EP2867281A1 - Film de polyuréthane diélectrique - Google Patents

Film de polyuréthane diélectrique

Info

Publication number
EP2867281A1
EP2867281A1 EP13734687.0A EP13734687A EP2867281A1 EP 2867281 A1 EP2867281 A1 EP 2867281A1 EP 13734687 A EP13734687 A EP 13734687A EP 2867281 A1 EP2867281 A1 EP 2867281A1
Authority
EP
European Patent Office
Prior art keywords
film
isocyanate
wet film
mixture
mbar
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Withdrawn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
EP13734687.0A
Other languages
German (de)
English (en)
Inventor
Joachim Wagner
Jens Krause
Dennis Hoenel
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 EP13734687.0A priority Critical patent/EP2867281A1/fr
Publication of EP2867281A1 publication Critical patent/EP2867281A1/fr
Withdrawn legal-status Critical Current

Links

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
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00349—Creating layers of material on a substrate
    • B81C1/0038—Processes for creating layers of materials not provided for in groups B81C1/00357 - B81C1/00373
    • 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
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
    • B81B3/00—Devices comprising flexible or deformable elements, e.g. comprising elastic tongues or membranes
    • B81B3/0018—Structures acting upon the moving or flexible element for transforming energy into mechanical movement or vice versa, i.e. actuators, sensors, generators
    • B81B3/0021—Transducers for transforming electrical into mechanical energy or vice versa
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
    • 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
    • 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
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
    • B29K2995/0006—Dielectric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/008—Wide strips, e.g. films, webs
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • 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
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • Y10T29/00—Metal working
    • Y10T29/43—Electric condenser making
    • 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 dielectric polyurethane film which is particularly suitable for use in electromechanical transducers. Further objects of the invention are a dielectric polyurethane film obtainable by the process according to the invention, a process for the production of an electrochemical converter and an electrochemical converter 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.
  • 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.
  • EAPs are a ductile dielectric that deforms in the electric field.
  • dielectric elastomers are mostly in film form (DEAP, dielectric electroactive polymer) which have a high electrical resistance and are coated on both sides with stretchable electrodes with high conductivity (electrode), as described, for example, in WO-A 01/06575.
  • Electroactive polymers as elastic dielectric in transducer systems must - depending on the application in different components: actuators / sensors or generators - have different properties.
  • Common electrical properties are: a high electrical internal resistance of the dielectric, a high dielectric strength, and a high dielectric constant in the frequency range of the application. These properties allow a large amount of electrical energy to be stored permanently in the smallest volume filled with the electroactive polymer.
  • Actuators are either too low in dielectric constant and / or breakthrough field strength or too high in 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 all to an electrical breakdown.
  • generators it is important that they produce a high electrical current yield with low losses. Typical losses occur at interfaces, loading and unloading of the dielectric elastomer, and leakage through the dielectric elastomer.
  • the resistance of the electrically conductive electrode layer of the EAP causes an energy loss; The electrode should therefore again have the lowest possible electrical resistance.
  • transducers which contain various polymers as a constituent of the electroactive layer, see, for example, WO-A 01/06575.
  • 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 a much too high creep under cyclic tensile loads
  • One-component polyurethane systems are only possible for linear, unbranched systems with a functionality of 2 and smaller that also the systems known from DE 10 2007 059 858 do not meet the requirements
  • a one-component solution of higher functionality would lead to a gel or powder, with infinite molecular weight, which makes coating / film formation impossible
  • a reversible strain-strain-process which has to be applied for EAPs, is not possible because the polymer flows, furthermore the electrical resistance of the described polyether systems is too low 034 describes polyether polyols which have too low an elect have political resistance.
