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WO2018050827A2 - A method for manufacturing a multi-layer film, a multi layer film, a sensor device, a sensor sheet, a sports gear, and a method for detecting movments of a target - Google Patents

A method for manufacturing a multi-layer film, a multi layer film, a sensor device, a sensor sheet, a sports gear, and a method for detecting movments of a target Download PDF

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Publication number
WO2018050827A2
WO2018050827A2 PCT/EP2017/073292 EP2017073292W WO2018050827A2 WO 2018050827 A2 WO2018050827 A2 WO 2018050827A2 EP 2017073292 W EP2017073292 W EP 2017073292W WO 2018050827 A2 WO2018050827 A2 WO 2018050827A2
Authority
WO
WIPO (PCT)
Prior art keywords
layer
polymer
carbon
conductive
dispersion
Prior art date
Application number
PCT/EP2017/073292
Other languages
French (fr)
Other versions
WO2018050827A3 (en
Inventor
Harri Repo
Original Assignee
Nordic Flex S.L
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nordic Flex S.L filed Critical Nordic Flex S.L
Priority to EP17768119.4A priority Critical patent/EP3513412A2/en
Publication of WO2018050827A2 publication Critical patent/WO2018050827A2/en
Publication of WO2018050827A3 publication Critical patent/WO2018050827A3/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
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    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D—TEXTILES; PAPER
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    • H—ELECTRICITY
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10007—Types of components
    • H05K2201/10037—Printed or non-printed battery
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10007—Types of components
    • H05K2201/10151—Sensor

Definitions

  • the present application relates to a method for manufacturing a multi-layer film with conductive coating, to the multi-layer film with conductive coating and to sensor devices and other applications containing the multi-layer film.
  • the present application also provides methods for detecting changes in the electric circuits of the multi-layer films, and for detecting movements of a target having the sensor device.
  • the present application also provides a method for manufacturing a conductive carbon dispersion, and a conductive carbon dispersion.
  • a conductive coating film may be used in a variety of applications, such as for providing wiring for electronics, for forming antennas, sensors, switches, coils, capacitors, and the like.
  • There are conventionally known methods for preparing such coated films such as a vacuum metal deposition method, a chemical deposition method, an ion sputtering method and a method in which metal particles are dispersed in a dispersing medium and the resulting metal colloidal solution is applied, heated and sintered.
  • these methods have problems such that organic solvents are used, complicate operation is needed, mass producibility is inferior, and heating at high temperature is required, etc. It is challenging to obtain coated conductive films having high stability. Further, there is a need for inexpensive conductive films, which are flexible, durable and may be used in several applications and for several purposes, as well as for manufacturing methods thereof. Summary
  • first dispersion also comprises non-nanoparticulate carbon or wherein the method comprises mixing non-nanoparticulate carbon to the first dispersion, such as carbon having an average particle size in the range of 1-20 ⁇ , such as 1-15 ⁇ ,
  • One embodiment provides a sensor device comprising a sensor module, such as a motion sensor module, connected to the conductors of the multi- layer film.
  • One embodiment provides a sports gear comprising the sensor device.
  • One embodiment provides a sensor sheet comprising the multi-layer film, the sensor sheet comprising at least two carbon sections of at least 100 x 100 mm.
  • One embodiment provides a method for detecting the presence or the movements of a subject, the method comprising
  • One embodiment provides a method for manufacturing a conductive carbon dispersion, the method comprising
  • One embodiment provides a conductive carbon dispersion obtained with said method.
  • One embodiment provides a printing ink composition comprising the conductive carbon dispersion.
  • the embodiments combine compounding chemistry and electronics together with mechanics to produce sensor devices which may be used for a variety of applications.
  • the devices may be attached to different kind of targets of different shapes and materials.
  • sports such as in hockey sticks, baseball bats, cricket bats, golf clubs, tennis rackets etc.
  • Another example includes a frame for dosing tablets and capsules for medical or nutritional purposes.
  • the present embodiments provide unique and novel carbon and optionally carbon/silver chemistries. Instead of organic solvents, the whole chemistry is waterborne and thus safe for environment and users. The development has led to flexible and easily mixable dispersion, which has a long and stable shelf life. The obtained products are non-toxic and safe for the users. The used dispersions and obtained products are practically VOC and SVOC free.
  • the manufacturing of sensors is optimized by using such materials and components that the products are new in the market, but their cost is most competitive and makes them affordable. Secondarily, the manufacturing of the products is able to serve the market with large amounts of units. For example 10 000 ice hockey stick sensors may be produced in two hours by printing/laminating. Cost of one unit is less than 20 € and the potential is more than 1 million units/year.
  • the newest sensor technology is especially suitable for the combinations and also the latest mobile technology trends open paths for easier access of suitable software for multiple uses of the embodiments
  • the embodiments may be used for example in dosing medicines or nutritional substrates timely and also in tracking various items or subjects, such as hired cars, electronics deliveries and persons. For example alarms may be provided in cases, when the device measures faulty function, such as collapse of a person carrying a sensor device or located on a sensor sheet.
  • the embodiments provide a combination of safe chemistry, tested laminated, printed and/or layered materials, robust mechanics, minimized electronics and easiness in using the "gadget".
  • the combination of xyz-conductive layer and the anisotropic z-conductive layer enables several functionalities.
  • the structure is very flexible, durable and provides a high foldability.
  • the multi-layer film or laminate may be bent or folded numerous of times without damaging the conductive layers.
  • the flexibility enables applying the layered structure onto challenging targets, such as elongated and/or angular objects, for example gaming equipment.
  • the multi-layer structure also provides elasticity, also in respect of the conductive materials without substantially affecting the conductive properties of the carbon layers.
  • the elasticity is at least 10%, and even up to 20%.
  • the materials of the multi-layer structure enable efficient attachment of electronic components or other components to the structure. Such constructions tolerate impacts, high acceleration forces and tensions.
  • Figure 1 shows an example of a cross-section of a sensor device comprising the multi-layer film in a form of a laminate.
  • Figure 2 shows an example of a sensor device seen from top
  • Figure 3 shows examples of printed circuits made of a xyz-conductive layer
  • Figure 4 shows parts of a sensor sheet seen from both sides
  • Figure 5 shows an example of a hockey stick having two sensor devices
  • the embodiments include four individual functions including a conductive coatings, a top layer, a back layer, and electronics.
  • the conductive coating includes two different conductive layers: a first xyz- conductive layer A for printing circuits, antennas, sensors, or the like based on carbon or for example carbon/metal hybrid, and a second z-conductive layer B, which is anisotropic one for printing as an overcoat for layer A, to allow electronics and other components to be heat bonded to the printed A layer.
  • the carbon/polymer mixtures used in the embodiments provide enhanced printability to obtain layers of such quality which has been possible previously with the same grammage only by using organic solvent based materials.
  • the materials used in the embodiments are water-based and approved for either direct or indirect food product contact.
  • the support which may act for example as a top layer in the final product, is a flexible carrier for the carbon printing which may be obtained by screen or flexographic/gravure printing.
  • the back layer may be for example polyolefine/polyester film laminate or polyester film.
  • the top or the back layer may be coated with adhesive having a release liner as a back protection.
  • the electronics unit or units may be for example 3 to 9 dimensional functioning sensors connected to a transmitter using carbon print as wiring and antenna.
  • Other electronics or components may be used as well depending on the application, such as such as resistors, capacitors, transistors, integrated circuits, diodes, LEDs, and the like, other sensors, such as light sensor(s) or temperature sensor(s), transmitters and/or receivers, RFID modules, memory modules, electro- mechanicals parts or modules, connectors, sockets, microphones, sound reproducing components such as loudspeakers, cameras, displays, connectors, and the like.
  • An electronic component is any basic discrete device or physical entity in an electronic system used to affect electrons or their associated fields.
  • Electronic components are mostly industrial products, available in a singular form. Electronic components have two or more electrical terminals (or leads) aside from antennas which may only have one terminal . These leads connect to create an electronic circuit with a particular function. Said components and other electronics are preferably suitable for surface or panel mounting or they may be connected to the conductive carbon circuits by separate connecting parts, such as metal wiring or prints. The connective carbon circuits or tracks may be arranged to transfer power and/or data, such as analog or digital data.
  • the multi-layer structure or laminate may act as a support for electronics.
  • the multi-layer structure or laminate may be cut to sizes suitable for each application.
  • a hockey sensor may have a size of 50 x 100 mm, and is arranged to be adhered around a hockey stick using adhesive.
  • One embodiment provides a multi-layer film with conductive coating, the film comprising the following layers:
  • the support layer may comprise one or more polymer(s), preferable organic polymers, such as plastic polymer(s).
  • the support layer comprises thermoplastic polymer, more particularly one or more thermoplastic polymer(s), copolymers, mixtures, derivatives or combinations thereof.
  • the support layer is a layer of one or more thermoplastic polymer(s).
  • the support layer comprises thermosetting polymer, more particularly one or more thermosetting polymer(s), copolymers, mixtures, derivatives or combinations thereof.
  • the support layer is a layer of one or more thermosetting polymer(s).
  • the support layer comprises more than one layer, such as at least one layer comprising thermoplastic polymer and at least one layer comprising fibers, for example a coated paper or cardboard, or a composite thereof, such as a plastic composite.
  • One embodiment provides a multi-layer film with conductive coating, the film comprising the following layers:
  • -a xyz-conductive layer comprising carbon nanoparticles and polymer
  • -a z-conductive anisotropic layer comprising carbon particles and polymer
  • One embodiment provides a multi-layer film with conductive coating, the fil comprising the following layers:
  • thermosetting polymer layer -a first thermosetting polymer layer
  • -a xyz-conductive layer comprising carbon nanoparticles and polymer
  • -a z-conductive anisotropic layer comprising carbon particles and polymer
  • polymer as used herein may refer to one or more polymer(s), more particularly one or more organic polymers, such as plastic polymers.
  • Plastic polymers may be synthetic or semi-synthetic. They may be thermoplastic polymers or thermosetting polymers, crystalline or amorphous, and/or semi-crystalline or semi-amorphous. Completely amorphous polymers include all thermosets, polystyrene and its copolymers and polymethyl methacrylate.
  • the polymer may be a cross-linkable polymer, including self- crosslinkability. In the final product the polymer may be cross-linked. In the final product the polymer may be cross-linked. In general cross-linkable thermoplastic polymers may exhibit lowered thermoplasticity after crosslinking.
  • the polymer may be a homopolymer or a copolymer of two or more monomers, or a mixture thereof.
  • the polymer may be a latex polymer.
  • Latex is a stable dispersion (emulsion) of polymer microparticles in an aqueous medium.
  • the polymers in the xyz-conductive layer and in the z-conductive anisotropic layer are dispersion polymers, more particularly aqueous dispersion polymers.
  • the dispersion polymers may be curable polymers, such as heat curable or UV curable, or they may be wet adhesion promoted polymers, cross-linkable or self-crosslinking polymers, such as acrylics.
  • precipitating polymers and/or film-forming polymers may be provided, for example for applications requiring elasticity.
  • a cross-linked polymer(s) may be obtained.
  • a cross-linking agent may be added, such as polyaziridine crosslinker, which improves especially carboxyl functional resins performance.
  • a cross-linking agent may be added in an amount of 1-3% (w/w) of the polymeric dispersion.
  • the thermoplastic or thermosetting polymer in the support layer may comprise or be any suitable thermoplastic or thermosetting polymer or combination of two or more thereof, which provides desired properties as a support for the multi-layer structure, such as flexibility, elasticity, printability, durability, heat resistance etc.
  • the thermoplastic or thermosetting polymer layer may comprise one or more thermoplastic or thermosetting polymer films or layers.
  • the thermoplastic polymer layer is a thermoplastic polymer film.
  • the thermosetting polymer layer is a thermosetting polymer film.
  • the thickness of the polymer layer may be adjusted according to the desired properties and may be in the general range of 20-500 ⁇ , such as 20-400 ⁇ , 20-300 ⁇ or 20-200 ⁇ .
  • the polymer layer has a thickness in the range of 23-100 ⁇ , such as 23-70 ⁇ , 25-80 ⁇ , 25-50 ⁇ , 30-100 ⁇ , 30-80 ⁇ , 50-100 ⁇ , or 40-100 ⁇ . These ranges are suitable for most applications and provide good tensile strength, tensile strain, thermal resistance and other mechanical properties.
  • Useful thermal range of a (thermoplastic) polymer may be in the range of -30-50°C, which is preferred especially for devices used in sport applications.
  • the thermoplastic polymer is provided in a foamed form.
  • a foamed thermoplastic polymer may exhibit elastic properties, which allow functionalities such as preparing pressable structures, which may be used in touch or pressure sensors.
  • Monoaxial orientation also referred to as uniaxial orientation, refers to the stretching provided only in one direction, either in machine direction or cross (transverse) direction.
  • Biaxial orientation refers to a film oriented (stretched) both in machine direction and in cross direction.
  • a multi-layer oriented polypropylene film is provided having two layers with different orientations, such as orientations perpendicular to each other. This kind of multi-layer film provides enhanced mechanical properties, such as high tear strength, and may be used as the first thermoplastic polymer layer and/or as the second thermoplastic polymer layer.
  • the fibrous support layer is a textile or a textile layer, or the support layer comprises textile or a textile layer, which may be also called as a fabric or cloth.
  • the fabric may be woven or nonwoven. In case of clothes, the fabric is usually woven. More particularly, textile refers to any material made of interlacing fibres. Fabric refers to any material made through weaving, knitting, spreading, crocheting, or bonding that may be used in production of further goods (garments, etc.). Cloth may be used synonymously with fabric but often refers to a finished piece of fabric used for a specific purpose (e.g., table cloth). Textiles can be made from many materials.
  • the support layer especially the thermoplastic or thermosetting polymer layer, may be heat-bonded to the next layer which is xyz-conductive layer comprising carbon nanoparticles (also called as xyz-conductive layer or xyz- layer).
  • the xyz-conductive layer may be printed and/or laminated onto the support layer, such as polymeric layer, for example thermoplastic or thermosetting polymer layer.
  • the xyz-conductive layer contains carbon nanoparticles, i.e. nanoparticulate carbon, having an average diameter, or an average particle size, in the range of 5-200 nm, or 10-200 nm, or 5-100 nm, such as 5-60 nm, 10-50 nm, or 10-40 nm, more particularly 15-30 nm.
  • the range of 15-30 nm was found to be especially advantageous providing a constant field in the conductive layer.
  • higher particle sizes such as over 200 nm, over 100 nm or even over 50 nm, gaps and therefore discontinuity were introduced into the conductive layer.
  • the glass-liquid transition or glass transition is the reversible transition in amorphous materials (or in amorphous regions within semicrystalline materials) from a hard and relatively brittle "glassy" state into a viscous or rubbery state as the temperature is increased.
  • the glass transition temperature T g of a material characterizes the range of temperatures over which this glass transition occurs. It is always lower than the melting temperature, T m , of the crystalline state of the material, if one exists. Glass transition temperature may be determined for example by using differential scanning calorimetry.
  • one polymer has a coalescing temperature in the range of -10-50°C, and the other polymer has a coalescing temperature of over 50°C. In one example one polymer has a coalescing temperature in the range of -10-5°C, and the other polymer has a coalescing temperature of over 90°C, for example a coalescing temperature in the range of 90-120°C.
  • These polymers may be also called as a first polymer and a second polymer, or a first polymer dispersion and a second polymer dispersion. The first polymer may be called as a film forming polymer and the second polymer may be called as a non-film forming polymer.
  • the z-conductive layer covers the circuits formed by the xyz- conductive layer.
  • the z-conductive layer may cover most of the multi-layer structure, or at least all the areas containing xyz-conductive circuits.
  • the z-conductive layer does not have to form such circuits as the xyz-layer because the conductivity is only in the z- direction and therefore a continuous z-conductive layer cannot cause shortcuts in the xyz-conductive circuits.
  • the z-conductive layer has a gray color, in contrast to the substantially black color of the xyz-conductive layer.
  • pigment such as a black pigment or other color
  • the color may be used to mask the xyz-conductive layer, for example to hide the conductive circuits.
  • the combination of xyz and z conductive layers provides enhanced flexural resistance for the multi-layer product, for example 10 to 100 fold flexural resistance compared to a conventional RF conductive layer.
  • the flexibility of the conductive layers enables preparation of structures which may be used in several applications. For example electronic components and modules may be integrated within the multi-layer structure and the structure may be attached to a variety of targets with different shapes.
  • Flexible sheets may be provided containing electronics and/or functionalities enabled by the conductive layers. Secure bonding of the components to the sheets may be obtained by selecting suitable support layer and conductive layers.
  • the further layer comprises polyurethane, preferably applied by extrusion technology.
  • a polyurethane layer is especially suitable for protecting electrical components and the like attached to the conductive layers, and may be applied to embodiments which are used in applications requiring shock resistance and other mechanical strength.
  • a multi-layer structure as described in the embodiments, preferably comprising a polyimide film or layer in or as a support layer, comprises said layer of polyurethane as a further layer.
  • the basic multi-layer structure for example as a band, may be wound on a roll. Before or after rolling the multi-layer structure may be supplemented with the required electrical components.
  • the structure is transferred to an extruder, and a polyurethane layer is extruded on top of the structure.
  • the assembly and/or bonding of the electronics may be carried out by using a robot unit.
  • the construction may comprise polymer layer, such as a thermoplastic polymer layer or thermosetting polymer layer, between two conductive carbon layers, such as between two conductive twin layers of xyz and z conductive layers. Such a layer in between the conductive layer may be called as a third layer. Such layer may be a foamed layer, as described herein.
  • polymer layer such as a thermoplastic polymer layer or thermosetting polymer layer
  • conductive carbon layers such as between two conductive twin layers of xyz and z conductive layers.
  • Such a layer in between the conductive layer may be called as a third layer.
  • Such layer may be a foamed layer, as described herein.
  • a paper liner may be for example super calandered kraft paper, glassine paper, clay coated kraft paper, machine finished kraft paper or machine glazed paper.
  • a plastic liner or film may be a BO-PET film, a BOPP film, or other polyolefin film such as HDLE, LDPE, or polypropylene.
  • Commonly used release agents for release liner include silicone, such as crosslinkable silicone, and other coatings and materials that have a low surface energy.
  • the two carbon layer sets which both include a xyz-conductive carbon layer and a z-conductive anisotropic carbon layer, may form a capacitor or other structures.
  • One or both of the carbon layer sets may contain supplementary metal parts, for example forming the structures of the capacitor, either partly or fully.
  • a foam layer or substrate, or a layer of any other elastic and/or flexible material, also called as a deformable layer or substrate, between the layers may enable movement of the two conductive layers in respect of each other.
  • Touch sensor or pressure sensor structures may be formed by using such a layered structure.
  • a conductive layer may have a first position and a second position in respect to another conductive layer providing a first capacitive value and a second capacitive value correspondingly.
  • a multi-layer film or laminate containing adhesive and a release liner is in the form of a self-adhesive label or sticker.
  • Such a construction may have a face layer on the top (on the other side than the adhesive), which may be printed or colored, and the construction may be called as a face laminate.
  • the support layer or the layer on the opposite side may be the face layer, or the face layer may be a separate layer on said layer.
  • the multi-layer film with conductive coating may be used for multiple purposes.
  • the multi-layer film comprises one or more conductor(s) formed by the xyz-conductive layer, the conductor(s) being connectable to one or more electronic component(s) or circuit(s).
  • a conductor as used herein refers to a conducting area designed to provide one or more functionalities, and it is present as a specific form, such as one or more elongated strip-like forms, such as tracks, acting as wiring for electronic connections, such as power and data connections, for example having a width in the range of 0.1-5.0 mm, in the range of 0.1-3.0 mm, such as 0.1- 2.0 mm, or 0.1-1 .0 mm or 0.1-0.5 mm, or wider conducting areas, such as oval or angular shape, which may be arranged to act as contact areas or sensors, or other shapes.
  • the width of the tracks is adapted to fit to the connectors or pins of the sensor, which may be for a small sensor in the range of 0.1-0.35 mm, such as in the range of 0.19-0.31 mm, for example about 0.25 mm.
  • the width of a track may be in the range of 0.2-1 mm, such as in the range of 0.2-0.8 mm, for example 0.5-0.8 mm or 0.5-1 .0 mm.
  • a conductor is supplied with a supplementary conductor, such as a metal tracks, wiring or lines, for example silver, copper, tin or gold tracks, wiring or lines, which may be applied on to a carbon conductor or to another location, to obtain a hybrid wiring or hybrid conductors, which may be used to minimize the structure.
  • a supplementary conductor such as a metal tracks, wiring or lines, for example silver, copper, tin or gold tracks, wiring or lines, which may be applied on to a carbon conductor or to another location, to obtain a hybrid wiring or hybrid conductors, which may be used to minimize the structure.
  • Silver may be printed for example by rotary screen printing using polymer type of silver paste wherein polyester resin is used as a binder. Due to its flexibility and good adhesion it is well suitable for making conductive circuit on plastic substrates. On the contrary copper, especially in nano forms, is difficult to process and has oxidation problems in aqueous environment. Further, the processed nanocopper is expensive and more harmful when compared for example to silver.
  • a capacitive displacement sensor may comprise two conductive parallel planes separated by dielectric material.
  • the planes may be formed by the conductive carbon layers, optionally supplemented with metal parts, as described herein.
  • the capacitance between the planes is inversely proportional to the square of the distances between them.
  • All sizes may be applied as printed conductive patterns having at least 2 cells, more particularly at least 2 x 2 cells up to of 2 x 8 cells, or even more, printed to cover substantially the whole width and whole length of the sensor sheet.
  • Individual cells are wired using conductive carbon print, which may be secured with printed silver lines to ensure the conductivity of the lines in long term use. For example 4-16 printed wires may be connected to a controlling device.
  • a sensor sheet may be for example fitted into a bed and therefore it may have dimensions such as about 80 x 210 cm, 100 x 210 cm, 120 x 210 cm, 160 x 210 cm, 180 x 210 cm, 80 x 200 cm, 100 x 200 cm, 120 x 200 cm, 160 x 200 cm, 180 x 200 cm and the like.
  • a sensor sheet arranged to be placed onto a floor may have for example a width in the range of 50-100 cm and a length in the range of 100-500 cm.
  • the controlling device is a device connected to the circuits of the sensor sheet, wired or wireless, the device being arranged to detect changes in the electric circuits connected to each carbon section, such as changes in capacitive, inductive or resistive properties of the carbon section or an electrical circuit including the carbon section.
  • the controlling device may comprise for example a processor, memory, an analog to digital (A/D) converter to convert the detected signals into digital form, a display or other outputting means, a network connection, and/or a software arranged to carry out the steps of detecting the signals and converting them to processed data.
  • the data may be visualized from a display, saved, processed, and/or it may be forwarded to another device.
  • the device may be a specific control unit, or it may be a server, a personal computer or other personal device, such as a wireless terminal, for example a mobile phone, a tablet, or the like.
  • the changes in the electric circuit(s) in respect of each carbon section of the sensor sheet may be used to detect the actions of the subject. For example it is possible to detect or see from the pattern formed by the changes in the electric circuits that a person is walking on the sensor sheet. It is also possible to detect the movements of a moving device, such as a robot, moving on the sensor sheet or touching it.
  • the multi-layer film may act for example as a lid for the pill dispenser, and it is connected to an electronics module or device monitoring the integrity of the circuits.
  • the pill dispenser may be formed of cardboard, which may be provided as a sheet designed to be folded into the final pill dispenser form.
  • the multi-layer film or structure may be already applied onto the cardboard, or the multi-layer structure may be provided separately, designed to be fitted and attached onto the cardboard.
  • any other support material may be used, such as plastics, coated cardboard, plastic-fiber composite and the like.
  • the body of a pill dispenser may comprise for example board, and the multi-layer film is attached onto the board.
  • the multi-layer film may be similarly applied to a bubble pack of pills or to any other similar construction.
  • different breakable areas are designed to provide different resistance, for example by providing different lengths of conductive carbon circuits or wirings at the different breakable areas. These different breakable areas may be connected to the same electrical circuit in parallel, so the circuits may be simplified as separate connections are not required for each breakable area.
  • the detectable change in the electrical circuit is different for each different breakable area having a different resistance, which enables the connected device to recognize which breakable area has been punched.
  • Figure 3 shows two examples of breakable areas 30, 31 defined by perforations 34 and having conductive carbon tracks printed on a cardboard and which areas may be removed from a package by punching.
  • the two breakable areas 30, 31 have different lengths of conductive carbon circuits 32, 33 and therefore different resistances. More particularly the track 32 is longer than the track 33 and therefore the track 32 provides higher resistance than the track 33.
  • the ends of the tracks are connected to larger continuous carbon printed areas 35, 36 which are connected to continuous printed areas (not shown) outside the breakable areas 30, 31 .
  • One embodiment provides a textile, such as a clothing, comprising the multi- layer film described herein, and comprising one or more conductor(s) formed by the xyz-conductive layer, the conductor(s) being connectable to one or more electronic component(s) or circuit(s).
  • the conductors may be in the side of the clothing which is arranged to be in contact with skin when in use, such as when worn, in practice inside clothing.
  • the conductive carbon is on acrylic styrene polyurethane polymer layer, which provides flexibility.
  • Such a construction may be used in intelligent clothing, for example wherein the conductors are used in the measurement of skin conductivity, for example to detect or measure sweating.
  • Examples of the clothing include underwear, such as underpants and undershirt, socks, gloves, headgear, shirts, pants, bands and the like. Clothing may be equipped with one or more devices arranged to be connected to the multilayer film, and which may be arranged to connect to an external device wirelessly or by using wires or cables.
  • the multi-layer films may contain one or more electrical components, connectors and/or modules described herein to enable the desired functionalities.
  • laminateating means the action of combining previously unconnected layers to become one product whose layers will remain together.
  • a layer may also be formed during the laminating process.
  • the obtained product may be called as a laminate.
  • a laminate may be prepared by using other methods as well.
  • a laminate is a permanently assembled object by heat, pressure, welding, chemical reaction or adhesives.
