EP2870189A1 - Procédé de fabrication d'un système de films de polyuréthane diélectriques multicouches - Google Patents

Procédé de fabrication d'un système de films de polyuréthane diélectriques multicouches

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Publication number
EP2870189A1
EP2870189A1 EP13732567.6A EP13732567A EP2870189A1 EP 2870189 A1 EP2870189 A1 EP 2870189A1 EP 13732567 A EP13732567 A EP 13732567A EP 2870189 A1 EP2870189 A1 EP 2870189A1
Authority
EP
European Patent Office
Prior art keywords
film
isocyanate
polyurethane
polyurethane film
weight
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP13732567.6A
Other languages
German (de)
English (en)
Inventor
Jens Krause
Joachim Wagner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
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 Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Priority to EP13732567.6A priority Critical patent/EP2870189A1/fr
Publication of EP2870189A1 publication Critical patent/EP2870189A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/32—Mixing; Kneading continuous, with mechanical mixing or kneading devices with non-movable mixing or kneading devices
    • B29B7/325—Static mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7404—Mixing devices specially adapted for foamable substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7404—Mixing devices specially adapted for foamable substances
    • B29B7/7409—Mixing devices specially adapted for foamable substances with supply of gas
    • B29B7/7419—Mixing devices specially adapted for foamable substances with supply of gas with static or injector mixer elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/86—Component parts, details or accessories; Auxiliary operations for working at sub- or superatmospheric pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/28—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on an endless belt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
    • B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/05—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
    • H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
    • H10N30/077—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/098—Forming organic materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/857—Macromolecular compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7471—Mixers in which the mixing takes place at the inlet of a mould, e.g. mixing chambers situated in the mould opening
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • the present invention relates to a process for producing a multi-layered electroactive polymer film system comprising layers of dielectric polyurethane and conductive electrode layer having a multi-layer actuator / multilayer actuator structure particularly suitable for use in electromechanical transducers. Further objects of the invention are a dielectric polyurethane film system obtainable by the process according to the invention and an electromechanical transducer obtainable by this process.
  • Transducers - also called electromechanical transducers - convert electrical energy into mechanical energy and vice versa. They can be used as part of sensors, actuators and / or generators.
  • EAP electroactive polymers
  • the basic structure of such a transducer consists of electroactive polymers (EAP).
  • EAP electroactive polymers
  • the construction principle and the operation are similar to those of an electrical capacitor. Between two conductive plates, to which a voltage is applied, there is a dielectric.
  • EAPs are a ductile dielectric that deforms in the electric field.
  • dielectric elastomers are mostly in the form of films (DEAP, dielectric electroactive polymer) which have a high electrical resistance and are coated on both sides with high conductivity, stretchable electrodes (electrode), as described for example in WO-A 01/006575.
  • This basic structure can be used in a variety of configurations for the production of sensors, actuators or generators. In addition to single-layered structures, multi-layered structures are also known.
  • electroactive polymers as elastic dielectrics in transducer systems must be divided into different components: Actuators / sensors or generators - different
  • the voltage in turn depends on the breakdown field strength, ie if the breakdown rupture field strength is very low, no high voltage can be applied. Since this value is squared in the equation for calculating the strain caused by the electrostatic attraction of the electrodes, the breakdown field strength must be correspondingly high.
  • a typical equation can be found in the book by Federico Carpi, Dielectric Elastomers as Electromechanical Transducers, Elsevier, page 314, Equation 30.1, as well as similarly in R. Peirine, Science 287, 5454, 2000, page 837, Equation 2. Equation The previous section makes a very important for the operation of dielectric elastomer actuators property: The smaller the layer thickness zo, the smaller the operating voltage of the actuators can be.
  • the dielectric is in the form of a silicone tube. This tube is cut in a spiral, then the cut surfaces are covered with conductive material, which serve as electrodes [F. CARPI, A. MIGLIORE, G. SERRA and D. DE ROSSI "Helical dielectric elastomer actuators" In: Smart Materials and Structures 14.6 (2005), pp. 1210-1216 CHUC et al Principle on the folding according to CARPI is based [N. I I. CHUC, JK PARK, DV THUY, I IS KIM, JC KCX), inter alia, "Multi-stacked artificial muscle actuator based on synthetic elastomer”.
  • the layers can often be disassembled after less than 100 load cycles, ie a delamination of the layers takes place. Also, such methods for polyurethane are still unknown.
  • the object of the invention was to produce monolithic multilayer films without boundary layers, so that no delamination and separation of the layers is possible.
  • actuators are either too low in the dielectric constant and / or the breakdown field strength or too high in the module.
  • a disadvantage of known solutions is also the low electrical resistance, which leads to high leakage currents in actuators and in the worst case to an electrical breakdown.
  • these actuators In order to achieve high deflections in actuators, these actuators must be constructed according to the equation multi-layered.
  • transducers which contain various polymers as a constituent of the electroactive layer are described, for example, in WO-A 01/006575, and processes for their preparation are described.
  • DE 10 2007 005 960 describes soot-filled polyether-based polyurethanes.
  • a disadvantage of this invention is the very low electrical resistance of the DEAP film, so that the loss due to heat is too high.
  • WO 2010/049079 describes one-component polyurethane systems in organic solvents.