  • EP2330649 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 dielectric polyurethane films to be produced by the continuous process should have one or more of the following properties: a) a tensile strength of> 2 MPa more preferably> 4, especially> 5 according to DIN 53 504 b) an elongation at break of> 200% according to DIN 53 504 c) A stress relaxation (Creep) at 10% deformation after 30 minutes according to DIN 53 441 of ⁇ 30% (particularly preferably ⁇ 20, very particularly ⁇ 10%) d) A breakdown field strength of> 40 V / ⁇ according to ASTM D 149 E) An electrical resistance of> 1.5E12 ohm m according to ASTM D 257 (particularly preferably> 2E12, very particularly,> 5 E12, very particularly> 1E13).
  • the object according to the invention is achieved by a process for the production of a dielectric polyurethane film in which at least the following steps are carried out continuously:
  • I) a mixture comprising a) an isocyanate group-containing compound having a content of isocyanate groups of> 10 wt .-% and ⁇ 50 wt .-%, b) an isocyanate-reactive group-containing compound having an OH number of> 20 and ⁇ 150, c) at least one solvent which has a vapor pressure at 20 ° C. of> 0.1 mbar and ⁇ 200 mbar, d) at least one wetting additive, is prepared, the sum of the number-average functionality of isocyanate groups and isocyanate-reactive groups of the compounds a) and b) being> 2.6 and ⁇ 6,
  • the dielectric polyurethane 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 an electromechanical converter with high efficiency.
  • 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4 and / or 2,4,4-trimethylhexamethylene diisocyanate the isomeric bis (4, 4'-isocyanatocyclohexyl) methanes (1,11-MDI) or mixtures thereof of any desired isomer content, 1,4-cyclohexylene diisocyanate, 4-1-cyano-hydra-1-octanediocyanate (nonane triisocyanate), 1,4-phenylene diisocyanate, 2,4- and / or 2,6- 1 luv lend ii socy an at (TDI), 1, -N apht hy lendi isocyanate, 2.2 * - and / or 2,4 * - and / or 4,4'-diphenylmethane diiso
  • TDI 1, -
  • modifications such as allophanate, uretdione, urethane, isocyanurate, biuret, iminooxadiazinedione or oxadiazinetrione containing compounds based on said diisocyanates are 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, 1 1 1 2-MI, TDI and MDI are particularly preferably used for the modification.
  • Particular preference is given to HDI.
  • Very particular preference is given to using a polyisocyanate based on FIDI having a functionality of> 2.6.
  • Especially preferred Biurets, allophanates, isocyanurates and Iminooxadiazindion- or Oxadiazintrion Geneva be used, most preferably biurets.
  • 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 is ordered from an aliphatic polyisocyanate, preferably hexamethylene diisocyanate and more preferably a biuret and / or isocyanurate of hexamethylene diisocyanate.
  • the Isocyanatgrappen may be partially blocked or blocked 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.
  • Typical blocking agents are, for example, caprolactam, methyl ethyl ketoxime, pyrazoles, such as, for example, 3,5-dimethyloyl-2-pyrazole or 1-pyrazole, triazoles, for example 1, 2,4-triazole, diisopropylamine, diethyl malonate, diethylamine, 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. Vitvyl, and / or carbinol Grappen act.
  • the isocyanate-reactive groups are particularly preferably hydroxyl and / or amine groups. It is advantageous if 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 KOH / 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) may be 1000-8000 g / mol, preferably 1500-4000 g / mol and more preferably 1500-3000 g / mol. It is furthermore preferred if the isocyanate-reactive G nippender of compound b) is a polymer.
  • the compound b) comprises or consists of a diol and particularly preferably a polyester diol and / or a polycarbonate diol.
  • the compound b) it is possible to use polyetherpolyols, polyetheramines, polyetheresterpolyols, polycarbonatepolyols, polyethercarbonatepolyols, polyesterpolyols, polybutadiene derivatives, polysiioxane-based derivatives and mixtures thereof.
  • b) preferably comprises or consists of a polyol having at least two isocyanate-reactive hydroxyl groups.
