherein conjugated conductive polymer is doped with doping agent.

4. according to the conductive polymer gel of claim 1, wherein conjugated conductive polymer is polypyrrole or Polythiophene.

5. according to the conductive polymer gel of claim 3, wherein doping agent is a polystyrolsulfon acid.

6. according to the conductive polymer gel of claim 1, it comprises the alkyl benzene sulphonate (ABS) as tensio-active agent.

7. according to the conductive polymer gel of claim 1, it comprises and contains at least a as alcohol in monohydroxy-alcohol with 3 or above carbon atom and the polyvalent alcohol.

8. method for preparing conductive polymer gel, the method includes the steps of:

In conjugated conductive polymer colloidal dispersion and conjugated conductive polymer solution at least a, add at least a in tensio-active agent and the alcohol and

The mixture that placement obtains makes at least a gelation in conjugated conductive polymer colloidal dispersion and the conjugated conductive polymer solution thus.

9. stopper, it comprises the stopper main body of being made by conductive polymer gel, and wherein conductive polymer gel comprises water, the conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and the alcohol.

10. iontophoretic treatment patch label, pad of being made by conductive polymer gel, the pair of electrodes that provides with regular interval on a surface of this pad are provided for it.

Wherein conductive polymer gel comprises water, the conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and the alcohol.

11. biomedical electrode, it comprises electrode device and with the element of electrode device and analyte electricity and physical connection, wherein the element conductive polymer gel is made, and described conductive polymer gel comprises water, conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and/or the alcohol.

12. toning agent, the resin part that it comprises the core body of being made by conductive polymer gel and provides on core surface, wherein conductive polymer gel comprises water, the conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and the alcohol.

13. according to the toning agent of claim 12, wherein conjugated conductive polymer is doped with doping agent.

14. a conductive functional, the current-carrying part that it comprises base material and provides at least one surface of base material, this current-carrying part is made by toning agent,

Wherein toning agent comprise the core body of making by conductive polymer gel and the resin part that on core surface, provides and

Conductive polymer gel comprises water, the conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and/or the alcohol.

15. one kind antistatic, the current-carrying part that it comprises base material and provides at least one surface of base material, this current-carrying part is made by toning agent,

Wherein current-carrying part has planeform,

Toning agent comprise the core body of making by conductive polymer gel and the resin part that on core surface, provides and

Conductive polymer gel comprises water, the conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and/or the alcohol.

16. a printed component part, the current-carrying part that it comprises base material and provides at least one surface of base material, this current-carrying part is made by toning agent,

Wherein current-carrying part is a planeform,

Toning agent comprise the core body of making by conductive polymer gel and the resin part that on core surface, provides and

Conductive polymer gel comprises water, the conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and/or the alcohol.

17. a conduction is stuck with paste, it comprises conductive polymer gel, conductive powder and resin glue,

Wherein conductive polymer gel comprises water, the conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and/or the alcohol.

18. the conduction according to claim 17 is stuck with paste, wherein conjugated conductive polymer is doped with doping agent.

19. a conductive functional, the current-carrying part that it comprises base material and provides at least one surface of base material, current-carrying part is pasted by conduction,

Wherein conduction stick with paste comprise conductive polymer gel, conductive powder and resin glue and

Conductive polymer gel comprises water, the conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and/or the alcohol.

20. a printed component part, the current-carrying part that it comprises base material and provides at least one surface of base material, current-carrying part is pasted by conduction,

Wherein conduction stick with paste comprise conductive polymer gel, conductive powder and resin glue and

Conductive polymer gel comprises water, the conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and/or the alcohol.

21. according to the printed component part of claim 20, wherein antenna is partly made with the IC chip by linear conductance and is connected with antenna.

22. an electrode for fuel cell, it comprises conductive polymer gel, and wherein conductive polymer gel comprises water, the conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and/or the alcohol.

23. according to the electrode for fuel cell of claim 22, wherein conjugated conductive polymer is doped with doping agent.

24. fuel cell, it comprises power generation part, this power generation part is made by mutual stacked one or more batteries, each battery comprises first and second electrodes, with be clipped in electrode intermediary ionogen, wherein at least one in first electrode and second electrode comprises conductive polymer gel, and this conductive polymer gel comprises water, conjugated conductive polymer as main ingredient, and at least a in tensio-active agent and/or the alcohol.

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