  • the disadvantage here is that only low degrees of branching can be used, so that the systems have too high a creep under cyclic tensile loads Functionality of 2 and smaller possible, so that even the systems known from DE 10 2007 059 858 do not meet the requirements.
  • a one-component solution of higher functionality in organic or aqueous solvents / dispersion
  • due to the linearity a reversible tensile-strain process, as it must be used in EAPs, not possible because it leads to a flow of the polymer
  • the electrical resistance of the described polyether is too low.
  • EP 2 280 034 describes polyether polyols which have too low electrical resistance.
  • E 2 0649 describes various approaches. Both the tensile strengths and the electrical resistances as well as the breakdown field strength are too low to arrive at technically relevant, high efficiencies.
  • WO 2010012389 describes amine-crosslinked isocyanates, but here too the electrical resistance and the breakdown field strength are too low.
  • the multi-layer actuators obtainable from this should have a very high returnability, furthermore they do not tend to flow and have a high electrical resistance.
  • the polyurethane process polyurethane film systems which can be produced by the process should have one or more of the following properties:
  • the object according to the invention is achieved by a method for producing a multilayer dielectric polyurethane film system (multilayer) in which at least the following steps are carried out:
  • Isocyanate groups of> 10% by weight and ⁇ 50% by weight b) an isocyanate-reactive group-containing compound having an Ol I number of> 20 and ⁇ 150, wherein the sum of the number average functionality of isocyanate groups and
  • III) curing of the wet film is to form the polyurethane film and IV) applying a, in particular structured, electrode layer to the almost completely dried film, in particular by spraying, pouring, knife coating, inkjet or the like, wherein the electrode optionally contains a binder and is optionally dried,
  • steps I) -IV) preferably> 2 and ⁇ 1,000,000 times, more preferably> 5 and ⁇ 100,000 and especially preferably> 10 and ⁇ 10,000, with very particular preference> 10 and ⁇ 5,000 and in particular very particularly preferably> 20 and ⁇
  • the multilayer film produced by the process according to the invention has good mechanical strength and high elasticity. Furthermore, it has good electrical properties such as a high breakdown field strength, a high electrical resistance and a high dielectric constant and can therefore be used advantageously in a elektr omechanis Chen converter with high efficiency.
  • the layers are produced in stacks, so that preferably each layer is just dry in order to prevent the next layer from flowing into the lower layer, but is still so sticky that an indestructible adhesion is present, which ideally still contains a chemical after-reaction ,
  • the 100% conversion of a coated layer is thus preferably carried out only by the drying, which experience the subsequent stories. This results in a monolithic layer structure without delamination of the layers.
  • the greatest advantage of the chemical process according to the invention is the strong adhesive and adhesive force of the polyurethane to the electrode layer, but especially the resulting monolithic structure with the lower polyurethane layer, in the case of a structured electrode surface which is smaller than the polyurethane surface.
  • the main disadvantage of a mechanical stacking process in comparison with this is that it always always first before application, the release film of the film must be removed. 1 Lierbei it comes to stretching of the film, which usually throws wrinkles or even breaks and in any case changes the structure under strain. As a result, it is mechanically impossible to add a layer exactly to the next layer so that, in the case of a construction with a high number of layers, in the worst case, there will be such a strong slippage that electrical breakdown occurs.
  • the chemical process can be used not only to structure layers in the manufacturing process, but also to precisely stack and process them one to one.
  • the adhesion of the polyurethane (which is generally higher than silicone) is higher due to the chemical process.
  • the process according to the invention has only one carrier on the lowest layer, so that it is only removed in the final step in the finalization of all layers and thus no strain is previously present.
  • Another advantage is that the layer thicknesses that are produced can be significantly lower. This is because with the mechanical variant, the layers always have to be removed from the carrier and thus tear with thin layers. This disadvantage is not given in the inventive method. Productivity is significantly higher due to the lack of robots to remove layers, and more accessible by today's carousel technology.
  • modifications such as allophanate, uretdione, urethane, isocyanurate, biuret.
  • Iminooxadiazindion- or Oxadiazintrion Will containing compounds based on said diisocyanates suitable building blocks of component a) and polynuclear compounds such as polymeric MDI (pMDI) and combinations of all.
  • Preferred are modifications having a functionality of from 2 to 6, preferably from 2.0 to 4.5 and more preferably from 2.6 to 4.2, and most preferably from 2.8 to 4.0 and most preferably from 2.8 used to 3.8.
  • Diisocyanates from the series HDI, IPDI, H12-MDI, TDI and MDI are particularly preferably used for the modification. Particular preference is given to HDI.
  • the preferred NGO content is> 10% by weight, more preferably> 15% and most preferably> 18% by weight.
  • the NGO content is particularly preferably between 18 and 25% by weight.
  • Very particular preference is given to using as a) modified aliphatic isocyanates based on HDI with a free, unreacted monomeric fraction of free isocyanate of ⁇ 0.5% by weight.
  • the compound a) has a number-average functionality of isocyanate groups of> 2.0 and ⁇ 4.
  • the compound a) comprises or consists of an aliphatic polyisocyanate, preferably hexamethylene diisocyanate and particularly preferably a biuret and / or isocyanurate of hexamethylene diisocyanate.
  • the isocyanate groups may also be blocked partially or completely until their reaction with the isocyanate-reactive groups, so that they can not react directly with the isocyanate-reactive group. This ensures that the reaction takes place only at a certain temperature (blocking temperature).