  • polyether polyether, polyester, polycarbonate and polyetherester polyols, polybutadiene polyols, polysiloxane polyols, particularly preferably polybutadienols, polysiloxane polyols, polyester polyols and / or polycarbonate polyols, most 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 hydroxycarboxylic acids or lactones.
  • the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters of lower alcohols can also be used to prepare the polyesters.
  • Polyester polyols are prepared in a conventional manner by polycondensation of 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 ring esters. provided, as the reaction component predominantly low molecular weight polyols having 2 to 12 carbon atoms are used.
  • suitable alcohols are ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (1,6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol esters or mixtures thereof, with hexanediol (1,6) and isomers, butanediol (1,4), neopentyl glycol and neopentyl glycol hydroxypivalate being preferred.
  • polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexan
  • polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, 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 examples include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid and / or 2,2-dimethylsuccinic acid are used.
  • the acid source used may also be the corresponding anhydrides.
  • monocarboxylic acids such as benzoic acid and hexanecarboxylic acid.
  • 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.
  • Hydroxycarboxylic acids which may be co-used as reactants in the preparation of a hydroxyl-terminated polyester polyol include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid or hydroxystearic acid, or mixtures thereof.
  • Suitable lactones are caprolactone, butyrolactone or homologs or 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. Dimethylearbonat or phosgene by 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, Neopentylglykoi, 1, 4-bishydroxymethylcyclohexane, 2nd - Methyl-l, 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 aforementioned kind or mixtures thereof.
  • the diol component preferably 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 OH groups.
  • Such derivatives are obtainable, for example, by reaction of hexanediol with excess caprolactone or by etherification of flexanediol 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 polycarbonate diol 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 starting agents.
  • suitable starter molecules for example, water, butyl diglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, sorbitol, ethylenediamine, triethanolamine, or 1, 4-butanediol or mixtures thereof can be used.
  • polyether polyols can be prepared by alkaline catalysis or by Doppeimetallcyanid- catalysis or optionally in stepwise reaction by means of alkaline catalysis and Doppelmetallcyanidkatalyse of a starter molecule and epoxides, preferably ethylene and / or Prepared propylene oxide and have terminal hydroxyl groups.
  • DMC catalysis double-metal cyanide 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.
  • mixtures of multiple starters can be used.
  • mixtures of several polyether polyols can be used as polyether polyols.
  • Suitable compounds b) are also ester diols such as a-hydroxybutyl-e-hydroxy-caproic acid ester, ro-hydroxyhexyl-y-hydroxybutyric acid ester, adipic acid (ß-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,
  • Tripropylene glycol monobutyl ether 2-ethylhexanol, 1-octanol, 1-dodecanol or 1-hexadecanol or mixtures thereof.
  • 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 extenders such as diethyltoluenediamine (DETDA), 3,3'-dichloro-4,4'-diaminodiphenylmethane (MBOCA), 3,5-diamino-4-chloro-isobutylbenzoate, 4-methyl 2,6-bis (methylthio) -1,3-diaminobenzene (Ethacure 300), trimethylene glycol di-p-aminobenzoate (Polacure 740M) and 4,4'-diamino-2,2'-dichloro-5,5 '-diethyldiphenylmethane (MCDEA) can be used.
  • DETDA diethyltoluenediamine
  • MOCA 3,
  • MBOCA 3,5-diamino-4-cbloro-isobutylbenzoate.
  • Components suitable for chain extension according to the invention are organic diamines or polyamines.
  • 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 OH groups.
  • primary secondary amines such as diethanolamine, 3-amino-1-methylaminopropane, - amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, alkanolamines such as N-aminoethylethanolamine, ethanolamine , 3-aminopropanol, neopentanolamine.
  • amines with an isocyanate-reactive group such as methylamine, ethylamine, propylamine, butyiamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine.
  • an isocyanate-reactive group such as methylamine, ethylamine, propylamine, butyiamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine.
