WO2015033025A1 - Composite body and method of manufacturing it - Google Patents
Composite body and method of manufacturing it Download PDFInfo
- Publication number
- WO2015033025A1 WO2015033025A1 PCT/FI2014/050680 FI2014050680W WO2015033025A1 WO 2015033025 A1 WO2015033025 A1 WO 2015033025A1 FI 2014050680 W FI2014050680 W FI 2014050680W WO 2015033025 A1 WO2015033025 A1 WO 2015033025A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nfc
- abrasive particles
- composite body
- body according
- mixture
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/008—Abrasive bodies without external bonding agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D11/00—Constructional features of flexible abrasive materials; Special features in the manufacture of such materials
- B24D11/001—Manufacture of flexible abrasive materials
- B24D11/005—Making abrasive webs
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/067—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of fibres or filaments
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L1/08—Cellulose derivatives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
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- D—TEXTILES; PAPER
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- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/52—Cellulose; Derivatives thereof
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
- F16D69/00—Friction linings; Attachment thereof; Selection of coacting friction substances or surfaces
- F16D69/02—Composition of linings ; Methods of manufacturing
- F16D69/025—Compositions based on an organic binder
- F16D69/026—Compositions based on an organic binder containing fibres
Definitions
- the present invention relates to composite body.
- the invention also relates to a method of manufacturing the composite body and use of the composite body.
- abrasive particles which are to be set in contact with workpieces to be processed.
- These tools and materials can be commonly designated “abrasive products”.
- the processing may be polishing, grinding, cutting or other mechanical work.
- the abrasive particles which are of sufficient hardness, are fixed to a support, which can take a variety of shapes.
- Grinding wheels are conventionally made of natural or synthetic abrasive particles fixed together in a matrix by means of binder.
- the components abrasive particles, binder
- the binder is allowed to cure, or the grinding wheel is fired if the binder is ceramic.
- Cutting wheel is another example of a tool which contains abrasive particles and which can be used for workpiece processing by cutting through material.
- the manufacture of a cutting wheel comprises similar steps as mentioned above. Some tools can be used both as grinding wheels and cutting wheels.
- the abrasive materials also include various abrasive cloths, abrasive nets, abrasive 3-dimensional fiber materials, abrasive papers, abrasive filaments etc., where the support is in form of a textile or paper structure or film. These materials are flexible and can be used especially in polishing and surface finishing. In manufacturing these materials, abrasive particles are usually fixed on the supporting material with the help of a resin binder. Also metals and melted non organic materials such as glass can be used as binders.
- Another problem in the manufacturing of abrasive products is heterogeneous distribution of the abrasive grains in the continuous matrix. This problem can be avoided by increasing viscosity of the unhardened composition, which may lead to problems in the deposition of the mixture eg. in spray coating of abrasive non wovens and cloths. Thus, there is a need for additive that can stabilize heavy grains and simultaneously allow easy spraying or coating of the formulation.
- Porosity also allows room for small chips of metal, known as swarf, and abrasive generated during the grinding process. Porosity also provides pathways that carry fluids used to control heat and improve the cutting characteristics of the abrasive grains. Without adequate porosity and spacing between abrasive grains, the wheel can become loaded with swarf and cease to cut properly.
- the problems associated with materials and tools where resin binders, such as commonly used phenolic resins are used for fixing the abrasive particles is that the binder tends to fill the pores between the abrasive particles, which lowers the number of active grinding edges. If sufficient porosity can be created for example due to the structure of the support, the problem of even distribution of the particles, their fixation to the support, and the permanence of the fixation still remains.
- the object is to provide a new composite body comprising binder and abrasive particles, which does not have problems associated with the prior art.
- a further object is to provide a composite body that can constitute or be part of an abrasive product.
- a further object is still to provide a composite body that can be used in applications where good friction is required.
- nanofibrillar cellulose can replace organic binders normally used in abrasive products either totally or partly.
- the nanofibrillar cellulose forms a continuous network of interconnected fibrils, which retain the abrasive particles physically and/or chemically through entangling the particles in the network.
- porosity in the form of voids, are left inside the network of nanofibrillar cellulose.