  • blocking temperature Typical blocking agents are found in the prior art and are selected so that they split off at temperatures between 60 and 220 ° C, depending on the substance, again from the isocyanate group and only then react with the isocyanate-reactive group.
  • blocking agents which are incorporated into the polyurethane and also those which remain in the polyurethane as a solvent or plasticizer or outgas from the polyurethane.
  • Blocki tert Typical blocking agents are, for example, caprolactam, methyl ethyl ketoxime, pyrazoles such as 3,5-dimethyl-3, 2-pyrazole or 1, pyrazole, triazoles such as 1, 2,4-triazole , Diisopropylamine, diethylmalonate, diethylmain, phenol or its derivatives or imidazole.
  • the isocyanate-reactive groups of compound b) are functional groups which can react to form covalent bonds with isocyanate groups.
  • these may be amine, epoxy, hydroxyl, thiol, mercapto, acrylic, anhydride, vinyl, and / or carbinol Act groups.
  • the isocyanate-reactive groups are particularly preferably hydroxyl and / or amine groups.
  • the compound b) has a number-average functionality of isocyanate-reactive groups of> 2.0 and ⁇ 4, wherein the isocyanate-reactive groups are preferably hydroxy and / or amine.
  • the compound b) may preferably have an OH number> 27 and ⁇ 150, more preferably> 27 and ⁇ 120 mg OH / g.
  • the average functionality of an isocyanate-reactive group in b) can be from 1.5 to 6, preferably from 1.8 to 4 and particularly preferably from 1.8 to 3.
  • the number average molecular weight of b) can be 1000-8000 g mol, preferably from 1500-4000 g / mol and more preferably from 1500-3000 g / mol.
  • the isocyanate-reactive groups of the compound b) is a polymer.
  • the compound b) is a diol and particularly preferably a polyester diol and / or a diol
  • Polycarbonate diol comprises or consists of.
  • Compound b) may contain polyether polyols, polyether amines, polyetherester polyols, polycarbonate polyols, polyethercarbonate polyols, polyester polyols, polybutadiene derivatives,
  • b) preferably comprises or consists of a polyol having at least two isocyanate-reactive hydroxyl groups.
  • polyether polyester, polycarbonate and polyetheresterpolyols, polybutadiene polyols, polysiloxane polyols, particularly preferably polybutadienols, polysiloxane polyols, polyester polyols and / or polycarbonate polyols, very particularly preferably polyester polyols and / or polycarbonate polyols.
  • Suitable polyester polyols may be polycondensates of di- and optionally tri- and tetraols and di- and optionally tri- and tetracarboxylic acids or hydroxy carb ons acids or lactones.
  • free polycarboxylic acids it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols for the preparation of the polyesters.
  • Polyester polyols are prepared in a manner known per se by polycondensation from aliphatic and / or aromatic polycarboxylic acids having 4 to 16 carbon atoms, optionally from their anhydrides and optionally from their low molecular weight esters, including R 2, predominantly low molecular weight polyols having 2 as reaction components to 12 carbon atoms are used.
  • suitable alcohols are ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols, such as polyethylene glycol, and also 1,2-propanediol.
  • polyols such as trimethylolpropane, glycerol, erythritol, pentachloride, trimethylolbenzene or trishydroxyethyl isocyanurate or mixtures thereof.
  • Diols are particularly preferably used, very particular preference is given to butanediol (1,4) and hexanediol (1,6), very particular preference to hexanediol (1,6).
  • dicarboxylic acids which may be mentioned are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrate, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, succinic acid, 2-methylsuccinic acid, 3, 3 Diethylglutar s äur e and / or 2,2-Dirnethylbemsteinklaw be used.
  • the acid source used may also be the corresponding anhydrides.
  • Preferred acids are aliphatic or aromatic acids of the abovementioned type. Particularly preferred are adipic acid, isophthalic acid and phthalic acid, most preferably isophthalic acid and phthalic acid.
  • Hydrooxycarboxylic acids which can be used as reactants in the preparation of a polyesterpolyol having terminal hydroxyl groups are, for example, hydroxycaproic acid, hydroxy oxybutric acid, hydroxydecic acid or hydroxy stearic acid or mixtures thereof.
  • Suitable lactones are caprolactone, butyrolactone or homologs of the mixtures thereof. Preference is given to caprolactone.
  • polyesterdiols very particularly preferably based on reaction products of adipic acid, isophthalic acid and phthalic acid with butanediol (1,4) and hexanediol (1,6).
  • Hydroxyl-containing polycarbonates for example polycarbonate polyols, preferably polycarbonate diols, can be used as isocyanate-reactive group-containing compound b). These can be obtained by reaction of carbonic acid derivatives such as diphenyl carbonate, dimethyl carbonate or phosgene by means of polycondensation with polyols, preferably diols.
  • diols examples include ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1, 4-bishydroxymethylcyclohexane, 2-methyl - 1, 3 -propanediol, 2,2,4-trimethylpentanediol-l, 3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A, 1.10-decanediol. 1,12-Dodecanediol or lactone-modified diols of the type mentioned above or mixtures thereof.
  • the diol component contains from 40 percent by weight to 100 percent by weight of hexanediol, preferably 1,6-hexanediol and or hexanediol derivatives.
  • hexanediol derivatives are based on hexanediol and may have ester or ether groups in addition to terminal Ol I groups.
