Patent Application
20090155571
The present invention relates to a sensor structure according to the preamble of claim 1.
The present invention also relates to the manufacturing method and the use of the sensor structure.
At the production or further processing stages, paper and cardboard products, among others, can have added thereto what is known as security symbols, which comprise an electrically conductive polymer, its electrical conductivity being locally changeable so that, deviating from the properties of the surrounding material, it is electrically conductive or, correspondingly, electrically non-conductive in order to form a desired security symbol patterning or pattern. Thus, the authenticity of the product can be confirmed by identifying the electrical conductivity of the paper or cardboard product on the region of the security symbol.
One special property of the electrically conductive polymers is the dependence of the conductivity on the pH. For example, when the pH is in the acidic range, polyaniline is electrically conductive. When changing the pH into basic, the polymer becomes electrically non-conductive. By utilizing the dependence of the conductivity on the pH, various applications can be provided to form conductive patterns in a controlled way. One simple way is to imprint a desired patterning, such as the logo of a company, onto a polymer layer, which is in its non-conductive form, using an acidic substance. When acidic, the patterning is electrically conductive. Correspondingly, the desired non-conductive patterning can also be made by imprinting it onto a polymer layer, which is in its conductive form, using a basic substance. The patterning can be identified from its surroundings by means of galvanic, capacity or inductive couplings; in this way, it serves as a guarantee of authenticity for a product or for example a document. It is easy to modify the acidic or basic patterning that is to be imprinted, whereby it is possible to make personified patterning.
Part of the markings made on paper products is based on the use of microcapsules. In the paper industry, microcapsules have typically been used to manufacture photographic paper, thermosensitive listing paper, self-copying paper and security paper. Generally, the operating principle of the capsules is that, when the microcapsules are ruptured, the substance contained in them causes a change in colour when reacting with another chemical contained in the paper or with the environment at that spot on the paper. Thus, the reaction typically requires two components. The capsules can contain a colouring agent or a chemical, one of the components being either placed on the paper or in some other environment, such as in the printing ink. The capsules can rupture under the action of mechanical pressure, heat, light, another radiation, chemical interaction or a combination thereof. The microcapsules can also be added to the paper during the printing stage. Samples of perfumes or foodstuff aromas or security elements can also be printed on the paper and cardboard products.
U.S. Pat. No. 6,440,898 presents the use of microcapsules in paper to implement both thermo-sensitive printing and a pressure-sensitive security feature.
European patent specification 0693383, in turn, suggests that a layer containing microcapsules be printed on the surface of documents, e.g., on the region of important figures, in connection with printing. If someone tries to change the figures after printing, the microcapsules rupture and release a colouring agent that cannot be deleted.
The invention described in U.S. Pat. No. 5,225,299 is an example of a material, in which microcapsules having a photosensitive coat are employed. When exposed to light, the strength of the coat changes according to the exposure by means of the mechanism of photopolymerization. The capsules contain a reagent, which forms a dye when reacting with a developer outside the capsules, when weaker capsules rupture under pressure.
One known release mechanism of the contents of the microcapsule is the mechanical rupture of the capsules. For example, carbonless copy paper uses this release mechanism (Trozenski R. M., New poly-urea capsules for carbonless copy paper, TAPPI 99 Proceedings, 89). In this application, the wall of the capsule is usually made of polyurea, polyamide, gelatine or urea and melamine-formaldehyde. The core comprises a liquid dye, a dye precursor or the like.
Electrically conductive polymers, such as polyaniline, polypyrrole and polythiophene in their basic forms are non-conductive and they are rendered conductive by doping, e.g., by means of a suitable acid. Correspondingly, the conductive form can be rendered non-conductive by dedoping. This is carried out in published application FI 20030491, which describes the manufacture of a multilayer paper or cardboard product that has a layer containing electrically conductive polymers. In the publication, the layer containing electrically conductive polymers is doped to change the electrical conductivity.
In the invention of U.S. Pat. No. 5,061,657, the conductors that connect an integrated circuit with a circuit board are formed so that the area in question is coated with a polymer in its non-conductive form and the conductors are made by chemical or physical doping of the polymer layer at the spots where the conductors are to be formed.
U.S. Pat. No. 5,091,122 presents a method of preparing microcapsules that contain a basic solution. The publication mentions the use of a polymer, which is hydrophobic at high pH values, to make the coat material.
European patent 0252410 presents a method, according to which an electrically non-conductive underlayer, such as paper or polyethene, is coated with a layer comprising a mixture of two kinds of microcapsules, of which a proportion contains pyrroles and another proportion contains an oxidizing agent, i.e. a doping agent, in addition to which the capsules may contain salt. When the capsules rupture under pressure, their contents react with one another and are polymerized, developing a layer of conductive polymer, polypyrrole, at that spot.