- the network of the nanofibrillar cellulose while fixing the particles in the composite structure, also leaves the particles well separated and prone to contact with the material to be worked.
- the same phenomenon occurs when the mixture is set on a substrate on which the composite body is to be formed and the fibrils of the NFC bind the abrasive particles to each other and to the substrate.
- the self-orientation of the NFC creates a very strong network of orientated fibrils binding the abrasive particles, which strive to become optimally arranged, together and to the possible substrate (support).
- the abrasive particles can be used in various sizes and grades. Their hardness is as a rule higher than that of quartz, above 7 as expressed on the Mohs scale.
- the abrasive particles that can be used include for example aluminium oxide, silicon carbide, boron carbide, boron nitride, zirconia alumina, corundum, diamond and ceramic abrasives. Preferably the hardness is equal to or above 8.
- Organic resin binder can be used in addition to the nanofibrillar cellulose in the binder component of the composite to increase water-resistance during the use of the abrasive product.
- the abrasive particles and the nanofibrillar cellulose in liquid dispersion are mixed in a predetermined proportion, and the mixture is dried by a suitable method where the composite body attains its final shape.
- the mixture can be placed in a mold or in a press where it gradually loses the liquid and attains its final shape.
- the mixture can also be extruded through a die or forced through orifices or nozzle to air or to a suitable bath for drying.
- the NFC is obtainable in various chemically modified grades, especially ionically charged, which include anionically charged NFC, such as oxidized NFC (from catalytic oxidation by heterocyclic nitroxyl catalyst) and carboxy- methylated NFC, and cationically charged NFC.
- anionically charged NFC such as oxidized NFC (from catalytic oxidation by heterocyclic nitroxyl catalyst) and carboxy- methylated NFC, and cationically charged NFC.
- the chemical constitution of the NFC can be utilized in improving the interaction between the abrasive particles and the fibrils of the NFC by ionic or covalent bonds, especially by choosing fibrils and particles of such surface charges that a charge complex can be formed from them, or by choosing such a chemical constitution that a covalent bond can be formed.
- the ionic charge of the NFC can also be utilized in enhancing the drying rate of the mixture of the NFC and the abrasive particles.
- the NFC can also be used for binding abrasive particles of very small dimensions.
- Fig. 1 shows the general principles of manufacturing the composite body
- Fig.2 shows the structure of a composite body that is part of an abrasive product
- Fig. 3 shows the struture of a composite body in more detail
- Fig. 4 shows an example of a composite body on a porous support
- Fig. 5 shows a composite body in the form of a grain
- Fig. 6 is a specific example of manufacture of composite bodies
- Fig. 7 is a cross-section of a composite body manufactured according to Fig. 6, and
- Figs. 8 - 1 1 are microscopic pictures of composite bodies that comprise abrasive particles and that can be used as abrasive products or parts thereof Detailed Description of the Embodiments
- the main components of the composite body are abrasive particles, nano- fibrillar cellulose (NFC), and optionally organic binder.
- the abrasive particles have a hardness above 7 on Mohs scale, which is a well-known scale used for indicating the hardness of materials.
- the particles can be aluminium oxide, silicon carbide, boron carbide, boron nitride, zirconia alumina, corundum, diamond, or ceramic abrasive, or any mixture of these.
- the invention is not limited to just the above-mentioned particles.
- the particle sizes of the abrasive particles can vary according to the use, from 100 nm to 1000 ⁇ , preferably 1 ⁇ to 500 ⁇ , expressed as weight average mean particle size.
- the fibrils of the NFC have small dimensions and are able to entangle closely even small particles, the NFC makes possible to also use particle sizes below 10 ⁇ , especially in miniaturized composite structures, like filaments, yarns and individual grains.
- the particles can be physically or chemically modified, especially to alter their surface properties and/or chemical surface structure, such as surface charge. This modification is made especially to match the abrasive particles to the NFC grade used.
- the NFC may also be derivatized as explained hereinafter.
- the term "nanofibrillar cellulose” (NFC) refers to a collection of isolated cellulose microfibrils or microfibril bundles derived from cellulose raw material . Microfibrils have typically high aspect ratio: the length might exceed one micrometer while the number-average diameter is typically below 200 nm. The diameter of microfibril bundles can also be larger but generally less than 1 ⁇ .