  • Such derivatives are obtainable, for example, by reaction of hexanediol with excess caprolactone or by etherification of hexanediol with itself to give di- or trihexylenglycol.
  • the amount of these and other components are chosen in the present invention in a known manner such that the sum does not exceed 100 weight percent, in particular 100 weight percent results.
  • Hydroxyl-containing polycarbonates especially polycarbonate polyols, are preferably linearly constructed. Particular preference is given to using a polycarboxylate ondiol based on 1,6-hexanediol.
  • polyether polyols can be used.
  • polytetramethylene glycol polyethers as obtainable by polymerization of tetrahydrofuran by means of cationic ring opening are suitable.
  • suitable polyether polyols may be the addition products of styrene oxide, ethylene oxide, propylene oxide, butylene oxide and / or epichlorohydrin to di- or polyfunctional starter molecules.
  • suitable starter molecules which may be used are water, butyldiglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, sorbitol, ethylenediamine, triethanolamine or 1,4-butanediol or mixtures thereof.
  • Hydroxy-functional oligobutadiene, hydrogenated hydroxy-functional oligobutadiene, hydroxy-functional siloxanes, glycerol or TMP monoallyl ethers can also be used alone or in any desired mixture.
  • polyether polyols can be prepared by alkaline catalysis or by double metal cyanide catalysis or optionally in stepwise reaction by alkaline catalysis and Dopp elmetallcy anidkataly s e of a starter molecule and epoxides, preferably ethylene and / or propylene oxide and have terminal hydroxyl groups.
  • DMC catalysis double metalloid catalyzed catalysts
  • Suitable starters are the compounds with hydroxyl and / or amino groups known to those skilled in the art, as well as water. The functionality of the starter is at least 2 and at most 6.
  • Suitable compounds b) are also ester diols such as a-hydroxybutyl-e-hydroxy-caproic acid ester, ro-hydroxyhexyl-y-hydroxybutyric acid ester, adipic acid (.beta.-hydroxyethyl) ester or
  • monofunctional compounds can also be used in step I).
  • monofunctional compounds are ethanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether,
  • chain extenders or crosslinking agents of compound b) may be added proportionately in step I).
  • compounds having a functionality of 2 to 3 and a molecular weight of 62 to 500 are preferably used.
  • aromatic or aliphatic amine chain extender such as diethyl toluene diamine (DETDA), 3,3, dichloro-4,4'-diamino-diphenyimethan (MBOCA), 3,5-diamino-4-chloro- isobutyl, 4-methyl 2,6-bis (methylthio) -1,3-diaminobenzene (Ethacure 300), trimethylene glycol di-p-aminobenzoate (Polacure 740M) and 4,4'-diamino-2,2'-dioro-5,5 '-diethyldiphenylmethane (MCDEA) can be used.
  • DETDA diethyl toluene diamine
  • MOCA 3,3, dichloro-4,4'-diamino-diphenyimethan
  • Ethacure 300 4,6-bis (methylthio) -1,3-diaminobenzene
  • Polycure 740M trim
  • MBOCA and 3,5-diamino 4-chloro-isobutylbenzoate Components suitable for chain extension according to the invention are organic di- or polyamines.
  • organic di- or polyamines for example, ethylenediamine, 1,2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, isophoronediamine, isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2 Methylpentamethylenediamine, diethylenetriamine, diaminodicyclohexylmethane or dimethylethylenediamine or mixtures thereof.
  • compounds which, in addition to a primary amino group also have secondary amino groups or, in addition to an amino group (primary or secondary), also Ol [groups.
  • primary secondary amines such as diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, and alkanolamines, such as N-aminoethylethanolamine , Ethanolamine, 3-aminopropanol, neopentanolamine.
  • amines with an isocyanate-reactive group such as methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine.
  • amide amines from diprimary amines and monocarboxylic acids amide amines from diprimary amines and monocarboxylic acids, monoketim of diprimary amines, primary / tertiary amines, such as N, N-dimethylaminopropylamine.
  • non-aminic chain extenders which are often used are, for example, 2,2'-thiodiethanol, 1,2-propanediol, 1,3-propanediol, glycerol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methylpropanediol 1,3, pentanediol-1,2, pentanediol-1,3, pentanediol-1,4, pentanediol-1,5, 2,2-dimethyl-1,2-propanediol, 2-methylbutanediol-1, 4, 2- Methylbutanediol-1,3,1,1,1-trimethylolethane, 3-methyl-l, 5-pentanedio
  • a) and b) have low levels of free water, residual acids and metal contents.
  • the residual water content of b) is preferably ⁇ 1% by weight, more preferably ⁇ 0.7% by weight (based on b)).
  • the residual acid content of b) is preferably ⁇ 1% by weight, more preferably ⁇ 0.7% by weight (based on B).
  • the residual metal contents caused, for example, by residues of catalyst constituents used in the preparation of the educts, should preferably be less than 1000 ppm and more preferably less than 500 ppm, based on a) or b).
  • the ratio of isocyanate-reactive groups to isocyanate groups in the mixture of step I) can be from 1: 3 to 3: 1, preferably from 1: 1.5 to 1.5: 1, more preferably from 1: 1.3 to 1, 3: 1 and most preferably from 1: 1.02 to 1: 0.95.
  • the mixture of step I) may additionally contain auxiliaries and additives.