  • a laminate may also be called as a multi-layer structure. For example a structure containing at least two polymeric film layers attached together, with or without other layers in-between, may be called a laminate or a multilayer film.
  • a laminate may also be obtained by printing one or more layer(s).
  • the module may also contain one or more processor(s), memory, software, and/or power source and the like, and is configured to output the processed information, for example by using wired connection or by using wireless technology.
  • the sensor device further comprises one or more antenna(s) formed by the xyz-conductive layer and/or other conductive layers.
  • One embodiment provides a sensor device comprising a sensor module, such as a motion sensor module, and preferably means for wireless communication both connected to the conductors of the multi-layer film.
  • the sensor module may be included in the multi-layer film, for example the sensor module may be between two layers of the multi-layer film or laminate.
  • the multi-layer film comprising one or more conductor(s) formed by the xyz- conductive carbon is connected to a sensor module, and optionally to a separate power source, such as a battery or a solar cell.
  • the power source may be rechargeable, such as by conducting a connector from a charger, or by using inductive charging.
  • inductive charging the required inductive coil for receiving the electromagnetic field from an inductive charger may be formed with the conductive carbon or with a separate metal layer, for example silver or the like as described herein.
  • the power source is a battery, such as a disc or button type of battery, for example a rechargeable battery, which may be included in between the layers, for example having a removable insulating layer preventing the contact of the battery to the electrical circuit.
  • the insulating layer may be removed prior to use to connect the battery and to turn the power on in the device.
  • the battery may be also installed in a separate base or battery holder which is mounted onto the film, such as a bayonet type of base, wherein the battery is removable.
  • Some sensor types consume relatively much energy, so in such cases the power source should have high capacity.
  • This may be implemented by using a rechargeable battery, such as one having a capacity of 150-1200 mAh.
  • Such a storage battery should have a dimension suitable for combining with the sensor structure. Batteries having a width in the range of 12-20 mm, length in the range of 17-50 mm and thickness in the range of 3-5 mm may be used in such devices.
  • the multi-layer film and the sensor module and any further components form a sensor unit or device, which may be attached to a suitable target, for example by using adhesive, such as pressure sensitive adhesive.
  • the sensor module and any other components may be located inside the multi-layer structure, for example between the z-conductive anisotropic layer and the second thermoplastic polymer layer or film. In such case the electronics are covered with the protective polymer layers. Adhesive may be added to cover any gaps inside the multi-layer structure.
  • the obtained construction is flexible and also exhibits elastic properties, such as having elasticity in the range of 10-15%, or even 10-20%. In general elasticity is the ability of a body to resist a distorting influence or stress and to return to its original size and shape when the stress is removed.
  • a motion sensor as used herein refers to a device comprising an accelerometer, and optionally gyroscope and/or geomagnetic sensor.
  • An accelerometer is a device that measures proper acceleration. For example, an accelerometer resting on the surface of the Earth will measure an acceleration due to Earth's gravity, straight upwards (by definition) of g ⁇ 9.81 m/s 2 .
  • Single- and multi-axis models of accelerometer are available to detect magnitude and direction of the proper acceleration, as a vector quantity, and can be used to sense orientation (because direction of weight changes), coordinate acceleration, vibration, shock, and falling in a resistive medium (a case where the proper acceleration changes, since it starts at zero, then increases).
  • Micromachined accelerometers are increasingly present in portable electronic devices and video game controllers, to detect the position of the device or provide for game input.
  • the sensors may have several detection axis, for example an accelerometer may have 3, 6, or 9 axis, and a gyroscope may have 2, 3, 6 or 9 axis.
  • a motion sensor may detect orientation, tilt, motion, acceleration, rotation, shock, vibration and heading.
  • the sensor may be a 3D-9D motion sensor.
  • the motion sensor contains a 3D acceleration sensor.
  • the new generation of electronics units provides advantages in size, energy consumption and shock resistance.
  • Bosch, STMicroelectronics and Xsens are already manufacturing 3D-9D sensors and represent suitable technology to be adapted.
  • the units require antennas, external energy sourcing and wiring; this is provided with the conductive layers of the embodiments, preferably in a laminate structure which will also protect the printed wires and electronics units.
  • a sensor module is MPU-9250 by TDK Invensense, which is a 9-axis MotionTracking device having dimensions 3x3x1 mm and containing gyroscope, accelerometer and compass functions. It has a power consumption of only 9.3 ⁇ .
  • the clock speed and power saving functions may be adjusted and optimized, it is possible to obtain an operating time of 6 months to even two years by using one 200-1000 mAh battery, for example in tracking applications.
  • the device may be programmed to gather data at a predetermined interval, such as every 1-60 minutes, for example 10 minutes, to save energy. On the other hand it is also possible to obtain data even hundreds times per second, if necessary, and depending on the sensor used.
  • the antenna may be formed by the conductors of the multi-layer film or it may be formed by separate metal layers, such as metal printing, for example silver.
  • the wireless communication may be for example Bluetooth or WLAN/WiFi communication, or any other suitable wireless communication, such as cellular communication which may be used to connect to an external or a remote device utilizing the similar wireless communication technology.
  • the means for wireless communication include a transmitter and a receiver, and usually memory and a processor.
  • the means for wireless communication may be provided as one or more separate module(s) which may be connected to the sensor, power source, antenna, and to any other necessary components with conductive carbon tracks. Such a module may be for example a miniaturized embedded Wi-Fi or Bluetooth module which types are commercially available.
  • the means for wireless communication are arranged to communicate with an external device, which may be a mobile device, such as a mobile phone, a tablet, a mobile computer, for example a laptop computer, another similar sensor device, a relay station, a router, or any other suitable remote device capable of communicating with the sensor device.
  • the external device may run any suitable operating system such as Android, Windows, iOS, Linux, UNIX and the like.
  • the terms external device and remote device may be used interchangeably and generally refer to a device which is separate from the sensor device.
  • the means for wireless communication may also include one or more control unit(s) for controlling the wireless communication and/or for converting the information obtained from the sensor into a form which can be transmitted to the external device.
  • the means for wireless communication may be included in the sensor module or it may be a separate unit or module, optionally containing memory, one or more processors, software arranged to carry out the functions described herein, and the means for wireless communication may be connected to an antenna, to a power source, to the sensor, and to any other suitable component with the conductive carbon circuits in the multi-layer film as described herein.
  • the sensor device comprises a radio frequency identification (RFID) module, which may be passive or active.
  • RFID uses electromagnetic fields to automatically identify and track tags attached to objects.
  • the tags contain electronically stored information.
  • Passive tags collect energy from a nearby RFID reader's interrogating radio waves.
  • Active tags have a local power source such as battery and may operate at hundreds of meters from the RFID reader.
  • An active tag has an on-board battery and periodically transmits its ID signal.
  • a battery-assisted passive (BAP) has a small battery on board and is activated when in the presence of an RFID reader.
  • a passive tag is cheaper and smaller because it has no battery; instead, the tag uses the radio energy transmitted by the reader.
  • Tags may either be read-only, having a factory- assigned serial number that is used as a key into a database, or may be read/write, where object-specific data can be written into the tag by the system user.
  • Field programmable tags may be write-once, read-multiple; "blank" tags may be written with an electronic product code by the user.
  • An RFID tag may contain at least two parts: an integrated circuit for storing and processing information, modulating and demodulating a radio-frequency (RF) signal, collecting DC power from the incident reader signal, and other specialized functions; and an antenna for receiving and transmitting the signal.
  • the tag information is stored in a non-volatile memory.
  • the RFID tag includes either fixed or programmable logic for processing the transmission and sensor data, respectively.
  • An RFID reader transmits an encoded radio signal to interrogate the tag.
  • the RFID tag receives the message and then responds with its identification and other information. This may be only a unique tag serial number, or may be product-related information such as a stock number, lot or batch number, production date, or other specific information. Since tags have individual serial numbers, the RFID system design can discriminate among several tags that might be within the range of the RFID reader and read them simultaneously.
  • the sensor device comprises memory and a software installed operative in the memory arranged to collect information detected by the sensor module, as discussed herein, and to communicate with the external device via the wireless communication to provide the collected information, either as such or as processed.
  • the collected information may be further processed in the external device and/or it may be forwarded to another device.
  • the external device may include a software arranged to process and/or display the information obtained from the sensor device. For example statistics may be created about the movement, location and/or use of the target whereto the sensor device has been attached.
  • the sensor device may be attached to a variety of targets thus enabling a variety of applications wherein the target is monitored.
  • the target may be also called as object, means, gear, equipment, or the like.
  • the sensor device comprising a motion sensor module included in the multilayer film may be used for such purposes.
  • the key issue is in measuring forces, for example when hitting a ball or a puck, simultaneously the speed is registered for comparison a further use.
  • the basic idea is in attaching a device having preferably several sensors, such as 3-6 types of sensors, to the tool, with which the game is played, or to any other equipment.
  • Personal information relating to the performance of a player or exercise may be collected, including the speed and the movement of the gaming means, such as a hockey stick, a bat, a racket or the like, which information may be used to monitor the playing technique of an individual.
  • Ice hockey is a useful general example of sports and related applications, and the other sports and gaming sectors may have modified units with additional or variable measurements and data handling.
  • Golf club version may be linked to weather services and may support in selecting of the club type during the game.
  • Golf version may have mobile contact to Android phone in order to collect and save data of each golf field and guide the player for improved game.
  • baseball and Finnish baseball could be involved by implementing intelligence into bats: the bat could send data and show the flying ball right from the strike. Each player could also obtain the results of their playing after each game as a feedback for preparing to the next game. Examples of gaming applications include ice hockey, bandy, baseball (including the Finnish version), tennis, badminton, golf, floor bandy and the like.
  • the sensor device comprising a motion sensor module connected to the conductors of the multi-layer film is arranged to be attached onto a gaming or sports means or gear, such as a club, a stick, a mallet, a racket, a bat, an oar, a paddle, a ski, a skate, a shoe, a glove or the like used in the game or any other sport or exercise.
  • a gaming or sports means or gear such as a club, a stick, a mallet, a racket, a bat, an oar, a paddle, a ski, a skate, a shoe, a glove or the like used in the game or any other sport or exercise.
  • sports gear, sports equipment, gaming means and sport means as used herein may be used interchangeably and are intended to cover all the examples disclosed herein.
  • the terms apply to all sports means wherein the data relating to the movement of the means is usable for analyzing the sports event. In these embodiments exercise data may be collected including accurate movements of the gaming
  • two or more sensor devices are attached to the gaming or sports means, preferable at different locations, for example at a distance of 10-50 cm. This allows gathering information from different locations of the gaming or sports means, which enables forming a better model of the movements of the means during the gaming or sports event.
  • two sensor devices are attached to the gaming or sports means. One of them may be a 3-D practicing sensor and the other one may be a 9-D unit programmed to send data.
  • One example of a commercial 3-D sensor is H3LIS331 DL by STMicroelectronics.
  • One embodiment provides a sports gear or a sports equipment comprising the sensor device of the embodiments attached.
  • the sports gear or equipment may be a stick, a bat, a club, a racket, an oar, a paddle, a ski, a skate, or the like, such as described in this disclosure.
  • a sports gear or equipment may be a handheld gear or equipment, a wearable gear or equipment, a projectile gear or equipment, or any other suitable gear or equipment.
  • handheld gears or equipment include (ice) hockey sticks, baseball bats, cricket bats, golf clubs, tennis rackets, paddles, and mallets.
  • wearable gears or equipment include helmets, shoes, gloves, wrist devices, clothes, protective gear.
  • projectile gears or equipment include balls, (hockey) pucks, discus, shuttlecocks or birdies, javelins, frisbees, and the like.
  • the hockey stick comprising the sensor device of the embodiments.
  • the hockey stick more particularly ice hockey stick, may be for example wooden or it may be made partly or completely of composite material(s), such as carbon fiber composite.
  • One example provides a cricket bat comprising the sensor device of the embodiments. Cricket bats are usually wooden bats which have a shape suitable for attaching a sensor sticker to the back of the bat.
  • One example provides an oar comprising the sensor device of the embodiments.
  • One example provides a paddle comprising the sensor device of the embodiments.
  • Oars and paddles may be used in training and exercising wherein the movements and forces thereof may be detected and measured.
  • the sensor devices may be used to optimize the use of the oars or paddles in rowing and paddling.
  • a water-proof sensor device may be attached in optimal position to monitor and transmit the data of action. Such constructions are useful for example in rowing competitions where ideal effort can lead to positive result.
  • the sensor device for such sports gear may contain adhesive for attaching the device to the sports gear, for example pressure sensitive adhesive or other adhesive.
  • the sensor device may be also provided in a casing or in other shell.
  • the sports gear may have an aperture, a slot or any other means for receiving the sensor device.
  • the sensor device may also be integrated to the sports gear, for example during manufacturing. The sports gear may therefore be provided as equipped with the sensor device.
  • One embodiment provides an arrangement comprising the sensor device, or a sports gear comprising the sensor device, and an external device arranged to communicate with the sensor device wirelessly, as described in previous.
  • Figure 5 shows an example wherein two sensor devices 51 , 52 at about 20 cm distance from each other have been attached to a hockey stick 50 by using pressure sensitive adhesive.
  • the sensor devices 51 , 52 contain an additional layer of closed cell plastic 54, which acts as shock-absorbing material and covers the electronics and a disc battery.
  • the device contains a Bluetooth antenna 53 formed by conductive carbon print, and another antenna (not shown) for passive RFID.
  • Figure 6 shows a prototype of a sensor device for an ice hockey stick comprising the electronics described herein, such as a Bluetooth module 20 connected to an antenna 22, a motion sensor 18, and a relatively large 200 mAh rechargeable battery 19.
  • the sensor device includes a USB connector 28 at the left for charging the battery.
  • When charging the battery it is necessary to plug a USB cord to the connector, which causes tension and other forces to the area of the multi-layer structure wherein the connector is attached to. Therefore it is important that the connector, as well as the other components, are securely bonded to the structure.
  • the received data indicating the movement of the target or the object may be converted into user-readable form in the device or in another device, such as in a remote computer, for example a server, such as a cloud server, wherefrom the processed data may be sent to a remote device.
  • the user- readable form may be text, number, a list, a table, a graph, an animation or a combination thereof. For example statistics may be created and optionally automatically saved in a remote database.
  • the data received and collected may include data such acceleration in one or more dimensions, geographical location, time stamp and the like.
  • Information may be derived from the data such as the speed of the target or the object, such as a gaming device, the geographical location of the target or the object at a time point and the like.
  • a model of the actual gaming or sports event may be created, which may be used for estimating the performance of the person playing or exercising and optionally to find the weaknesses in the performance which need improving.
  • One embodiment provides a sensor device comprising one or more camera module(s) and preferably means for wireless communication connected to the conductors of the multi-layer film.
  • the camera is arranged to provide still images or video, or both.
  • the lens of the camera may be exposed through a corresponding aperture in an outer film or layer, or the lens may be covered with a transparent film.
  • Such a sensor device may be used for example as a surveillance device, which may be attached easily to a desired location, for example by using an adhesive included in the device.
  • Such a sensor device may also contain a sound module configured to receive sound.
  • the microphone of the sound module may be exposed through a corresponding aperture in an outer film or layer, or the microphone may be covered with a transparent film, which may be perforated.
  • the detected image, video and/or sound may be wirelessly sent to a remote device wherein it may be monitored and/or stored.
  • the unit i.e. the sensor device
  • the unit may contain one or more layers of protective material, such as shock- absorbing material, for example foamed material, closed cell plastic, polyurethane, fibrous material or a combination thereof.
  • the foamed material may be a foamed layer as described herein.
  • a layer of protective material may have a thickness for example in the range of 100-3000 ⁇ , 100-2000 ⁇ , or 100-1000 ⁇ , such as 100-500 ⁇ .
  • a release liner is stripped off to reveal a pressure sensitive adhesive, and the sensor unit is adhered to a stick.
  • the device To attach the device to an ice hockey stick, it has to be flexible and include adhesion properties, but it also has to be rigid on the areas of electronics. Further, the device must be bendable round the 90 degree angles without cracking the printed circuit.
  • the selected films are both flexible and shock resistant.
  • the conductive and the anisotropic print are extremely flexible having flex crack resistance tested with 1000 times 180 degree folds without breakages. The challenge is in positioning electronic units on both sides of the stick in such a way that application of ready-made sensor unit is simple and needs no precision tools, because the actual attachment of said device is taken care manually. In one example a Bosch BMX055 sensor module was used in a device containing the following electronics.
  • Mobile unit 25 x 50 x 4.5 mm (optional for professional use)
  • Bosch BNO055 was used, because of availability and options it offered.
  • the first pilot versions did not work due to ten times higher output request, that was specified by the manufacturer. So instead of an easy set-up there was a long way to go before the sensor was able to register and feed data.
  • Flexible electronics were combined with BNO055 to make it work technically and the system was combined with tailored software in such an order, that not only the sensor collects requested data but also feeds it with application support to portable device running an application which provides visualization and monitors the qualities in the game in question, such as use of a hockey stick, other bats or the like.
  • the sensor device may be programmed to switch to a low-power mode, when it is not in actual action. This allows prolonging of active use with tenfold and reduces the need of charging of cells with 75-80%, meaning the average of 120 h of active playing.
  • the technology is not limited to games only, it can be used for example in packaging - to prevent theft or loss of packed goods.
  • the technology may involve electronics suppliers and also their software for using it, or other software. That may also include mobile applications.
  • the sensor device comprising a motion sensor module connected to the conductors of the multi-layer film is arranged to be attached to an item used for transport, such as onto a vehicle, such as a bicycle, moped, motorcycle, car, snow scooter, boat, drone or the like.
  • the device may be activated, when the mode of transport is made passive. If the vehicle is moved while in this mode, the tracking is activated and data sent to selected target device.
  • Application of this solution reduces theft risks in long term, when the knowledge of tracking risks gets known to thieves.
  • Information may be collected, such as the location of the package, temperature, and the like. For example falling of the package may be detected, or exposure to an undesired temperature.
  • the tracking system may be used for example to control original deliveries and also to prevent illegal copies or generic versions of drugs entering to legally acting pharmacies.
  • a sensor equipment with power source is laminated between polymer layers and connected with two-layer carbon print.
  • the first layer has xyz-conductivity for RFID and power supply purposes and the second layer has z-conductivity to amorphous connecting with heat bonding the electronics to said printed carbon carbon/silver dispersion lines.
  • the top surface comprises a polymer film having a thickness in the range of 23-100 microns and a polymer coating for heat bonding the further layers, out of which carbon ones are coated to the back side of the said layer and electronics with power source are bonded before their back is covered with a third polymer layer in molten form adhered to heat resistant film of thickness in the range of 23-50 microns and coated on its outer surface with contactive adhesive, on which a removable release paper or film is attached for protection.
  • the layers and printed structures may vary in thickness, but the set-up has generally similar functions in all applications.
  • Top surface may be PET-, PEN- or PES-film for most applications providing a support layer for printing conductive layers.
  • the conductive layers are made of carbon dispersed in polymer dispersion, such as a dispersion of acrylic, styrene acrylic and/or ethylene acrylic acid polymer(s).
  • polymer dispersion such as a dispersion of acrylic, styrene acrylic and/or ethylene acrylic acid polymer(s).
  • the high conductivity carbon with nano sized particles (15-30 nm) in the xyz-conductive layer is provided in acrylic styrene copolymer dispersion, generally having film forming temperature in the range of 0-20°C.
  • the anisotropic carbon with larger particles (1-20 microns) is provided in EAA or similar dispersion.
  • the dispersions may be modified with long chain alcohol and other necessary additives in accordance with conversion machine requirements.
  • the electronic units are bonded to conductive print using anisotropic layer and heat.
  • the anisotropic coating is non-conductive in XY-directions.
  • a first dispersion comprising carbon nanoparticles and polymer, such as acrylic dispersion polymer,
  • One embodiment comprises providing an amount of non-nanoparticulate carbon in the first dispersion or mixing an amount of non-nanoparticulate carbon to the first dispersion, such as carbon having an average particle size in the range of 1-20 ⁇ , such as 1-15 ⁇ ,
  • ingredients disclosed herein add up to 100% of the total dispersion by optionally including added water or any other aqueous solution, or other ingredients, which may be ingredients, such as additives, generally used in such dispersions.
  • the conductive layers may be printed by providing specific print dispersions, preferably aqueous dispersions.
  • a dispersion A for printing the xyz-conductive layer may comprise 10-40% (w/w) of polymeric dispersion and 50-80% (w/w) of nanoparticulate carbon dispersion.
  • a dispersion A for printing the xyz-conductive layer comprises (w/w):
  • Nanoparticulate carbon dispersion 70.0-75.0% In one embodiment a dispersion A for printing the xyz-conductive layer comprises (w/w): Polymeric dispersion
  • the carbon material may be for example an aqueous dispersion of graphite and/or carbon black.
  • Examples of commercial products which may be used include Timrex ⁇ NeroMix E series (for example E12) by Imerys.
  • the non-predispersed conductive carbon products are preferably powdered/granulated to avoid dusting problems in dosing.
  • binder or “powdered” refers to a collection of fine, freely flowing particles.
  • Carbon granules and powders may be specified using two measured properties according to standards D6556 and D2414.
  • D6556 norm is split in two versions: NSA Surface area and/or STSA Surface area. Both are reported in square meters/gram and finer particles obtain larger figures in this test.
  • the complete dispersion A, or the polymeric or the carbon dispersion may contain one or more auxiliary agents to facilitate the formation of the dispersion and to enhance the properties of the dispersion, such as one or more of dispersants and/or surfactants.
  • Dispersant refers to a chemical compound that assists in keeping the particles of a material separated from one another when they are distributed in a medium in which they would otherwise agglomerate. Dispersants may also act as wetting agents. Wetting agents are substances which decrease surface or interfacial tension and improve the wetting of solids, thereby acting as surfactants. Dispersing agents prevent particles flocculating by various mechanisms. In the dispersion process the solid particles are first wetted. To lower the surface or interfacial tension of the liquid to enhance the wetting, a wetting functionality is required. A wetting agent in general contains a hydrophobic tail and a hydrophilic head.
  • Dispersing functionality is required to prevent the flocculation and to stabilize the particles by various mechanisms, such as electrostatically or sterically.
  • Dispersants may be ionic (anionic or cationic), non-ionic, or amphoteric.
  • the charged groups to within the ionic dispersant coats a particle, and imparts a net charge to the particle surface.
  • the net charges on all like particles are all positive or all negative, the particles will therefore repel one another.
  • a non-ionic dispersant can include a high molecular weight polymer with a polar group.
  • the polar group interacts with the particle to be dispersed through hydrogen bonding, dipole-dipole interactions, London dispersion forces, and/or van der Waals interactions, while the high molecular weight component possesses sufficient bulk to achieve separation of dispersed particles due to steric effects.
  • a dispersing agent may be provided in a dispersion.
  • the dispersing agent may be an ionic dispersant, such as an anionic dispersant, for example polycarboxylic polymer, or a nonionic dispersant, for example polyurethane or polyacrylate.
  • the amount of the dispersing agent may be in the range of 5-30% (w/w) of dry weight of the carbon dispersion, such as 5-15%, 5-20%, 10-20%, 10-15%, 15-30% or 20-30%.
  • a "dispersing and wetting additive” comprises both wetting and dispersing functionalities in one substance or product, such as in one molecule. Such additives are amphiphilic compounds, i.e. they are both hydrophilic and lipophilic.
  • the dispersing and wetting additives may be categorized according to the head group as anionic, cationic, amphoteric and non-ionic types.
  • a dispersing and wetting additive contains one or more adhesion group(s), which have an effect to the dispersing and wetting effectiveness.
  • Adhesion groups also called as pigment affinic groups, are functional groups which have a special affinity for pigment surfaces. The pigment affinic groups cause adsorption of the additives upon the pigment surface.
  • a pigment affinic group may comprise carboxylic acid, amine, such as tertiary amine, isocyanate or derivatives thereof, or a salt structure which is produced by neutralisation of amine moieties with a mixture of acid- functional polymers.
  • the dispersing and wetting additives may be high molecular weight polymeric dispersing and wetting additives, which contain a considerably large number of pigment affinic groups. Such additives provide complete deflocculation and differ from the conventional low molecular weight analogs through molecular weight sufficiently high to allow the attainment of resin-like character.
  • the dispersion may also comprise one or more surfactants.
  • the surfactant(s) may also act as emulsifier(s).
  • the dispersion may also comprise one or more stabilizer(s), chelating agent(s), defoamer(s), filler(s), biocide(s), or other additives.
  • Carbon dispersion is mixed with slow speed dispersing with polymer dispersion having pH adjusted with ammonia. 2.
  • Coalescing agent and retarder are added with antifoaming agent using slow speed mixing.
  • Powder form conductive non-nanoparticulate carbon is dosed to mixer, speeding the mixing head up to 1200-2000 rpm in order to thicken the dispersion with carbon instead of rheology modifier or thickener, such as polyurethane thickener.
  • the final phase of dispersing is done with slow speed, adding anti foam agent and letting it act in order to obtain foam free dispersion for distribution.
  • a dispersion A for printing the xyz-conductive layer comprises (w/w):
  • the polymer may be any suitable polymer, one or more, such as heat curing dispersion polymer, as described herein.
  • the polymer(s) may be provided as a dispersion polymer composition.
  • a dispersion B for printing the z-conductive anisotropic layer comprises (w/w):
  • the dispersion B may contain similar auxiliary agents as explained for the dispersion A in previous.
  • the acrylic dispersion may be for example acrylic styrene copolymer dispersion or acrylic styrene polyurethane copolymer dispersion.
  • the polymer(s) may be provided as a dispersion polymer composition.
  • This aqueous carbon dispersion may be manufactured from carbon agglomerates, such as granules or particles, having a larger average particle size, such as an average particle size in the range of 1-50 ⁇ , or 10-50 ⁇ , for example 20-50 ⁇ .
  • the particle size is adjusted by dispersing the granules into aqueous solution to disintegrate the agglomerates is such way that the dispersing process is interrupted to obtain agglomerated carbon having the desired particle size in the range of 1-20 ⁇ .