Polycarbonates, such as polyethylene and polypropylene carbonates, can be used as thermally decomposable and sacrificial materials in the fabrication of microchannels, as is the case in the publication of Reed et al (Reed H. A., White C. E., Rao V., Bidstrup Allen S. A., Henderson C. L., Kohl P. A., Fabrication of microchannels using polycarbonates as sacrificial materials, J. Micromech. Microeng., 11, 2001, 733). The system is heated, whereby the polycarbonate decomposes and a cavity remains. The method requires that the disintegration products be able to penetrate the layer of coat. The height of the microchannels is about 5 μm and the width varies from 25 to 140 μm depending on the coating material of the capsules, among other things.
Alkaline substances have been used in paper and cardboard products to add security symbols directly on the products. However, a security pattern implemented by this method often remains slightly indistinct.
Identification (ID) solutions, or what are known as RFID tags, which are produced by means of conductive polymers and which are readable at the radio frequency (RF), have been developed in the field of smart products, among others. It has been recognized that one obstacle in the way of the RFID technology becoming common is the invasion of consumer privacy, because the tags often continue their functioning at the homes of the consumers.
Being often transported for long distances before becoming available to the consumers, the intactness and the freshness of products in the transport chain are increasingly important to the consumers at present. Regarding foodstuffs, it is particularly important that the products have not been kept or transported at temperatures higher than permitted.
There are various temperature sensor solutions, which can be used to control the transport chain of products. These can be divided into two classes, chemical and electronic. Generally, the only thing the chemical sensors are capable of doing is to report, whether or not a set temperature limit has been exceeded. The result can be read visually on the sensor. Such sensor solutions are manufactured, for example, by 3M (MonitorMark™) and Vitsab (Check Point®). Typically, the electronic sensors can be read visually by means of a visual display unit or a cordless measuring device and the sensor is generally capable of controlling momentary temperatures and entering them in its memory. Electronic temperature sensors are manufactured, for example, by Sensitech (TagAlert™) and KSW-Microtec (TempSense).
However, the price is a problem for both solutions, i.e., they are suited to control special products only, and thus no good for consumer products. The sensors are often added to a product in a form of a sticker, which can possibly be detached or replaced by a new one; thus, they are not reliable enough. The separate stickers also cost more than solutions, which are directly integrated into the product or its package.
The visual identification frequently used in chemical sensors is not very suitable for consumer products, as in that case, the consumers would choose nothing but the freshest products of the shop, causing considerable costs to the shopkeepers. An advantageous method of reading would be a cordless reading by means of a simple scanner, which the shopkeepers could use in the quality-control of the products they sell or receive. Consequently, there is a demand for advantageous sensor solutions, which would enable large-scale quality control of consumer products regarding too high storage temperatures, for example.
The purpose of the present invention is to solve at least some of the problems related to the known technology. To be more precise, the object of the present invention is to provide structures and methods, which can be used to make markings for different uses, or sensors, which are easy to verify when being activated or when activating.
The present invention is based on the use of microcapsules. The microcapsules are filled with an acidic or alkaline substance, which, when coming into contact with an electrically conductive polymer, changes the electrical conductivity of the polymer. The microcapsules that are filled with the acidic or alkaline substance can be used as activating or deactivating elements, for example, is smart packages implemented using conductive polymers.
As the acidic or alkaline substance, which changes the electrical conductivity of the polymer, is not printed as such on top of the polymer layer, but is instead added inside the microcapsules, the electrical conductivity of the polymer can be changed at an exact moment in time by rupturing the capsules.
The present invention provides a new method of marking the products. The invention further provides a new method for controlling the state of the products regarding, e.g., mechanical or thermal stresses, and a method of manufacturing irreversible mechanical connectors, the state of which is electrically identifiable.
The method according to the invention uses small microcapsules with a diameter of about 4 μm (the mean value) or bigger microcapsules with a diameter of about 50 to 500 μm, which can be filled with an acid or a base or an acidic or basic dye, or a precursor of a dye. The capsules can be ruptured using a mechanical strength, light, laser, some other radiation or heat.
The sensor structure according to the invention comprises
The sensor structure is manufactured and added to a product or onto a product by
To be more precise, the sensor structure according to the present invention is characterized by what is stated in the characterizing parts of claim 1.
The method according to the invention, in turn, is characterized by what is stated in claims 29 and 30, and the use of the sensor structure according to the invention is characterized by what is stated in claims 27 and 28.
The method according to the invention is used to manufacture products that contain an electrically conductive polymer and microcapsules that contain a base or an acid either in one and the same layer or in independent layers. The products may be, for example, various sensor structures or paper or cardboard products. According to the method, the electrical conductivity of the polymer is changed by doping the electrically non-conductive polymer by adding onto the product or to the product microcapsules that contain an acid solution, the microcapsules being then ruptured, or by dedoping the electrically conductive polymer by adding onto the product or to the product microcapsules that contain an alkali solution, the microcapsules being then ruptured. By using active substances suitable for the purpose, such as acidic or basic dyes or precursors of dyes, it is also possible to obtain a colour reaction at the same time. A colour reaction is also obtained, when the polymer changes its state of conductivity; for example, polyaniline in its conductive form is green and in its non-conductive form blue.