  • auxiliaries and additives are crosslinkers, thickeners, solvents, thixotropic agents, stabilizers, antioxidants, light stabilizers, emulsifiers, surfactants, adhesives, plasticizers, water repellents, pigments, fillers rheology improvers, plasticizers, degassing and defoaming agents, wetting additives and catalysts and fillers.
  • the mixture of step I) particularly preferably contains wetting additives. Usually, the wetting additive is contained in an amount of 0.05 to 1.0% by weight in the mixture.
  • Typical wetting additives are available, for example, from Altana (Byk additives such as: polyester-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane or acrylate copolymeric polymers, and, for example, C6F13 fluorotelomers).
  • the mixture of step I) comprises fillers having a high dielectric constant.
  • these are ceramic fillers, in particular barium titanate, titanium dioxide and piezoelectric ceramics such as quartz or lead zirconium titanate, as well as organic fillers, in particular those having a high electrical polarizability, for example phthalocyanines, poly-3-hexythiophene.
  • a higher dielectric constant can also be achieved by introducing electrically conductive fillers below the percolation threshold.
  • electrically conductive fillers below the percolation threshold.
  • examples of such materials are carbon black, graphite, graphene, fibers, single-walled or multi-walled carbon nanotubes, electrically conductive polymers such as polythiophenes, polyanilines or polypyrroles, or mixtures thereof.
  • electrically conductive polymers such as polythiophenes, polyanilines or polypyrroles, or mixtures thereof.
  • those types of carbon black which have a surface passivation and therefore at higher concentrations below the percolation threshold increase the dielectric constant and nevertheless do not lead to an increase in the conductivity of the polymer.
  • additives for increasing the dielectric constant and / or the electrical breakdown field strength can also be added after the film formation in steps II) and III). This can be achieved, for example, by producing one or more further layers or by penetrating the polyurethane film, for example by
  • aqueous and organic solvents can be used.
  • a solvent may be used which has a vapor pressure at 20 ° C of>
  • the films of the invention can be prepared on a roll coating device.
  • the polyurethane film may have a layer thickness of 0.1 ⁇ m to 1000 ⁇ m, preferably from 1 ⁇ m to 500 ⁇ m, more preferably from 5 ⁇ m to 200 ⁇ m, and very particularly preferably from 10 ⁇ m to 100 ⁇ m.
  • the application of the mixture of step I) to the carrier in step II) can be carried out, for example, by knife coating, brushing, pouring, spinning, spraying, extrusion in a batch process, i. in a repetitive process with coating steps and intervening drying steps.
  • the mixture is applied to the carrier with a squeegee (such as a squeegee, quark, or the like), rollers (such as anilox rollers, gravure rollers, burnishing rollers, or the like) or a nozzle.
  • a squeegee such as a squeegee, quark, or the like
  • rollers such as anilox rollers, gravure rollers, burnishing rollers, or the like
  • a nozzle may be part of a nozzle application. It is also possible to operate several commissioned works simultaneously or in succession. Several layers can be applied simultaneously with a commissioned work.
  • a nozzle is used, and more preferably a residence time optimized and / or recirculation-free nozzle.
  • the distance of the nozzle to the carrier is less than three times the thickness of the wet film, preferably less than twice the thickness of the wet film and more preferably less than one and a half times the thickness of the wet film. If, for example, 150 ⁇ m wet film is coated (if the wet film contains 20% by weight of solvent, this corresponds to 120 ⁇ m of cured film), then the distance between the nozzle and the substrate should be ⁇ 300 ⁇ m. If the distance of the nozzle to the support is chosen as described above, a roller coater can be used to make the films.
  • a wet film having a thickness of from 10 to 300 ⁇ m, preferably from 10 to 300 ⁇ m, may be used. 5 to 150 ⁇ , more preferably from 20 to 120 ⁇ and very particularly preferably from 20 to 80 ⁇ is produced.
  • the wet film is cured in step III) by being passed through a first drying section, which preferably has a temperature> 40 ° C and ⁇ 120 ° C, more preferably> 60 ° C and ⁇ 1 10 ° C and particularly preferably> 60 ° C and ⁇ 100 ° C.
  • the wet film may also be passed through a second drying section after the first drying section, which preferably has a temperature> 60 ° C and ⁇ 130 ° C, more preferably> 80 ° C and ⁇ 20 ° C and particularly preferably> 90 ° C and ⁇ 120 ° C has.
  • the wet film can also be passed through a third drying section, which preferably has a temperature> 110 ° C. and ⁇ 180 ° C., more preferably> 110 ° C. and ⁇ 150 ° C. and particularly preferably> 110 ° C. and ⁇ 140 ° C.
  • Drying can be done in suspension or in roller dryers, such as those from Kröner !. Coatema, Drytec or Polytype offered on the market. Alternatively, infrared or UV curing / drying can be used.
  • the typical speed at which the wet film is carried on the carrier through the drying section (s) is> 0.5 m / min and ⁇ 600 mmin, more preferably> 0.5 m / min and ⁇ 500 m / min and more preferably> 0.5 m / min and ⁇ 100 m / min.
  • the dry section length and the supply air of the dry sections are adapted to the speed.
  • the total residence time of the wet film in the dry section (s) is> 10 seconds and ⁇ 60 minutes, preferably> 30 seconds and ⁇ 40
  • the dielectric polyurethane film according to the invention is provided with a further conductive layer according to method IV. This can be done on one side or on both sides, in one layer or in several layers one above the other, by complete or by surface partial coating.