- the smallest microfibrils are similar to so called elementary fibrils, which are typically 2-12 nm in diameter.
- the dimensions of the fibrils or fibril bundles are dependent on cellulose raw material and disintegration method.
- the nanofibrillar cellulose may also contain some hemicelluloses; the amount is dependent on the plant source.
- Mechanical disintegration of the cellulose raw material is carried out with suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer.
- suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer.
- the cellulose raw material most commonly used is fibrous raw material obtained from plants.
- the nanofibrillar cellulose is prepared normally from cellulose raw material of plant origin.
- the raw material can be based on any plant material that contains cellulose.
- the raw material can also be derived from certain bacterial fermentation processes.
- Plant material may be wood.
- Wood can be from softwood tree such as spruce, pine, fir, larch, douglas-fir or hemlock, or from hardwood tree such as birch, aspen, poplar, alder, eucalyptus or acacia, or from a mixture of softwoods and hardwoods.
- the cellulose raw material could be also derived from cellulose-producing micro-organisms.
- the micro-organisms can be of the genus Acetobacter, Agrobacterium, Rhizobium, Pseudomonas or Alcaligenes, preferably of the genus Acetobacter and more preferably of the species Acetobacter xylinum or Acetobacter pasteurianus.
- NFC can be directly isolated from certain fermentation processes of these micro-organisms.
- the source can be wood or non-wood plant material.
- wood fibers are one abundant source of the NFC.
- the nanofibrillar cellulose can be manufactured by disintegrating wood-derived or non-wood derived fibrous raw material to the level of microfibrils or microfibril bundles.
- the raw material can be for example chemical pulp.
- the pulp can be for example softwood pulp or hardwood pulp or a mixture of these.
- the fibrils originating in secondary cell walls are essentially crystalline with degree of crystallinity of at least 55 %.
- the NFC can be especially ionically charged, because the ionic charge of the cellulose weakens the internal bonds of fibrous raw material and facilitates the disintegration to NFC.
- the ionic charge can be achieved by chemical or physical modification of the cellulose.
- the NFC can be anionically or cationic- cally charged. Most commonly used chemical modification methods for making an anionic charge are oxidation and carboxymethylation.
- a cationic charge in turn can be created chemically by cationization by attaching a cationic group to the cellulose, such as quaternary ammonium group.
- the nanofibrillar cellulose is preferably made from fibrous raw material where the cellulose has been modified to ionically charged cellulose.
- the primary hydroxyl groups of cellulose are oxidized catalytically by a heterocyclic nitroxyl compound, for example 2,2,6,6- tetramethylpiperidinyl-1 -oxy free radical, "TEMPO".
- TEMPO 2,2,6,6- tetramethylpiperidinyl-1 -oxy free radical
- the fibrils of the NFC containing aldehyde groups can be bound covalently internally to NFC, to the abrasive particles, or to the possible substrate.
- the binding takes preferably place through acetal or hemiacetal formation reaction
- Various grades of NFC can be made depending on the type of the modification, such as kind of ionic charge (anionic/cationic), and/or kind of chemical agent or chemical process used in the modification.
- Various grades can also be made by altering the degree of modification. In case of oxidized cellulose, these grades can be expressed as carboxylate content, that is, as mmol COOH/g NFC (based on dry NFC), and in case of carboxymethylated NFC or cationized NFC, as degree of substitution.
- the carboxylate content is preferably 0.3 - 1 .5 mmol/g NFC, and in carboxymethylated NFC, the degree of substitution is preferably 0.05 - 0.3.
- the degree of substitution is preferably 0.05-0.8.
- the NFC used can also be unmodified.
- the unmodified NFC can be either untreated native or treated native where the positively charged counterions are changed to sodium. This pretreatment is preferably performed to fibrous raw material before its disintegration to NFC.
- the NFC has characteristic rheological behaviour.
- the NFC including all derivatized grades, is not soluble to water, but forms a gel already at relatively low consistencies (1 -2%) when dispersed in aqueous medium (a hydrogel).