One advantage of the present method is that markings or sensors are provided for different purposes, which, when activating or being activated, can easily be verified, for example, by means of electrical or optical measuring.
The other details and advantages of the invention become evident from the following detailed description.
The following components are included if the figures:
Micro bubbles can be defined as small, unstable balls filled with gas and contained in a solution. A micro bubble is kept together by a thin liquid wall, known as a film. The microcapsules, in turn, are stabilized micro bubbles. They are particles with a mean diameter of about 1 to 1000 μm, consisting of one or more cores and a generally solid capsule wall. The core can be gas, liquid or solid matter and the wall can be natural material or synthetic material. The shape of the capsules can be more or less round and their surface can be smooth or wrinkly depending on the material used or the method of manufacture. Depending on the purpose of use, the wall can be permeable, partly permeable or impermeable.
Micro bubbles and microcapsules have mainly been manufactured of starch or other natural or synthetic polymers either by drying a material that has been made swell in liquid or by using emulsion techniques. At their best, both methods have provided micro bubbles/microcapsules with the smallest diameter of less than 5 μm. When using starch, the smallest capsules are obtained, when the starch is allowed to swell in water at a temperature lower than the gelatinization temperature.
The life period of the micro bubble is mainly shortened by surface tension forces, which increase the pressure of the gas inside the bubble. The bubbles can be stabilized by different methods, of which the most common is cross-linking by surfactants, whereby the surface tension decreases. As a result, an often crusty microcapsule is provided, the crust consisting of an organic material.
“Sensor” in the present invention refers to a structure, which is activated by a change in the conditions and, when activating, causes a verifiable change in the structure.
The electrically conductive polymer can be bound to the product both in an electrically conductive and an electrically non-conductive form. Therefore, the term “electrically conductive polymer” also refers to a polymer that is non-conductive at the moment of examination, which, however, can be brought into an electrically conductive form by a suitable doping agent treatment, for example.
The “doping agent” in the present invention refers to an acidic substance, which reacts with the polymer in its non-conductive form, doping the same (e.g., by doping or some other treatment) to form charge carriers (such as free electrons) in the polymer. Typical doping agents include organic sulphonic acids and inorganic mineral acids. Correspondingly, the “dedoping agent” in the present invention refers to an agent, which is capable of reacting with the acid group of the protonic acid used as a dopant by reducing it. Typically, such substances comprise substances, such as NaOH, KOH and ammonia, which function as bases in an aqueous solution.
According to a preferred embodiment of the invention, the electrical conductivity of the polymer is changed by doping the electrically non-conductive polymer by adding onto the product or to the product microcapsules containing an acidic solution, the microcapsules being then ruptured.
According to another preferred embodiment of the invention, the electrical conductivity of the polymer is changed by dedoping the electrically conductive polymer by adding onto the product or to the product microcapsules containing a basic solution, the microcapsules being then ruptured.
In both embodiments mentioned above, the activation or deactivation, i.e., doping or dedoping, is obtained by rupturing the coat of the microcapsules and then releasing their contents. This can preferably be carried out by using a mechanical force. For example, lines or patterns can be drawn on the product with a pen, whereby a security symbol can be made on the product, being visible upon examining the electrical conductivity of the product.
The method of this preferred embodiment, which uses a pen to rupture the microcapsules in the product, is used to obtain a more accurate patterning than what is possible by the conventional printing techniques.
In addition to the mechanical force, the microcapsules can preferably be ruptured by using heat treatment or radiation. The above-mentioned patterning in the product can thus also be provided by means of a laser or the like. Other possible rupturing methods of microcapsules include the temperature range, mechanical, chemical, biodegradation, sensitivity to salt, pressure sensitivity, radiation, photochemical, the pH range or dissolution in solutions.
The microcapsules can also preferably be made so that they slowly rupture of their own accord, slowly dissolve or slowly release their contents, whereby the conductivity of the polymer would slowly change in the course of time. In that way, the microcapsule structure could also work as a timer or an element, which in some other way showed the time. Generally, microcapsules of a larger size degrade faster than those of a smaller size.
In the encapsulation, it is possible to change the diameter of the capsule, the thickness of the wall, the material of the capsule's coat, and the composition of its contents. For example, by changing the thickness of the capsule's wall, it is possible to adjust the sensitivity of the capsule to rupture and, thus, the switching limit of the sensor structure, which can be a force, temperature, or the unit of another rupturing method.