  • an isocyanate-reactive group such as methylamine, ethylamine, propylamine, butyiamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine.
  • üibutylamin an iso
  • N-methylaminopropylamine diethyl (methyl) aminopropylamine, morpholine, piperidine, or suitable substituted derivatives thereof, amide amines of diprimary amines and monocarboxylic acids, monocrimets of diprimary amines, primary / tertiary amines such as N, N-dimethylaminopropylamine.
  • 6-1 lexanediol 1, 7-1 leptanediol, 2-l: ethyl-1, 6-1-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol 1 .1 1-undecanediol, 1 .12 Dodecanediol, diethylene glycol, triethylene glycol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol and water used.
  • 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, degassing and defoaming agents, wetting additives and catalysts.
  • 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 copolymers, 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, and organic fillers, in particular those having a high electrical polarizability, for example phthalocyanines, poly-3-hexylthiophene.
  • the dielectric constant of the polyurethane film can be increased.
  • a higher dielectric constant can also be achieved by introducing 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.
  • 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 done for example by generating one or more further layers or by penetration of the polyurethane film, for example by diffusion.
  • aqueous and organic solvents can be used.
  • a solvent which has a vapor pressure at 20 ° C. of> 0.1 mbar and ⁇ 200 mbar, preferably> 0.2 mbar and ⁇ 150 mbar and particularly preferably> 0.3 mbar and ⁇ 120 mbar.
  • This solvent may in particular be the mixture of the step I) are added. It is particularly advantageous that the films of the invention can be produced on a roller coating system.
  • the polyurethane film may have a layer thickness of 0.1 ⁇ m to 1000 ⁇ m, preferably from 1 ⁇ m to 500 ⁇ m, particularly 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 support in step II) can be carried out, for example, by knife coating, brushing, casting, spinning, spraying, extrusion in a roll-to-roll process.
  • 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.
  • the 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), the distance between the nozzle and the substrate should be selected to be less than 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 10 to 300 ⁇ m, preferably of 15 to 150 ⁇ m, more preferably of 20 to 120 ⁇ m and very particularly preferably of 20 to 80 ⁇ m can be produced in step II).
  • the wet film is cured in step III) by being passed through a first drying section, which preferably has a temperature> 40 ° C and ⁇ 1 20 ° C, more preferably> 60 ° C and ⁇ 110 ° C and particularly preferably> 60 ° C and ⁇ 100 ° C.
  • the wet film can 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 ⁇ 120 ° 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 Krönen. Coatema, Drytec or Po! Y type are offered on the market.
  • the typical rate at which the wet film on the support passes through the drying section (s) is> 0.5 m / min and ⁇ 600 m / min, 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 or sections is> 10 seconds and ⁇ 60 minutes, preferably> 30 seconds and ⁇ 40 minutes, more preferably> 40 seconds and ⁇ 30 minutes, and most preferably> 40 seconds and ⁇ 10 mins.
  • the dielectric polyurethane film according to the invention can be provided with further functional layers, for example conductive layers, barrier layers against solvents and gases, and / or adhesive layers. 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.
  • further functional layers for example conductive layers, barrier layers against solvents and gases, and / or adhesive layers. 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.
  • 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 kan on one or both sides, for example, be coated 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, acrylic ni tri I -butadiene-s tyro I, acrylonitrile / chlorinated polyethylene / styrene, acrylonitrile / methyl methacrylate, butadiene rubber, butyl rubber, casein plastics, artificial horn, cellulose acetate, cellulose hydrate, cellulose nitrate, chloroprene rubber, chitin, chitosan, Cyclo-olefin copolymers, epoxy resin, ethylene-ethyl acrylate copoly
  • Polychlorotrifluoroethylene polyester, polyester amide, polyether block amide, polyetherimide, polyether ketones, polyethersulfone, polyhydroxyalkanoates, polyhydroxybutyrate, polyimide, polyisobutyls, polylactic acid, polyniethacylimethylmide, polymethylterephthalate, polymethyl methacrylate, polymethylpentene, polyoxymethylene or polyacetal, polyphenylene ethers , Poiyphenylensuifid, polyphthalamide, polypynol, polystyrene, polysulfone, polytetrafluoroethylene, polyurethane PUR, polyvinyl acetate, polyvinyl butyral, polyvinyl chloride, polyvinylidene fluoride, polyvinylpyrrolidone, silicone, styrene-acrylonitrile copolymer, styrene-butadiene rubber, styrene-butad
  • 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 with pressure or corona.
