FI127417B - A multi-layer film with conductive coating and a method for manufacturing thereof - Google Patents

A multi-layer film with conductive coating and a method for manufacturing thereof Download PDF

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Publication number
FI127417B
FI127417B FI20165688A FI20165688A FI127417B FI 127417 B FI127417 B FI 127417B FI 20165688 A FI20165688 A FI 20165688A FI 20165688 A FI20165688 A FI 20165688A FI 127417 B FI127417 B FI 127417B
Authority
FI
Finland
Prior art keywords
layer
carbon
conductive
sensor
film
Prior art date
Application number
FI20165688A
Other languages
Finnish (fi)
Swedish (sv)
Other versions
FI20165688A (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 FI20165688A priority Critical patent/FI127417B/en
Priority to EP17768119.4A priority patent/EP3513412A2/en
Priority to PCT/EP2017/073292 priority patent/WO2018050827A2/en
Publication of FI20165688A publication Critical patent/FI20165688A/en
Application granted granted Critical
Publication of FI127417B publication Critical patent/FI127417B/en

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    • 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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    • 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
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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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    • B32B7/04—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
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    • 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
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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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    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Arrangements For Transmission Of Measured Signals (AREA)

Abstract

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 having an average diameter in the range of 15–30 nm, and a z-conductive anisotropic layer comprising carbon. One embodiment provides a method for manufacturing the multi-layer film. Other embodiments provide 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 multi-layer film with conductive coating and a method for manufacturing thereof
Field of the application
The present application relates to a 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.
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 the 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.
EP 2982727 A1 discloses a conductive adhesive, an anisotropic conductive film, and an electronic device using the same. The conductive adhesive comprises conductive fillers and a binder resin, the binder resin comprising an epoxy (meth) acrylate resin. The anisotropic conductive film comprises conductive particles and a binder resin, the binder resin comprising an epoxy (meth) acrylate resin.
US 2008/0191174 A1 discloses a heat-activated adhesive for manufacturing of intelligent devices comprising an electronic module and printed conductive electronics, like conductive traces, antennas on a flexible substrate, wherein the adhesive is an anisotropic electrically conductive thermoplastic adhesive and is applied on the substrate as a thin film which can be used for adhering
20165688 prh 02 -05- 2018 components to the substrate, for electrical connections and tor providing mechanical stability to the printed conductive traces.
WO 2004/078787 A1 discloses a packaging and a method for monitoring a 5 packaging of a disposable material in a chain of logistics. As an integral part of the packaging, the packaging has an electronic module. The packet is printed with a plurality of traces using electrically conductive ink to form an integral part of the package. The printed traces are preferably printed using carbon-graphite based ink in a thermoplastic resin.
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 thermoplastic polymer, and
-a z-conductive anisotropic layer comprising carbon particles and thermoplastic polymer.
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 thermoplastic polymer,
-optionally mixing non-nanoparticulate carbon to the first dispersion, such as carbon having an average particle size in the range of 1-20 pm, such as 115 pm,
-proving a second dispersion comprising carbon particles and thermoplastic polymer,
-printing a xyz-conductive layer onto the support layer by using the first dispersion, and
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-printing a z-conductive 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 multilayer film.
One embodiment provides a method for detecting the movements of a target 10 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.
The main embodiments are characterized in the independent claims. Various embodiments are disclosed in the dependent claims. The embodiments recited in dependent 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
20165688 prh 02 -05- 2018 hockey sticks, baseball bats, golf clubs, tennis rackets etc.) to monitor and report the functions of tools in question. One 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 processable dispersion, which has a long and stable shelf life.
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 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 laminating or layered materials, robust mechanics, minimized electronics and easiness in using the “gadget”.
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The combination of xyz-conductive layer and the anisotropic z-conductive layer enables several functionalities. The structure is very flexible 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 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%.
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
Detailed description
All the percentage values disclosed herein refer to percentages by weight (w/w) unless otherwise mentioned.
In one aspect the embodiments include four individual functions including the conductive coatings, the top layer, the back layer, and the electronics.
The conductive coating includes two different conductive layers. The xyzconductive layer A for printing circuits, antennas , sensors, or the like based on carbon or for example carbon/metal hybrid, and the z-conductive layer B,
20165688 prh 02 -05- 2018 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 10 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, which 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 LEDs, electronic components such as resistors, capacitors, transistors, integrated circuits, diodes and the like, other sensors, transmitters and/or receivers, RFID modules, memory modules, electro-mechanicals parts or modules, 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
20165688 prh 02 -05- 2018 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. 5 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.