The coat materials can comprise, among others, proteins, polysaccharides, starches, waxes, fats, natural or synthetic polymers and resins. One preferred coat material is melamine formaldehyde. The coat material is selected so that it can be ruptured, for example, by using a mechanical force, radiation or heat, or more than one of these. The capsules can be ruptured by means of the mechanical force, light, laser, some other radiation or heat. For example, the mechanical force can be provided by a pen that is used to write on a paper or another product. The mechanical force can also be provided by opening the package, for example. One alternative would be to form capsules, which in the course of time would perish and break or the material used in their coat would dissolve.
The size, or the diameter of the microcapsules can vary within a range of 100 nm to 6 mm according to the contents, among others, and the amount of contents in relation to the total composition (the filling ratio) of the microcapsule may vary from 20% to 95%. The present invention uses microcapsules having a high filling ratio, preferably about 50 to 95%, more preferably about 80 to 95%.
The diameters of the capsules used can be about 1 to 10 μm, preferably about 1-5 μm. The layer formed by the microcapsules in the product has a thickness of about 1 μm-1 mm, preferably about 1-10 μm according to the diameter of the microcapsules used. The thickness of the layer formed by the microcapsules in the product is always at least as large as the diameter of the microcapsules used. Thus, the thinnest layers of capsules (1 to 10 μm) can only be obtained by the said microcapsules having a diameter not higher than 10 μm. For the method according to the present invention, microcapsules of a larger size can also be used, having a diameter of as large as 500 μm.
The microcapsules according to the present invention can be produced by various methods. The coat material of the capsule walls can consist of both a hydrophilic and a lipophilic substance, such as protein, hydrocolloid, rubber, wax, and resin or formaldehyde urea polymer. However, the material should endure (basic or acidic) aqueous contents.
The manufacturing methods of the microcapsules can be divided into mechanical and chemical methods. The mechanical methods include, among others, spray drying, spray cooling, rotary disc grinding, fluidized bed coating, stationary nozzle coextrusion, centrifugal head coextrusion, submerged nozzle coextrusion, and pan coating. The chemical methods include, among others, phase separation, solvent evaporation, solvent extraction, interfacial polymerization, simple and complex coacervation, in situ polymerization, liposome technology, and nanoencapsulation methods.
Various encapsulation techniques can be used to provide microcapsules of different size categories. Table 1 presents assessments of size categories obtained by the conventional methods.
The above-mentioned encapsulation techniques can be used to encapsulate solutions, gases, and suspensions, among others.
In the complex coacervation, the substance to be encapsulated is dispersed as droplets in an aqueous polymer solution, such as gelatine. Another water-soluble polymer, such as Arabic gum, is then added to the emulsion. After mixing, the pH is adjusted by means of a diluted acetic acid. After adding the acid, two phases are formed, one of which, called coacervate, has high contents of both polymers, and the other one, known as a supernatant, has low contents of polymer. If the materials are correctly selected, the coacervate is adsorbed on the surface of the dispersed core drops, thus forming microcapsules. Generally, the capsules are first hardened by cooling and then by means of a chemical reaction by adding a cross-linking substance, such as formaldehyde.
In the coextrusion, both the liquid core material and the capsule material are pumped through coaxial openings, the core material flowing in the middle opening and the capsule material flowing through the outer ring. In this way, a combination drop is formed, consisting of a drop of the core liquid, which is encapsulated in a layer of the capsule solution. The capsule is then hardened by conventional methods, such as chemical cross-linking, e.g., in the case of polymers, cooling, e.g., in the case of fats or waxes, or by solvent evaporation.
The capsules are formed in two modes, in a drop or jet mode, according to the flow rates of the core and capsule solutions. In the drop mode, the flows of both solutions are slow and a combination drop begins to form at the tip of the nozzle. The surface tension prevents the drop from falling away immediately. Instead, the drop will not fall away from the tip of the nozzle until the drop is large enough for the separating force caused by its weight to exceed the retentivity caused by the surface tension. This mode can be used to achieve capsules of a uniform size, even large ones. If the flow rates are increased enough, no more capsules are formed at the tip of the nozzle but a combination jet is formed, consisting of both the core and the capsule solutions. By the force of the surface tension, the combination jet is soon dispersed into combination drops.
According to a preferred embodiment of the invention, the microcapsules are prepared by spinning two different substances. After obtaining drops of a certain size, the spraying technique is used to superimpose two bubbles, of which the outer one is hardened.
In the preparation of the products according to the invention, for example, polyaniline, polypyrrole, polyacetylene, polyparaphenylene or polythiophene or their derivatives or mixtures can be used as the electrically conductive polymer. Regarding the derivatives, the alkyl and aryl derivatives and the chlorine- and bromine-substituted derivatives of the above-mentioned polymers can be mentioned in particular. When necessary, other electrically conductive particles, such as metal, graphite or carbon black can also be used as additives. Conjugated double bonds of the backbone chain are common to all electrically conductive polymers, enabling the movement of the charge carriers (such as electrons). The electrically conductive polymers can have both ionic and electronic conductivity, and this conductivity may vary within the whole conductivity range, from the insulant to the metallic conductor. Generally, a polymer is considered electrically conductive, if is resistivity is not higher than 1011 ohm (as surface resistivity).