  • the films can also be reinforced. Typical reinforcements are fabrics such as textile or glass fibers.
  • a support made of glass, plastic or paper and preferably 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 during stripping.
  • the carrier is provided with a structure. This is also called an imprint.
  • 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 embossing is preferably embossed in a roll-to-roll process in the carrier. For example, hot or coagulated hot through a roll into a thermoplastic is applied here. Typical embossings are described for example in EP 1 919 071.
  • Figure 1 shows the schematic structure of the coating system used.
  • the individual components have the following reference numerals:
  • Component b) was introduced into one of the two storage containers 1 of the coating installation. In the second reservoir 1, the component a) was filled. Both components were then conveyed through the metering devices 2 to the vacuum degassing device 3 and degassed. From here they were then each passed through the filter 4 in the static mixer 5, in which the mixing of the components took place. The resulting liquid mass was then fed to the coating device 6.
  • the coating device 6 in the present case was a slot nozzle. With the aid of the coating device 6, the mixture was applied to a carrier 8 as a wet film and then cured in the circulating air dryer 7. In this case, a dielectric polyurethane film was obtained, which was then provided with a covering layer 9 and wound up.
  • Another object of the present invention is obtainable by the process according to the invention dielectric polyurethane film.
  • a further subject matter of the invention is a layer structure comprising a carrier substrate, a dielectric polyurethane film according to the invention applied thereon and optionally a covering layer applied on the side of the film remote from the carrier substrate.
  • the layer structure may have one or more covering layers on the film in order to protect it from dirt and environmental influences.
  • plastic films or Foiienverbundsysteme, but also clearcoats can be used.
  • covering layers it is preferred to use film materials analogous to the materials used in the support, wherein these may have a thickness of typically 5 to 200 ⁇ m, preferably 8 to 125 ⁇ m, particularly preferably 20 to 50 ⁇ m.
  • cover layers PE or PET films of a thickness of 20 to 60 ⁇ are preferably used. Particularly preferred is a polyethylene film with a thickness of 40 ⁇ used.
  • a method for producing an electromechanical transducer in which a dielectric polyurethane film is produced in a first step by a method according to the invention and in a second step an electrode is arranged on opposite sides of the dielectric polyurethane film.
  • the electrodes can be applied, for example, via a printing process such as ink-jet, flexographic printing, screen printing 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 polyurethane dielectric film may be disposed between the electrodes such that the polyurethane dielectric film contacts at least one of the electrodes.
  • the polyurethane dielectric film may also be disposed between the electrodes such that the electrodes on opposite sides of the polyurethane dielectric film are adjacent thereto.
  • the dielectric polyurethane films according to the invention can be coated on both sides with electrodes.
  • the electrodes and the dielectric polyurethane film in separate steps and to add them together afterwards. Typical methods would be gluing or laminating, for example.
  • 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 the electro-mechanical and electro-acoustic field, in particular in the field of energy from mechanical vibrations (energy harvesting), acoustics, ultrasound, medical diagnostics, acoustic microscopy, mechanical sensors, in particular pressure -, force and / or strain sensors, robotics and / or communication technology are realized.
  • Typical examples include pressure sensors, electroacoustic transducers, microphones, loudspeakers, vibration transducers, light deflectors, diaphragms, optical fiber modulators, pyroelectric detectors, capacitors and control systems, and "intelligent" floors, as well as systems for converting water wave energy, particularly sea-wave energy, into electrical energy. Examples:
  • NCO contents were determined volumetrically in accordance with DIN EN ISO 11909, unless expressly stated otherwise.