  • the coating can be full-surface or structured or segmented, i. take place only in subregions of the surface of the underlying layer, with a specifiable geometrical structure.
  • Glass, release paper, films and plastics, from which the produced polyurethane dielectric film can be easily separated, are particularly suitable as carriers for the production of a polymer film from the reaction mixture.
  • Particularly preferred paper or films are used. Paper can be coated on one or both sides, for example, with silicone or plastics.
  • the coating and / or the film can be made, for example, of plastics such as polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, Teflon, polystyrene, polybutadiene, polyurethane, acrylic ester-styrene-acrylonitrile, acrylonitrile / butadiene / acrylate, acrylonitrile il-butadiene styrene, acrylonitrile / chlorinated polyethylene / styrene, acrylonitrile / methyl methacrylate, butadiene rubber, butyl chut chuk, casein plastics, Artificial horn, cellulose acetate, cellulose hydrate, cellulose nitrate, chloroprene rubber, chitin, chitosan, cyclo-olefin copolymers, epoxy resin, ethylene-ethyl acrylate cop
  • these plastics can also be used directly as support materials and / or additionally provided with further internal or external release agents or layers.
  • the layers may have barrier functions or may also contain conductive structures which may optionally be transferred to the polyurethane dielectric film.
  • the plastics may be axially or biaxially oriented or stretched and may be pretreated by pressure or corona.
  • the films can also be reinforced. Typical reinforcements are fabrics such as textile or glass fibers.
  • a carrier made of glass, plastic or paper and preferably made of silicone or plastic-coated paper can be used.
  • the film or paper can be peeled off directly after coating and reused.
  • the film can be moved in a circle and the dielectric polyurethane film can be transferred directly to a new carrier when it is peeled off.
  • the carrier is provided with a structure. In the same way one speaks of a coinage.
  • the embossment is such that the structure transfers to the polyurethane dielectric film in such a manner that the embossment is formed only in the surface of the polyurethane dielectric film.
  • the embossing is smooth when the film is stretched.
  • the embossment is made such that an electrode layer on the film is stretched when stretched without significantly stretching that layer itself.
  • the embossment is preferably embossed in a roll-to-roll process in the carrier. For example, it gets cold or over here Cooling process hot stamped over a roll in a thermoplastic. Typical embossings are described for example in EP 1 919 071.
  • the electrode layers applied according to method step IV) can be applied, for example, via a printing process such as ink-jet, flexographic printing, screen printing, spraying or via a doctor blade, a nozzle or roller and via a metallization in a vacuum.
  • Typical materials are carbon based or based on metals such as silver, copper, aluminum, gold, nickel, zinc or other conductive metals as well as materials.
  • the metal can be applied as a salt or as a solution, as a dispersion or emulsion and also as a precursor. The adhesion is adjusted so that the layers in each case still adhere to each other.
  • Fig. 3 is a process diagram illustrating the Heinrichsprozes ses of a multilayer polyurethane coating system.
  • FIG 1 shows the schematic structure of the coating system used.
  • the individual components have the following reference numerals:
  • Optional cover layer Component b) is introduced into one of the two storage containers 1 of the coating installation.
  • the component a) is filled.
  • Both components are then conveyed through the metering devices 2 to the vacuum degassing device 3 and degassed. From here they are then each passed through the filter 4 in the static mixer 5, in which the mixing of the components takes place. The resulting liquid mass is then fed to the coating device 6.
  • the coating device 6 in the present case is a slot nozzle or a squeegee.
  • the mixture is applied to a support with the aid of the coating device 6, the aforesaid mixture being applied on a conveyor belt 8 as a wet film (station 1 in FIG. 3) and then cured in the circulating-air dryer 7 (station 2 in FIG. 3).
  • a dielectric polyurethane is obtained on a support, which is then optionally provided with a cover layer 9 (dust reduction), which is then removed again in a subsequent step.
  • a cover layer 9 is not preferred.
  • the conveyor belt 8 is a linear conveyor belt, the sample is subsequently removed therefrom and fed to a further coating station (station 3 in FIG.
  • Typical embodiments include a repetitive production system (dashed lines) Arrows in Fig. 3), such as a circulating conveyor belt or a carousel. This is a quasi-continuous process (solid parts in FIG. 3), wherein the intermediate layers are not isolated.
  • a further subject of the present invention is a multilayer dielectric polyurethane film system produced by the process according to the invention.
  • electromechanical transducer is the subject of the invention.
  • the electrode layer is applied to the layers in such a way that it can be contacted from the sides and does not stand above the dielectric film edge, since otherwise breakdowns occur. It is usual to allow a safety margin between the electrode and the dielectric so that the electrode area is smaller than the dielectric area.
  • the electrode is structured such that a conductor track is led out for electrical contacting. A typical picture is shown in FIG. 2.
  • the converter can be advantageously used in a variety of configurations for the production of sensors, actuators and / or generators.
  • Another object of the present invention is therefore an electronic and / or electrical device, in particular a module, automaton, instrument or a component comprising an electromechanical transducer according to the invention.
  • the present invention relates to the use of an electromechanical transducer according to the invention in an electronic and / or electrical device, in particular in an actuator, sensor or generator.