In the invention, polyaniline is quite preferable to be used as the electrically conductive polymer. The monomer in the polyaniline is aniline or its derivative, its nitrogen atom being mainly bonded to the carbon of the para position of the benzene ring of the next unit. The non-substituted polyaniline may occur in various forms, of which the so called emeraldine form is generally used for the applications of conductive polymers, being typical of its bright emerald green colour, which stands for its name. By means of doping, the electrically neutral polyaniline can be converted into a conductive polyaniline complex.
The microcapsules can be added to the product either in the same layer as the electrically conductive polymer or they can be added to the product in different layers. If the microcapsules and the electrically conductive polymer are added to the product in different layers, the addition of the microcapsules can also be carried out at a later stage than that of the electrically conductive polymer. In that case, the layer of microcapsules and the polymer layer are kept separate at least during the production stage, and they are not brought tightly together until at a further processing or refining stage or at a subsequent stage so that a reaction can be generated.
A binder should also be used in the layer of microcapsules, attaching the microcapsule to the product. If the microcapsules are situated in the same layer as the conducting polymer, the conducting polymer as such can work as the binder. However, a separate binder is often needed, which can be the same as or another than that of the conductive polymer. Suitable binders include, for example, starch-based binders, dextrines, carboxymethyl cellulose or polymer-based binders, such as polyvinyl alcohol and polyvinyl acetate. However, a bulking agent can also be used in the layer of microcapsules, when needed, to protect the capsules against premature rupturing, e.g., during transportation.
If the microcapsules are added to the product in a separate layer from the electrically conductive polymer, especially, if the microcapsules are added to the product at a different stage than the polymer in question, a binding material can be used, if needed, to keep the layer of microcapsules in place. Suitable materials for this purpose include stickers, tapes or other films or corresponding materials, which have an adhesive provided on the surface thereof.
The product according to the invention thus includes at least one “first layer”, which comprises at least an electrically conductive polymer that is mixed with a binder constituting a matrix. This layer, which is possibly the only one, is either continuous or discontinuous. If there is only one layer in the product, this layer comprises the microcapsules as well. The microcapsules can also be in a different layer than the polymer. The microcapsules in the “second layer” can also possibly be mixed with a binder, which can be the same as or different from the binder in the first layer. The “matrix” refers to a polymer network or layer, which is at least partly continuous so that it is capable of forming uniform surfaces and layers. Due to the electrically conductive polymer, the first layer is at least partly electrically conductive or it can be rendered electrically conductive. Typically, the surface resistivity of the first layer in its electrically conductive form is about 102 to 1011 ohm, preferably about 103 to 1010 ohm, particularly about 104 to 109 ohm.
In addition to the above, the multilayer products can have an intermediate layer between the first and second layers, enhancing the mutual adhesion of the layers. Such a “tie layer” may consist of a binder that is the same as or different from that in the first or second layers. The layer can also comprise a thermoplast.
In addition to the previous layers, the multilayer product typically comprises an additional layer, which is fitted on top of the first or the second layer. Such an additional layer may consist of a plastic film—e.g., a polyolefin film—which is extruded on the surface of the product. Alternatively, the additional layer can comprise a coating layer that is applied on top of the surface layer. The additional layer thus forms the surface layer of the product or gives the product properties of barrier or sealability. Consequently, the product can be attached to a plastic underlaying by means of the additional layer, for example.
In addition to the preceding alternatives, the lamellar structure according to the invention can be freely modified according to the intended use. Various barrier layers, such as layers of polyester and EVAL, and aluminium films, can be incorporated into the structure.
Generally, the structure has 1 to 10 layers, particularly 2 to 5 layers, whereby it is essential that at least one of the layers is a conductive polymer layer (i.e., the “first layer”), preferably so that its conductivity can be determined through the layers on top of it.
The amount of binder used in the different layers can vary within a broad range but, typically, it is about 0.1 to 10 g/m2, preferably about 0.5 to 5 g/m2, more preferably about 1 to 3.5 g/m2. The binder used is a binder that is soluble or dispersible in water, comprising, for example, dextrine, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl acetate or a binder based on starch or a starch derivative.
The binder is used in a form that allows it to be spread at room temperature or at a slightly elevated temperature, typically about 10 to 50° C. Generally, such a binder mixture comprises a binder that is mixed with or dispersed in a medium, such as water or a solvent, preferably water. The dry content of the binder composition is about 1 to 80% by weight, preferably about 5 to 75% by weight, according to the binder. It is essential that the binder composition can be spread to form a layer.