  • -adding water preferably 3-10% (w/w) of the total dispersion, -mixing the dispersion, preferably at 500-2000 rpm, for 15-40 minutes to obtain a conductive carbon dispersion having an average carbon particle size in the range of 1-20 ⁇ , preferably until a viscosity of 1000-1500 cp of the dispersion is obtained.
  • the wetting and/or dispersing agent(s) may be initially mixed with water, if necessary, and provided as an aqueous solution.
  • the carbon granules may be then added to the aqueous solution of wetting/dispersing agent(s). This facilitates mixing and dispersing of the carbon granules to the solution.
  • the carbon granules may be initially mixed at about 100-300 rpm, after addition to a mixing vessel or container, and the mixing speed may be increased gradually to about 500 rpm in 10-20 minutes.
  • the mixing may be carried out by using a mixer, such as a coaxial shaft mixer.
  • the mixer has one or more blades, such as a disc type blade, which may have saw tooth type of structures.
  • the homogeneity of the dispersion is obtained, and for example the carbon particles from the surface are mixed into the dispersion.
  • Water is usually added before the second mixing phase to lower the viscosity, for example about 5% (w/w) of water.
  • the dispersing process may be enhanced by recycling the mixture through a filter back to the mixer blade.
  • the aim is to pump 1000 liters of the mixture 6 to 10 times during two minutes to obtain evenly distributed particles and the final viscosity of the dispersion.
  • Additives may be added to the obtained dispersion.
  • the method comprises adding one or more polymer(s) to the dispersion, preferably by mixing, for example in a similar process as described.
  • the method comprises adding one or more retarder(s).
  • the method comprises adding one or more thickener(s).
  • the dispersion may be finished by thickening in slow mixing until a printer viscosity is obtained.
  • the viscosity may be adjusted to the range of 200-300 cp.
  • the viscosity may be optimized, for example for 24-48 hours.
  • One or more thickener(s) may be added for example in the range of 1-2.5% (w/w) of the total dispersion to obtain an elevated viscosity, such as a viscosity in the range of 1500 cp or more, for example 1500-2000 cp.
  • the viscosity may be measured by using any suitable method and device known for a person skilled in the art, such as by using a viscometer.
  • the viscosity is presented as centipoises (cp), which equals to milllipascal seconds (mPa-s).
  • cp centipoises
  • mPa-s milllipascal seconds
  • the viscosity may be measured at room temperature (RT) and/or at atmospheric pressure.
  • the thickener comprises acrylic/polyurethane thickener.
  • the dispersion may be an anionic modified acrylic styrene copolymer dispersion.
  • One embodiment provides a conductive carbon dispersion manufactured with the method described in previous.
  • One embodiment provides a method for manufacturing a multi-layer film as described herein, comprising providing the conductive carbon dispersion as the second aqueous dispersion comprising carbon particles and polymer.
  • One embodiment provides use of the conductive carbon dispersion in the manufacture of conductive coatings or films or multi-layer films.
  • One embodiment provides (conductive) printing ink composition comprising the conductive carbon dispersion.
  • the printing ink composition may be formulated as described herein, as an aqueous dispersion for printing the z conductive layer, oras an aqueous dispersion for printing another type of conductive layer, such as the xyz conductive layer.
  • the carbon coatings of the embodiments are all aqueous and need drying when coated. Their major difference to solvent-based ones, which dominate the market, is a short drying cycle. DuPont and Henkel recommend 24 hours drying before applying second print. Both xyz-conductive and anisotropic coatings of the embodiments are usually dried for 30-60 seconds when using a standard three segment oven of a screen printing machine. The oven has three chambers, of which the first is most important for film forming; it blows heated air through having a temperature of 80-100°C. The second one is sucking air and blowing it off from the section, in general at a temperature range of 55-70°C, to allow for the third one to cool down the surface of conductive print to 30-45°C and down to room temperature.
  • the carbon layers may be heat-treated to finalize the structure.
  • a structure will be obtained having enhanced flexural resistance and other structural and functional features described herein.
  • the heat treatment may be carried out after printing.
  • the temperature used may be in the range of 80-100°C, preferably for a time of 10-30 seconds.
  • the heat treatment may be carried out in an air flow.
  • the method comprises heat-treating the printed conductive layers at a temperature in the range of 80-100°C, preferably for a time of 10-30 seconds.
  • the method comprises providing an adhesive, such as a pressure sensitive adhesive, and applying the adhesive onto a surface or a side of the multi-layer film, such as onto the support layer or onto another layer, such as onto a protective layer on top of the z-conductive layer.
  • an adhesive such as a pressure sensitive adhesive
  • the development of the conductive coatings was challenging.
  • the first conductive dispersions had large particle sizes (12-20 microns) and caused problems in printing with screen. They were later dispersed with premixed smaller sized carbon mix, but still some printing problems existed. Conductivity with 20 micron coating was acceptable for printing antennas and resistors in intelligent packaging.
  • Original formulation included Timrex granules with Timcal dispersion mixed into acrylic copolymer dispersion having additives included. These old formulations were tested by printing companies but due to problems in the properties of the materials, they were rejected.
  • the formulation for preparing the z-conductive layer is as follows:
  • Dispersing the formulations was carried on using Dispermat AE dissolver device with appropriate stainless steel dissolver disc.
  • This high speed disperser has adjustable speed running a mixing blade with diameter 33% of the inner diameter of mixing vessel.
  • Sawlike disc rotates with selected speed adjustment and causes a flow of liquid, which captures and then splits the agglomerates to particles wetting them completely with polymer dispersion.
  • the formulation having a premixed nano carbon dispersion mixed with polymer and additives was finalized with dispersing carbon granules in to it in order to obtain suitable viscosity for screen printing.
  • the mixture was prepared to fit screen printing requirements and to offer long term stability without settling problems of particles.
  • the formulation contained NeroMix E-10 51 %, Ensaco 250G 9% (dry) and polymer/additive blend 40%. Test stripe conductivity was in the range of 100- 120 Ohms/sqr. Production of NF-400
  • an aqueous carbon dispersion called NF-400 was used as the conductive dispersion of the above formulas.
  • NF-400 was manufactured using carbon granules having the size and shape described in Ensaco 250 G technical leaflet.
  • the formulation is aqueous and includes NeroMix E-12 type additives with water and conductive carbon granules.
  • a manufacturing process and a device for batch production of aqueous dispersion is described in the following.
  • the process includes two phases.
  • the mixing speed is adjusted according to the phase of the process; the first phase involves a rough dispersing of carbon granules in water, that has been modified with wetting/dispersing agent in order to allow dispersing forces to wet the carbon granules and to allow the phase two to be started.
  • Mixing speed is 100 rpm in the carbon dosing phase and adjusted gradually to 500 rpm in 10-20 minutes. Water or water and wetting agent mixture is added.
  • Mixing of carbon and water may be done using dispersing disc type blade, having saw tooth-type structure.
  • the saw blade is of special type wherein the saw teeth bent to two directions, and the shaft attached to it using metal discs on both sides.
  • the shaft is rotated with adjustable speed by a 10-20 kW motor for each batch, such as 1000 litres batch.
  • Polimix DPS-OR OEM y Batlle
  • the blade is 30-50% of the mixing vessel diameter. This will gain circulation of the liquid.
  • the height of the blade is 25-30% of the liquid height, measured from the vessel bottom.
  • the mixing process is started by dosing water and dispersing/wetting agent in to the mixer.
  • the blade is running at slow speed, such as at 100-300 rpm, when the carbon granules are added.
  • the viscosity is 5000-6000 cp until 5% of water/wetting agent mix is added.
  • Agitation at the second phase is started by adjusting the speed of mixing blade to 1000-1500 rpm, when the carbon has been added.
  • the solids content is 35-40% in addition of the carbon, which causes high shear.
  • Phase two involves a formula: 20-40% conductive carbon granules; 4-10% wetting/dispersing agent and 52-76% water. Phase two is carried on at 500- 2000 rpm speed for 15-30 minutes to obtain a completely dispersed carbon in particulate form.
  • the mixer is adjusted to disperse the viscosity down to 1000-1400 cp. Simultaneously the recycling pump is started to run liquid back at a rate of 1000 1/1-5 min. This phase lasts for 40 minutes and when finished, the liquid dispersion is pumped to a container. The dispersion is kept in the container for 12-48 hours for stabilization. Polymers are added in a next phase using similar mixing process. Most of additives are mixed using medium speed and short cycle of 3-5 minutes. To finish the mixture, addition and slow speed mixing of a retarder and a thickener is carried out for 2-4 minutes. The obtained viscosity is in the range of 200-300 cp.
  • the elevated viscosity is obtained with an 1-2.5% addition of thickener as finishing.
  • the viscosity is optimized for 24-48 hours and is on level of 1500 cp or more.
  • Ensaco 250G 30% mixed with 6% dispersing agent and 64% water.
  • Ensaco 250G is a granulated conductive carbon having surface area of 65 sqm/gram and oil absorption of 190 ml/kg.
  • K Ultra 35% mixed with 7% dispersing agent and 58% water.
  • K Ultra has surface area of 185 sqm/gram and oil absorption of 1 15 ml/kg.
  • the dispersing/wetting agent may be any suitable wetting agent.
  • Dispersing/wetting agent in the examples was Disperbyk-160, which is a solution of a high molecular weight block copolymer with pigment affinic groups.
  • NF-400 products may require stabilization before further processing to prevent micro foam build up in final dispersions. Therefore antifoaming agent may be added.
  • the mixing machine was equipped with adjustable disc speed and programmable inverting unit to obtain 100% stable carbon mixtures. Viscosity was measured with DinCup 4 for 40-45 s. Therefore, in one example the formulation for preparing the xyz-conductive layer is as follows.
  • Typical example of the obtained NF-400 product has a solid content in the range of 33.0-37.0%, pH in the range of 8.5-9.5%, and viscosity (Brookfield Digital Viscometer, RTV, 2/100) in the range of 100-1000 mPa s.
  • This product includes an anionic emulsion system.
  • the viscosity measured by the Brookfield device is a combination of two viscosities: 100 is flexo version and 1000 is screen version. Brookfield viscometers are suitable and internationally approved for viscosity measurement of viscous liquids.
  • the formulation for preparing the z-conductive layer is as follows:
  • Acrylic dispersion 82.0% (NeoCryl A-1092/NeoCryl A-1091 90/10-50/50%) Conductive dispersion 8.0% (NF-100)
  • MFT film forming temperature
  • T g glass transition temperature
  • -NeoCryl A-2092 tough and flexible acrylic styrene copolymer; with high elongation
  • Z-conductivity was measured using three different devices: Perel surface checker, Vermason: Surface resistance meter and Trek Model 152-1 . All units were from Perel Oy, an electronics and electricity specialist company. They also verify the results and calibrated all devices used in tests.
  • Timcal Timrex LB1300 is a stable binder free aqueous dispersion of graphite powder having a solids content of 27.5% (w/w) and an average particle size of 6.5 m.
  • Printing with screen is the most likely practical way of production due to optimal suitability of the method for producing selected printing thicknesses and fine lines.
  • the conductivity of printed carbon/polymer was measured and the nominal resistance was below 1000 Ohms and even 100 Ohms when using Haiti sports underwear in tests.

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Abstract

The present application provides a method for manufacturing a multi-layer film with conductive coating, the film comprising the following layers: a support layer, a xyz-conductive layer comprising carbon nanoparticles and polymer printed on the support layer, and a z-conductive anisotropic layer comprising carbon and polymer printed on the xyz-conductive layer. The present application also provides a multi-layer film, and a sensor device comprising a motion sensor module and means for wireless communication connected to the conductors of the multi-layer film; and a sensor laminate comprising the multi-layer film.

Description

A method for manufacturing a multi-layer film, a multi-layer film, a sensor device, a sensor sheet, a sports gear, and a method for detecting movements of a target Field of the application
The present application relates to a method for manufacturing a multi-layer film with conductive coating, to the multi-layer film with conductive coating and to sensor devices and other applications containing the multi-layer film. The present application also provides methods for detecting changes in the electric circuits of the multi-layer films, and for detecting movements of a target having the sensor device. The present application also provides a method for manufacturing a conductive carbon dispersion, and a conductive carbon dispersion.
Background
A conductive coating film may be used in a variety of applications, such as for providing wiring for electronics, for forming antennas, sensors, switches, coils, capacitors, and the like. There are conventionally known methods for preparing such coated films, such as a vacuum metal deposition method, a chemical deposition method, an ion sputtering method and a method in which metal particles are dispersed in a dispersing medium and the resulting metal colloidal solution is applied, heated and sintered. However, these methods have problems such that organic solvents are used, complicate operation is needed, mass producibility is inferior, and heating at high temperature is required, etc. It is challenging to obtain coated conductive films having high stability. Further, there is a need for inexpensive conductive films, which are flexible, durable and may be used in several applications and for several purposes, as well as for manufacturing methods thereof. Summary
One embodiment provides a multi-layer film with conductive coating, the film comprising the following layers:
-a support layer,
-a xyz-conductive layer comprising carbon nanoparticles and polymer, printed on the support layer, and
-a z-conductive anisotropic layer comprising carbon particles and polymer, printed on the xyz-conductive layer.
One embodiment provides a method for manufacturing a multi-layer film, the method comprising
-providing a support layer,
-providing a first aqueous dispersion comprising carbon nanoparticles and polymer,
-optionally wherein the first dispersion also comprises non-nanoparticulate carbon or wherein the method comprises mixing non-nanoparticulate carbon to the first dispersion, such as carbon having an average particle size in the range of 1-20 μιτι, such as 1-15 μιτι,
-proving a second aqueous dispersion comprising carbon particles and polymer,
-printing a xyz-conductive layer onto the support layer by using the first dispersion, and
-printing a z-conductive anisotropic layer onto the xyz-conductive layer by using the second dispersion
to obtain the multi-layer film
One embodiment provides a sensor device comprising a sensor module, such as a motion sensor module, connected to the conductors of the multi- layer film.
One embodiment provides a sports gear comprising the sensor device.
One embodiment provides a method for detecting the movements of a target having the sensor device attached thereto, the method comprises
-wirelessly connecting the sensor device to a remote device, -receiving data indicating the movement of the target from the sensor device in the remote device, and
-interpreting the data to detect the movements. One embodiment provides a sensor sheet comprising the multi-layer film, the sensor sheet comprising at least two carbon sections of at least 100 x 100 mm.
One embodiment provides a method for detecting the presence or the movements of a subject, the method comprising
-providing the sensor sheet connected to a controlling device arranged to detect changes in the electric circuit of the sensor sheet, and
-detecting changes in the electric circuit in respect of each carbon section of the sensor sheet, wherein the changes in the electric circuit indicate the presence or the movement of the subject on the sensor sheet.
One embodiment provides a method for manufacturing a conductive carbon dispersion, the method comprising
-providing wetting and/or dispersing agent(s) in aqueous solution,
-providing carbon granules having an average particle size in the range of 1- 50 μιτι,
-forming a mixture comprising 20-40% (w/w) conductive carbon granules; 4- 10% (w/w) wetting/dispersing agent and 52-76% water (w/w),
-mixing the mixture, preferably with 100-500 rpm, preferably for 10-20 minutes, to obtain a dispersion, preferably until a viscosity of 5000-6000 cp of the dispersion is obtained,
-adding water, preferably 3-10% (w/w) of the total dispersion,
-mixing the dispersion, preferably with 500-2000 rpm, for 15-40 minutes to obtain a conductive carbon dispersion having an average carbon particle size in the range of 1-20 μιτι, preferably until a viscosity of 1000-1500 cp of the dispersion is obtained.
One embodiment provides a conductive carbon dispersion obtained with said method. One embodiment provides a printing ink composition comprising the conductive carbon dispersion.
One embodiment provides a use of the conductive carbon dispersion in the manufacture of conductive coatings or films or multi-layer films.
The main embodiments are characterized in the independent claims. Various embodiments are disclosed in the dependent claims. The embodiments recited in the claims and in the description are mutually freely combinable unless otherwise explicitly stated.
The embodiments combine compounding chemistry and electronics together with mechanics to produce sensor devices which may be used for a variety of applications. The devices may be attached to different kind of targets of different shapes and materials. One example includes sports (such as in hockey sticks, baseball bats, cricket bats, golf clubs, tennis rackets etc.) to monitor and report the functions of tools in question. Another example includes a frame for dosing tablets and capsules for medical or nutritional purposes.
The present embodiments provide unique and novel carbon and optionally carbon/silver chemistries. Instead of organic solvents, the whole chemistry is waterborne and thus safe for environment and users. The development has led to flexible and easily mixable dispersion, which has a long and stable shelf life. The obtained products are non-toxic and safe for the users. The used dispersions and obtained products are practically VOC and SVOC free.
The embodiments provide adjustable conductivity suiting to all requirements of printing. No decay of conductivity has been measured in long term (at least 5 years) use. Also the flexibility of the products remains at high level. The composite products of the embodiments formed by the carbon and the polymer(s) are stable and durable and have desirable mechanical properties.
The manufacturing of sensors is optimized by using such materials and components that the products are new in the market, but their cost is most competitive and makes them affordable. Secondarily, the manufacturing of the products is able to serve the market with large amounts of units. For example 10 000 ice hockey stick sensors may be produced in two hours by printing/laminating. Cost of one unit is less than 20€ and the potential is more than 1 million units/year. The newest sensor technology is especially suitable for the combinations and also the latest mobile technology trends open paths for easier access of suitable software for multiple uses of the embodiments
The embodiments may be used for example in dosing medicines or nutritional substrates timely and also in tracking various items or subjects, such as hired cars, electronics deliveries and persons. For example alarms may be provided in cases, when the device measures faulty function, such as collapse of a person carrying a sensor device or located on a sensor sheet. The embodiments provide a combination of safe chemistry, tested laminated, printed and/or layered materials, robust mechanics, minimized electronics and easiness in using the "gadget".
The combination of xyz-conductive layer and the anisotropic z-conductive layer enables several functionalities. The structure is very flexible, durable and provides a high foldability. The multi-layer film or laminate may be bent or folded numerous of times without damaging the conductive layers. The flexibility enables applying the layered structure onto challenging targets, such as elongated and/or angular objects, for example gaming equipment.
The multi-layer structure also provides elasticity, also in respect of the conductive materials without substantially affecting the conductive properties of the carbon layers. In general, the elasticity is at least 10%, and even up to 20%.
The materials of the multi-layer structure enable efficient attachment of electronic components or other components to the structure. Such constructions tolerate impacts, high acceleration forces and tensions. Brief description of the drawings
Figure 1 shows an example of a cross-section of a sensor device comprising the multi-layer film in a form of a laminate.
Figure 2 shows an example of a sensor device seen from top
Figure 3 shows examples of printed circuits made of a xyz-conductive layer
Figure 4 shows parts of a sensor sheet seen from both sides
Figure 5 shows an example of a hockey stick having two sensor devices
Figure 6 shows a prototype of a sensor device for an ice hockey stick
Detailed description
All the percentage values disclosed herein refer to percentages by weight (w/w) unless otherwise mentioned.
In one example the embodiments include four individual functions including a conductive coatings, a top layer, a back layer, and electronics.
The conductive coating includes two different conductive layers: a first xyz- conductive layer A for printing circuits, antennas, sensors, or the like based on carbon or for example carbon/metal hybrid, and a second z-conductive layer B, which is anisotropic one for printing as an overcoat for layer A, to allow electronics and other components to be heat bonded to the printed A layer. The carbon/polymer mixtures used in the embodiments provide enhanced printability to obtain layers of such quality which has been possible previously with the same grammage only by using organic solvent based materials. However, the materials used in the embodiments are water-based and approved for either direct or indirect food product contact. The support, which may act for example as a top layer in the final product, is a flexible carrier for the carbon printing which may be obtained by screen or flexographic/gravure printing. The back layer may be for example polyolefine/polyester film laminate or polyester film. The top or the back layer may be coated with adhesive having a release liner as a back protection.
Different types of one or more electronic components, modules or circuits may be connected to conducting carbon layers. The electronics unit or units may be for example 3 to 9 dimensional functioning sensors connected to a transmitter using carbon print as wiring and antenna. Other electronics or components may be used as well depending on the application, such as such as resistors, capacitors, transistors, integrated circuits, diodes, LEDs, and the like, other sensors, such as light sensor(s) or temperature sensor(s), transmitters and/or receivers, RFID modules, memory modules, electro- mechanicals parts or modules, connectors, sockets, microphones, sound reproducing components such as loudspeakers, cameras, displays, connectors, and the like. An electronic component is any basic discrete device or physical entity in an electronic system used to affect electrons or their associated fields. Electronic components are mostly industrial products, available in a singular form. Electronic components have two or more electrical terminals (or leads) aside from antennas which may only have one terminal . These leads connect to create an electronic circuit with a particular function. Said components and other electronics are preferably suitable for surface or panel mounting or they may be connected to the conductive carbon circuits by separate connecting parts, such as metal wiring or prints. The connective carbon circuits or tracks may be arranged to transfer power and/or data, such as analog or digital data.
The multi-layer structure or laminate may act as a support for electronics. The multi-layer structure or laminate may be cut to sizes suitable for each application. For example a hockey sensor may have a size of 50 x 100 mm, and is arranged to be adhered around a hockey stick using adhesive. One embodiment provides a multi-layer film with conductive coating, the film comprising the following layers:
-a support layer,
-a xyz-conductive layer comprising carbon nanoparticles, and
-a z-conductive anisotropic layer comprising carbon particles.
The support layer may comprise one or more polymer(s), preferable organic polymers, such as plastic polymer(s). In one embodiment the support layer comprises thermoplastic polymer, more particularly one or more thermoplastic polymer(s), copolymers, mixtures, derivatives or combinations thereof. In one embodiment the support layer is a layer of one or more thermoplastic polymer(s). In one embodiment the support layer comprises thermosetting polymer, more particularly one or more thermosetting polymer(s), copolymers, mixtures, derivatives or combinations thereof. In one embodiment the support layer is a layer of one or more thermosetting polymer(s). In one embodiment the support layer comprises more than one layer, such as at least one layer comprising thermoplastic polymer and at least one layer comprising fibers, for example a coated paper or cardboard, or a composite thereof, such as a plastic composite.
One embodiment provides a multi-layer film with conductive coating, the film comprising the following layers:
-a first thermoplastic polymer layer,
-a xyz-conductive layer comprising carbon nanoparticles and polymer, and -a z-conductive anisotropic layer comprising carbon particles and polymer.
One embodiment provides a multi-layer film with conductive coating, the fil comprising the following layers:
-a first thermosetting polymer layer,
-a xyz-conductive layer comprising carbon nanoparticles and polymer, and -a z-conductive anisotropic layer comprising carbon particles and polymer.
In general, "polymer" as used herein may refer to one or more polymer(s), more particularly one or more organic polymers, such as plastic polymers. Plastic polymers may be synthetic or semi-synthetic. They may be thermoplastic polymers or thermosetting polymers, crystalline or amorphous, and/or semi-crystalline or semi-amorphous. Completely amorphous polymers include all thermosets, polystyrene and its copolymers and polymethyl methacrylate. The polymer may be a cross-linkable polymer, including self- crosslinkability. In the final product the polymer may be cross-linked. In the final product the polymer may be cross-linked. In general cross-linkable thermoplastic polymers may exhibit lowered thermoplasticity after crosslinking. The polymer may be a homopolymer or a copolymer of two or more monomers, or a mixture thereof. The polymer may be a latex polymer. Latex is a stable dispersion (emulsion) of polymer microparticles in an aqueous medium. Preferably the polymers in the xyz-conductive layer and in the z-conductive anisotropic layer are dispersion polymers, more particularly aqueous dispersion polymers. The dispersion polymers may be curable polymers, such as heat curable or UV curable, or they may be wet adhesion promoted polymers, cross-linkable or self-crosslinking polymers, such as acrylics. Also precipitating polymers and/or film-forming polymers may be provided, for example for applications requiring elasticity. During curing a cross-linked polymer(s) may be obtained. In some cases a cross-linking agent may be added, such as polyaziridine crosslinker, which improves especially carboxyl functional resins performance. A cross-linking agent may be added in an amount of 1-3% (w/w) of the polymeric dispersion.
The thermoplastic or thermosetting polymer in the support layer may comprise or be any suitable thermoplastic or thermosetting polymer or combination of two or more thereof, which provides desired properties as a support for the multi-layer structure, such as flexibility, elasticity, printability, durability, heat resistance etc. The thermoplastic or thermosetting polymer layer may comprise one or more thermoplastic or thermosetting polymer films or layers. In one embodiment the thermoplastic polymer layer is a thermoplastic polymer film. In one embodiment the thermosetting polymer layer is a thermosetting polymer film. The thickness of the polymer layer may be adjusted according to the desired properties and may be in the general range of 20-500 μητι, such as 20-400 μηη, 20-300 μηη or 20-200 μηη. In one embodiment the polymer layer has a thickness in the range of 23-100 μιτι, such as 23-70 μηη, 25-80 μηη, 25-50 μηη, 30-100 μηη, 30-80 μηη, 50-100 μιτι, or 40-100 μιτι. These ranges are suitable for most applications and provide good tensile strength, tensile strain, thermal resistance and other mechanical properties. Useful thermal range of a (thermoplastic) polymer may be in the range of -30-50°C, which is preferred especially for devices used in sport applications. In one embodiment the thermoplastic polymer is provided in a foamed form. A foamed thermoplastic polymer may exhibit elastic properties, which allow functionalities such as preparing pressable structures, which may be used in touch or pressure sensors. In one embodiment the thermoplastic polymer is polyester. Polyester is a category of polymers that contain an ester functional group in their main chain. Polyesters may be aliphatic, such as homopolymers polyglycolic acid (PGA), polylactic acid (PLA), polycaprolactone (PCL), polyhydroxybutyrate (PHB), or copolymers polyethylene adipate (PEA), polybutylene succinate (PBS), poly(3-hydroxybutyrate-co-3-hydroxyvalerat) (PHBV); semi-aromatic such as copolymers polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT) and polyethylene naphthalate (PEN); or aromatic copolymers such as vectran. Polyesters provide desired mechanical properties for the most applications described herein. In one embodiment the thermoplastic polymer is polysulfone or polyethersulfonate (PES).