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).
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 thermoplastic polymer, and
-a z-conductive anisotropic layer comprising carbon particles and thermoplastic polymer.
The thermoplastic polymer in the support layer may be any suitable thermoplastic 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 etc. The thermoplastic polymer layer may comprise one or more thermoplastic polymer films or layers. In one embodiment the thermoplastic polymer layer is a thermoplastic polymer film. The thickness of the thermoplastic polymer layer may be adjusted according to the desired properties and may be in the general range of 20-500 pm, such as 20-400 pm, 20-300 pm or 20-200 pm. In one embodiment the
20165688 prh 02 -05- 2018 thermoplastic polymer layer has a thickness in the range of 23-100 pm, such as 23-70 pm, 25-80 pm, 25-50 pm, 30-100 pm, 30-80 pm, 50-100 pm, or 40-100 pm. These ranges are suitable for most applications and? provide good tensile strength, tensile strain, thermal resistance and other mechanical properties. Useful thermal range of the polymer may be in the range of -3050°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 a polyethylene terephthalate (PET), polyethylenen naphthalate (PEN) or 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).
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 nonannealed. The thermoplastic polymer film may be machine direction
20165688 prh 02 -05- 2018 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 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 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.
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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.
In one embodiment the support layer comprises fibers such as natural fibers or synthetic fibers. 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, board or the like. The synthetic fibers may comprise glass fibers, nylon, modacrylis, olefin, acrylic, polymester, 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. In one example the support comprises a paper or board coated with kaolin.
In one embodiment the fibrous support layer is a textile layer, or the support layer comprises textile, 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, aramid, acrylic, Nylon, Spandex, olefib fibers, Ingeo, Lurex, and carbon fibers.
20165688 prh 02 -05- 2018
In one embodiment the support layer comprises a textile, such as a textile for clothing. 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. 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 support layer, especially the thermoplastic polymer layer may be heatbonded to the next layer which is xyz-conductive layer comprising carbon nanoparticles (also called as xyz-conductive layer or xyz-layer). The xyz15 conductive layer may be printed and/or laminated onto the thermoplastic polymer layer. In one embodiment the xyz-conductive layer contains carbon nanoparticles, i.e. nanoparticulate carbon, having an average diameter 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 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. 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 pm, such as 18-22 pm, for example about 20 pm. 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
20165688 prh 02 -05- 2018 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 5 polymeric layer, such as a thermoplastic polymer layer. More particularly the layer comprises carbon comprising carbon nanoparticles and one or more thermoplastic 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 thermoplastic polymer is acrylic polymer. 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 thermoplastic polymer is acrylic styrene copolymer. In one embodiment the thermoplastic polymer is acrylic styrene polyurethane, which was found to provide especially high impact resistance and elasticity. The polymer is provided as a dispersion wherein the carbon is provided as predispersed nanoparticle. The 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 7020 80% (w/w), and the content of the thermoplastic polymer is in the range of 545% (w/w), 15-35% (w/w), 15-30% (w/w) in the final product, such as 7580% (w/w) of conductive carbon and 15-25% (w/w) of thermoplastic 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, thermoplastic polymer(s) and optionally one or more of other additives of auxiliary agents, preferably in the ranges disclosed herein.
In one embodiment maximum conductivity is 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.
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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 5 carbon and thermoplastic polymer, and
-a z-conductive anisotropic layer comprising carbon and thermoplastic polymer.
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 1-20 pm, such as 1-15 pm. 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 xyzconductive 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%.
The xyz conductive layer is next to, i.e. in contact with, the anisotropic zconductive layer (also called as z-layer), which may be printed and/or laminated to the xyz conductive layer. Therefore the conductivity of the xyzlayer 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 in the range of 1-20 pm, such as 1-15 pm. 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 zlayer 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
20165688 prh 02 -05- 2018 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 5 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 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 zconductive 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 touchsensitive applications or connecting the conductive circuits to electronics.
The anisotropic z-conductive layer may have a thickness in the range of 1525 30 pm, such as 18-22 pm, for example about 20 pm.