The binder mixture can include one or more binder components. Regarding starch-based binders, for example, the mixture can have added thereto polyvinyl alcohol or ethylene/vinyl alcohol copolymer (in an amount of 0 to 35% by weight, a typical minimum amount being about 1% by weight); if so desired, a tacking resin (in an amount of 0 to 70% by weight, the typical minimum amount being about 1% by weight) or antioxidants (in an amount of 0 to 3% by weight, the typical minimum amount being about 0.1% by weight). It can also include anti-moulding agents and other biocides, typically about 0.1 to 3% by weight.
The electrically conductive polymer is mixed with the binder in the form of dispersion, for example. It is preferable to select a dispersant that corresponds to the solvent of the binder. Hence, polyaniline can be used as a water paste in case of aqueous binders. Its polyaniline content is, e.g., from 0.1 to 25% by weight, preferably from about 0.5 to 20% by weight, particularly from about 5 to 17% by weight. Polyaniline is most preferably in the conductive form, whereby the above-mentioned amount contains the amount of doping agent. Generally, the amount of polyaniline (without the doping agent) is from about 0.1 to 15% by weight. When added to non-aqueous adhesives, polyaniline is first dispersed in organic solvents (such as toluene). The amounts of use are the same as above.
According to the invention, a polymer binder mixture is provided, wherein the content of the electrically conductive polymer (with its doping agent) is about 10 to 90%, preferably about 30 to 70% of the weight of the mixture.
The binder jointly with the electrically conductive polymer forms a mixture, which generally is “homogeneous”. In that case, the homogeneity of the mixture is examined visually as a film on top of a cardboard, wherein the mixture seems homogeneous. In practice, however, every mixture is a dispersion to some degree, also including tiny particles; therefore, the mixture is hardly ever perfectly homogeneous.
The mixture of the polymer and the binder can be applied with a roll, a rod, by spraying, atomizing or spreading. The mixture can also be fed from an adhesive nozzle as a continuous layer or film, enabling a non-contact application (the distance between the nozzle and the surface of the product can be about 1 to 50 mm). The mixture can also be spread by typical printing methods, such as the offset, flexo, gravure, screen or inkjet printing methods.
The objective of the application is to make a layer of adhesive on the surface of a product (e.g., a cardboard package), the layer being at least partly continuous and adhering to the surface after spreading. If the electrically conductive polymer is in its electrically conductive form, it is preferable to spread it on an area that is acidic or slightly basic, at the most, in order for the electrical conductivity of the polymer to remain unchanged. The pH value of the area in this case is preferably not higher than 8.
The doping agents used in the present invention may vary extensively and they can be substances, which are well-known for doping conjugated polymers into the electrically conductive or semi-conductive form. Such doping agents contain inorganic and organic acids and their derivatives, of which the following examples should be mentioned: mineral acids, phosphoric acids, sulphonic acids, picric acid, n-nitrobenzene acid, dichloroacetic acid, and polymer acids. More than one doping acid can be used, when so desired. When selecting the doping agent, the objective is to reach a state, wherein the affinity of the mutual bonding of the electrically conductive polymer and the product, to which the polymer is added, is as high as possible. The affinity is dependent on the material of the surface, to which the polymer is attached. As these materials can be different (both hydrophobic and hydrophilic), there is also a need for polymers that have very different functional groups (such as aliphatic or aromatic), and thus, ways of bonding.
A functional acid, such as sulphonic acid, aromatic sulphonic acid in particular, is preferably used for doping, containing one aromatic ring or two fused rings, whereby at least one ring may have a polar or non-polar substituent, such as a functional group or a hydrocarbon chain.
Especially preferably acids include dodecyl benzene sulphonic acid (DBSA), camphor sulphonic acid, para toluene sulphonic acid and phenol sulphonic acid.
Too low pH values can have an adverse effect on the mechanical properties of the products manufactured by the method according to the invention, especially the fibres that constitute the framework of paper and cardboard products, which is why a preferable pH range in the “activated area”, i.e., the area, to which the microcapsules have been added, is about 2 to 6, more preferably 2 to 4, in the products after the acidic microcapsules have ruptured.
Basic solutions work as possible dedoping agents for polyaniline or other polymers, the most common ones of them being sodium hydroxide, potassium hydroxide, and sodium carbonate solutions. Other conventional hydroxide, carbonate, and amine solutions can also be considered. Generally, both acids and bases are used as relatively diluted solutions (solutions of about 0.01-10 M), especially when treating paper or other fibrous products with them, in order for the fibre matrix under treatment not to become exceedingly fragile.