  • the invention in a variety of different applications in elektr omechanis chen and elektr oakustis chen area, especially in the field of energy from mechanical vibrations (energy harvesting), acoustics, ultrasound, medical diagnostics, acoustic microscopy, the mechanical Sensor technology, in particular pressure force and / or strain sensors, the robotics and / or communication technology can be realized.
  • Typical examples include pressure sensors, electro-acoustic transducers, microphones, loudspeakers, vibration transducers, light deflectors, diaphragms, optical fiber modulators, pyroelectric detectors, capacitors and control systems, and "intelligent" floors, as well as mechanical energy conversion systems, in particular rotating or oscillating movements. into electrical energy.
  • NCO contents were determined volumetrically in accordance with DIN EN ISO 1 1909, unless expressly stated otherwise.
  • the indicated viscosities were determined by rotational viscometry according to DIN 53019 at 23 ° C with a rotary viscometer Anton Paar Germany GmbH, Germany, I felmulli-l lirth- Str 6, 73760 Ostfildern.
  • the determination of the permanent elongation was carried out by means of a tractor Zwicki Zwick / Roell equipped with a load cell of the total measuring range of 50 N, on a S2 rod of the sample to be examined.
  • the determination of the stress relaxation was also carried out on the tractor Zwick; the instrumentation corresponds to the attempt to determine the permanent strain.
  • the sample used was a strip-shaped sample of the dimension 60 ⁇ 10 mm 2 , which was clamped with a clamp spacing of 50 mm. After a very rapid deformation to 55 mm, this deformation was held constant for a period of 30 minutes and during this time the catheter was closed. The stress relaxation after 30 minutes is the percentage decrease in stress, relative to the initial value immediately after deformation to 55 mm.
  • the measurements of the dielectric constant in accordance with ASTM D 1 50-98 were carried out using a measuring setup from Novocontrol Technologies GmbH & Co. KG, Obererbacher Strasse 9, 56414 Hundsangen, Germany. Germany (measuring bridge: Alpha-A Analyzer, measuring head: ZGS Active Sample Cell Test Interface) with a diameter of the test piece of 20 mm. Analyzes it was a frequency range of 10 7 Hz to 10 "2 Hz. As a measure of the dielectric constant of the investigated material, the real part of the dielectric constant has been selected at 10 to 0.01 Hz. The determination of the electrical recovery prior done by means of a Laborau tbaus Fa. Keithley Instruments (Keithley Instruments GmbH, Landsberger Strasse 65, D-82 1 10 Germering Germany) Model No .: 6517 A and 8009 according to ASTM D 257, a method for determining the insulation resistance of materials.
  • Fracture field strength was determined according to ASTM D 149-97a using a model HypotMAX high voltage source from Associated Research Inc, 13860 W Laurel
  • the sample holder contacts the homogeneously thick polymer samples with only a small amount of mechanical force
  • the non-prestressed polymer film is statically loaded in this structure with increasing voltage until an electrical breakdown takes place through the film. Measurement result is that achieved at break-through
  • a confocal microscope confocal laser scanning microscopy, LSCM
  • LSCM confocal laser scanning microscopy
  • Desmophen® C2201 polycarbonate polyol based on 1.6-1 lex andiol. manufactured by
  • Ketjenblack EC 300 J Product of Akzo Nobel AG
  • Cabot CCI-300 (silver dispersion from Cabot)
  • Hostaphan R N 2SLK release film from Mitsubishi based on polyethylene terephthalate with
  • Silicone coating A 300 mm wide film was used.
  • Baytubes® C150P Multilayered carbon nanotubes from Bayer MaterialScience AG Release paper: Polymethylpentene-coated release paper.
  • a squeegee system from Zehntner was used for the dielectric film.
  • the substrate was dried as follows:
  • a first drying section was at 80 ° C (2 m / s supply air), a second drying section at 100 ° C (3 m / s supply air), a third drying section at 1 10 ° C (8 m / s supply air), a fourth drying section operated at 130 ° C (7, 5, 2, 2 m's supply air).
  • the web speed of the carrier was controlled at 1 m / min; as incoming air, dry air was blown into the drying sections.
  • the layer thickness of the finished dielectric polyurethane film was 100 ⁇ .
  • the electrodes were applied.
  • a spraying device from Hansa airbrush
  • a screen printing machine from Thieme Model 3030 an inkjet printer from Fujifilm Di mal ix
  • a doctor blade from Zehntner Zehntner
  • the isocyanate (Desmodur N100) was used at 40 ° C
  • the polyol mixture (P200H / DS with TIB Kat 220) at 80 ° C.
  • the respective components were heated to 40 ° C and 80 ° C, respectively.
  • the static mixer was heated to 6 5 ° C, the doctor blade had 60 ° C.
  • the ratio of NGO to OH groups was 1, 07. It was poured onto the Hostaphan film.
  • Desmodur N100 There were 21.39 parts by weight of Desmodur N100, reacted with a polyol mixture of 0.0024 parts by weight of Tib Kat 220 and 100 parts by weight of Desmophen C2201 with each other.
  • the isocyanate (Desmodur N100) was used at 40 ° C
  • the hoses of the respective components were heated to 40 ° C respectively 80 ° C.
  • the static mixer was heated to 65 ° C, the squeegee had 60 ° C.
  • the ratio of NGO to OH groups was 1, 07. It was poured onto the Hostaphan film.