In one embodiment the carbon in the z-conductive anisotropic layer is included in a polymeric layer, such as a thermoplastic polymer layer. In one embodiment the thermoplastic polymer layer comprises ethylene acrylic acid (EAA) copolymer, or is a layer thereof. Ethylene acrylic acid (EAA) copolymer in a tacky solid form, with an acrylic acid (AA) content of for example about 20%, is suitable for promoting adhesion to various substrates 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. This prevents copying of the configuration of the layers and connections therein. Examples of commercially useful EAA grades include
20165688 prh 02 -05- 2018 ethylene acrylate dispersion E-799 by Triib 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 thermoplastic polymer is in the range of 75-90% (w/w), 80-90% (w/w), 8389% (w/w) in the final product, such as 6-10% (w/w) of carbon and 85-89% (w/w) of thermoplastic 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 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 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
20165688 prh 02 -05- 2018 agglomerates 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 xyz5 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 z10 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.
In one embodiment the multi-layer film comprises a further thermoplastic polymer layer attached to the z-conductive anisotropic layer comprising carbon. If the support layer is a (first) thermoplastic polymer layer, this layer may be called 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 pm, such as 20-80 pm. In one embodiment the further thermoplastic polymer layer has a thickness in the
20165688 prh 02 -05- 2018 range of 23-50 pm. In one embodiment the further thermoplastic 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 pm, 100-2000 pm, or 100-1000 pm, such as 100-500 pm. 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.
The construction may comprise a thermoplastic 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 thermoplastic 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
20165688 prh 02 -05- 2018 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 5 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 polymer(s), such as described herein for the first, second and thirds polymeric layers, or it may contain foamed material, such as foamed thermoplastic 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 of other structures. 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
20165688 prh 02 -05- 2018 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 11 and is heat-bonded to the xyzconductive 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 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
20165688 prh 02 -05- 2018 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 xyzconductive 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 0.12.0 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,
20165688 prh 02 -05- 2018 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 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.
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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.
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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 2x2 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
20165688 prh 02 -05- 2018 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 5 combination of conductive carbon printed and hybrid wired laminate having a layer of foamed material, such as foamed thermoplastic polymer, which 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 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
20165688 prh 02 -05- 2018 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 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
20165688 prh 02 -05- 2018 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 multilayer 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
20165688 prh 02 -05- 2018 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 and/or modules described herein to enable the desired functionalities.
As used herein a multi-layer film refers to a film structure containing more 10 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 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, 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.
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
20165688 prh 02 -05- 2018 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.
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.
The multi-layer film comprising one or more conductor(s) formed by the xyzconductive 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, 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.
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 film, 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
20165688 prh 02 -05- 2018 also exhibits elastic properties, such as having elasticity in the range of ΙΟΙ 5%, 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 be 3, 6, or 9 axis, and a gyroscope may be 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.
Different types of sensor modules are commercially available and they 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 3axis 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.
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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 the 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. In the remote device the data it is received and 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 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
20165688 prh 02 -05- 2018 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 factoryassigned 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
20165688 prh 02 -05- 2018 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.
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, such as a club, stick, mallet, racket, bat or the like used in the game or any other sport or exercise. The terms gaming means and sport means as used herein may be used interchangeably and are intended to cover all the examples disclosed herein. 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 ST H3LIS331DL.
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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 packet or parcel, such as a packed in storage or a packet to be mailed.
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 vehicle, such as a car, bicycle, moped, motorcycle, snow scooter, or the like.
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 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 from the sensor device in the remote device, and interpreting the data to detect the movements. The target may be any target described herein, such as the gaming or sports means, packet or parcel, vehicle, or any other suitable target. The sensor device may be attached to the target by adhesive, such as pressure sensitive adhesive, or it may be integrated into the target, for example in may be laminated in the target. The data indicating the movement of the target 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
20165688 prh 02 -05- 2018 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.
The received data indicating the movement of the target 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 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, such as a gaming device, the geographical location of the target 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.
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, when hitting ball or bucket, simultaneously the speed is registered for comparison a further use. The basic idea is in attaching a device having
20165688 prh 02 -05- 2018 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.
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.
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 could 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.
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 a combination thereof. 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.
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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 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.
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.