In one embodiment the thermoplastic polymer is selected from polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polyethersulfonate PES, for example as a film layer or a film. These materials provide high flexibility, durability and impact resistance. In one embodiment the thermoplastic polymer is a polyolefin, such as polyethylene (PE) or polypropylene (PP). In one embodiment the support layer comprises or is made of polyester, such as polyethylene terephthalate (PET), polyethylenen naphthalate (PEN) or polyethersulfonate PES.
In one embodiment the polymer is polyimide, which may be thermoplastic or thermosetting. Polyimide is very durable material having a high thermal stability and good chemical resistance. It also has excellent mechanical properties, such as low weight and flexibility. Polyimide layers have good mechanical elongation and tensile strength, which also enhances adhesion between polyimide layers or between polyimide layer and other layers, such as metal or carbon layer. Examples of polyimide films include Apical, Kapton, UPILEX, VTEC PI, Norton TH and Kaptrex. Using polyimide, or other polymer with high thermal stability such as PET, PEN or PES, especially as a support layer, enables using high temperatures for bonding electronic components, modules, connectors and the like to the multi-layer structure. This enhances the attachment of the components to the structure and secures the contact of the components to the conductive layers. Therefore it is possible to manufacture electronic devices which tolerate impacts, acceleration forces and tension or other forces. Such devices are useful for example for use with sports gear.
In one embodiment the support layer comprises polyimide. A support layer comprising or made of polyimide is especially suitable for sport applications, such as for devices which are arranged to be attached onto sports gear or equipment, such as sticks, bats, clubs, rackets, oars, paddles and the like. In one embodiment the support layer comprises polymer selected from polyester and polyimide.
The thermoplastic polymer film may be made of any of the mentioned polymers, or copolymers, derivatives and coextrusion blends thereof. The thermoplastic polymer film may be oriented or non-oriented, annealed or non- annealed. The thermoplastic polymer film may be machine direction orientated, cross direction orientated, or biaxially orientated. In one example the thermoplastic polymer film is an oriented polypropylene film. For example in the sport applications described herein polyimide, PET, PEN, and PES films, as well as oriented polypropylene were found especially preferred, for example if the film layer acts as an "inner layer", i.e. it is against the sport or gaming gear or means, but also if the film layer is on the "outer layer". In one example the first polymer layer, which acts as the top layer, is made of polyester (PET) film of thickness 23-100 microns.
The orientation of the film derives from the manufacturing process thereof. Through the machine direction orientation (MDO) process, the film is uniaxially stretched in the machine direction of the film i.e. in the direction of the movement of the film. Stretching is normally done by means of a machine direction orienter via rolls by gradually increasing speed or by rapidly increasing speed. The rolls are heated sufficiently to bring the film to a suitable temperature, which is normally below the melting temperature (Tm), or around the glass transition temperature (Tg) of the polymer. Transverse direction orientation (TDO), also referred to as cross direction orientation (CDO), means the direction perpendicular to a movement of the film. Monoaxial orientation, also referred to as uniaxial orientation, refers to the stretching provided only in one direction, either in machine direction or cross (transverse) direction. Biaxial orientation (BO) refers to a film oriented (stretched) both in machine direction and in cross direction. In one example a multi-layer oriented polypropylene film is provided having two layers with different orientations, such as orientations perpendicular to each other. This kind of multi-layer film provides enhanced mechanical properties, such as high tear strength, and may be used as the first thermoplastic polymer layer and/or as the second thermoplastic polymer layer.
Annealing refers to a thermal treatment involving heating a material to above its critical temperature, maintaining a suitable temperature, and then cooling. This heat-setting may be used to anneal the internal stresses generated to a film during the stretching process. The annealing process decreases the modulus and stiffness of the films.
A film in general may be transparent or it may be opaque, or it may have transparent parts and opaque parts. In this way a final multi-layer product may be obtained wherein part of the product is masked with an opaque layer, for example circuits made with conductive carbon, and/or part of the product is transparent, for example parts containing areas which need to be visible, such as LEDs, user-touchable parts, windows in a finals product, or the like. A film may be coloured, such as having one or more desired colours, prints, or the like. A pigment may be included in the film or the film may be printed.
However, some polymers are not desired in the layers, such as the conductive layers. These include polymers which need to be applied in organic solvents, and/or polymers which do not provide the desired properties, such as flexibility, elasticity, printability, durability etc. In one example the polymers do not comprise epoxy polymers, such as epoxy(meth)acrylates. In one example the polymers do not comprise inorganic polymers. In one embodiment the support layer comprises fibers such as natural fibers or synthetic fibers, organic or inorganic. In one embodiment the support layer comprises a fibrous layer. In one embodiment the support layer is a fibrous layer. The natural fibers may comprise cellulosic fibers, for example in the form of paper, cardboard or the like. The synthetic fibers may comprise glass fibers, nylon, modacrylis, olefin, acrylic, polyester, rayon or the like fibers. A combination of fibers described herein either together or with one or more thermoplastic polymers, kaolin or other suitable substance, such as a inorganic filler, for example as a composite or a laminate, may also be used. In one example the support comprises a paper or board coated with a thermoplastic polymer layer or a thermosetting polymer layer. In one example the support comprises a paper or board coated with kaolin.
In one embodiment the fibrous support layer is a textile or a textile layer, or the support layer comprises textile or a textile layer, which may be also called as a fabric or cloth. The fabric may be woven or nonwoven. In case of clothes, the fabric is usually woven. More particularly, textile refers to any material made of interlacing fibres. Fabric refers to any material made through weaving, knitting, spreading, crocheting, or bonding that may be used in production of further goods (garments, etc.). Cloth may be used synonymously with fabric but often refers to a finished piece of fabric used for a specific purpose (e.g., table cloth). Textiles can be made from many materials. These materials come from four main sources: animal (wool, silk), plant (cotton, flax, jute), mineral (asbestos, glass fibre), and synthetic (nylon, polyester, acrylic). In the past, all textiles were made from natural fibres, including plant, animal, and mineral sources. Examples of fibers used in synthetic textiles include polyester, polypropylene, aramid, acrylic, Nylon, Spandex, olefib fibers, Ingeo, Lurex, and carbon fibers.
In one embodiment the support layer comprises a textile, such as a textile for clothing or garment. In one embodiment the support layer is on a textile, such a textile coated with a thermoplastic polymer layer described herein. One example includes acrylic styrene polyurethane polymer with carbon to provide a flexible solution for printing conductive patterns on inner surfaces of fabrics used in clothing. One example provides a conductive carbon print in direct skin contact to allow for measurement of sweat chemistry changes, such as electrical resistance. The textiles having the multi-layer structure exhibit elasticity, such as in the range of 10-20% or more, wash resistance, and wear resistance.
The dispersion for use especially with textiles has to be easily curable so the polymer combination is preferably selected from variations having low film forming temperature. This is because most of the fibers used in sports clothing or sports underwear are heat sensitive.
The coating has to adhere to the inner side of the clothing during the use, such as sportswear, to be in direct contact with skin. It is also important, that the flexibility of coated material is not reduced. The cloth has to stretch in designed way to connect the inner surface properly to the skin of sportswear user. The coating has to retain preferably 70-80% of its conductivity when used and washed, and the print design has to allow for such change without the loss of data transfer to the control device.
The printing coat weight is reflected by the type of fibrous material and the method of printing. With strongly absorbing materials it is advisable to use R2R screen printing machine to obtain required coat weight or run the printing with flexographic machine having 2-3 printing stations running in precise register. According to an example, an average coat weight, when measured from compact coat should be 12-14 grams/sqm dry weight and accordingly wet coat should be 25-30 grams/sqm. However the wet coat may vary in a large scale, such as in the range of 10-30 grams/sqm. In one example A conductive coating on the back of tambrite 200-300 g board was 20 grams wet coat for 50 ohms/sqr resistance. In another example a conductive coating on PET film was 14 grams wet for 50 ohms/sqr resistance In another example an anisotropic coating on top of a conductive coating was 12 grams wet to obtain z-direction conductivity. Typical sports shirts, trousers and underwear are made of synthetic materials like polypropylene or polyamide in order to let sweat penetrate through them. These materials are also best suited for measuring body functions while training or jogging etc. The anisotropic layer protects the xyz-conductive layer, especially during washing.
This new application of conductive carbon offers requested conductivity and can be used instead of more expensive silver and hybrid coatings The major surprise in tests was the way of coating behaviour on the garment; it did not migrate through the fibrous material, but stayed neatly on top of its back as if it was designed to do so.
In one example the fibrous support layer is printed or coated with conductive dispersion layer, which has elongation properties similar to the support layer material . The conductive print or coat is further over coated using anisotropic dispersion, which is used to offer wear protection in areas, which are used for transmitting measured data from skin. This is used in both wire protection and z-directionally connecting the electronics to sensor/printed sensing fields.
The embodiments provide using polymer dispersion carriers for conductive pigments in controlling precise properties of dried conductive coating, such as heat resistance, flexibility, elongation at break, friction, migration, low temperature flexibility, stability when washed and wear resistance without losing the target conductivity in long term use.
In the coatings, both in conductive and amorphous layers, matching nano particulate silver pastes and/or dispersions as well as graphene coatings may be used in applications requiring nominal conductivity of 100 Ohms/sqr. This will serve printing companies with aqueous and migration risk free coatings as well as affordable materials for volume applications.
The support layer, especially the thermoplastic or thermosetting polymer layer, may be heat-bonded to the next layer which is xyz-conductive layer comprising carbon nanoparticles (also called as xyz-conductive layer or xyz- layer). The xyz-conductive layer may be printed and/or laminated onto the support layer, such as polymeric layer, for example thermoplastic or thermosetting polymer layer. In one embodiment the xyz-conductive layer contains carbon nanoparticles, i.e. nanoparticulate carbon, having an average diameter, or an average particle size, in the range of 5-200 nm, or 10-200 nm, or 5-100 nm, such as 5-60 nm, 10-50 nm, or 10-40 nm, more particularly 15-30 nm. The range of 15-30 nm was found to be especially advantageous providing a constant field in the conductive layer. With higher particle sizes, such as over 200 nm, over 100 nm or even over 50 nm, gaps and therefore discontinuity were introduced into the conductive layer.
The carbon material may be for example an aqueous dispersion of graphite and/or carbon black. Carbon black comprises fine carbon material, which may be colloidal and amorphous. It may be made from partial combustion or thermal cracking of natural gas, oil, hydrocarbons etc. In general carbon black is an aggregation of primary particles, which are spherical and nano- sized particles, for example having a particle diameter of about 40 nm, to secondary particles, which are porous and structured, and may have a particle diameter of hundreds of nanometers to micrometer range. These may be agglomerated into ternary particles. The surface area of carbon black may be in the range of 50-770 m2/g. Graphite, which may be natural or synthetic, on the other hand is micro-sized having d90 of >4 μιτι and surface are in the range of 8-250 m2/g. Carbon black is nano-crystalline having Lc (crystallite size) in the range of 1-2 nm, and graphite is micro-crystalline having Lc over 100 nm.
Examples of commercial products which may be used include Timrex ©NeroMix E series (for example E10 or E12) by Imerys. The xyz-conductive layer may have a thickness in the range of 15-30 μιτι, such as 18-22 μιτι, for example about 20 μιτι. Carbon nanoparticles or carbon particles discussed herein do not include carbon nanotubes or graphene, as they are not suitable for the embodiments. Preferably the embodiments do not contain carbon nanotubes or graphene.
Xyz-conductivity as used herein refers to material which conducts electricity through the thickness (the Z-axis) and the plane of the material (X, Y planes), such as the thickness Z of the conductive layer and the planes X, Y of the conductive layer. Preferably the conductivity is isotropic, i.e. it is uniform in all orientations. The resistance of the xyz-conductive layer is generally in the range of 0-100 Ohms. In one embodiment the carbon in the xyz-conductive layer is included in a polymeric layer, more particularly in an organic polymer layer, such as a thermoplastic polymer layer or thermosetting polymer layer. Preferably the polymer is dispersion polymer, such as aqueous dispersion polymer, or obtained from such as dispersion polymer. More particularly the layer comprises carbon comprising carbon nanoparticles and one or more polymers, such as thermoplastic polymers, thermosetting polymers, copolymers, mixtures, derivatives or combinations thereof. In one embodiment other carbon material is also included, such as non- nanoparticulate carbon particles. In one embodiment the polymer is acrylic polymer, such as acrylic dispersion polymer. In one embodiment the polymer is acrylic styrene polymer, such as acrylic styrene dispersion polymer, or a mixture of acrylic and polyurethane (dispersion) polymers. In general, acrylic polymers provide elasticity, high adhesion and excellent conductivity, especially at low temperatures such as even at -80— 40°C. In one embodiment the polymer is acrylic styrene copolymer, such as acrylic styrene dispersion copolymer. In one embodiment the polymer is acrylic styrene polyurethane, which was found to provide especially high impact resistance and elasticity. In one embodiment the polymer is anionic modified styrene copolymer in combination with acrylic styrene copolymer. The polymer, or at least one polymer in a combination of polymers, is preferably high temperature resistant polymer. Such polymer may have a relatively high minimum film forming temperature and/or glass transition temperature, such as a MFT at least 70°C, such as in the range of 70-100°C, for example 80- 90°C and/or glass transition temperature at least 70°C, such as in the range of 70-120°C, for example 95-100°C.
In one embodiment the polymer comprises a latex polymer, such as a cross- linkable latex polymer or copolymer. In one embodiment the polymer comprises styrene/butadiene copolymer, such as anionic carboxylated styrene/butadiene copolymer. According to one definition the minimum film forming temperature (MFT or MFFT) is the lowest temperature at which a polymer or solid portion of an aqueous polymer dispersion, such as latex, self-coalesces in the semi dry state to form a continuous polymer film. As a rough rule of thumb, the lower the MFT of a polymer the more flexible and elastomeric it will be. However, with modern polymer systems this rule may not apply. Flexibility is very monomer dependent: For example, pure acrylic and a styrene acrylic copolymer emulsions may have exactly the same MFT but not have the same flexibility/elasticity. Further, in general the higher the MFT, the harder the final polymer film and the less thermoplastic the polymer will be. If the exact monomeric build-up of a polymer is known, it is possible to calculate the MFT of a dispersion polymer. The MFT may be also determined for example by simply using a copper bar heater/ice and thermocouples/thermometers, or by using a MFFT-Bar instrument. The determination of MFT is specified by ASTM D 2354, ISO 21 15, and DIN 53787.
According to one definition the glass-liquid transition or glass transition is the reversible transition in amorphous materials (or in amorphous regions within semicrystalline materials) from a hard and relatively brittle "glassy" state into a viscous or rubbery state as the temperature is increased. The glass transition temperature Tg of a material characterizes the range of temperatures over which this glass transition occurs. It is always lower than the melting temperature, Tm, of the crystalline state of the material, if one exists. Glass transition temperature may be determined for example by using differential scanning calorimetry.
In one embodiment the xyz-conductive layer comprises two polymers having a different minimum film forming temperature and/or glass transition temperature, such as one having non-overlapping ranges. In one embodiment the layer comprises two polymers having a different minimum film forming temperature. In one embodiment the layer comprises two polymers having a different glass transition temperature. In one example one polymer has a at low minimum film forming temperature of below 50°C and the other polymer has a higher minimum film forming temperature of 50°C or above. In one example one polymer has a minimum film forming temperature in the range of 0-20°C and the other has a minimum film forming temperature in the range of 70-100°C. In one example one polymer has a at low glass transition temperature of below 50°C and the other polymer has a higher glass transition temperature of 50°C or above. In one example one polymer has a glass transition temperature in the range of 5-20°C and the other has a glass transition temperature in the range of 70-120°C. In one embodiment these polymers are acrylic styrene copolymers. The polymers may be divided into two classes according to their coalescing temperatures. In one example one polymer has a low coalescing temperature of below 50°C and the other polymer has a higher coalescing temperature of 50°C or above. In one example one polymer has a coalescing temperature in the range of -10-50°C, and the other polymer has a coalescing temperature of over 50°C. In one example one polymer has a coalescing temperature in the range of -10-5°C, and the other polymer has a coalescing temperature of over 90°C, for example a coalescing temperature in the range of 90-120°C. These polymers may be also called as a first polymer and a second polymer, or a first polymer dispersion and a second polymer dispersion. The first polymer may be called as a film forming polymer and the second polymer may be called as a non-film forming polymer. In one example the ratio of the polymer having lower MFT, Tg and/or coalescing temperature to the polymer having higher MFT, Tg and/or coalescing temperature is in the range of 3- 7:1 , such as 4-6:1 , for example about 5:1 .
The polymer is provided as a dispersion wherein the carbon is provided as predispersed nanoparticles. Polyolefins were not found to be especially suitable for the purposes of the present embodiments. In one example the content of the conductive carbon in the xyz-conductive layer is in the range of 50-90% (w/w), 60-80% (w/w), or 70-80% (w/w), and the content of the polymer is in the range of 5-45% (w/w), 15-35% (w/w), or 15-30% (w/w) in the final product, such as 75-80% (w/w) of conductive carbon and 15-25% (w/w) of polymer. Other additives may be included for example in an amount in the range of 0.1-5 %. In one embodiment the xyz-conductive layer consists of the carbon nanoparticles, polymer(s) and optionally one or more of other additives or auxiliary agents, preferably in the ranges disclosed herein. The "conductive carbon" in xyz-conductive layer embraces both carbon nanoparticles and to the optional non-nanoparticulate carbon. A maximum conductivity may be obtained by using particulate carbon as a thickener in the mixture of polymers and carbon dispersion. For example carbon granules are dispersed to aqueous media to allow them to be equally dispersed and then letting the absorption of liquids take place by elapse of time. According to measured results, this method improves nominal conductivity with 20-50% and keeps the dispersion stable in storage for prolonged time and without need for remixing or stirring. One embodiment provides a multi-layer film with conductive coating, the film comprising the following layers:
-a first thermoplastic polymer layer,
-a xyz-conductive layer comprising carbon nanoparticles and particulate carbon and thermoplastic polymer, and
-a z-conductive anisotropic layer comprising carbon and polymer.
One embodiment provides a multi-layer film with conductive coating, the film comprising the following layers:
-a first thermoplastic polymer layer,
-a xyz-conductive layer comprising carbon nanoparticles and particulate carbon and acrylic polymer, and
-a z-conductive anisotropic layer comprising carbon and acrylic styrene or ethylene acrylic acid polymer. The first thermoplastic polymer layer may be alternatively replaced with thermosetting polymer layer, fibrous layer, or a textile layer, or with a combinations thereof, as described herein.
The particulate carbon refers to non-nanoparticulate carbon or substantially non-nanoparticulate carbon, for example at least 90% (w/w) of the carbon in the z-layer is non-nanoparticulate, such as at least 95% (w/w), at least 97%, at least 98%, or at least 99% (w/w). The non-nanoparticulate carbon may have an average particle size in the range of 1-50 μιτι, or 1-20 μιτι, such as 1-15 μιτι. The non-nanoparticulate carbon may comprise for example particles or granules, and during the manufacturing of the xyz-conductive layer it may be added as dry or solid matter to a dispersion containing the nanoparticulate carbon. In one example the content of the particulate carbon in the xyz-conductive layer is in the range of 2-10%, such as 5-10% (w/w), 6-9% (w/w), or 6-8% (w/w), or 3-8% (w/w) of the total layer. Nanoparticles agglomerated into granules or particles having a particle size of 1 μιτι or more may be considered as non-nanoparticulate.
The xyz conductive layer is next to, i.e. in contact with, the anisotropic z- conductive layer (also called as z-layer), which may be printed and/or laminated to the xyz conductive layer. Therefore the conductivity of the xyz- layer is connected to the conductivity of the z-layer. In one embodiment the anisotropic z-conductive layer contains carbon particles, which may be also called as particulate carbon, which may have an average diameter, or an average particle size, in the range of 1-20 μιτι, such as 1-15 μιτι. The carbon used in the z-conductive anisotropic layer may comprise granulated particles of conductive carbon, for example pressed carbon pieces. Preferably the z- conductive layer does not comprise nanoparticulate carbon, or substantial amounts of nanoparticulate carbon, i.e. the carbon in the z-layer is non- nanoparticulate or substantially non-nanoparticulate, for example at least 90% (w/w) of the carbon in the z-layer is non-nanoparticulate, such as at least 95% (w/w), at least 97%, at least 98%, or at least 99% (w/w). The carbon material may be provided as an aqueous dispersion, for example an aqueous dispersion of graphite and/or carbon black. Examples of commercial products which may be used include Imerys Ensaco 250G. Z-conductivity as used herein refers to material which conducts electricity only through the thickness (the Z-axis) and not through the plane of the material (X, Y planes). Such conductivity is anisotropic, i.e. it is not uniform in all orientations. The optimal z-conductivity is obtained by selecting suitable particle size and content of the carbon in the layer. The z-conductive layer exhibits a high resistance of 10 000-100 000 Ohms in the xy-directions, but a resistance of 100-1000 Ohms, or less, at the z-direction in the final product, after the heat treatment. The feature of the z-conductive layer that it is both conductive and non-conductive (insulator) provides several technical effects. The z-conductive layer covers the xyz-conductive layer providing enhanced mechanical properties, such as foldability and durability. The z-conductive layer forms a bridged composite structure with the xyz-conductive layer when heat-treated or heat-bonded. The heat-treatment may be detected from the final product for example using microscopic methods. The z-conductive layer enables electrical contact with the actual xyz-conductive layer through the covering z-conductive layer. For example an electrical contact with a conductive circuit may be made through the z-conductive layer by touching exposed z-conductive layer. This enables using the multi-layer film in touch- sensitive applications or connecting the conductive circuits to electronics.
The anisotropic z-conductive layer may have a thickness in the range of 15- 30 μιτι, such as 18-22 μιτι, for example about 20 μιτι.
In one embodiment the carbon in the z-conductive anisotropic layer is included in a polymeric layer, more particularly in an organic polymer layer, such as a thermoplastic polymer layer or a thermosetting polymeric layer. The polymer may be a plastic polymer, as explained herein. Preferably the polymer is dispersion polymer, such as aqueous dispersion polymer, or obtained from such as dispersion polymer. The polymer may be a latex polymer. The polymer may be a cross-linkable polymer, including self- crosslinkability. In the final product the polymer may be cross-linked. Also precipitating polymers and/or film-forming polymers may be provided, for example for applications requiring elasticity. During curing a cross-linked polymer(s) may be obtained. In some cases a cross-linking agent may be added, such as polyaziridine crosslinker, which improves especially carboxyl functional resins performance. A cross-linking agent may be added in an amount of 1-3% (w/w) of the polymeric dispersion.
In one embodiment the polymer is acrylic polymer. A thermoplastic dispersion of acrylic polymer is called acrylic latex. Acrylic polymers may be present also as thermoplastic solutions or thermosetting solutions. In one embodiment the thermosetting polymer is acrylic polymer. The acrylic polymers used herein are preferably present as aqueous dispersions. In general, acrylic polymers provide elasticity, high adhesion and excellent conductivity, especially at low temperatures such as even at -80— 40°C. In one embodiment the polymer is acrylic styrene copolymer. In one embodiment the polymer is acrylic styrene polyurethane, which was found to provide especially high impact resistance and elasticity. In one embodiment the polymer is anionic modified styrene copolymer in combination with acrylic styrene copolymer. The polymer, or at least one polymer in a combination of polymers, is preferably high temperature resistant polymer. Such polymer may have a relatively high minimum film forming temperature and/or glass transition temperature, such as a MFT at least 70°C, such as in the range of 70-100°C, for example 80-90°C and/or glass transition temperature at least 70°C, such as in the range of 70-120°C, for example 95-100°C.
In one embodiment the polymer comprises a latex polymer, such as a cross- linkable latex polymer or copolymer. In one embodiment the polymer comprises styrene/butadiene copolymer, such as anionic carboxylated styrene/butadiene copolymer.
In one embodiment the z-conductive anisotropic layer comprises two polymers having a different minimum film forming temperature and/or glass transition temperature, such as one having non-overlapping ranges. In one embodiment the layer comprises two polymers having a different minimum film forming temperature. In one embodiment the layer comprises two polymers having a different glass transition temperature. In one example one polymer has a at low minimum film forming temperature of below 50°C and the other polymer has a higher minimum film forming temperature of 50°C or above. In one example one polymer has a minimum film forming temperature in the range of 0-20°C and the other has a minimum film forming temperature in the range of 70-100°C. In one example one polymer has a at low glass transition temperature of below 50°C and the other polymer has a higher glass transition temperature of 50°C or above. In one example one polymer has a glass transition temperature in the range of 5-20°C and the other has a glass transition temperature in the range of 70-120°C. In one embodiment these polymers are acrylic styrene copolymers. The polymers may be divided into two classes according to their coalescing temperatures. In one example one polymer has a low coalescing temperature of below 50°C and the other polymer has a higher coalescing temperature of 50°C or above. In one example one polymer has a coalescing temperature in the range of -10-50°C, and the other polymer has a coalescing temperature of over 50°C. In one example one polymer has a coalescing temperature in the range of -10-5°C, and the other polymer has a coalescing temperature of over 90°C, for example a coalescing temperature in the range of 90-120°C. These polymers may be also called as a first polymer and a second polymer, or a first polymer dispersion and a second polymer dispersion. The first polymer may be called as a film forming polymer and the second polymer may be called as a non-film forming polymer. In one example the ratio of the polymer having lower MFT, Tg and/or coalescing temperature to the polymer having higher MFT, Tg and/or coalescing temperature is in the range of 3- 7:1 , such as 4-6:1 , for example about 5:1 .