- aqueous nanofibrillar cellulose dispersions obtained are also characterized by typical shear thinning behavior; that is, when the viscosity is measured in a rotational rheometer, the shear thinning behaviour is seen as a decrease in viscosity with increasing shear rate.
- the hydrogels of NFC also have plastic behaviour, that is, a certain shear stress is required before the material starts to flow readily. This critical shear stress is often called the yield stress.
- the viscosity of the NFC can be best characterized by zero- shear viscosity, which corresponds to the "plateau" of constant viscosity at small shearing stresses approaching zero.
- the zero-shear viscosity of the NFC measured with a stress controlled rotational rheometer at a concentration of 0.5% (aqueous medium) is typically between 1000 and 100000 Pa.s, preferably 5000 and 50000 Pa.s. For non-derivatized NFC this value is typically in the range of 1000 - 10000 Pa.s.
- the yield stress of the NFC determined by the same method is between 1 and 50 Pa, preferably in the range of 3 - 15 Pa.
- the rheological characteristics make the a gel-like NFC dispersion ideal for carrier and dispersing medium of relative heavy (high-density) abrasive particles, because in static conditions it keeps the particles well distributed in the medium, but on the other hand the mixture can be made easily flowable by applying shear to it, for example when the mixture is spread on a substrate by spraying or by other means. Once the shear forces cease, the mixture is stable again.
- Optional binders are organic binders, especially curable organic resins.
- Phenolic resins such as phenol-formaldehyde resins, or urea-formaldehyde are preferably used.
- Other suitable binders include acrylic resins, latex, epoxy, polyimid, PEEK, cyanoacrylate, polyurethanes and sol-gel adhesives.
- the surface of the composite body can be finished by means of so-called supersizers.
- Supersizers are functional additives that raise surface hardness, repellent and/or antistatic qualities, and they can be mixtures of two or more functional agents.
- the supersizer contains binder.
- the supersizers can contain calcium stearate, zinc stearate, fluoroadditives, silanes and cutting fluid coolant.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Braking Arrangements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
Claims
Priority Applications (5)
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EP14772166.6A EP3041911B1 (en) | 2013-09-05 | 2014-09-05 | Composite body and method of manufacturing it |
US14/916,236 US9963625B2 (en) | 2013-09-05 | 2014-09-05 | Composite body and method of manufacturing it |
JP2016539604A JP6511449B2 (en) | 2013-09-05 | 2014-09-05 | Composite and method of making it |
ES14772166T ES2893435T3 (en) | 2013-09-05 | 2014-09-05 | Composite material body and method of manufacturing it |
CN201480049048.XA CN105531345B (en) | 2013-09-05 | 2014-09-05 | complex and its manufacturing method |
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FI20135896 | 2013-09-05 | ||
FI20135896A FI126837B (en) | 2013-09-05 | 2013-09-05 | Composite articles and process for its manufacture |
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WO2015033025A1 true WO2015033025A1 (en) | 2015-03-12 |
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PCT/FI2014/050680 WO2015033025A1 (en) | 2013-09-05 | 2014-09-05 | Composite body and method of manufacturing it |
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US (1) | US9963625B2 (en) |
EP (1) | EP3041911B1 (en) |
JP (1) | JP6511449B2 (en) |
CN (1) | CN105531345B (en) |
ES (1) | ES2893435T3 (en) |
FI (1) | FI126837B (en) |
WO (1) | WO2015033025A1 (en) |
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JP2018024076A (en) * | 2016-08-09 | 2018-02-15 | ▲高▼藏工業株式会社 | Abrasive grain, grindstone and method for producing abrasive grain |
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Also Published As
Publication number | Publication date |
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FI126837B (en) | 2017-06-15 |
US9963625B2 (en) | 2018-05-08 |
EP3041911A1 (en) | 2016-07-13 |
EP3041911B1 (en) | 2021-08-25 |
JP6511449B2 (en) | 2019-05-15 |
CN105531345A (en) | 2016-04-27 |
FI20135896A (en) | 2015-03-06 |
CN105531345B (en) | 2018-10-02 |
ES2893435T3 (en) | 2022-02-09 |
JP2016536428A (en) | 2016-11-24 |
US20160208153A1 (en) | 2016-07-21 |
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