One example of a laminate structure is presented in Figure 1:
PET-film top 50 microns
Treatment at the back of the film
Conductive carbon print 20 microns
Anisotropic print 20 microns
18,19 Electronics including sensor (18) and energy source (19) 0.95-2.0 mm
Adhesive layer to cover the gap
PET-film
Contactive adhesive 5-6 microns
Release paper 90 microns
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In one example the size of an 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, 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 1003000 pm, 100-2000 pm, or 100-1000 pm, such as 100-500 pm. 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)
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.
Ice hockey has been an example of applications and the other gaming sectors may have modified units with additional or variable measurements and data handling. Golf club version may be linked to weather services and
20165688 prh 02 -05- 2018 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.
In one example a sensoring 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.
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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. 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 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.
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.
Examples of gaming applications include ice hockey, bandy, baseball (including the Finnish version), tennis, badminton, golf, floor bandy and the like. The device may be attached to a club, stick, mallet, racket, bat or the like used in the game or any other sport or exercise.
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In one embodiment the device is attached to an item used for transport. The item may be a bicycle, moped, motorcycle, car, snow scooter, 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.
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.
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 thermoplastic polymer,
-optionally mixing an amount of non-nanoparticulate carbon to the first dispersion, such as carbon having an average particle size in the range of 135 20 pm, such as 1-15 pm,
-proving a second dispersion comprising carbon particles and thermoplastic polymer,
-printing a xyz-conductive layer onto the support layer by using the first dispersion, and
-printing a z-conductive layer onto the xyz-conductive layer by using the second dispersion to obtain the multi-layer film
The amounts of ingredients disclosed herein add up to 100% of the total 10 dispersion by optionally including added water or any other aqueous solution, or other ingredients.
The conductive layers may be printed by providing specific print dispersions, preferably aqueous dispersions. 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%
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20165688 prh 02 -05- 2018
In one embodiment a dispersion comprises (w/w):
Polymeric dispersion 5 Nanoparticulate carbon dispersion
Propylene glycol Isopropanol
Ammonia (25% aqueous solution) Water
Thickener
A for printing the xyz-conductive layer
15.0-20.0%
70.0-75.0%
4.0-5.0%
1.0-3.0%
0.05-0.15%
1.0-2.0%
1.5-2.5%
The polymer may be any suitable thermoplastic polymer described herein. 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.
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 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% of the carbon material has said average diameter, or at least 95%. 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.
As used herein, “powder” or “powdered” refers to a collection of fine, freely flowing particles and “granule” or “granular” refers to a macroscopic agglomerate of interacting particles. Both graphite and carbon black can exist in granular and powdered forms.
The complete dispersion A, or the polymeric or the carbon dispersion may contain one or more auxiliary agents to facilitate the formation of the
20165688 prh 02 -05- 2018 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 5 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 are also believed to act as wetting agents. 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, such as 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%, 1025 15%, 15-30% or 20-30%.
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,
20165688 prh 02 -05- 2018 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-C11 alcohol having an average of approximately 6 moles of ethylene oxide per mole of alcohol, having a density of approximately 0.976 kg/l, 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 10 6 manufactured by Shell Chemicals.
The surfactant may be an anionic surfactant. Examples of anionic surfactants include alcohol phosphates and phosphonates, alkyl alkoxy carboxylates, alkyl aryl sulfates, alkyl aryl sulfonates, alkyl carboxylates, alkyl ether carboxylates, alkyl ether sulfates, alkyl ether sulfonates, alkyl phosphates, alkyl polyethoxy carboxylates, alkyl polyglucosides, alkyl polyglucoside sulfates, alkyl polyglucoside sulfonates, alkyl succinamates, alkyl sulfates, alkyl sulfonates, aryl sulfates, aryl sulfonates, fatty taurides, isethionates, Nacyl 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 5 agent and letting it act in order to obtain foam free dispersion for distribution.
In one embodiment a dispersion comprises (w/w):
Polymer dispersion:
Nanoparticulate carbon dispersion Carbon powder
In one embodiment a dispersion comprises (w/w):
Polymer dispersion: Nanoparticulate carbon dispersion Carbon powder
Propylene glycol Isopropanol Aqueous ammonia Antifoam
A for printing the xyz-conductive layer
12.0-22.0%
52.0-70.0%
5.0-10.0%
A for printing the xyz-conductive layer
12.0-22.0%
52.0-70.0%
5.0-10.0%
3.0-5.0%
1.0-3.0%
0.1-0.2%
0.1-0.3%
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Using conductive carbon powder or granulated particles as thickener make the dispersion stable and improve conductivity of 20 micron coating with 4550%. 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 one embodiment a dispersion B for printing the z-conductive anisotropic layer comprises:
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:
Acrylic dispersion Carbon dispersion Propylene glycol Isopropanol
Ammonia (25% aqueous solution)
Thickener
80.0-85.0%
6.0-10.0%
4.0-5.0%
2.0-2.5%
0.15-0.25%
2.0-4.0%
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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.