According to a preferred embodiment of the invention, the microcapsules cause a colour reaction when reacting with the polymer or another substance in the product. The precursor of the dye can either be incorporated into the product or it can be in the microcapsule as an acid or a base. Thus, identification can be provided on the product, being visible to the naked eye or verifiable by means of an optical visual aid. It should also be possible to combine the colour change reaction with the change in the electrical conductivity.
The present invention is based on the use of microcapsules, which preferably contain a filling agent consisting of a substance, preferably a liquid, which has either an acidic or basic pH. The filler of the microcapsules can also comprise a basic dye, such as the dye that reacts with the bentonite in paper, or a precursor of the dye. The basic liquid can be used to dedope the conductive polymer, among others, i.e. to change it into its non-conductive form. The capsules can be broken and dedoped, for example, by heat treatment, radiation, by mechanical, chemical or photochemical rupture, biodegradation, rupturing them by means of the sensitivity to salt or the pH range, the pressure sensitivity or radiation, or by dissolving in various solvents. The microcapsules can preferably also be prepared so that they slowly rupture themselves, slowly dissolve or slowly release their contents, whereby the conductivity of the polymer would slowly change in the course of time.
When the microcapsules break, their doping or dedoping effect does not cover a very wide area, but if a sufficiently large number of capsules are used, the dedoping or doping effects can be implemented on a macro scale. If the effect is not extensive, the change in the conductivity of the area can, however, be verified by using a capacitive measuring method.
A contact is not necessary for measuring the conductivity. Non-contact measuring can be carried out at a short distance, for example, by using capacitive measuring, as above. The possibility to carry out the non-contact measurement is preferable in the embodiment according to the invention, wherein the conductive polymer is not located in the outermost layer of the product. Other viable measuring methods include the galvanic and the inductive methods. On the other hand, the contacting measurement method has its advantages in certain cases, especially if the electrically conductive polymer is in the outermost layer of the product.
By varying the amount of electrically conductive polymer, a selected level of conductivity can be reached, for example, 102-1011 ohm/square, preferably about 104-108 ohm/square. When the square resistance is 108 ohm or lower, it is easy to distinguish the product from a non-conductive product.
According to the invention, products can be provided, having an electrical conductivity that either remains for long periods of time or changes in the course of time.
The most significant advantages for using the microcapsules in the product to activate or deactivate the electrically conductive polymer located in the same product are:
The products according to the present invention can be used, among others, in the manufacture of sensors, in antistatic applications, the storage of identification data, and security symbols.
According to the method of the present invention, the security applications can be used to make security symbols on packages and other products, whereby the authenticity of the product can be verified by making the capsules in the product rupture, whereby electrically conductive patterns are obtained. The security symbols could also be markings located in product packages, such as mobile phone packages, being activated by a finger pressure, for example, thus proving that the package has been opened, and cannot be reused after opening. This would prove to the customer that the product he/she has bought is new.
The rupture of the microcapsules' coat and the release of their contents can be carried out knowingly, to make the security patterns, for example, as described above. In addition, the sensitivity of the microcapsules to break could be utilized to manufacture sensor structures that indicate the transportation conditions of the product, for example, or it could be used to indicate any measures carried out on the product, e.g., the above-described opening of the package. Any measures observed or carried out can also be identified electrically, as the contents released by the microcapsules cause a change in the conductivity of the conductive polymer.
Identifying the undesirable opening of a package is a great challenge in connection with some expensive or otherwise significant products, such as consumer electronics and medicines. For example, the manufacturers of mobile phones and digital cameras want to make sure that, when a consumer buys their products, the package includes the original auxiliary instruments. In some market areas, such as Asia, for example, the packages of branded products are often opened and the original auxiliary instruments are replaced by false products. For example, fake batteries may explode and thus, in addition to economic losses, also cause health hazards.
For some medicines, there is the further problem of replacing the primary packages of the original drugs (known as blisters) with adulterated drugs inside the original secondary packages. Often, adulterated drugs do not have the same effect as the original ones, and this may even cause deaths. Therefore, it would be advisable to have some kind of a mechanism also for drug packages, identifying a possible opening of the package or a replacement of the drugs. At present, the most advanced solutions are so called “tamper-evident” seals that optically show whether or not the package has been opened. However, as the technique is fairly common and the optical identification is not completely reliable, these solutions do not give a complete protection against the attempts of forgers.
The structure according to the present invention can preferably be used to measure the conditions inside the product package or to measure the conditions outside the product package, or to measure both of them. The same product may contain microcapsules that break in different ways. For example, one product can contain microcapsules that are sensitive to both heat and moisture, whereby the sensor or another security application, to which these microcapsules have been added, can be activated by a change in both the temperature and the moisture. Theses ways of activation can also be made dependent on the time consumed.
By examining the conditions inside the package it is possible to see without opening the package, if for example the conditions surrounding a medicine in a drug package have remained within the required limits. Similarly, by examining the outer conditions of the drug package, it can be seen whether or not the package has been stored according to proper conditions.