  • Desmodur N75 MPA Desmodur N75 MPA
  • a polyol blend of 0.02 parts by weight of Tib Kat 220 and 536.84 parts by weight of P200H / DS, 3.24 parts by weight of Byk 310 and 308 41 parts by weight of methoxypropyl acetate reacted with each other.
  • the isocyanate (Desmodur N75 MPA) was used at 23 ° C
  • the polyol mixture P200H / DS with TIB Kat 220
  • the hoses, the static mixer and the squeegee were each at 23 ° C.
  • the ratio of NGO to Ol I groups was 1, 07. It was poured onto the paper.
  • Desmodur N75 BA there were 1 13.62 parts by weight of Desmodur N75 BA, with a polyol mixture of 0.01 parts by weight of Tib Kat 220 and 459.30 parts by weight of P200H / DS, 2.77 parts by weight of Byk 3441 and 158.31 parts by weight of butyl acetate reacted with each other.
  • the isocyanate (Desmodur N75 BA) was used at 23 ° C
  • the polyol mixture P200H / DS with TIB Kat 220
  • the hoses, the static mixer and the squeegee were each at 23 ° C.
  • the ratio of NGO to OH groups was 1, 07. It was poured onto the paper.
  • Example 6-9 1 was alternately 5 so that 500 layers could be made. Accordingly, 2-4 in combination with 5 were used.
  • Two polyurethane films prepared according to Example 4 were used. Two foils of polyurethane were stacked on top of each other and laminated with a laminator with two rubber rollers under 3 bar pressure and a blowing speed of 5 mm / second.
  • Two polyurethane films prepared according to Example 4 were used. Two polyurethane films were stacked on top of each other and laminated with a laminator with two rubber rollers under 3 bar pressure and 100 ° C temperature (roll tempera- ture) and a blowing speed of 5 mm / second.
  • Two polyurethane films prepared according to Example 1 were used. For this purpose, two films of polyurethane were placed on each other and laminated with a laminator with two rubber rollers under 3 bar pressure and 100 ° C temperature (roller temperature) and a speed of 5 mm / second.
  • Two polyurethane films prepared according to Example 2 were used. For this purpose, two polyurethane films were stacked on top of each other and with a laminator with two rubber rollers under 3 bar pressure and 100 ° C temperature (Rollentemp er atur) and a speed of 5 mm /
  • the layers could be pulled apart again after lamination.
  • Two polyurethane films prepared according to Example 3 were used. For this purpose, two films of polyurethane were placed on each other and laminated with a laminator with two rubber rollers under 3 bar pressure and 100 ° C temperature (roller temperature) and a speed of 5 mm / second.
  • the layers could be pulled apart again after lamination.
  • Two polyurethane films prepared according to Example 4 were used. For this purpose, two films of polyurethane were placed on each other and laminated with a laminator with two rubber rollers under 3 bar pressure and 100 ° C temperature (roller temperature) and a speed of 5 mm / second.
  • the layers could be pulled apart again after lamination. It turns out that a solid layer composite is only possible by the process according to the invention by the layers are gradually chemically crosslinked to each other.
  • Example 5 the resistance was determined to be I, 10E + 04, so that it is a conductive layer.
  • All films showed a very high electrical resistance and high breakdown field strength.
  • the films according to the invention can be used in particular for the production of electromechanical converters with particularly good efficiencies. Due to the 500-layer structure, a 500-fold deflection could be achieved. The multi-layer structure had no negative effects on the properties and even after several cycles the properties were unchanged and there were no delaminations. The layers behaved for one shift.

Abstract

L'invention concerne un procédé de fabrication d'un système de films de polyuréthane diélectriques multicouches. Ledit procédé comprend les étapes qui suivent : I) la préparation d'un mélange comprenant a) un composé contenant des groupes isocyanate, ayant une teneur en groupes isocyanate > 10 % en poids et ≤ 50 % en poids, b) un composé contenant des groupes réactifs vis-à-vis des isocyanates, ayant un indice d'OH ≥ 20 et ≤ 150, la somme des fonctionnalités moyennes en nombre en groupes isocyanate et en groupes réactifs vis-à-vis des isocyanates des composés a) et b) étant ≥ 2,6 et ≤ 6 ; II) le dépôt du mélange immédiatement après sa préparation sous la forme d'un film humide sur un substrat ; III) le durcissement du film humide pour former le film de polyuréthane ; et IV) le dépôt d'une couche d'électrodes sur le film presque entièrement séché ; V) la répétition des étapes I) à IV) pour obtenir un système multicouches. L'invention concerne en outre un système de films de polyuréthane diélectriques multicouches, ainsi qu'un convertisseur électromécanique.
EP13732567.6A 2012-07-03 2013-07-01 Procédé de fabrication d'un système de films de polyuréthane diélectriques multicouches Withdrawn EP2870189A1 (fr)

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PCT/EP2013/063852 WO2014006005A1 (fr) 2012-07-03 2013-07-01 Procédé de fabrication d'un système de films de polyuréthane diélectriques multicouches
EP13732567.6A EP2870189A1 (fr) 2012-07-03 2013-07-01 Procédé de fabrication d'un système de films de polyuréthane diélectriques multicouches

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KR20150035799A (ko) 2015-04-07
US20150357554A1 (en) 2015-12-10
WO2014006005A1 (fr) 2014-01-09
JP2015533671A (ja) 2015-11-26
CN104379625A (zh) 2015-02-25

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