In one embodiment the polymer layer comprises ethylene acrylic acid (EAA) copolymer, or is a layer thereof. Ethylene acrylic acid (EAA) copolymer is a tacky solid form, with an acrylic acid (AA) content of for example about 20%, is suitable for promoting adhesion to various substrates, such as paper or board. The ethylene monomers provide thermoplastic properties whereas the acrylic acid monomers provide dispersion stability. Uncrosslinked EAA copolymers are thermoplastic by nature and will generally melt flow at sufficiently high temperatures. Crosslinking reactions will significantly influence the thermoplasticity behavior of EAA copolymers. The ethylene acrylic acid provides low heat sealing properties. Ethylene acrylic acid enables heat pressing the layers together into a laminate which cannot be delaminated. Such heat pressing prevents copying of the configuration of the layers and connections therein. Examples of commercially useful EAA grades include ethylene acrylate dispersion E-799 by Trub Emulsions Chemie. As the ethylene acrylic acid has a negative effect to the conductivity, it is not desired to use it in the xyz-conductive layer.
The carbon granules may be dispersed in to EAA polymer dispersion, which has very high solids content due to polymerizing technology utilizing high temperature and high pressure. This provides smaller amount of free water and facilitates obtaining complete dispersions of agglomerates. This result is ideal when producing anisotropic conductive polymer dispersions.
In anisotropic dispersion, the EAA polymer is used to ease the desired semi dispersed result in which agglomerates form anisotropic phenomena when dispersion is applied, dried and heat sealed or electronics attached. Suitability of EAA high pressure and high temperature polymerized dispersion is detected by comparing other dispersion chemistry. EAA is also used due to low temperature heat sealability and lamination strength, when adhering carbon printed surfaces together in actual packages. In one example the content of the carbon in the z-conductive layer is in the range of 5-20% (w/w), 5-15% (w/w), or 6-12% (w/w), and the content of the polymer, such as thermoplastic polymer, is in the range of 75-90% (w/w), 80-90% (w/w), 83-89% (w/w) in the final product, such as 6-10% (w/w) of carbon and 85-89% (w/w) of polymer, such as EAA (dispersion) polymer. Other additives may be included for example in an amount in the range of 0.1-5 %. In one embodiment the z-conductive layer consists of the carbon, the polymer(s), such as thermoplastic polymer(s), and optionally one or more of other additives of auxiliary agents, preferably in the ranges disclosed herein.
When preparing the dispersion for obtaining the z-conductive anisotropic layer, it is important to obtain and/or to maintain the size of the carbon particles, which are in general present as agglomerates. Most thermoplastic polymers require using such a high dispersing power that the carbon agglomerates tend to disintegrate and/or further agglomerate during the process. This leads to undesired particle size and to uneven particle distribution and to formation of foam. It was surprisingly found out that when using ethylene acrylic acid as a polymer it was possible to maintain the integrity of the carbon particles or agglomerates of desired size and to obtain a high quality z-conductive anisotropic layer with advantageous properties.
In general, the z-conductive layer covers the circuits formed by the xyz- conductive layer. Usually the area covered by the z-conductive layer is larger than the area covered by the xyz-conductive layer. The z-conductive layer may cover most of the multi-layer structure, or at least all the areas containing xyz-conductive circuits. The z-conductive layer does not have to form such circuits as the xyz-layer because the conductivity is only in the z- direction and therefore a continuous z-conductive layer cannot cause shortcuts in the xyz-conductive circuits. Inherently the z-conductive layer has a gray color, in contrast to the substantially black color of the xyz-conductive layer. It is, however, possible to include pigment, such as a black pigment or other color, to the dispersion for making the z-conductive layer to obtain a desired color of the z-conductive layer, such as black color. The color may be used to mask the xyz-conductive layer, for example to hide the conductive circuits.
The combination of xyz and z conductive layers provides enhanced flexural resistance for the multi-layer product, for example 10 to 100 fold flexural resistance compared to a conventional RF conductive layer. The flexibility of the conductive layers enables preparation of structures which may be used in several applications. For example electronic components and modules may be integrated within the multi-layer structure and the structure may be attached to a variety of targets with different shapes. Flexible sheets may be provided containing electronics and/or functionalities enabled by the conductive layers. Secure bonding of the components to the sheets may be obtained by selecting suitable support layer and conductive layers.
In one embodiment the multi-layer film comprises a further polymer layer, such as a thermoplastic polymer layer, attached to the z-conductive anisotropic layer comprising carbon. If the support layer is a (first) polymer layer or a (first) thermoplastic polymer layer, this layer may be called a second polymer layer or a second thermoplastic polymer layer. The further thermoplastic polymer may be a layer of any thermoplastic polymer(s) or film described herein. In one embodiment the (second) (thermoplastic) polymer layer has a thickness in the range of 19-100 μιτι, such as 20-80 μιτι. In one embodiment the further polymer layer, has a thickness in the range of 23-50 μιτι. In one embodiment the further polymer layer is a foamed layer. A foamed layer may be thicker than a non-foamed layer, for example in the range of 100-3000 μηη, 100-2000 μηη, or 100-1000 μηη, such as 100-500 μιτι. Parts of the z-conductive layer, which need to be in contact with electronics, other connectors, user etc. may be left uncoated to obtain an exposed area of z-conductive layer. Such exposed area may contain one or more connectors of the multi-layer sheet, or any functional parts, such as a contact area, a switch or the like. Electronic components, modules, circuits or other devices may be connected to such exposed areas, for example by heat-bonding and/or by using any suitable bonding chemistry. Such a further layer may be applied for example by using extrusion. In one embodiment the further layer comprises polyurethane, preferably applied by extrusion technology. Such a polyurethane layer is especially suitable for protecting electrical components and the like attached to the conductive layers, and may be applied to embodiments which are used in applications requiring shock resistance and other mechanical strength. In one example a multi-layer structure, as described in the embodiments, preferably comprising a polyimide film or layer in or as a support layer, comprises said layer of polyurethane as a further layer. The basic multi-layer structure, for example as a band, may be wound on a roll. Before or after rolling the multi-layer structure may be supplemented with the required electrical components. The structure is transferred to an extruder, and a polyurethane layer is extruded on top of the structure. The assembly and/or bonding of the electronics may be carried out by using a robot unit.
The construction may comprise polymer layer, such as a thermoplastic polymer layer or thermosetting polymer layer, between two conductive carbon layers, such as between two conductive twin layers of xyz and z conductive layers. Such a layer in between the conductive layer may be called as a third layer. Such layer may be a foamed layer, as described herein.
In one embodiment the multi-layer film comprises further an adhesive, such as a pressure sensitive adhesive, and optionally a release liner on the adhesive. The adhesive may be attached to the first or to the second polymer layer, such as thermoplastic or thermosetting polymer layer, or to another support layer. Pressure sensitive adhesive, also known as self-stick adhesive, forms a bond when pressure is applied at room temperature. PSA labels can be adhered to most surfaces through an adhesive layer without the use of a secondary agent such as solvents or heat to strengthen the bond. Examples of pressure sensitive adhesives include emulsion and water based PSAs, solvent based PSAs and solid PSAs. A release liner is a paper or plastic-based film sheet (usually applied during the manufacturing process) used to prevent a sticky surface from prematurely adhering. It is coated on one or both sides with a release agent, which provides a release effect against any type of a sticky material such as an adhesive or a mastic. A paper liner may be for example super calandered kraft paper, glassine paper, clay coated kraft paper, machine finished kraft paper or machine glazed paper. A plastic liner or film may be a BO-PET film, a BOPP film, or other polyolefin film such as HDLE, LDPE, or polypropylene. Commonly used release agents for release liner include silicone, such as crosslinkable silicone, and other coatings and materials that have a low surface energy.
In one embodiment the adhesive is applied on polymer foam film and covered with pieces of release liner, such as a film. The multi-layer film, laminate or more particularly a device containing the same may be adhered to the target by peeling off the release liner tape, for example in case of two separate release liner parts in similar way as when using a plaster, and adhering the laps of the multi-layer film on the target, such as on top of each other around the target. The laps may contain RFID and/or UHF antenna(s) printed inside
In one embodiment the multi-layer structure contains two conductive carbon layer sets, preferably separated by an insulating or dielectric layer, which may be called as a first conductive carbon layer and a second conductive carbon layer, and which may be similar or different. One or both of the conductive carbon layers may contain the xyz- and the z-conductive layers described herein. In one example the other conductive carbon layer is replaced or supplemented with a metal layer. The separating layer may be a layer comprising thermoplastic or thermosetting polymer(s), such as described herein for the first, second and thirds polymeric layers, or it may contain foamed material, such as foamed thermoplastic or thermosetting polymer, or it is a combination thereof. The foamed material may be elastic material . The two carbon layer sets, which both include a xyz-conductive carbon layer and a z-conductive anisotropic carbon layer, may form a capacitor or other structures. One or both of the carbon layer sets may contain supplementary metal parts, for example forming the structures of the capacitor, either partly or fully. A foam layer or substrate, or a layer of any other elastic and/or flexible material, also called as a deformable layer or substrate, between the layers may enable movement of the two conductive layers in respect of each other. Touch sensor or pressure sensor structures may be formed by using such a layered structure. In one example a conductive layer may have a first position and a second position in respect to another conductive layer providing a first capacitive value and a second capacitive value correspondingly. Pressing the structure, which may be elastic, is arranged to cause a change in the capacity formed by the two layers, which change may be detected. In one example an inductor formed by the conductive carbon, such as a coil, is provided on the elastic and/or flexible material, wherein a first inductance value and a second inductance values are provided in similar way as described for the capacitive example. Pressing the structure is arranged to cause a change in the inductance formed by the two layers, which change may be detected.
A multi-layer film or laminate containing adhesive and a release liner is in the form of a self-adhesive label or sticker. Such a construction may have a face layer on the top (on the other side than the adhesive), which may be printed or colored, and the construction may be called as a face laminate. The support layer or the layer on the opposite side may be the face layer, or the face layer may be a separate layer on said layer.
Figure 1 shows an example of a multi-layer structure or laminate containing a sensor 18, such as a motion sensor, and a battery 19. An example of such a construction is the sensor device discussed herein. A first thermoplastic polymer layer 10 comprises a treatment 1 1 and is heat-bonded to the xyz- conductive layer 12. Next to the xyz-conductive layer 12 is the z-conductive anisotropic carbon layer 13. The sensor 18 and the battery 19 are connected to the conductors formed by the xyz-conductive layer 12 via the z-conductive anisotropic layer 13. The electronics 18, 19 are covered with a second protective thermoplastic polymer layer 15, and the voids are filled with adhesive 14. A pressure sensitive adhesive layer 16 is attached to the second thermoplastic polymer layer 15 and is covered with a release liner 17 to form a structure which may be attached to a target simply by removing the release liner to expose the pressure sensitive adhesive. The multi-layer structure may be folded especially at the area between the electronics 18 and 19. In Figure 1 the carbon layers cover the whole multi-layer structure, but in many applications especially the area covered by the xyz-conductive layer may be smaller. A schematic example of a similar sensor device is shown in Figure 2 seen from the top. The motion sensor 18 and the battery 19 are connected by conductive tracks 24 arranged to transfer power. The device contains also a Bluetooth module 20 connected to an UHF antenna 22 formed by conductive carbon connected to the sensor 18 with several carbon tracks 25 arranged to transfer data and power. The device contains also an RFID module 21 connected to a RFID antenna 23 and to the battery 19 via conductive carbon tracks 26 in case of active RFID. The RFID components 21 , 23 are for identification of the device, and the Bluetooth components 20, 22 are for communication with an external device. In one example the device does not contain the RFID part, or the RFID part is passive and therefore not connected to the power source. The conductive tracks are formed by the xyz- conductive layer, and are covered by a z-conductive anisotropic layer 27 having a larger area.
The multi-layer film with conductive coating may be used for multiple purposes. In one embodiment the multi-layer film comprises one or more conductor(s) formed by the xyz-conductive layer, the conductor(s) being connectable to one or more electronic component(s) or circuit(s). A conductor as used herein refers to a conducting area designed to provide one or more functionalities, and it is present as a specific form, such as one or more elongated strip-like forms, such as tracks, acting as wiring for electronic connections, such as power and data connections, for example having a width in the range of 0.1-5.0 mm, in the range of 0.1-3.0 mm, such as 0.1- 2.0 mm, or 0.1-1 .0 mm or 0.1-0.5 mm, or wider conducting areas, such as oval or angular shape, which may be arranged to act as contact areas or sensors, or other shapes. For sensor devices the width of the tracks is adapted to fit to the connectors or pins of the sensor, which may be for a small sensor in the range of 0.1-0.35 mm, such as in the range of 0.19-0.31 mm, for example about 0.25 mm. For a larger sensor the width of a track may be in the range of 0.2-1 mm, such as in the range of 0.2-0.8 mm, for example 0.5-0.8 mm or 0.5-1 .0 mm.
It is possible to print flexible conductive patterns, which may be applied in electrical circuits. The conductive layers may be used to form a touch sensor, for example an inductive touch sensor, a capacitive touch sensor and/or a resistive touch sensor. One type of touch sensor is pressure sensor. The touch sensor may or may not require direct electrical contact with the user. The touch sensor may be also called a tactile sensor, which is a device capable of measuring the properties of a contact between a sensing device and an external stimuli. The most common measurands are contact and force. The one or more conductors may form a variety of functional patterns on the film, such as electrical wiring, sensors, antennas, coils, capacitors, resistors, or switches or breakable areas. The conductive layers may also be supported with a separate metal printing. A switch may be formed by two separate portions which may be electrically connected by touching, for example by finger or by stepping or by touching with any part of the body. A contact area may be formed by a (continuous) conducting area having a width, length, height and/or diameter in such a range that a user may touch the area, and wherein touching the area or a layer on top of the area will cause a detectable change in the electric circuit connected to said contact area. The conductive layers may further contain metallic materials in dispersed or in film forms. Typical variants are silver pastes, aluminum films and copper foils. They may be converted directly to optimal configuration of the flexible circuit of the device.
In one example a conductor is supplied with a supplementary conductor, such as a metal tracks, wiring or lines, for example silver, copper, tin or gold tracks, wiring or lines, which may be applied on to a carbon conductor or to another location, to obtain a hybrid wiring or hybrid conductors, which may be used to minimize the structure. Silver may be printed for example by rotary screen printing using polymer type of silver paste wherein polyester resin is used as a binder. Due to its flexibility and good adhesion it is well suitable for making conductive circuit on plastic substrates. On the contrary copper, especially in nano forms, is difficult to process and has oxidation problems in aqueous environment. Further, the processed nanocopper is expensive and more harmful when compared for example to silver. Further, copper is not durable in flexible structures. Therefore the use of copper may not be desired. A capacitive displacement sensor may comprise two conductive parallel planes separated by dielectric material. The planes may be formed by the conductive carbon layers, optionally supplemented with metal parts, as described herein. The capacitance between the planes is inversely proportional to the square of the distances between them. By using elastic material between the two planes it is possible to obtain a structure wherein external force may change the capacitance, for example by pressing or pushing the structure to change the distance of the two planes. This change in the capacitance is arranged to be detected by a device coupled to the structure. In one example capacitive touch sensing is based on the principle that a touch on a touch sensitive film means, from electrical point of view, coupling an external capacitance to the measurement circuitry to which the touch sensitive film is connected. With sufficiently high sensitivity of the touch sensitive film, even no direct contact on the touch sensitive film is necessitated but a capacitive coupling can be achieved by only bringing a suitable object to the proximity of the touch sensitive film. The capacitive coupling is detected in the signals of the measurement circuitry of a connected device. A resistive sensor may be based on the principle that electric resistance of an elastic conductive material changes under applied pressure. The electric resistance changes under applied force since the cross section of the membrane decreases while its conductive length increases. The elastic properties of the multi-layer structure enable forming a durable resistive sensor, wherein the conductive carbon is arranged to be pressed and the pressing is arranged to change the resistance of the xyz-conductive layer. Such a structure requires usually space for the multi-layer film to stretch, which may be arranged by an empty space or elastic material behind the touch area, for example a foamed layer.
For example a sensor laminate or a sensor sheet, which terms may be used interchangeably, may be formed having one or more contact areas or carbon sections arranged in such way that a target, such as a person or an animal, touching the sheet or stepping on the sheet will touch the contact areas thus causing detectable changes in the electric circuit, which may be detected and analyzed by one or more devices connected to the connectors of the sheet. The effect of the person or the like to the electric circuit may be inductive, resistive or capacitive. For example the presence of a person's finger, or more precisely the water in it, will change the relative static permittivity causing a shift in capacitance. Another type of capacitive sensor is the capacitive displacement sensor, which works by measuring change in capacitance from the change in dimensions of the capacitor. Such a sensor sheet may be placed for example onto a floor, onto a bed, onto a seat or to any other location which is to be monitored. It is therefore possible to detect if a person is walking on the sheet, or if a person is lying on a bed, and so on. Such sensor sheets may be utilized for example to monitor elderly or sick people, for example to control sleep and to enhance security. For example a person falling onto floor may be detected by sudden contacts on several contact areas caused by the person lying on the laminate.
A sensor sheet may comprise carbon sections having sizes of for example 200 x 200 mm, 200 x 300 mm, 200 x 400 mm, 200 x 500 mm, 300 x 300 mm, 300 x 400 mm, 300 x 500 mm, 400 x 400 mm, 400 x 500 mm, 400 x 800 mm, 400 x 1000 mm, 500 x 500 mm, 500 x 1000 mm, 600 x 1000 mm or any other suitable size. The carbon sections, carbon areas or contact areas, which terms may be used interchangeably, may be continuous areas wherein the conductive print covers the whole area or section, and it usually continued by a narrowing conductive wiring which is to be connected to an external device sensing the measurable changes in the circuit, such as depicted in Figure 4. All sizes may be applied as printed conductive patterns having at least 2 cells, more particularly at least 2 x 2 cells up to of 2 x 8 cells, or even more, printed to cover substantially the whole width and whole length of the sensor sheet. Individual cells are wired using conductive carbon print, which may be secured with printed silver lines to ensure the conductivity of the lines in long term use. For example 4-16 printed wires may be connected to a controlling device.
One embodiment provides a sensor sheet comprising the multi-layer film described herein, the sensor sheet comprising at least two carbon sections of at least or about 100 x 100 mm, such as 2-20, for example 4-16 carbon sections, for example 4, 6, 8, 10, 12, 14, 16 or more. In practice a sensor sheet comprising maximum of 16 carbon sections was found still practical, but adding more carbon sections would not provide any further usability or information, but would merely make the construction more complex and more difficult to control and manufacture. A sensor sheet may have a length and/or width in the range of 10-1000 cm, for example 100-500 cm. A sensor sheet may be for example fitted into a bed and therefore it may have dimensions such as about 80 x 210 cm, 100 x 210 cm, 120 x 210 cm, 160 x 210 cm, 180 x 210 cm, 80 x 200 cm, 100 x 200 cm, 120 x 200 cm, 160 x 200 cm, 180 x 200 cm and the like. A sensor sheet arranged to be placed onto a floor may have for example a width in the range of 50-100 cm and a length in the range of 100-500 cm.
One example of sensor structure, such as a sensor sheet or laminate, is a combination of conductive carbon printed and hybrid wired laminate having a layer of foamed material, such as foamed polymer, for example foamed thermoplastic polymer, which sensor structure acts as a pressure sensor and offers more details in sensing the quality of sleep and also detecting seizures and/or changes in human functions. Figure 4 shows parts of a sensor sheet. A part of a continuous xyz carbon section 40, 41 printed onto a support layer 44 can be seen connected to a narrow conductor track 45, which leads to a separate connector part for connecting to a control device (not shown) together with the other similar conductors 42, 43, which are each connected to separate carbon sections at the other parts of the sensor sheet. On the other side of the sensor sheet silver lines can be seen on the carbon conductors 42 thus forming hybrid conductors.
One embodiment provides a method for controlling presence or movement of a subject, the method comprising
-providing the sensor sheet connected to a controlling device arranged to detect changes, such as capacitive, inductive or resistive changes, in the electric circuit of the sensor sheet, and
-detecting changes in the electric circuit in respect of each carbon section of the sensor sheet, wherein a change in the electric circuit indicates the presence or the movement of the subject on the sensor sheet. The subject may be a human, an animal or any other subject, such as a moving device or a machine, which is capable of providing a detectable change in the electric circuit in the sensor sheet in respect of a carbon section. The presence or the movement of the subject may cause for example an inductive, a resistive or capacitive change in the electric circuit connected to a carbon section which may be detected. The controlling device is a device connected to the circuits of the sensor sheet, wired or wireless, the device being arranged to detect changes in the electric circuits connected to each carbon section, such as changes in capacitive, inductive or resistive properties of the carbon section or an electrical circuit including the carbon section. The controlling device may comprise for example a processor, memory, an analog to digital (A/D) converter to convert the detected signals into digital form, a display or other outputting means, a network connection, and/or a software arranged to carry out the steps of detecting the signals and converting them to processed data. The data may be visualized from a display, saved, processed, and/or it may be forwarded to another device. The device may be a specific control unit, or it may be a server, a personal computer or other personal device, such as a wireless terminal, for example a mobile phone, a tablet, or the like.
The changes in the electric circuit(s) in respect of each carbon section of the sensor sheet may be used to detect the actions of the subject. For example it is possible to detect or see from the pattern formed by the changes in the electric circuits that a person is walking on the sensor sheet. It is also possible to detect the movements of a moving device, such as a robot, moving on the sensor sheet or touching it.
A breakable area may be arranged into the multi-layer film in such way that an action breaking an electric circuit on the specific area of the film is detected as a loss of electrical current in the circuit. For example the film may be placed onto a surface having an area which may be pressed, and the pressing causes a conductor in the breakable area to break thus causing a detectable change in the electric circuit, i.e. a loss of electrical current in the circuit. One example of such application is a pill dispenser, which comprises pigeonholes for pills, such as one or more holes, compartments or apertures per day, for example one, two, three or four. The multi-layer film may be designed to fit to the pill dispenser in such way that on each hole there is a corresponding breakable area in the multi-layer film. The multi-layer film may act for example as a lid for the pill dispenser, and it is connected to an electronics module or device monitoring the integrity of the circuits. The pill dispenser may be formed of cardboard, which may be provided as a sheet designed to be folded into the final pill dispenser form. The multi-layer film or structure may be already applied onto the cardboard, or the multi-layer structure may be provided separately, designed to be fitted and attached onto the cardboard. Instead of cardboard any other support material may be used, such as plastics, coated cardboard, plastic-fiber composite and the like. When a user punches the lid on the location of a specific hole or aperture, which may be perforated or otherwise weakened to define a removable or breakable area, the breakable area is broken and the action may be electrically detected. This action indicates that the user has taken the medication dedicated for the specific date or time on the specific location of the pill dispenser. The body of a pill dispenser may comprise for example board, and the multi-layer film is attached onto the board. The multi-layer film may be similarly applied to a bubble pack of pills or to any other similar construction. In one example different breakable areas are designed to provide different resistance, for example by providing different lengths of conductive carbon circuits or wirings at the different breakable areas. These different breakable areas may be connected to the same electrical circuit in parallel, so the circuits may be simplified as separate connections are not required for each breakable area. The detectable change in the electrical circuit is different for each different breakable area having a different resistance, which enables the connected device to recognize which breakable area has been punched. Figure 3 shows two examples of breakable areas 30, 31 defined by perforations 34 and having conductive carbon tracks printed on a cardboard and which areas may be removed from a package by punching. The two breakable areas 30, 31 have different lengths of conductive carbon circuits 32, 33 and therefore different resistances. More particularly the track 32 is longer than the track 33 and therefore the track 32 provides higher resistance than the track 33. The ends of the tracks are connected to larger continuous carbon printed areas 35, 36 which are connected to continuous printed areas (not shown) outside the breakable areas 30, 31 .
One embodiment provides a textile, such as a clothing, comprising the multi- layer film described herein, and comprising one or more conductor(s) formed by the xyz-conductive layer, the conductor(s) being connectable to one or more electronic component(s) or circuit(s). The conductors may be in the side of the clothing which is arranged to be in contact with skin when in use, such as when worn, in practice inside clothing. In one example the conductive carbon is on acrylic styrene polyurethane polymer layer, which provides flexibility. Such a construction may be used in intelligent clothing, for example wherein the conductors are used in the measurement of skin conductivity, for example to detect or measure sweating. Examples of the clothing include underwear, such as underpants and undershirt, socks, gloves, headgear, shirts, pants, bands and the like. Clothing may be equipped with one or more devices arranged to be connected to the multilayer film, and which may be arranged to connect to an external device wirelessly or by using wires or cables. The multi-layer films may contain one or more electrical components, connectors and/or modules described herein to enable the desired functionalities.
As used herein a multi-layer film refers to a film structure containing more than one layers, or at least two layers, attached together. The multi-layer film may be obtained by using a variety of methods, such as by printing, laminating, adhesive bonding, or by combinations thereof. The layers may be completely or partially overlapping. For example a conductive layer may form patterns, which partially overlap with a structural polymer layer. In a preferred embodiment the layers are formed by printing, more particularly by printing the xyz-conductive layer on a support layer, and subsequently printing the z- conductive anisotropic layer onto the xyz-conductive layer. This enables a fast and safe process, especially when the aqueous dispersions disclosed herein are used.
In general "laminating" means the action of combining previously unconnected layers to become one product whose layers will remain together. A layer may also be formed during the laminating process. The obtained product may be called as a laminate. However a laminate may be prepared by using other methods as well. In general a laminate is a permanently assembled object by heat, pressure, welding, chemical reaction or adhesives. A laminate may also be called as a multi-layer structure. For example a structure containing at least two polymeric film layers attached together, with or without other layers in-between, may be called a laminate or a multilayer film. A laminate may also be obtained by printing one or more layer(s). One embodiment provides a sensor device comprising one or more sensor module(s), and preferably means for wireless communication, connected to the conductors of the multi-layer film. A sensor module refers to a unit capable of sensing, receiving or detecting information, for example a motion sensor, a light sensor, such as a photodetector, an image sensor, such as a camera or a camera module, a sound sensor, such as a module containing a microphone, a radiation sensor, thermal sensor, geographical sensor, such as a GPS sensor, or the like. A sensor module usually contains electronics configured to convert the sensed, received or detected information into electronic form, more particularly into digital form. The module may also contain one or more processor(s), memory, software, and/or power source and the like, and is configured to output the processed information, for example by using wired connection or by using wireless technology. Preferably the sensor device further comprises one or more antenna(s) formed by the xyz-conductive layer and/or other conductive layers.