  • the indicated viscosities were determined by means of a rotational viscometer according to DIN 53019 at 23 ° C. using a rotational viscometer from Anton Paar Germany GmbH, Germany, in the state of the art! irth-
  • the tensile tests were carried out by means of a tractor from Zwick, model number 1455, equipped with a load cell of the total measuring range IkN according to DIN 3 5 4 at a pulling speed of 50 mm / min. S2 specimens were used as specimens. Each measurement was carried out on three identically prepared test specimens and the mean of the data obtained was used for the evaluation. Specifically, in addition to the tensile strength in [MPa] and the elongation at break in [%], the stress in [MPa] at 100% and 200% elongation was determined.
  • the determination of the permanent elongation was carried out by means of a tractor Zwicki Zwick / Roeli, equipped with a load cell of the total measuring range of 50 N, on a S2 rod of the sample to be examined.
  • the value for 50% deformation is measured.
  • 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 fast deformation to 55 mm, this deformation was kept constant for a period of 30 minutes and during this time the force curve was determined. 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 150-98 were carried out using a measuring setup from Novocontrol Technologies GmbH & Co.
  • the electrical resistance was determined by means of a laboratory setup from Keithley Instruments (Keithley Instruments GmbH, Landsberger Strasse 65, D-82110 Germering Germany) Model No .: 6 17 A and 8009 according to ASTM D 257, a method for determining the insulation resistance of materials.
  • the breakdown field strength according to ASTM D 149-97a was determined using a model HypotMAX model hypotMAX, Associated Research Inc, 13860 W Laurel Drive, Lake Forest, IL 600045-4546, US A, and a self-constructed sample holder. The sample holder contacts the homogeneous-thickness polymer samples with little mechanical preload and prevents the operator from coming into contact with the tension.
  • the non-prestressed polymer film is statically loaded in this structure with increasing voltage until an electrical breakdown takes place through the film.
  • the result of measurement is the voltage reached at break-through, based on the thickness of the polymer film in ⁇ ]. There are 5 measurements per slide and the mean value is given. Substances used and abbreviations:
  • Desmophen® C2201 polycarbonate polyol based on 1 .6-1 hexanediol. manufactured by
  • PolyTHF molecular weight Mn 650 g / mol PolyTHF ® 1000, BASF AG
  • Desmophen ® C 1200 Linear, aliphatic polycarbonate polyester Bayer MaterialScience AG
  • Release paper polymethylpentene coated release paper.
  • a coating plant from Finna Coatema with 7 dryers in a continuous roll-to-roll process was used. Commissioned by: Slot nozzle of TSE Troiler, Switzerland. Unless otherwise stated, the nozzle to carrier distance has been set to 100 ⁇ m.
  • a two-component low-pressure casting machine with two gear pumps (heated), stirred and heated containers, heatable hoses and filters was used. In addition, a static, heatable mixer was used.
  • 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 the support 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 ⁇ .
  • Example 1 The examples according to the invention could be prepared continuously for more than 8 hours without the applicator being added or coating problems occurring.
  • Example 1 Example 1:
  • Desmodur N100 there were 21, 39 parts by weight Desmodur N100, with a polyol mixture of 0.0024 parts by weight doctrine Kat 220 and 100 parts by weight P200H / DS implemented.
  • the isocyanate (Desmodur Nl 00) was used at 40 ° C
  • the polyol mixture (P200H / DS with T1 B cat 220) at 80 ° C.
  • the hoses of the respective components were heated to 40 ° C respectively 80 ° C.
  • the static mixer was heated to 65 ° C, the nozzle had 60 ° C.
  • the ratio of NGO to OH groups was 1, 07. It was poured onto the Hostaphan film.