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 in the range of 1-20 pm, such as 1-15 pm. In one example at least 90% of the carbon material has said average diameter, 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) and granulated Raven grades by Birla Carbon. 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 z47
20165688 prh 02 -05- 2018 conductive product is obtained, which may be used in several applications and has several advantages.
The conductive carbon layers described above may be obtained by printing 5 onto the first thermoplastic polymer 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 s, 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
20165688 prh 02 -05- 2018 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 hazard free 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 airflow.
Examples
Printing with flexo was carried on using photopolymer plates with precision 15 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 65-110 using smiflexible 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.
20165688 prh 02 -05- 2018
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 the printing problem 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:
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 dem. water/Rheotec)
In one example the formulation for preparing the z-conductive layer is as follows:
Labseal AI B anisotropic dispersion:
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 dem. water/Rheotec)
20165688 prh 02 -05- 2018
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.
In development phases there have been following sizes of mixing units performing similar dispersion output for testing and evaluations:
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 acrylicdisp.
20165688 prh 02 -05- 2018
DSM Neocryl A-1092, A-2092,A-1093,XK-85 acrylicstyrene cop. Disp. Propylene glycol, Isopropanol, Ammonia (25%): Algol Oy Antifoaming agents: Goldsmith AG
Electronics: Bosch AG, BMX055, BMX160+assembly kits, software 5 Siemens, test kit
Xsens, Orientation Sensor/lnertial measurement unit, test kit+software Adhesive laminate: 3M
Acessories, configuring and production: Elcoflex Oy
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 pm.

Claims (16)

1. Menetelmä monikerroskalvon valmistamiseksi, jossa menetelmässä -järjestetään saataville tukikerros, tunnettu siitä, ettäA method for producing a multilayer film, wherein a support layer is provided, characterized in that 5 - järjestetään saataville ensimmäinen vesidispersio, joka käsittää hiilinanopartikkeleita ja kestomuovipolymeeriä,5 - providing a first aqueous dispersion comprising carbon nanoparticles and a thermoplastic polymer, - valinnaisesti sekoitetaan ensimmäiseen dispersioon ei-nanopartikkelimuodossa olevaa hiiltä, kuten hiiltä, jonka keskimääräinen partikkelikoko on 1-20 pm, kuten 1-15 pm,optionally mixing the first dispersion with non-nanoparticulate carbon, such as carbon having an average particle size of 1 to 20 µm, such as 1 to 15 µm, 10 -järjestetään saataville toinen vesidispersio, joka käsittää hiilipartikkeleita ja kestomuovipolymeeriä,10, providing a second aqueous dispersion comprising carbon particles and a thermoplastic polymer, - painetaan tukikerrokselle xyz-suunnissa sähköä johtava kerros käyttämällä ensimmäistä dispersiota, jaapplying an electrically conductive layer to the support layer in the xyz directions using the first dispersion, and - painetaan xyz-suunnissa sähköä johtavalle kerrokselle z-suunnassa säh15 köä johtava anisotrooppikerros käyttämällä toista dispersiota monikerroskalvon aikaansaamiseksi.