One embodiment provides a sensor device comprising a sensor module, such as a motion sensor module, and preferably means for wireless communication both connected to the conductors of the multi-layer film. The sensor module may be included in the multi-layer film, for example the sensor module may be between two layers of the multi-layer film or laminate.
The multi-layer film comprising one or more conductor(s) formed by the xyz- conductive carbon is connected to a sensor module, and optionally to a separate power source, such as a battery or a solar cell. The power source may be rechargeable, such as by conducting a connector from a charger, or by using inductive charging. In case of inductive charging the required inductive coil for receiving the electromagnetic field from an inductive charger may be formed with the conductive carbon or with a separate metal layer, for example silver or the like as described herein. In one example the power source is a battery, such as a disc or button type of battery, for example a rechargeable battery, which may be included in between the layers, for example having a removable insulating layer preventing the contact of the battery to the electrical circuit. The insulating layer may be removed prior to use to connect the battery and to turn the power on in the device. The battery may be also installed in a separate base or battery holder which is mounted onto the film, such as a bayonet type of base, wherein the battery is removable. Some sensor types consume relatively much energy, so in such cases the power source should have high capacity. This may be implemented by using a rechargeable battery, such as one having a capacity of 150-1200 mAh. Such a storage battery should have a dimension suitable for combining with the sensor structure. Batteries having a width in the range of 12-20 mm, length in the range of 17-50 mm and thickness in the range of 3-5 mm may be used in such devices. The battery may be connected to a connector for connecting to a power source for recharging, such as a socket, for example a USB connector, so that there is no need to remove the battery from the sensor device. The connector may be heat-bonded to the conductive carbon layers.
The multi-layer film and the sensor module and any further components form a sensor unit or device, which may be attached to a suitable target, for example by using adhesive, such as pressure sensitive adhesive. The sensor module and any other components may be located inside the multi-layer structure, for example between the z-conductive anisotropic layer and the second thermoplastic polymer layer or film. In such case the electronics are covered with the protective polymer layers. Adhesive may be added to cover any gaps inside the multi-layer structure. The obtained construction is flexible and also exhibits elastic properties, such as having elasticity in the range of 10-15%, or even 10-20%. In general elasticity is the ability of a body to resist a distorting influence or stress and to return to its original size and shape when the stress is removed. Solid objects will deform when forces are applied on them. If the material is elastic, the object will return to its initial shape and size when these forces are removed. A motion sensor as used herein refers to a device comprising an accelerometer, and optionally gyroscope and/or geomagnetic sensor. An accelerometer is a device that measures proper acceleration. For example, an accelerometer resting on the surface of the Earth will measure an acceleration due to Earth's gravity, straight upwards (by definition) of g ~ 9.81 m/s2. Single- and multi-axis models of accelerometer are available to detect magnitude and direction of the proper acceleration, as a vector quantity, and can be used to sense orientation (because direction of weight changes), coordinate acceleration, vibration, shock, and falling in a resistive medium (a case where the proper acceleration changes, since it starts at zero, then increases). Micromachined accelerometers are increasingly present in portable electronic devices and video game controllers, to detect the position of the device or provide for game input. The sensors may have several detection axis, for example an accelerometer may have 3, 6, or 9 axis, and a gyroscope may have 2, 3, 6 or 9 axis. In general, a motion sensor may detect orientation, tilt, motion, acceleration, rotation, shock, vibration and heading. The sensor may be a 3D-9D motion sensor. In a basic example the motion sensor contains a 3D acceleration sensor.
The new generation of electronics units provides advantages in size, energy consumption and shock resistance. For example Bosch, STMicroelectronics and Xsens are already manufacturing 3D-9D sensors and represent suitable technology to be adapted. The units require antennas, external energy sourcing and wiring; this is provided with the conductive layers of the embodiments, preferably in a laminate structure which will also protect the printed wires and electronics units.
Different types of commercially available sensor modules generally have relatively small dimensions, such as in the range of millimeters for motion sensors. For example an Xsens MTi-1 MEMS sensor has dimensions 12.1 x 12.1 x 2.55 mm and it is capable of outputting 3D orientation, 3D rate of turn, 3D accelerations, and 3D magnetic field, depending on the product configuration. A Bosch BMX160 9-axis absolute orientation sensor has dimensions 2.5 x 3.0 x 0.95 mm and it comprises a 3-axis accelerometer, gyroscope and geomagnetic sensor in a single package. A Bosch BMX055 has dimensions 3.0 x 4.5 x 0.95 mm and it comprises triaxial 16 bit gyroscope, a triaxial 12 bit accelerometer and a geomagnetic sensor.
One example of a sensor module is MPU-9250 by TDK Invensense, which is a 9-axis MotionTracking device having dimensions 3x3x1 mm and containing gyroscope, accelerometer and compass functions. It has a power consumption of only 9.3 μΑ. As the clock speed and power saving functions may be adjusted and optimized, it is possible to obtain an operating time of 6 months to even two years by using one 200-1000 mAh battery, for example in tracking applications. In general the device may be programmed to gather data at a predetermined interval, such as every 1-60 minutes, for example 10 minutes, to save energy. On the other hand it is also possible to obtain data even hundreds times per second, if necessary, and depending on the sensor used.
The sensor device comprising a motion sensor module connected to the conductors of the multi-layer film may be used in a variety of applications. If the sensor device contains an adhesive part, it can be easily attached to the target thus allowing monitoring of the movement of the target. In most applications the sensor device also comprises means for wireless communication, such as a transmitter, receiver, antenna, and a controlling means for controlling the communication. The means for wireless communication are used for wirelessly connecting the sensor device to a remote device. In practice this means data communication, wherein data from the sensor device is transmitted to the remote device. The data is received by the remote device and it is preferably further processed. Also data from the remote device may be transmitted to the sensor device. The data may include measured sensor data but also other data, such as regular data relating to the wireless communication protocol. The antenna may be formed by the conductors of the multi-layer film or it may be formed by separate metal layers, such as metal printing, for example silver. The wireless communication may be for example Bluetooth or WLAN/WiFi communication, or any other suitable wireless communication, such as cellular communication which may be used to connect to an external or a remote device utilizing the similar wireless communication technology. The means for wireless communication include a transmitter and a receiver, and usually memory and a processor. The means for wireless communication may be provided as one or more separate module(s) which may be connected to the sensor, power source, antenna, and to any other necessary components with conductive carbon tracks. Such a module may be for example a miniaturized embedded Wi-Fi or Bluetooth module which types are commercially available. The means for wireless communication are arranged to communicate with an external device, which may be a mobile device, such as a mobile phone, a tablet, a mobile computer, for example a laptop computer, another similar sensor device, a relay station, a router, or any other suitable remote device capable of communicating with the sensor device. The external device may run any suitable operating system such as Android, Windows, iOS, Linux, UNIX and the like. The terms external device and remote device may be used interchangeably and generally refer to a device which is separate from the sensor device. The means for wireless communication may also include one or more control unit(s) for controlling the wireless communication and/or for converting the information obtained from the sensor into a form which can be transmitted to the external device. The means for wireless communication may be included in the sensor module or it may be a separate unit or module, optionally containing memory, one or more processors, software arranged to carry out the functions described herein, and the means for wireless communication may be connected to an antenna, to a power source, to the sensor, and to any other suitable component with the conductive carbon circuits in the multi-layer film as described herein.
In one example the sensor device comprises a radio frequency identification (RFID) module, which may be passive or active. The module may also be called as a tag. RFID uses electromagnetic fields to automatically identify and track tags attached to objects. The tags contain electronically stored information. Passive tags collect energy from a nearby RFID reader's interrogating radio waves. Active tags have a local power source such as battery and may operate at hundreds of meters from the RFID reader. An active tag has an on-board battery and periodically transmits its ID signal. A battery-assisted passive (BAP) has a small battery on board and is activated when in the presence of an RFID reader. A passive tag is cheaper and smaller because it has no battery; instead, the tag uses the radio energy transmitted by the reader. Tags may either be read-only, having a factory- assigned serial number that is used as a key into a database, or may be read/write, where object-specific data can be written into the tag by the system user. Field programmable tags may be write-once, read-multiple; "blank" tags may be written with an electronic product code by the user.
An RFID tag may contain at least two parts: an integrated circuit for storing and processing information, modulating and demodulating a radio-frequency (RF) signal, collecting DC power from the incident reader signal, and other specialized functions; and an antenna for receiving and transmitting the signal. The tag information is stored in a non-volatile memory. The RFID tag includes either fixed or programmable logic for processing the transmission and sensor data, respectively. An RFID reader transmits an encoded radio signal to interrogate the tag. The RFID tag receives the message and then responds with its identification and other information. This may be only a unique tag serial number, or may be product-related information such as a stock number, lot or batch number, production date, or other specific information. Since tags have individual serial numbers, the RFID system design can discriminate among several tags that might be within the range of the RFID reader and read them simultaneously.
The sensor device comprises memory and a software installed operative in the memory arranged to collect information detected by the sensor module, as discussed herein, and to communicate with the external device via the wireless communication to provide the collected information, either as such or as processed. The collected information may be further processed in the external device and/or it may be forwarded to another device. The external device may include a software arranged to process and/or display the information obtained from the sensor device. For example statistics may be created about the movement, location and/or use of the target whereto the sensor device has been attached. The sensor device may be attached to a variety of targets thus enabling a variety of applications wherein the target is monitored. The target may be also called as object, means, gear, equipment, or the like. There is a rapidly growing market of various kinds of electronics, used for exercising and training. Companies like Suunto, Polar, Nokia and Withings sell device for monitoring human body functions and analyze the individual effort by using GPS, Heart rate and Blood pressure monitoring during the programmed jogging, cycling, skating etc.
General exercising data can be transmitted and stored using for instance Sports Tracker with Android or Windows connection. This solution is excellent for personal training and mental motivation, but it is not suited to support the control of sports gear or equipment, such as bats, sticks, clubs etc.
The sensor device comprising a motion sensor module included in the multilayer film may be used for such purposes. The key issue is in measuring forces, for example when hitting a ball or a puck, simultaneously the speed is registered for comparison a further use. The basic idea is in attaching a device having preferably several sensors, such as 3-6 types of sensors, to the tool, with which the game is played, or to any other equipment. Personal information relating to the performance of a player or exercise may be collected, including the speed and the movement of the gaming means, such as a hockey stick, a bat, a racket or the like, which information may be used to monitor the playing technique of an individual.
Ice hockey is a useful general example of sports and related applications, and the other sports and gaming sectors may have modified units with additional or variable measurements and data handling. Golf club version may be linked to weather services and may support in selecting of the club type during the game. Golf version may have mobile contact to Android phone in order to collect and save data of each golf field and guide the player for improved game. These features may be also applied to the other types of sensor devices discussed herein.
Golf version has emphasis on altitude alteration, which is not the case in ice hockey; another factor is wind, which affects the ball in the air. The key issue is anyhow the same: measured force of the ball contact registered to individual spot in relation of the measured conditions by each individual golf course and hole. To learn the golf game and to improve the skills as well as collecting new documented data is the number one issue of this invention; it causes positive feelings, communication and successful holidays and also prevents fooling and false game by registering all individual strokes. Intelligence in golf is something, that is needed to tempt younger generations to golf courses as they are not much interested in club culture, but would enjoy green surroundings and fresh air combined with intelligence. The invention could be useful in mental issues as well offering new topics. Baseball and Finnish baseball could be involved by implementing intelligence into bats: the bat could send data and show the flying ball right from the strike. Each player could also obtain the results of their playing after each game as a feedback for preparing to the next game. Examples of gaming applications include ice hockey, bandy, baseball (including the Finnish version), tennis, badminton, golf, floor bandy and the like.
In one embodiment the sensor device comprising a motion sensor module connected to the conductors of the multi-layer film is arranged to be attached onto a gaming or sports means or gear, such as a club, a stick, a mallet, a racket, a bat, an oar, a paddle, a ski, a skate, a shoe, a glove or the like used in the game or any other sport or exercise. The terms sports gear, sports equipment, gaming means and sport means as used herein may be used interchangeably and are intended to cover all the examples disclosed herein. The terms apply to all sports means wherein the data relating to the movement of the means is usable for analyzing the sports event. In these embodiments exercise data may be collected including accurate movements of the gaming or sports means. In one example two or more sensor devices are attached to the gaming or sports means, preferable at different locations, for example at a distance of 10-50 cm. This allows gathering information from different locations of the gaming or sports means, which enables forming a better model of the movements of the means during the gaming or sports event. In one example two sensor devices are attached to the gaming or sports means. One of them may be a 3-D practicing sensor and the other one may be a 9-D unit programmed to send data. One example of a commercial 3-D sensor is H3LIS331 DL by STMicroelectronics. One embodiment provides a sports gear or a sports equipment comprising the sensor device of the embodiments attached. The sports gear or equipment may be a stick, a bat, a club, a racket, an oar, a paddle, a ski, a skate, or the like, such as described in this disclosure. In general such a sports gear or equipment may be a handheld gear or equipment, a wearable gear or equipment, a projectile gear or equipment, or any other suitable gear or equipment. Examples of handheld gears or equipment include (ice) hockey sticks, baseball bats, cricket bats, golf clubs, tennis rackets, paddles, and mallets. Examples of wearable gears or equipment include helmets, shoes, gloves, wrist devices, clothes, protective gear. Examples of projectile gears or equipment include balls, (hockey) pucks, discus, shuttlecocks or birdies, javelins, frisbees, and the like.
One example provides a hockey stick comprising the sensor device of the embodiments. The hockey stick, more particularly ice hockey stick, may be for example wooden or it may be made partly or completely of composite material(s), such as carbon fiber composite. One example provides a cricket bat comprising the sensor device of the embodiments. Cricket bats are usually wooden bats which have a shape suitable for attaching a sensor sticker to the back of the bat.
One example provides an oar comprising the sensor device of the embodiments. One example provides a paddle comprising the sensor device of the embodiments. Oars and paddles may be used in training and exercising wherein the movements and forces thereof may be detected and measured. The sensor devices may be used to optimize the use of the oars or paddles in rowing and paddling. A water-proof sensor device may be attached in optimal position to monitor and transmit the data of action. Such constructions are useful for example in rowing competitions where ideal effort can lead to positive result.
The sensor device for such sports gear may contain adhesive for attaching the device to the sports gear, for example pressure sensitive adhesive or other adhesive. The sensor device may be also provided in a casing or in other shell. The sports gear may have an aperture, a slot or any other means for receiving the sensor device. The sensor device may also be integrated to the sports gear, for example during manufacturing. The sports gear may therefore be provided as equipped with the sensor device.
One embodiment provides an arrangement comprising the sensor device, or a sports gear comprising the sensor device, and an external device arranged to communicate with the sensor device wirelessly, as described in previous.
Figure 5 shows an example wherein two sensor devices 51 , 52 at about 20 cm distance from each other have been attached to a hockey stick 50 by using pressure sensitive adhesive. The sensor devices 51 , 52 contain an additional layer of closed cell plastic 54, which acts as shock-absorbing material and covers the electronics and a disc battery. The device contains a Bluetooth antenna 53 formed by conductive carbon print, and another antenna (not shown) for passive RFID.
Figure 6 shows a prototype of a sensor device for an ice hockey stick comprising the electronics described herein, such as a Bluetooth module 20 connected to an antenna 22, a motion sensor 18, and a relatively large 200 mAh rechargeable battery 19. The sensor device includes a USB connector 28 at the left for charging the battery. When charging the battery it is necessary to plug a USB cord to the connector, which causes tension and other forces to the area of the multi-layer structure wherein the connector is attached to. Therefore it is important that the connector, as well as the other components, are securely bonded to the structure.
Ice hockey is a good example of a game requiring a lot of practice right from the start. There are special schools, where to train and wherein the attachable sensor device of the embodiments allows coaches and trainers collect individual information of handling the stick. This helps in building up personal training plans for players and also helps in selecting the players for different rolls in the future team. Another example is using the "intelligent stick" during the games and then monitoring collected data afterwards. Still another example would be rather commercial; in NHL and KHL the key players would have their action shown on big screen - particularly, when they score a goal. This kind of function may be used for example in baseball, golf and tennis, having numeric figures shown to the audience and also in some cases having a virtual player included to televised action.
In one embodiment the sensor device comprising a motion sensor module or geographical sensor module connected to the conductors of the multi-layer film is provided in a credit card size, such as format ID-1 size (85.60 mm χ 53.98 mm), of format ID-2 size (105 x 74 mm), or format ID-3 size (125 x 88 mm). Such a sensor device may be provided with out without the adhesive. The standard credit card size enables including the device into a wallet or the like, and it may be used to track the location of the wallet. The thickness of such a device may be in the range of 1 .1-1 .3 mm, such as about 1 .2 mm. The device may be arranged to provide the location data wirelessly, and it may be monitored using software run in a mobile terminal and/or in a server, such as a cloud server.
One embodiment provides a method for detecting the movements of a target or an object having the sensor device described herein attached thereto, the method comprises
-wirelessly connecting the sensor device to a remote device, and
-receiving data indicating the movement of the target or the object from the sensor device in the remote device, and interpreting the data to detect the movements. The target or the object may be any target or object described herein, such as the gaming or sports means, gear or equipment, packet or parcel, vehicle, or any other suitable target. The sensor device may be attached to the target or the object by adhesive, such as pressure sensitive adhesive, or it may be integrated into the target, for example in may be laminated in the target or the object. The data indicating the movement of the target or the object may include geographical data or motion data, such as acceleration and/or other data, and time data, such as motion or geographical data combined with a corresponding time stamp. A plurality of such data sets may be interpreted, i.e. converted into a user-readable form, to obtain a map or other graphical presentation, or a model or a dataset, such as a table, depicting the movement of the sensor device, and accordingly the target or the object. The received data indicating the movement of the target or the object may be converted into user-readable form in the device or in another device, such as in a remote computer, for example a server, such as a cloud server, wherefrom the processed data may be sent to a remote device. The user- readable form may be text, number, a list, a table, a graph, an animation or a combination thereof. For example statistics may be created and optionally automatically saved in a remote database. The data received and collected may include data such acceleration in one or more dimensions, geographical location, time stamp and the like. Information may be derived from the data such as the speed of the target or the object, such as a gaming device, the geographical location of the target or the object at a time point and the like. A model of the actual gaming or sports event may be created, which may be used for estimating the performance of the person playing or exercising and optionally to find the weaknesses in the performance which need improving.
One embodiment provides a sensor device comprising one or more camera module(s) and preferably means for wireless communication connected to the conductors of the multi-layer film. The camera is arranged to provide still images or video, or both. The lens of the camera may be exposed through a corresponding aperture in an outer film or layer, or the lens may be covered with a transparent film. Such a sensor device may be used for example as a surveillance device, which may be attached easily to a desired location, for example by using an adhesive included in the device. Such a sensor device may also contain a sound module configured to receive sound. The microphone of the sound module may be exposed through a corresponding aperture in an outer film or layer, or the microphone may be covered with a transparent film, which may be perforated. The detected image, video and/or sound may be wirelessly sent to a remote device wherein it may be monitored and/or stored.
One example provides such a device including a camera, means for wireless communication, antenna and a power source. The maximum size of the device may be about 30 x 60-50 x 100 mm and the thickness of the laminate about 2-3 mm. The device may be implemented in a transparent laminate, or a partially transparent laminate, with adhesive back, which may be adhered for example to windows of houses and summer cottages in order to alarm if the window is broken. It may also take a still photo or record video of a subject, such as an intruder.
One example of a multi-layer structure is presented in Figure 1 :
10 PET-film top 50 microns
1 1 Treatment at the back of the film
12 Conductive carbon print 20 microns
13 Anisotropic print 20 microns
18, 19 Electronics including sensor (18) and energy source (19) 0.95-2.0 mm
14 Adhesive layer to cover the gap
15 PET-film
16 Contactive adhesive 5-6 microns
17 Release paper 90 microns
One example provides an ice hockey stick unit, wherein the size of the individual ice hockey stick unit is 50 x 100-140 mm. The unit, i.e. the sensor device, may contain one or more layers of protective material, such as shock- absorbing material, for example foamed material, closed cell plastic, polyurethane, fibrous material or a combination thereof. The foamed material may be a foamed layer as described herein. A layer of protective material may have a thickness for example in the range of 100-3000 μιτι, 100-2000 μιτι, or 100-1000 μιτι, such as 100-500 μιτι. A release liner is stripped off to reveal a pressure sensitive adhesive, and the sensor unit is adhered to a stick. To attach the device to an ice hockey stick, it has to be flexible and include adhesion properties, but it also has to be rigid on the areas of electronics. Further, the device must be bendable round the 90 degree angles without cracking the printed circuit. The selected films are both flexible and shock resistant. The conductive and the anisotropic print are extremely flexible having flex crack resistance tested with 1000 times 180 degree folds without breakages. The challenge is in positioning electronic units on both sides of the stick in such a way that application of ready-made sensor unit is simple and needs no precision tools, because the actual attachment of said device is taken care manually. In one example a Bosch BMX055 sensor module was used in a device containing the following electronics.
LGA package: 3 x 4.5 x 0.95 mm (the current size of sensor itself)
Coin cell unit: 25 x 25 x 2.0 mm
Mobile unit: 25 x 50 x 4.5 mm (optional for professional use)
In another example Bosch BNO055 was used, because of availability and options it offered. The first pilot versions did not work due to ten times higher output request, that was specified by the manufacturer. So instead of an easy set-up there was a long way to go before the sensor was able to register and feed data. Flexible electronics were combined with BNO055 to make it work technically and the system was combined with tailored software in such an order, that not only the sensor collects requested data but also feeds it with application support to portable device running an application which provides visualization and monitors the qualities in the game in question, such as use of a hockey stick, other bats or the like.
Energy consumption level is to be minimized. The sensor device may be programmed to switch to a low-power mode, when it is not in actual action. This allows prolonging of active use with tenfold and reduces the need of charging of cells with 75-80%, meaning the average of 120 h of active playing. The technology is not limited to games only, it can be used for example in packaging - to prevent theft or loss of packed goods. The technology may involve electronics suppliers and also their software for using it, or other software. That may also include mobile applications. In one embodiment the sensor device comprising a motion sensor module connected to the conductors of the multi-layer film is arranged to be attached to an item used for transport, such as onto a vehicle, such as a bicycle, moped, motorcycle, car, snow scooter, boat, drone or the like. The device may be activated, when the mode of transport is made passive. If the vehicle is moved while in this mode, the tracking is activated and data sent to selected target device. Application of this solution reduces theft risks in long term, when the knowledge of tracking risks gets known to thieves.
In one embodiment the device is attached to stock deliveries, such as medicine stock, deliveries to prevent stealing and loss of items on the way to target, such as stores or pharmacies. The stores or pharmacies also gain a control of goods they receive. The device may be also attached to good in a warehouse. In one embodiment the sensor device comprising a motion sensor module connected to the conductors of the multi-layer film is arranged to be attached onto a package, such as a packet or a parcel, such as a packet or a package in a storage or a packet to be mailed. One example of such a package is a package of medicines, which may be tracked from a factory to a wholesale storage and further to pharmacies, other stores and hospitals. Other packed goods may be tracked as well. Information may be collected, such as the location of the package, temperature, and the like. For example falling of the package may be detected, or exposure to an undesired temperature. The tracking system may be used for example to control original deliveries and also to prevent illegal copies or generic versions of drugs entering to legally acting pharmacies.
Further examples include a sensor/tracker for packages of electronics, cosmetics and spare parts. Sensing is split in two functions: cardboard or corrugated boxes have a hidden printed antenna attached with a tracker and the actual product is attached with an active device to control the whole delivery chain. Intelligent tracking system collects data during the delivery and if any damage of goods is noticed, data in 9-D form, for example, is available to find reasons for it.
In one example a sensor equipment with power source is laminated between polymer layers and connected with two-layer carbon print. The first layer has xyz-conductivity for RFID and power supply purposes and the second layer has z-conductivity to amorphous connecting with heat bonding the electronics to said printed carbon carbon/silver dispersion lines. The top surface comprises a polymer film having a thickness in the range of 23-100 microns and a polymer coating for heat bonding the further layers, out of which carbon ones are coated to the back side of the said layer and electronics with power source are bonded before their back is covered with a third polymer layer in molten form adhered to heat resistant film of thickness in the range of 23-50 microns and coated on its outer surface with contactive adhesive, on which a removable release paper or film is attached for protection. The layers and printed structures may vary in thickness, but the set-up has generally similar functions in all applications. Top surface may be PET-, PEN- or PES-film for most applications providing a support layer for printing conductive layers. The conductive layers are made of carbon dispersed in polymer dispersion, such as a dispersion of acrylic, styrene acrylic and/or ethylene acrylic acid polymer(s). In one embodiment the high conductivity carbon with nano sized particles (15-30 nm) in the xyz-conductive layer is provided in acrylic styrene copolymer dispersion, generally having film forming temperature in the range of 0-20°C. In one embodiment the anisotropic carbon with larger particles (1-20 microns) is provided in EAA or similar dispersion. The dispersions may be modified with long chain alcohol and other necessary additives in accordance with conversion machine requirements. The electronic units are bonded to conductive print using anisotropic layer and heat. The anisotropic coating is non-conductive in XY-directions.
The back layer may be polyimide, PET-, PEN- or PES-film having optimally polyolefine layer for internal lamination and having sticking layer with release film or paper protection to be stripped off, when adhering the device to use. The middle of structure includes a measuring device with energy source and is connected using the carbon coatings of the laminate. Manufacture
One embodiment provides a method for manufacturing a multi-layer film, the method comprising
-providing a support layer,
-providing a first dispersion comprising carbon nanoparticles and polymer, such as acrylic dispersion polymer,
-proving a second dispersion comprising carbon particles and polymer, such as acrylic or EAA dispersion polymer,
-printing a xyz-conductive layer onto the support layer by using the first dispersion, and
-printing a z-conductive anisotropic layer onto the xyz-conductive layer by using the second dispersion
to obtain the multi-layer film
One embodiment comprises providing an amount of non-nanoparticulate carbon in the first dispersion or mixing an amount of non-nanoparticulate carbon to the first dispersion, such as carbon having an average particle size in the range of 1-20 μιτι, such as 1-15 μιτι,
The amounts of ingredients disclosed herein add up to 100% of the total dispersion by optionally including added water or any other aqueous solution, or other ingredients, which may be ingredients, such as additives, generally used in such dispersions.