According to the method of the present invention, by combining, in the sensors or detectors that occur in different products, the microcapsules that have basic or acidic contents and the electrically conductive polymer, it is possible to bring the sensor property of the sensor applications into the electrical form. The releasing methods of the contents comprise mechanical force, which is preferably provided by a pen, radiation, which is preferably provided by a laser, heat treatment, chemical degradation, biodegradation, sensitivity to salt, pressure sensitivity, photochemical degradation, sensitivity to the pH range, and dissolving in solvents. The microcapsules in the sensor can rupture when exposed to the substance indicated by the sensor. Thus, many types of sensor solutions can be made from the combination of polyaniline and microcapsules. Examples of the sensor applications include the opening indicator, rupture/pressure indicator, light detector and solvent sensor. There can be two different structural types of sensor constructions (see
The sensor or the detector is activated by means of the substances released by the broken microcapsules. The activation either takes place by breaking the capsules at a desired point of time or by allowing them to break by themselves in the course of time.
The microcapsules can be added to the structure of the sensor in a different layer from the polymer, or mixed with the polymer according to
In the previously mentioned RFID technique [identification (ID) readable on radio frequency (RF)], the method according to the present invention can also be used to change the RFID circuits, which are manufactured with conductive polymers or contain conductive polymers, into the non-conductive form by dedoping, using base-containing microcapsules, and thus make the RFID circuits inactive, i.e., reset them to zero to make them illegible.
Acidic or basic microcapsules can be used, among others, to form writable RFID circuits that are manufactured using conductive polymers. Thus, the capsules can be used to make new conductors or shut off old ones. The writable ID can be used, among others, to establish an individual identity for each package on the packaging line by utilizing various rupturing techniques of microcapsules, such as the laser.
The following unlimited example illustrates the invention.
According to
In the conductive patterns, parts 6 with sizes of 26 mm×28 mm were used to measure the resistances between the points. The dual point measurement was used as the measuring method and the Wavetek Meterman 37XR multimeter was used as the meter, its measuring range being limited to 40 MΩ at the maximum. The measuring error of the meter is about ±2%. In practice, the measurements were read with an accuracy of two significant numbers, and the error was always rounded up to an accuracy of the smallest significant number. The measuring sensors used are round and their diameter is 17 mm. The measuring points 6 are connected by a fairly thin line 7 to 11, which is polymer in its conductive form. The widths of the lines were 1 mm (7), 2 mm (8), 4 mm (9), 6 mm (10) and 8 mm (11). The length of the line in every pattern is 36 mm. The patterns were measured for resistances by means of the dual point measurement before spreading the microcapsules (see Table 2). The marking “Max” means that the measured resistance higher than the operating range of the meter. Sample 1 was too weakly conductive; therefore, the sample was not used in the following stages. Otherwise, the measured resistances behaved logically regarding both the different widths of the line and the thicknesses of the polymer layers.
An area of about 10 mm×10 mm was added on top of the lines 7 to 11, consisting of microcapsules 2 in a sufficiently thick layer. The microcapsules were attached to the underlaying by means of a separate polymer film that had a layer of adhesive on its surface. The coat of the microcapsules was paraffin wax and the contents were sodium hydroxide (NaOH). The size of the microcapsules was about 400 to 500 μm. The patterns were measured for resistances by means of the dual point measurement after spreading the microcapsules before breaking them (see Table 2). It was observed that some samples showed a slight increase in resistance, which was probably caused by the fact that the contents of some microcapsules had leaked out and, thus, slightly changed the conductivity of the line.
The microcapsules, which had been spread, were ruptured and the NaOH contained in them was released by means of mechanical force. In this case, a relatively great mechanical force was used, as the coat layer of the microcapsules used was quite thick. By changing the thickness and the material of the layer, it is possible to adjust the sensitivity to break. The resistance between the measuring points was measured 4 hours after rupturing the microcapsules (see Table 2), as both the dedoping effect and the spreading of the dedoping agent requires a certain time of action before the effect is visible in the resistance test.
By examining Table 2, it can be observed that the resistances of Samples 2, 3, 6, 7 and 8 showed a significant increase after rupturing the microcapsules. Thus, the most functional structure for a structure that measures the mechanical force is one, wherein the width of the sensor area changing its conductivity is fairly small and, thus, the gradient of the change is the greatest. Furthermore, it is preferable for the sensor to have a thick, i.e., a well-conducting line. This can be observed when comparing Samples 1 and 6.
No effect could be observed on the greatest line widths (Samples 4, 5, 9 and 10). This is probably because the NaOH contained in the microcapsules, because of its small volume, is not spread extensively and, therefore, it is easy for the wide line to keep its conductivity.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20050731 | Jul 2005 | FI | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/FI2006/000242 | 7/5/2006 | WO | 00 | 7/11/2008 |