- applying an electrically conductive anisotropic layer to the electrically conductive layer in the xyz directions using a second dispersion to provide a multilayer film. 2. Sähköä johtavalla päällysteellä varustettu monikerroskalvo, joka kalvo käsittää seuraavat kerrokset:2. A multilayer film with an electrically conductive coating, the film comprising the following layers: 20 - tukikerroksen (10), tunnettu siitä, että se käsittää lisäksi20 - a support layer (10), characterized in that it further comprises - xyz-suunnissa sähköä johtavan kerroksen (12), joka käsittää hiilinanopartikkeleita ja kestomuovipolymeeriä, ja valinnaisesti ei-nanopartikkelimuotoista hiiltä, kuten hiiltä, jonka keskimääräinen partikkelikoko on ΙΣΟ pm, kuten 1-15 pm, painettuna tukikerroksen päälle,- in the xyz directions, an electrically conductive layer (12) comprising carbon nanoparticles and a thermoplastic polymer, and optionally a non-nanoparticulate carbon such as carbon having an average particle size of ΙΣΟ pm, such as 1-15 pm, printed on the support layer, 25 - z-suunnassa sähköä johtavan anisotrooppikerroksen (13), joka käsittää hiilipartikkeleita ja kestomuovipolymeeriä, painettuna xyz-suunnissa sähköä johtavan kerroksen päälle.25-z electrically conductive anisotropic layer (13) comprising carbon particles and a thermoplastic polymer imprinted in xyz direction on electrically conductive layer. 3. Patenttivaatimuksen 2 mukainen monikerroskalvo, jossa tukikerrosThe multilayer film according to claim 2, wherein the support layer 30 (10) käsittää kestomuovipolymeeriä.30 (10) comprises a thermoplastic polymer. 4. Patenttivaatimuksen 2 mukainen monikerroskalvo, jossa tukikerros (10) käsittää kuitukerroksen, kuten kerroksen, joka käsittää luonnonkuituja, esimerkiksi selluloosaa, tai kerroksen, joka käsittää synteettisiä kuituja, taiThe multilayer film according to claim 2, wherein the support layer (10) comprises a fiber layer, such as a layer comprising natural fibers, for example cellulose, or a layer comprising synthetic fibers, or 35 tekstiilikerroksen.35 layers of textile. 20165688 prh 02 -05- 201820165688 prh 02 -05- 2018 5. Patenttivaatimuksen 2 tai 3 mukainen monikerroskalvo, jossa kestomuovipolymeerikerros käsittää polyesteriä, kuten polyeteenitereftalaattia (PET), polyeteeninaftalaattia (PEN) tai polyeetterisulfonaattia (PES), esimerkiksi kalvokerroksena.The multilayer film according to claim 2 or 3, wherein the thermoplastic polymer layer comprises a polyester such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN) or polyether sulfonate (PES), for example as a film layer. 6. Jonkin patenttivaatimuksen 2-5 mukainen monikerroskalvo, jossa nanopartikkeleiden keskimääräinen halkaisija on 10-200 nm, kuten 1050 nm, esimerkiksi 15-30 nm.The multilayer film according to any one of claims 2 to 5, wherein the nanoparticles have an average diameter of 10-200 nm, such as 1050 nm, for example 15-30 nm. 1010 7. Jonkin patenttivaatimuksen 2-6 mukainen monikerroskalvo, jossa xyzsuunnissa sähköä johtavassa kerroksessa (12) oleva hiili on sisällytetty akryyli-styreenikopolymeeriin tai akryyli-styreeni-polyuretaanikopolymeeriin.The multilayer film according to any one of claims 2 to 6, wherein the carbon in the x-directionally conductive layer (12) is incorporated in an acrylic-styrene copolymer or acrylic-styrene-polyurethane copolymer. 8. Jonkin patenttivaatimuksen 2-7 mukainen monikerroskalvo, jossa z15 suunnassa sähköä johtavassa anisotrooppikerroksessa (13) olevan hiilen keskimääräinen halkaisija on 1-20 pm, kuten 1-15 pm.The multilayer film according to any one of claims 2 to 7, wherein the carbon in the z15 electrically conductive anisotropic layer (13) has an average diameter of from 1 to 20 µm, such as from 1 to 15 µm. 9. Jonkin patenttivaatimuksen 2-8 mukainen monikerroskalvo, jossa zsuunnassa sähköä johtavassa anisotrooppikerroksessa (13) oleva hiili onThe multilayer film according to any one of claims 2 to 8, wherein the carbon in the z-conductive anisotropic layer (13) is 20 sisällytetty eteeni-akryylihappo (EAA) -kopolymeeriin.20 incorporated into the ethylene-acrylic acid (EAA) copolymer. 10. Jonkin patenttivaatimuksen 2-9 mukainen monikerroskalvo, joka käsittää yhden tai useamman sähkönjohtimen (22, 23, 24, 25, 26), joka on muodostettu xyz-suunnissa sähköä johtavalla kerroksella, joka sähkönjohdin/The multilayer film according to any one of claims 2 to 9, comprising one or more electrical conductors (22, 23, 24, 25, 26) formed in the xyz direction by an electrically conductive layer which 25 jotka sähkönjohtimet on/ovat liitettävissä yhteen tai useampaan elektroniikkakomponenttiin, -moduuliin tai -piiriin (18, 19, 20, 21).25 which electrical conductors are / can be connected to one or more electronic components, modules or circuits (18, 19, 20, 21). 