The conductive layers may be printed by providing specific print dispersions, preferably aqueous dispersions. In general a dispersion A for printing the xyz-conductive layer may comprise 10-40% (w/w) of polymeric dispersion and 50-80% (w/w) of nanoparticulate carbon dispersion. In one embodiment a dispersion A for printing the xyz-conductive layer comprises (w/w):
Polymeric dispersion 15.0-20.0%
Nanoparticulate carbon dispersion 70.0-75.0% In one embodiment a dispersion A for printing the xyz-conductive layer comprises (w/w): Polymeric dispersion
Nanoparticulate carbon dispersion
Propylene glycol
Isopropanol
Ammonia (25% aqueous solution)
Water
Thickener The polymer may be any suitable polymer, one or more, such as heat curable or otherwise cross-linkable dispersion polymer, as described herein. The polymer(s) may be provided as a dispersion polymer composition. In one example the polymeric dispersion is acrylic dispersion, such as acrylic styrene copolymer dispersion or acrylic styrene polyurethane dispersion. The dispersion may contain 40-65% (w/w), for example 52-66% (w/w), of water.
The inventors carried out extensive tests trying to find out suitable polymers for the dispersions. One problem was the precipitation of a combination of polymers. Finally it was surprisingly found out that a combination of two different types of acrylic styrene copolymers, which are not known to be compatible, provided excellent properties.
In one embodiment the polymeric dispersion comprises two polymers having a different minimum film forming temperature and/or glass transition temperature, such as one having non-overlapping ranges. In one embodiment the polymeric dispersion comprises two polymers having a different minimum film forming temperature. In one embodiment the polymeric dispersion comprises two polymers having a different glass transition temperature. In one example one polymer has a minimum film forming temperature in the range of 0-20°C and the other has a minimum film forming temperature in the range of 70-100°C. In one example one polymer has a glass transition temperature in the range of 5-20°C and the other has a glass transition temperature in the range of 70-120°C. In one embodiment these polymers are acrylic styrene copolymers. In general the carbon material may be provided as an aqueous dispersion, for example an aqueous dispersion of graphite and/or carbon black. In general an aqueous dispersion containing 65-70% of water is used. The carbon black may be a powder, granule, or a combination thereof. In some aspects, the carbon black may form aggregates and agglomerates. The carbon nanoparticles may have an average diameter or particle size in the range of 5-100 nm, such as 5-60 nm or 10-50 nm, more particularly 15-30 nm. In one example at least 90% (w/w) of the carbon material has said average diameter, or at least 95% (w/w). The carbon material may be for example an aqueous dispersion of graphite and/or carbon black. Examples of commercial products which may be used include Timrex ©NeroMix E series (for example E12) by Imerys. The non-predispersed conductive carbon products are preferably powdered/granulated to avoid dusting problems in dosing.
Particle size as used herein may refer to particle diameter, such as to the diameter of a carbon nanoparticle or a non-nanoparticular carbon particle. However, particles are usually present as an ensemble (collection) of particles. Real systems are practically always polydisperse, which means that the particles in an ensemble have different sizes. The notion of particle size distribution reflects this polydispersity. Therefore a certain average particle size for the ensemble of particles may be referred to. The terms average particle size, mean average particle size and average particle diameter used herein are meant to describe the same feature of a particle and therefore may be used interchangeably.
As used herein, "powder" or "powdered" refers to a collection of fine, freely flowing particles. A "granule" or "granular" refers to a macroscopic agglomerate of interacting particles, which particles itself may be nanosized, such as having a particle size in the range of 10-20 nm, or 15-20 nm. Both graphite and carbon black can exist in granular and powdered forms.
Carbon granules and powders may be specified using two measured properties according to standards D6556 and D2414. D6556 norm is split in two versions: NSA Surface area and/or STSA Surface area. Both are reported in square meters/gram and finer particles obtain larger figures in this test.
In one example tests were carried out using two Conductex products having NSA STSA figures 185/125 and 55/50. The latter one was easier to disperse into water using equal solids amounts. This is probably because of lower force of the mixing plate in breaking the granules, which have less surface area in primary particles. D2414 norm is used in the measurement of oil absorption. The selected Conductex granules had absorption 141 and 170 cubic centimeters / 100 grams granules. These figures were close to each other and obviously not relevant in dispersing the granules into water. Tests have proven that the final coating product should have as little amount of water involved as possible. It should be preferably produced without polymeric thickeners, just using the thickening effect of carbon granules splitting into primary particles in the water/additives/polymers mixture. NeroMix E-12 has 30.3% of carbon in the mix of additives and water; laboratory comparison indicates 6.8-7.0% of wetting agent used and the rest is water. For carbon mixes there is a maximum "saturation" level of carbon, that still allows the mixing to work an also the use of the mixture in further processes.
The complete dispersion A, or the polymeric or the carbon dispersion may contain one or more auxiliary agents to facilitate the formation of the dispersion and to enhance the properties of the dispersion, such as one or more of dispersants and/or surfactants.
"Dispersant" or "dispersing agent" refers to a chemical compound that assists in keeping the particles of a material separated from one another when they are distributed in a medium in which they would otherwise agglomerate. Dispersants may also act as wetting agents. Wetting agents are substances which decrease surface or interfacial tension and improve the wetting of solids, thereby acting as surfactants. Dispersing agents prevent particles flocculating by various mechanisms. In the dispersion process the solid particles are first wetted. To lower the surface or interfacial tension of the liquid to enhance the wetting, a wetting functionality is required. A wetting agent in general contains a hydrophobic tail and a hydrophilic head. As the solid particles attract each other, energy is needed to separate the particles from each other in the next step of the dispersion process to prevent flocculation. Dispersing functionality is required to prevent the flocculation and to stabilize the particles by various mechanisms, such as electrostatically or sterically.
Dispersants may be ionic (anionic or cationic), non-ionic, or amphoteric. Without wishing to be bound by theory, the charged groups to within the ionic dispersant coats a particle, and imparts a net charge to the particle surface. Here, the net charges on all like particles are all positive or all negative, the particles will therefore repel one another. Meanwhile, also not wishing to be bound by theory, a non-ionic dispersant can include a high molecular weight polymer with a polar group. The polar group interacts with the particle to be dispersed through hydrogen bonding, dipole-dipole interactions, London dispersion forces, and/or van der Waals interactions, while the high molecular weight component possesses sufficient bulk to achieve separation of dispersed particles due to steric effects.
A dispersing agent may be provided in a dispersion. The dispersing agent may be an ionic dispersant, such as an anionic dispersant, for example polycarboxylic polymer, or a nonionic dispersant, for example polyurethane or polyacrylate. The amount of the dispersing agent may be in the range of 5-30% (w/w) of dry weight of the carbon dispersion, such as 5-15%, 5-20%, 10-20%, 10-15%, 15-30% or 20-30%. A "dispersing and wetting additive" comprises both wetting and dispersing functionalities in one substance or product, such as in one molecule. Such additives are amphiphilic compounds, i.e. they are both hydrophilic and lipophilic. Their structure allows them to enable or facilitate dispersion of pigments and fillers in the solvent. The dispersing and wetting additives may be categorized according to the head group as anionic, cationic, amphoteric and non-ionic types. A dispersing and wetting additive contains one or more adhesion group(s), which have an effect to the dispersing and wetting effectiveness. Adhesion groups, also called as pigment affinic groups, are functional groups which have a special affinity for pigment surfaces. The pigment affinic groups cause adsorption of the additives upon the pigment surface. A pigment affinic group may comprise carboxylic acid, amine, such as tertiary amine, isocyanate or derivatives thereof, or a salt structure which is produced by neutralisation of amine moieties with a mixture of acid- functional polymers. The dispersing and wetting additives may be high molecular weight polymeric dispersing and wetting additives, which contain a considerably large number of pigment affinic groups. Such additives provide complete deflocculation and differ from the conventional low molecular weight analogs through molecular weight sufficiently high to allow the attainment of resin-like character. The dispersion may also comprise one or more surfactants. The surfactant(s) may also act as emulsifier(s). The surfactant may be an anionic surfactant, a nonionic surfactant or a combination thereof. Examples of nonionic surfactants useful herein include alkoxylated fatty acid esters, alkoxylated fatty alcohols, alkyl glucosides, alkyl polyglucosides, amine oxides, cocoamine oxide, glyceryl monohydroxystearate, glyceryl stearate, hydroxy stearic acid, lauramine oxide, laureth-2, polyhydroxy fatty acid amides, polyoxyalkylene stearates, propylene glycol stearate, sorbitan monostearate, sucrose cocoate, sucrose esters, sucrose laurate, steareth-2, and mixtures thereof. Examples of commercial nonionic surfactants include Triton® X-180, Triton® X-193, and Triton® X-405 available from Dow Chemical; and Empilan® MAA and Emplian® NP-S from Albright and Wilson, Ltd. In one example the nonionic surfactant is an alkoxylated fatty alcohol. In one example the alkoxylated fatty alcohol is a C9-C1 1 alcohol having an average of approximately 6 moles of ethylene oxide per mole of alcohol, having a density of approximately 0.976 kg/I, having an HLB number of about 12.5, and having a kinematic viscosity at 40° C. of about 21 cSt, such as, for example, TOMADOL® 91 -6 manufactured by Air Products or NEODOL® 91 - 6 manufactured by Shell Chemicals. The surfactant may be an anionic surfactant. Examples of anionic surfactants include alcohol phosphates and phosphonates, alkyl alkoxy carboxylates, alkyi aryl sulfates, alkyi aryl sulfonates, alkyi carboxylates, alkyi ether carboxylates, alkyi ether sulfates, alkyi ether sulfonates, alkyi phosphates, alkyi polyethoxy carboxylates, alkyi polyglucosides, alkyi polyglucoside sulfates, alkyi polyglucoside sulfonates, alkyi succinamates, alkyi sulfates, alkyi sulfonates, aryl sulfates, aryl sulfonates, fatty taurides, isethionates, N- acyl taurates, nonoxynol phosphates, octoxynol phosphates, sarcosinates, sulfated fatty acid esters, taurates, and mixtures thereof. One example of a commercial anionic surfactant is the sulfated fatty acid known as Modical® S, manufactured by the Henkel Corporation.
The dispersion may also comprise one or more stabilizer(s), chelating agent(s), defoamer(s), filler(s), biocide(s), or other additives.
In one example, especially to enhance the stability, the dispersion is manufactured in three phases, such as with the following procedure:
1 . Carbon dispersion is mixed with slow speed dispersing with polymer dispersion having pH adjusted with ammonia. 2. Coalescing agent and retarder are added with antifoaming agent using slow speed mixing. Powder form conductive non-nanoparticulate carbon is dosed to mixer, speeding the mixing head up to 1200-2000 rpm in order to thicken the dispersion with carbon instead of rheology modifier or thickener, such as polyurethane thickener.
3. The final phase of dispersing is done with slow speed, adding anti foam agent and letting it act in order to obtain foam free dispersion for distribution.
In one embodiment a dispersion A for printing the xyz-conductive layer comprises (w/w):
Polymer dispersion: 12.0-22.0%
Nanoparticulate carbon dispersion 52.0-70.0%
Carbon powder 5.0-10.0% In one embodiment a dispersion A for printing the xyz-conductive layer comprises (w/w):
Polymer dispersion: 12.0-22.0%
Nanoparticulate carbon dispersion 52.0-70.0%
Carbon powder 5.0-10.0%
Propylene glycol 3.0-5.0%
Isopropanol 1 .0-3.0%
Aqueous ammonia 0.1-0.2%
Antifoam 0.1-0.3%
Using conductive carbon powder or granulated particles as thickener make the dispersion stable and improve conductivity of 20 micron coating by 45- 50%. The carbon particles will absorb the free water from the mixture. It was experimentally shown that the calculated formula works as was predicted at least for the used carbon species, such as NeroMix E-12 supplemented with fully dispersed Ensaco 250R. The final product reached the final stabile viscosity during 24 hours without synthetic thickeners, which were required in the prior art formulations.
In general a dispersion B for printing the z-conductive anisotropic layer may comprise 50-90% (w/w) of polymeric dispersion and 5-20% (w/w) of carbon dispersion. In one embodiment a dispersion B for printing the z-conductive anisotropic layer comprises (w/w):
Polymeric dispersion 80.0-85.0%
Carbon dispersion 6.0-10.0%
The polymer may be any suitable polymer, one or more, such as heat curing dispersion polymer, as described herein. The polymer(s) may be provided as a dispersion polymer composition.
In one embodiment a dispersion B for printing the z-conductive anisotropic layer comprises (w/w):
Acrylic dispersion 80.0-85.0% Carbon dispersion 6.0-10.0%
In one embodiment a dispersion B for printing the z-conductive anisotropic layer comprises (w/w):
Acrylic dispersion 80.0-85.0%
Carbon dispersion 6.0-10.0%
Propylene glycol 4.0-5.0%
Isopropanol 2.0-2.5%
Ammonia (25% aqueous solution) 0.15-0.25%
Thickener 2.0-4.0%
The dispersion B may contain similar auxiliary agents as explained for the dispersion A in previous. The acrylic dispersion may be for example acrylic styrene copolymer dispersion or acrylic styrene polyurethane copolymer dispersion. The polymer(s) may be provided as a dispersion polymer composition.
In general, the carbon used in the z-conductive anisotropic layer may comprise granulated particles of conductive carbon, for example pressed carbon pieces. The carbon particles may have an average diameter or size in the range of 1-20 μιτι, such as 1-15 μιτι. In one example at least 90% of the carbon material has said average diameter or size, or at least 95%. The carbon used in the z-conductive anisotropic layer may comprise granulated particles of conductive carbon, for example pressed carbon pieces. The carbon material may be provided as an aqueous dispersion, for example an aqueous dispersion of graphite and/or carbon black.
Examples of commercially available suitable carbon include Imerys Ensaco 250G (granular, particle size of about 45 μιτι) and granulated Raven grades by Birla Carbon. An ideal granulate is non-dusting, and the used G grades are close to such materials. The particle size may be adjusted by dispersing into aqueous solution is such way that the dispersing process is interrupted in a controlled way, preferably to obtain agglomerated carbon having the desired particle size. In such case a z-conductive product is obtained, which may be used in several applications and has several advantages. One embodiment provides an aqueous carbon dispersion comprising carbon powder and wetting agent. The carbon powder comprises carbon granules and/or aggregates having an average particle size in the range of 1-20 μιτι. This carbon dispersion may be used for providing the non-nanoparticulate carbon discussed herein. In one example the dispersion in anionic dispersion.
This aqueous carbon dispersion may be manufactured from carbon agglomerates, such as granules or particles, having a larger average particle size, such as an average particle size in the range of 1-50 μιτι, or 10-50 μιτι, for example 20-50 μιτι. The particle size is adjusted by dispersing the granules into aqueous solution to disintegrate the agglomerates is such way that the dispersing process is interrupted to obtain agglomerated carbon having the desired particle size in the range of 1-20 μιτι.
In one example the carbon dispersion formulation comprises (w/w):
Water 52-76%
Wetting/dispersing agent 4-10%
Carbon 20-40%
The wetting agent may be any suitable wetting agent. In one example Disperbyk-160 was used as a wetting agent, which is a solution of a high molecular weight block copolymer with pigment affinic groups.
One embodiment provides a method for manufacturing a conductive carbon dispersion, the method comprising
-providing wetting and/or dispersing agent(s) in aqueous solution,
-providing carbon granules having an average particle size in the range of 1- 50 μιτι, such as 10-50 μιτι, for example 20-50 μιτι,
-forming a mixture comprising 20-40% (w/w) conductive carbon granules; 4- 10% (w/w) wetting/dispersing agent and 52-76% water (w/w),
-mixing the mixture, preferably at 100-500 rpm, preferably for 10-20 minutes, to obtain a dispersion, preferably until a viscosity of 5000-6000 cp of the dispersion is obtained,
-adding water, preferably 3-10% (w/w) of the total dispersion, -mixing the dispersion, preferably at 500-2000 rpm, for 15-40 minutes to obtain a conductive carbon dispersion having an average carbon particle size in the range of 1-20 μιτι, preferably until a viscosity of 1000-1500 cp of the dispersion is obtained.
The wetting and/or dispersing agent(s) may be initially mixed with water, if necessary, and provided as an aqueous solution. The carbon granules may be then added to the aqueous solution of wetting/dispersing agent(s). This facilitates mixing and dispersing of the carbon granules to the solution.
In the first mixing phase the carbon granules may be initially mixed at about 100-300 rpm, after addition to a mixing vessel or container, and the mixing speed may be increased gradually to about 500 rpm in 10-20 minutes. The mixing may be carried out by using a mixer, such as a coaxial shaft mixer. In one example the mixer has one or more blades, such as a disc type blade, which may have saw tooth type of structures. In the first mixing the homogeneity of the dispersion is obtained, and for example the carbon particles from the surface are mixed into the dispersion. Water is usually added before the second mixing phase to lower the viscosity, for example about 5% (w/w) of water.
In the second mixing phase the mixing speed is increased. The mixing speed may be adjusted to 1000-1500 rpm. The mixing may be carried out until a viscosity of 1000-1400 cp is obtained and/or until the desired particle size is obtained. The obtained dispersion may be stabilized for 12-48 hours, for example in a container, which may be same or different than what was used for mixing.
The dispersing process may be enhanced by recycling the mixture through a filter back to the mixer blade. In one example the aim is to pump 1000 liters of the mixture 6 to 10 times during two minutes to obtain evenly distributed particles and the final viscosity of the dispersion.
Additives may be added to the obtained dispersion. In one example the method comprises adding one or more polymer(s) to the dispersion, preferably by mixing, for example in a similar process as described. In one example the method comprises adding one or more retarder(s). In one example the method comprises adding one or more thickener(s).
The dispersion may be finished by thickening in slow mixing until a printer viscosity is obtained. The viscosity may be adjusted to the range of 200-300 cp. The viscosity may be optimized, for example for 24-48 hours. One or more thickener(s) may be added for example in the range of 1-2.5% (w/w) of the total dispersion to obtain an elevated viscosity, such as a viscosity in the range of 1500 cp or more, for example 1500-2000 cp.
The viscosity may be measured by using any suitable method and device known for a person skilled in the art, such as by using a viscometer. The viscosity is presented as centipoises (cp), which equals to milllipascal seconds (mPa-s). The viscosity may be measured at room temperature (RT) and/or at atmospheric pressure.
In one embodiment the thickener comprises acrylic/polyurethane thickener. The dispersion may be an anionic modified acrylic styrene copolymer dispersion.
One embodiment provides a conductive carbon dispersion manufactured with the method described in previous. One embodiment provides a method for manufacturing a multi-layer film as described herein, comprising providing the conductive carbon dispersion as the second aqueous dispersion comprising carbon particles and polymer. One embodiment provides use of the conductive carbon dispersion in the manufacture of conductive coatings or films or multi-layer films. One embodiment provides (conductive) printing ink composition comprising the conductive carbon dispersion. The printing ink composition may be formulated as described herein, as an aqueous dispersion for printing the z conductive layer, oras an aqueous dispersion for printing another type of conductive layer, such as the xyz conductive layer.
The conductive carbon layers described above may be obtained by printing onto the support layer, such as the first polymer layer, such as thermoplastic polymer layer or thermosetting polymer layer, or fibrous or textile layer. Examples of suitable printing techniques include screen printing and flexographic/gravure printing. The dispersions described herein may be directly dried in the printing machine, which simplifies and speeds up the manufacturing process. Screen printing is a push-through process where ink is pushed through a fine fabric screen made of plastic or metal threads. The non-image areas of the screen are covered with a stencil that determines the printed image. The screen is flooded with ink which is pushed through the image areas of the screen by means of a squeegee. Rotary screen printing enables higher printing speeds and increases the print quality. The screen has a cylinder shape and the ink is placed inside this cylinder. The stationary squeegee located inside the cylinder pushes ink through the screen apertures onto the substrate as the cylinder rotates. Reel-to-reel (R2R) screen printing is a printing technique especially suitable for the conductive carbon layers of the embodiments. In general, in a reel-to-reel manufacturing method a film-like circuit board material is handled as long ribbons rolled to coils or rolls. The different manufacturing stages occur in the manufacturing equipment on the straight section arranged between the starting roll and the receiving roll. There can be several successive manufacturing stages. The reel-to-reel technique is well suited to be used when the manufacturing batches are large.
The carbon coatings of the embodiments are all aqueous and need drying when coated. Their major difference to solvent-based ones, which dominate the market, is a short drying cycle. DuPont and Henkel recommend 24 hours drying before applying second print. Both xyz-conductive and anisotropic coatings of the embodiments are usually dried for 30-60 seconds when using a standard three segment oven of a screen printing machine. The oven has three chambers, of which the first is most important for film forming; it blows heated air through having a temperature of 80-100°C. The second one is sucking air and blowing it off from the section, in general at a temperature range of 55-70°C, to allow for the third one to cool down the surface of conductive print to 30-45°C and down to room temperature. All this is possible due to the aqueous and non-hazardous carbon formulation. The carbon layers may be heat-treated to finalize the structure. A structure will be obtained having enhanced flexural resistance and other structural and functional features described herein. The heat treatment may be carried out after printing. The temperature used may be in the range of 80-100°C, preferably for a time of 10-30 seconds. The heat treatment may be carried out in an air flow. In one embodiment the method comprises heat-treating the printed conductive layers at a temperature in the range of 80-100°C, preferably for a time of 10-30 seconds. In one embodiment the method comprises providing an adhesive, such as a pressure sensitive adhesive, and applying the adhesive onto a surface or a side of the multi-layer film, such as onto the support layer or onto another layer, such as onto a protective layer on top of the z-conductive layer. Examples
The development of the conductive coatings was challenging. The first conductive dispersions had large particle sizes (12-20 microns) and caused problems in printing with screen. They were later dispersed with premixed smaller sized carbon mix, but still some printing problems existed. Conductivity with 20 micron coating was acceptable for printing antennas and resistors in intelligent packaging. Original formulation included Timrex granules with Timcal dispersion mixed into acrylic copolymer dispersion having additives included. These old formulations were tested by printing companies but due to problems in the properties of the materials, they were rejected.
In the present embodiments the problems were solved. In one example the formulation for preparing the xyz-conductive layer is as follows for conductivity of 50 ohms/square:
Labseal RF 50 (w/w):
Acrylic dispersion 17.5% (NeoCryl A-1092/DSM)
Carbon dispersion 72.5% (NeroMix 12 Imerys/Timcal)
Propylene glycol 4.5% Isopropanol 2.0%
Ammonia (25% aqueous solution) 0.1 %
Water 1 .3%
Thickener 2.1 % (50/50 demineralized water/Rheotec)
In one example the formulation for preparing the z-conductive layer is as follows:
Labseal Al B anisotropic dispersion (anisotropic formulation using granulated carbon Ensaco 250 G) (w/w):
Acrylic dispersion 82.0% (EAA/Eastman)
Conductive disp. 8.0% (Imerys Ensaco 250G)
Propylene glycol 4.5%
Isopropanol 2.3%
Ammonia (25% aqueous solution) 0.2%
Thickener 3.0% (50/50 demineralized water/Rheotec)
Dispersing the formulations was carried on using Dispermat AE dissolver device with appropriate stainless steel dissolver disc. This high speed disperser has adjustable speed running a mixing blade with diameter 33% of the inner diameter of mixing vessel. Sawlike disc rotates with selected speed adjustment and causes a flow of liquid, which captures and then splits the agglomerates to particles wetting them completely with polymer dispersion.
The formulation having a premixed nano carbon dispersion mixed with polymer and additives was finalized with dispersing carbon granules in to it in order to obtain suitable viscosity for screen printing. The mixture was prepared to fit screen printing requirements and to offer long term stability without settling problems of particles.
The formulation contained NeroMix E-10 51 %, Ensaco 250G 9% (dry) and polymer/additive blend 40%. Test stripe conductivity was in the range of 100- 120 Ohms/sqr. Production of NF-400
In one example an aqueous carbon dispersion called NF-400 was used as the conductive dispersion of the above formulas. NF-400 was manufactured using carbon granules having the size and shape described in Ensaco 250 G technical leaflet. The formulation is aqueous and includes NeroMix E-12 type additives with water and conductive carbon granules.
NF-400 formulation (w/w):
Water 59.0%
Wetting agent 7.0%
Carbon 34.0%
A manufacturing process and a device for batch production of aqueous dispersion is described in the following. The process includes two phases. The mixing speed is adjusted according to the phase of the process; the first phase involves a rough dispersing of carbon granules in water, that has been modified with wetting/dispersing agent in order to allow dispersing forces to wet the carbon granules and to allow the phase two to be started. Mixing speed is 100 rpm in the carbon dosing phase and adjusted gradually to 500 rpm in 10-20 minutes. Water or water and wetting agent mixture is added.
Mixing of carbon and water may be done using dispersing disc type blade, having saw tooth-type structure. Preferably the saw blade is of special type wherein the saw teeth bent to two directions, and the shaft attached to it using metal discs on both sides. The shaft is rotated with adjustable speed by a 10-20 kW motor for each batch, such as 1000 litres batch. In the tests a coaxial shaft mixer Polimix DPS-OR (Oliver y Batlle) was used. The blade is 30-50% of the mixing vessel diameter. This will gain circulation of the liquid. The height of the blade is 25-30% of the liquid height, measured from the vessel bottom.
In one specific example the mixing process is started by dosing water and dispersing/wetting agent in to the mixer. The blade is running at slow speed, such as at 100-300 rpm, when the carbon granules are added. The viscosity is 5000-6000 cp until 5% of water/wetting agent mix is added.