11. Jonkin patenttivaatimuksen 2-10 mukainen monikerroskalvo, joka käsittää sideainetta, kuten paineherkkää liimaa (16), ja valinnaisesti side30 aineen päällä olevan irrokepaperin (17).A multilayer film according to any one of claims 2 to 10, comprising a binder, such as a pressure sensitive adhesive (16), and optionally a release paper (17) on top of the binder. 12. Jonkin patenttivaatimuksen 2-11 mukainen monikerroskalvo, joka on saatu patenttivaatimuksen 1 mukaisella menetelmällä.A multilayer film according to any one of claims 2 to 11 obtained by the process of claim 1. 3535 13. Anturilaite, joka käsittää anturimoduulin, kuten liikeanturimoduulin (18), sekä langattomat tiedonsiirtovälineet (20, 21), tunnettu siitä että ne on liitetty jonkin patenttivaatimuksen 10-12 mukaisen monikerroskalvon johtimiin (22, 23, 24, 25, 26).A sensor device comprising a sensor module, such as a motion sensor module (18), and wireless communication means (20, 21), characterized in that they are connected to the conductors (22, 23, 24, 25, 26) of a multilayer film according to any one of claims 10-12. 14. Anturiarkki, tunnettu siitä että se käsittää patenttivaatimuksen 10 taiA sensor sheet, characterized in that it comprises claim 10 or 5 12 mukaisen monikerroskalvon, joka anturiarkki käsittää ainakin kaksi hiiliosiota (40, 41), joiden koko on vähintään 100 x 100 mm, edullisesti 220 hiiliosiota, esimerkiksi 4-16 hiiliosiota.The multilayer film of claim 12, wherein the sensor sheet comprises at least two carbon sections (40, 41) having a size of at least 100 x 100 mm, preferably 220 carbon sections, for example 4 to 16 carbon sections. 15. Menetelmä kohteen liikkeiden havaitsemiseksi, tunnettu siitä että 10 kohteessa on patenttivaatimuksen 13 mukainen anturilaite, joka sisältää siihen liitetyn liikeanturimoduulin, jossa menetelmässäA method for detecting subject motions, characterized in that the subject has a sensor device according to claim 13, comprising a motion sensor module attached thereto, - liitetään anturilaite langattomasti etälaitteeseen,- wirelessly connecting the sensor device to the remote device, - vastaanotetaan anturi laitteelta etälaitteeseen tietoja, jotka osoittavat kohteen liikettä, jareceiving data from the device to the remote device indicating movement of the target, and 15 - tulkitaan tiedot kohteen liikkeiden havaitsemiseksi.15 - interpret data to detect subject motions. 16. Menetelmä kohteen läsnäolon tai liikkeiden havaitsemiseksi, tunnettu siitä että menetelmässä16. A method for detecting the presence or movements of an object, characterized in that -järjestetään saataville patenttivaatimuksen 14 mukainen anturiarkki, joka on 20 liitetty ohjauslaitteeseen, joka on järjestetty havaitsemaan anturiarkin sähkövirtapiirin muutoksia, kuten kapasitiivisia, induktiivisia tai resistiivisiä muutoksia, ja- providing a sensor sheet according to claim 14 coupled to a control device arranged to detect changes in the electrical current circuit of the sensor sheet, such as capacitive, inductive or resistive changes, and - havaitaan sähkövirtapiirin muutoksia anturiarkin kunkin hiiliosion osalta, jolloin sähkövirtapiirin muutos osoittaa kohteen läsnäolon tai liikkeen- detecting changes in the electrical circuit for each carbon portion of the sensor sheet, whereby the change in electrical circuit indicates the presence or movement of the target; 25 anturiarkilla.25 sensor sheets.
FI20165688A 2016-09-16 2016-09-16 A multi-layer film with conductive coating and a method for manufacturing thereof FI127417B (en)

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PCT/EP2017/073292 WO2018050827A2 (en) 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

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