Agitation at the second phase is started by adjusting the speed of mixing blade to 1000-1500 rpm, when the carbon has been added. The solids content is 35-40% in addition of the carbon, which causes high shear.
Phase two involves a formula: 20-40% conductive carbon granules; 4-10% wetting/dispersing agent and 52-76% water. Phase two is carried on at 500- 2000 rpm speed for 15-30 minutes to obtain a completely dispersed carbon in particulate form.
In one specific example the mixer is adjusted to disperse the viscosity down to 1000-1400 cp. Simultaneously the recycling pump is started to run liquid back at a rate of 1000 1/1-5 min. This phase lasts for 40 minutes and when finished, the liquid dispersion is pumped to a container. The dispersion is kept in the container for 12-48 hours for stabilization. Polymers are added in a next phase using similar mixing process. Most of additives are mixed using medium speed and short cycle of 3-5 minutes. To finish the mixture, addition and slow speed mixing of a retarder and a thickener is carried out for 2-4 minutes. The obtained viscosity is in the range of 200-300 cp.
The elevated viscosity is obtained with an 1-2.5% addition of thickener as finishing. The viscosity is optimized for 24-48 hours and is on level of 1500 cp or more.
It was found out that selecting suitable acrylic/polyurethane thickener mixture for thickening was especially advantageous. Anionic NeoCryl acrylic copolymer dispersions suits fine with polyurethane thickeners. The whole process was found to save 40-50% of dispersing energy requirements due to low viscosity mixing instead of mixing the formulation having a viscosity of 1500 cp or more.
Further, is was also advantageous to calculate the carbon maximum according to NSA STSA comparative data. Surface area (ASTM D6556) and oil absorption (D 2414) may be defined. A high surface area and oil absorption values of the carbon enable using a lower amount of the carbon in the mixture.
An example of carbon is Ensaco 250G 30% mixed with 6% dispersing agent and 64% water. Ensaco 250G is a granulated conductive carbon having surface area of 65 sqm/gram and oil absorption of 190 ml/kg.
Another example of carbon is K Ultra 35% mixed with 7% dispersing agent and 58% water. K Ultra has surface area of 185 sqm/gram and oil absorption of 1 15 ml/kg.
The dispersing/wetting agent may be any suitable wetting agent. Dispersing/wetting agent in the examples was Disperbyk-160, which is a solution of a high molecular weight block copolymer with pigment affinic groups.
NF-400 products may require stabilization before further processing to prevent micro foam build up in final dispersions. Therefore antifoaming agent may be added.
The mixing machine was equipped with adjustable disc speed and programmable inverting unit to obtain 100% stable carbon mixtures. Viscosity was measured with DinCup 4 for 40-45 s. Therefore, in one example the formulation for preparing the xyz-conductive layer is as follows.
Typical example of the obtained NF-400 product has a solid content in the range of 33.0-37.0%, pH in the range of 8.5-9.5%, and viscosity (Brookfield Digital Viscometer, RTV, 2/100) in the range of 100-1000 mPa s. This product includes an anionic emulsion system. The viscosity measured by the Brookfield device is a combination of two viscosities: 100 is flexo version and 1000 is screen version. Brookfield viscometers are suitable and internationally approved for viscosity measurement of viscous liquids.
Labseal RF 50 with NF-400 (w/w): Acrylic dispersion 17.5% (NeoCryl A-1092/DSM)
Nano-sized carbon dispersion 72.5% (NF-400) Propylene glycol 4.5%
Isopropanol 2.0%
Ammonia (25% aqueous solution) 0.1 %
Water 1 .3%
Thickener 2.1 % (50/50 dem. water/Rheotec)
In one example the formulation for preparing the z-conductive layer is as follows:
Labseal Al B anisotropic dispersion with NF-100 (w/w):
Acrylic dispersion 82.0% (NeoCryl A-1092/NeoCryl A-1091 90/10-50/50%) Conductive dispersion 8.0% (NF-100)
Propylene glycol 4.5%
Isopropanol 2.3%
Ammonia (25% aqueous solution) 0.2%
Thickener 3.0% (50/50 dem. water/Rheotec)
Both carbon dispersions represent a new technology step in manufacturing conductive dispersion coatings. There no more exist a need of aqueous carbon formula supplies. Further, risks of transportation damages for example during winter time are eliminated.
There have been problems in using aqueous inks with all kinds of printing presses; polymers tend to dry on printing plates and screens. Conventionally inks have been formulated using retarders and stabilizers. A typical example is Dowfax 2A1 , alkyldiphenyloxide disulfonate, which is combined with long chain alcohols, thickeners, antifoaming agents, pH modifiers, pigment dispersants, carbon pigments and chemical retarders, which caused stability problems in final ink product..
The whole formulation, which had been based on acrylic styrene copolymer emulsion having minimum film forming temperature (MFT) 0-10°C and glass transition temperature (Tg) 6-12°C, had to be reconsidered. MFT and Tg are the turning points, when the polymer is cured to final form.
The present inventor had tested high temperature resistant polymers for paper and board coatings: their MFT was 80-90°C and Tg 95-100°C. Those polymers are normally not designed to be mixed with "softer" ones, but when having a "hard" non-film-forming styrene acrylic copolymer dispersion, which has similar emulsifying system as the "film former" one, it was surprisingly possible to combine the properties of two aqueous systems. According to test results this formulation provided advantageous printing dispersion properties. The dispersion polymers used were anionic modified styrene copolymers (NeoCryl A-1091 ), and modified acrylic styrene copolymers (NeoCryl A-2091 , NeoCryl A-2092, NeoCryl A-1092). Further tests revealed an especially advantageous combination having 5 parts "soft" polymer (NeoCryl A-1092 or A-2092) and 1 part "hard" polymer (NeoCryl A-1091 or A-2091 ). For maximum stability is was especially advantageous to combine A-1092 with A-1091 or A-2092 with A-2091 . In general the hard ones should be preferably premixed with the soft polymer dispersion before adding any other chemicals.
Third test phase involved polyurethane dispersions as polymeric additives into acrylic ones. Results of using NeoRez grades in formulations 10-50% of the whole polymer dispersion combination were stable and when applied on any carrier material, proved to be flexible and well adhering. Elongation at brake was 200+% and adhesion to plastic films was superior, when compared to any acrylic copolymer dispersion. A Scotch tape test on BOPP was excellent. When the formulation were tested accordingly with a screen printing press ideal results were obtained at Merkkimestarit Oy Svecia with semiautomatic printing press.
In one example a stable formulation comprises (w/w):
- NeoCryl A-1092 15.0%
- NeoCryl A-1091 3.0% - Antifoam 0.2%
- pH modifier 0.1 %
- Isopropanol/water 50/50 2.0%
- Propylene glycol 4.0%
- Retarder 4.0%
- Cond.. carbon slurry 71 .7%
In development phases there have been following sizes of mixing units performing similar dispersion output for testing and evaluations:
1 I laboratory mixer with speeds 100-1500 rpm
140 I pilot mixer with speeds 50-1000 rpm
1000 I production mixer, programmable to run mixing phases according to viscosity requirement; maximum speed 2000 rpm only for full vessel due to long shaft from the gear box to the blade
All materials for anisotropic and conductive coatings are commercially available, for example by Timcal and NeoCryl. The following materials and manufacturers were used in the tests:
Films/laminates: DuPont Teijin Films; various PET/coating structures
Dispersions: Imerys Timcal: Neromix E10 and E12 conductive dispersion Conductive carbon powder: Imerys Ensaco 250G
Polymer dispersions: Trueb Emulsions Chemie: Tecseal E-797 EAA; Tecylen E-952 acrylic dispersions
DSM Neocryl A-1091 , A-1092, A-2091 , A-2092, A-1093,XK-85 acrylic styrene copolymer dispersions
Propylene glycol, Isopropanol, Ammonia (25%): Algol Oy
Antifoaming agents: Goldsmith AG
Electronics: Bosch AG, BMX055, BNO055, BMX160+assembly kits, software
Siemens, test kit
Xsens, Orientation Sensor/lnertial measurement unit, test kit+software
Adhesive laminate: 3M
Acessories, configuring and production: Elcoflex Oy Polymers tested in conductive and anisotropic dispersion formulations:
1 . Water-borne acrylic emulsions:
-NeoCryl A-2092: tough and flexible acrylic styrene copolymer; with high elongation
-NeoCryl A-1092: perfect film former acrylic; for coating plastic film structures -NeoCryl A-2091 : non film forming acrylic; temperature resistant "polymer additive"
-NeoCryl A-1091 : non film forming acrylic; robust chemistry allows use of tap water
-NeoCryl BT-67: metal cross linking; heat resistant primer grade for aluminum foils
-NeoCryl XK-85: cross linkable; low MVTR to protect coated layers absorbing humidity
2. Water-borne urethanes:
-NeoRez R-1007: anionic polyurethane dispersion offering high elongation of 650%
-NeoRez R-972: anionic freeze/thaw resistant with elongation of 410%
-NeoRez R-600: anionic dispersion for primer mixes
3. Water borne EAA dispersions:
-Michem Prime 4938-HAS.E: EAA dispersion for anisotropic carbon formulations
-Tecseal E-797: EAA dispersion for anisotropic formulations
4. Crosslinkers:
-Crosslinker CX-100: polyaziridine crosslinker improving carboxyl functional resins performance; addition 1-3% in water based system
All the polymers were tested individually with carbon dispersions and carbon pigments. Polymer combinations were tested to obtain most suitable version for each application. Pot life tests were carried on with all variants and Crosslinker CX-100 was found losing key properties in final formulation during the first weeks, so it has to be added during the print production. Another group of suitable polymers which may be used in the dispersions are latex polymers, i.e latex dispersions. Litex® polymers by Synthomer were used in further tests, such as Litex 9480, PX 9082, PX 9306, PX 9330, and cross-linkable Litex SBV 600, Litex NX 1200, Litex 9076 and Litex 9077. Such latex polymers are about 45-50% more inexpensive than acrylic styrene copolymers. The later polymers may have a glass transition temperature in the range of 10-30°C, such as in the range of 12-22°C as with the used PX 9082, PX 9306, and PX 9330, which are aqueous anionic carboxylated styrene/butadiene copolymer dispersions. Croass-linkable latex polymers may have a glass transition temperature in the range of -50— 30°C, such as in the range of -44— 35°C as with the used NX1200 and 9076. Litex S 9076 is an aqueous, anionic dispersion of a self-crosslinking butadiene styrene copolymer containing a non-staining antioxidant. LITEX NX 1200 is an aqueous, plasticizer-free and formaldehyde reduced dispersion of a butadiene-acrylonitrile copolymer that can be crosslinked by heat. LITEX NX 1200 contains an anionic-nonionic emulsifier system and is stabilized with an antioxidant.
The conductivity of several conductive carbon types were tested on a Tambrite® fully coated folding boxboard A4 sheet back with RK Koater bar 3 applying two layers of coating. The carbon mixtures were applied on the back of the cardboard at 3x7 g/m2. Z samples were approved, when having a conductivity of 10-100 000 Ohms. XYZ samples were prepared with same manner and measured accordingly The results are reported in Ohms/square using a 3 mm wide and 210 mm long cut stripe.
Z-conductivity was measured using three different devices: Perel surface checker, Vermason: Surface resistance meter and Trek Model 152-1 . All units were from Perel Oy, an electronics and electricity specialist company. They also verify the results and calibrated all devices used in tests.
Examples of XYZ-conductivities were measured using Trek Model 152-1 and Fluke digital multimeter. Timrex LB1300 in Labseal RF mixture: 600-660 Ohm
Timcal RE-270 in Labseal RF mixture: 510-560 Ohm NeroMix E-10 in Labseal mixture: 440-480 Ohm
Timcal RE-270 49% + Ensaco 250G 8% + polymer mixture 43%: 220-240 Ohm
NeroMix E-12 + Ensaco 250G + polymer mixture: less than 100 Ohm
The best conductivity for Timcal NeroMix E-10 dispersed as explained herein was about 100 Ohm. However, the conductivity measurements are application specific because layers having the same thickness but applied on different materials do not provide the same conductivity. For example Tambrite on folding boxboard requires an extra layer compared to biaxially oriented polyester film, to obtain the same conductivity.
Timcal Timrex LB1300 is a stable binder free aqueous dispersion of graphite powder having a solids content of 27.5% (w/w) and an average particle size of 6.5 m.
Printing with semiflex was carried on using photopolymer plates with precision assembly of printing stations; optimally using robots. Consultation with Ctec Manuel Xifra Boada Technological Centre and Comexi R&D Team led to a 2+2 station printing to obtain constant conductivity for layers 1 +2 and complete coverage of them with layers 3+4.
Printing with screen is the most likely practical way of production due to optimal suitability of the method for producing selected printing thicknesses and fine lines.
The printing was carried on with sheet fed machine having three drying units. Sheet sizes were maximum of 700x1000 mm and configurations were done in accordance; all sheets were one side printed with standard colours and other side printed with conductive carbon print overcoated with anisotropic coat - leaving gaps to areas of electric contact. Printing was carried on with metal mesh 65-1 10 using semiflexible stencil. The speed was 800-1200 sheets/hour and drying temperatures: oven 1 : 85 degrees; oven 2: 65 degrees and oven 3: 45 degrees. The last one was with blowers to cool the surface of print for stacking. Conductivity and function of anisotropic print were suitable for further conversion. R2R screen printing was carried on in Elcoflex, Kempele. Dispersions were modified to match the viscosity requirements of rotary screen. Textiles
Tests were carried out using textiles of technical underwear; such as shirt made of polypropylene, and a cycling underbodice. The printed carbon coating was functional and the anisotropic layer protected the xyz-conductive layer, especially during washing.
In the tests carbon coating was applied on the inner side of Haiti training underwear. The coating was designed for screen printing process and created a perfect cover on fibers, when applied twice with Rod number 4 of RK Coater; the drying was done with 50 degrees Celsius air blow and Medium Wave IR.
The conductivity of printed carbon/polymer was measured and the nominal resistance was below 1000 Ohms and even 100 Ohms when using Haiti sports underwear in tests.

Claims

Claims
1 . A method for manufacturing a multi-layer film, the method comprising -providing a support layer,
-providing a first aqueous dispersion comprising carbon nanoparticles and polymer,
-proving a second aqueous dispersion comprising carbon particles and polymer,
-printing a xyz-conductive layer onto the support layer by using the first dispersion, and
-printing a z-conductive anisotropic layer onto the xyz-conductive layer by using the second dispersion
to obtain the multi-layer film.
2. The method of claim 1 , wherein the first dispersion also comprises non-nanoparticulate carbon, such as carbon particles having an average size in the range of 1-20 μιτι, such as 1-15 μιτι.
3. The method of claim 1 or 2, wherein the support layer comprises thermoplastic polymer or thermosetting polymer.
4. The method of claim 3, where in the thermoplastic polymer comprises polyester, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or polyethersulfonate (PES).
5. The method of any of the claims 1-3, where in the polymer of the support layer comprises polyimide.
6. The method of any of the preceding claims, wherein the support layer comprises a fibrous layer, such as a layer comprising natural fibers, for example cellulose, or a layer comprising synthetic fibers, or a textile layer.
7. The method of any of the claims 1-6, wherein the support layer comprises textile.
8. The method of any of the preceding claims, wherein the polymer in the first aqueous dispersion and/or the second aqueous dispersion is aqueous dispersion polymer.
9. The method of any of the preceding claims, wherein the polymer in the first aqueous dispersion and/or the second aqueous dispersion is thermoplastic polymer.
10. The method of claim 9, wherein the thermoplastic polymer comprises polyester, such as polyethylene terephthalate (PET), polyethylenen naphthalate (PEN), or polyethersulfonate (PES).
1 1 . The method of any of the preceding claims, wherein the polymer in the first aqueous dispersion and/or the second aqueous dispersion is a cross- linkable polymer.
12. The method of any of the preceding claims, wherein the polymer in the first aqueous dispersion and/or in the second aqueous dispersion comprises acrylic styrene copolymer, acrylic styrene polyurethane copolymer or ethylene acrylic acid (EAA) copolymer.
13. The method of any of the preceding claims, wherein the polymer in the first aqueous dispersion and/or in the second aqueous dispersion comprises latex polymer, such as anionic carboxylated styrene/butadiene copolymer.
14. The method of any of the preceding claims, wherein the polymer in the first aqueous dispersion and/or in the second aqueous dispersion comprises two polymers having a different minimum film forming temperature and/or glass transition temperature.
15. The method of claim 14, wherein one polymer has a minimum film forming temperature in the range of 0-20°C and the other polymer has a minimum film forming temperature in the range of 70-100°C.
16. The method of claim 14 or 15, wherein one polymer has a glass transition temperature in the range of 5-20°C and the other polymer has a glass transition temperature in the range of 70-120°C.
17. The method of any of the claims 14-16, wherein the polymers are acrylic styrene copolymers.
18. The method of any of the preceding claims, wherein the carbon nanoparticles have an average size in the range of 10-200 nm.
19. The method of claim 18, wherein the carbon nanoparticles have an average size in the range of 10-50 nm, such as in the range 15-30 nm.
20. The method of any of the preceding claims, wherein the carbon in the z-conductive anisotropic layer comprises particles having an average size in the range of 1-20 μιτι, such as 1-15 μιτι.
21 . The method of any of the preceding claims, wherein the polymer in the z-conductive anisotropic layer comprises ethylene acrylic acid (EAA) copolymer.
22. The method of any of the preceding claims, wherein the dispersion for printing the xyz-conductive layer comprises (w/w):
Polymeric dispersion 15.0-20.0%,
Nanoparticulate carbon dispersion 70.0-75.0%,
Propylene glycol 4.0-5.0%,
Isopropanol 1 .0-3.0%,
Ammonia (25% aqueous solution) 0.05-0.15%,
Water 1 .0-2.0%, and
Thickener 1 .5-2.5%.
23. The method of any of the preceding claims, wherein the dispersion for printing the z-conductive anisotropic layer comprises (w/w):
Acrylic dispersion 80.0-85.0%, Carbon dispersion 6.0-10.0%,
Propylene glycol 4.0-5.0%,
Isopropanol 2.0-2.5%,
Ammonia (25% aqueous solution) 0.15-0.25%,
Thickener 2.0-4.0%.
24. The method of any of the preceding claims, comprising forming one or more conductor(s) with the xyz-conductive layer.
25. The method of any of the preceding claims, wherein the printing is carried out by screen printing or flexographic/gravure printing.
26. The method of any of the preceding claims, comprising heat-treating the printed conductive layers at a temperature in the range of 80-100°C, preferably for a time of 10-30 seconds.
27. The method of any of the preceding claims, comprising providing an adhesive, such as a pressure sensitive adhesive, and applying the adhesive adhesive onto a surface or a side of the multi-layer film, such as onto the support layer.
28. The method of claim 27, comprising providing a release liner and applying the release liner onto the adhesive.
29. A multi-layer film with conductive coating, the film comprising the following layers:
-a support layer,
-a xyz-conductive layer comprising carbon nanoparticles and polymer, printed on the support layer, and
-a z-conductive anisotropic layer comprising carbon particles and polymer, printed on the xyz-conductive layer.
30. The multi-layer film of claim 29, wherein the xyz-conductive layer also comprises non-nanoparticulate carbon, such as carbon having an average particle size in the range of 1-20 μιτι, such as 1-15 μιτι.
31 . The multi-layer film of claim 29 or 30, wherein the support layer comprises thermoplastic polymer or thermosetting polymer.
32. The multi-layer film of claim 31 , where in the thermoplastic polymer comprises polyester, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or polyethersulfonate (PES).
33. The multi-layer film of any of the claims 29-31 , where in the polymer of the support layer comprises polyimide.
34. The multi-layer film of any of the claims 29-33, wherein the support layer comprises a fibrous layer, such as a layer comprising natural fibers, for example cellulose, or a layer comprising synthetic fibers, or a textile layer.
35. The multi-layer film of any of the claims 29-34, wherein the support layer comprises textile.
36. The multi-layer film of any of the claims 29-35, wherein the polymer in the xyz-conductive layer and/or the z-conductive anisotropic layer is dispersion polymer, or obtained from a dispersion polymer.
37. The multi-layer film of any of the claims 29-36, wherein the polymer in the xyz-conductive layer and/or the z-conductive anisotropic layer is thermoplastic polymer.
38. The multi-layer film of claim 37, wherein the thermoplastic polymer comprises polyester, such as polyethylene terephthalate (PET), polyethylenen naphthalate (PEN), or polyethersulfonate (PES).
39. The multi-layer film of any of the claims 29-38, wherein the polymer in the xyz-conductive layer and/or the z-conductive anisotropic layer is a cross- linked polymer.
40. The multi-layer film of any of the claims 29-39, wherein the polymer in the xyz-conductive layer and/or the z-conductive anisotropic layer comprises acrylic styrene copolymer, acrylic styrene polyurethane copolymer or ethylene acrylic acid (EAA) copolymer.
41 . The multi-layer film of any of the claims 29-40, wherein the polymer in the xyz-conductive layer and/or the z-conductive anisotropic layer comprises latex polymer, such as styrene/butadiene copolymer, such as anionic carboxylated styrene/butadiene copolymer.
42. The multi-layer film of any of the claims 29-41 , wherein the polymer in the xyz-conductive layer and/or the z-conductive anisotropic layer comprises two polymers having a different minimum film forming temperature and/or glass transition temperature.
43. The multi-layer film of claim 42, wherein one polymer has a minimum film forming temperature in the range of 0-20°C and the other polymer has a minimum film forming temperature in the range of 70-100°C.
44. The multi-layer film of claim 42 or 43, wherein one polymer has a glass transition temperature in the range of 5-20°C and the other polymer has a glass transition temperature in the range of 70-120°C.
45. The multi-layer film of any of the claims 42-44 wherein the polymers are acrylic styrene copolymers.
46. The multi-layer film of any of the claims 29-45, wherein the polymer in the z-conductive anisotropic layer comprises ethylene acrylic acid (EAA) copolymer.
47. The multi-layer film of any of the claims 29-46, wherein the carbon nanoparticles have an average size in the range of 10-200 nm.
48. The multi-layer film of claim 47, wherein the carbon nanoparticles have an average size in the range of 10-50 nm, such as 15-30 nm.
49. The multi-layer film of any of the claims 29-48, wherein the xyz- conductive layer comprises 50-90% (w/w) of conductive carbon and 5-45% (w/w) of polymer, such as 75-80% (w/w) of conductive carbon and 15-25% (w/w) of polymer.
50. The multi-layer film of any of the claims 29-49, wherein the carbon in the z-conductive anisotropic layer comprises particles having an average size in the range of 1-20 μιτι, such as 1-15 μιτι.
51 . The multi-layer film of any of the claims 29-50 obtained with the method of any of the claims 1-28.
52. The multi-layer film of any of the claims 29-51 , comprising one or more conductor(s) formed by the xyz-conductive layer, the conductor(s) being connectable to one or more electronic component(s), module(s) or circuit(s).
53. The multi-layer film of any of the claims 29-52, comprising an adhesive, such as a pressure sensitive adhesive, and optionally a release liner on the adhesive.
54. A sensor device comprising a sensor module, such as a motion sensor module, and means for wireless communication connected to the conductors of the multi-layer film of claim 52 or 53.
55. A sports gear comprising the sensor device of claim 54.
56. The sports gear of claim 55 selected from handheld gears, wearable gears, and projectile gears.
57. The sports gear of claim 55 or 56, wherein the gear is a hockey stick, such as an ice hockey stick.
58. The sports gear of claim 55 or 56, wherein the gear is a cricket bat.
59. The sports gear of claim 55 or 56, wherein the gear is an oar or a paddle.
60. A sensor sheet comprising the multi-layer film of claim 52, the sensor sheet comprising at least two carbon sections of at least 100 x 100 mm, preferably 2-20 carbon sections, for example 4-16 carbon sections.
61 . A method for detecting movements of a target having the sensor device of claim 54 containing a motion sensor module attached thereto, the method comprising
-wirelessly connecting the sensor device to a remote device,
-receiving data indicating the movement of the target from the sensor device in the remote device, and
-interpreting the data to detect the movements of the target.
62. The method of claim 61 , wherein the target is the sports gear of claim 55-59.
63. The method of claim 61 wherein the target is a package or a vehicle.
64. A method for detecting presence or movements of a subject, the method comprising
-providing the sensor sheet of claim 60 connected to a controlling device arranged to detect changes in the electric circuit of the sensor sheet, such as capacitive, inductive or resistive changes, and
-detecting changes in the electric circuit in respect of each carbon section of the sensor sheet, wherein a change in the electric circuit indicates the presence or the movement of the subject on the sensor sheet.
65. A method for manufacturing a conductive carbon dispersion, the method comprising
-providing wetting and/or dispersing agent(s) in aqueous solution,
-providing carbon granules having an average particle size in the range of 1- 50 μιτι,
-forming a mixture comprising 20-40% (w/w) conductive carbon granules; 4- 10% (w/w) wetting/dispersing agent and 52-76% water (w/w),
-mixing the mixture, preferably with 100-500 rpm, preferably for 10-20 minutes, to obtain a dispersion, preferably until a viscosity of 5000-6000 cp of the dispersion is obtained, -adding water, preferably 3-10% (w/w) of the total dispersion,
-mixing the dispersion, preferably with 500-2000 rpm, for 15-40 minutes to obtain a conductive carbon dispersion having an average carbon particle size in the range of 1-20 μιτι, preferably until a viscosity of 1000-1500 cp of the dispersion is obtained.
66. Conductive carbon dispersion manufactured with the method of claim 65.
67. Printing ink composition comprising the conductive carbon dispersion of claim 66.
68. Use of the conductive carbon dispersion of claim 66 in the manufacture of conductive coatings or films or multi-layer films.
PCT/EP2017/073292 2016-09-16 2017-09-15 A method for manufacturing a multi-layer film, a multi layer film, a sensor device, a sensor sheet, a sports gear, and a method for detecting movments of a target WO2018050827A2 (en)

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