  • Desmodur N100 39 parts by weight of Desmodur N100 were reacted with a polyol mixture of 0.0024 part by weight of Tib Kat 220 and 100 parts by weight of Desmophen C2201.
  • 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 nozzle had 60 ° C.
  • the ratio of NGO to OH groups was 1, 07. It was poured onto the Hostaphan film.
  • Example 3 151.50 parts by weight of Desmodur N75 MPA, with a polyol mixture 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 Reacted 310 and 308.41 parts by weight of methoxypropyl acetate.
  • the isocyanate (Desmodur N75 MPA) was used at 23 ° C
  • the polyol mixture P200FI / DS with TIB Kat 220
  • the hoses, the static mixer and the nozzle were each at 23 ° C.
  • the ratio of NGO to oil 1 groups was 1, 07. It was poured onto the paper.
  • Desmodur N75 BA there were 1 13.62 parts by weight Desmodur N75 BA, with a polyol mixture of 0.01 parts by weight Tib Kat 220 and 459.30 parts by weight P200H / DS, 2.77 parts by weight Byk 3441 and 158.31 parts by weight! reacted butyiacetate.
  • the isocyanate (Desmodur N75 BA) was used at 23 ° C
  • the polyol mixture (P200H / DS with TIB Kat 220) at 23 ° C.
  • the hoses, the static mixer and the nozzles were each at 23 ° C.
  • the ratio of NCO to OH groups was 1.07. It was poured onto the paper.
  • Comparative Example A-3/4 The procedure was as in Examples 3 and 4, but was dispensed with BYK 310 and Byk 3441. It could be on the roll coater used to produce no film because the polyurethane resulted in no wetting.
  • Example 3 The procedure was as in Example 3 and 4, but the distance of the nozzle was increased to 400 ⁇ . No film could be produced on the roll coater used because the wetting was very irregular.
  • the raw materials used were not degassed separately.
  • 50.0 g of Desmophen ® C2201 and 0.05 g Irganox ® 1076 were weighed into a polypropylene beaker, mixed by Speedmixer at 3000 revolutions per minute for a duration of 1 minute, and thereafter vorgechinnt to 60 ° C. After the stabilizer Irganox® 1076 has completely dissolved, 0.01 g DBTDL was added and this mixture was again homogenized for 1 min at 3000 revolutions per minute. 10.79 g of Desmodur ® N 3300 was added to this weighed homogeneous mixture and again mixed in this mixture Speedmixer at 3000 revolutions per minute for a period of 1 minute.
  • films of a wet layer thickness of 1 mm were laced by hand on glass plates. All films were cured after production at 100 ° C in the oven for a period of 1 h. The films could easily be released from the glass plate according to I land.
  • the pot life of the mixture was too low at 1 minute to use the mixture in a roll-to-roll process. Also, the one-component procedure is unsuitable because the mixture is solidified before application in a roll-to-roll process in the commissioned work after a few minutes and so a continuous coating is not possible. Also, the drying time was much too long with one hour.
  • a glass plate is an unfeasible carrier that is not suitable as a release film in a roll-to-roll process. In addition, the dielectric constant was only 4.6 and the elongation at break was only 175%.
  • Comparative Example B-10 The raw materials used were not degassed separately. 50.0 g of Desmophen ® C2200 and 0.05 g Irganox ® 1076 were weighed into a polypropylene beaker, mixed by Speedmixer at 3000 revolutions per minute for a duration of 1 minute, and then preheated to 60 ° C. After the stabilizer Irganox ® is completely dissolved 1076, 0.15 g Desmorapid SO ® was added and this mixture is homogenized again for a period of 1 min at 3000 rpm. 1 1.48 g of Desmodur ® N was added to this weighed 100 homogeneous mixture and again mixed in this mixture Speedmixer at 3000 revolutions per minute for a period of 1 minute.
  • films of a wet layer thickness of 1 mm were laced by hand on glass plates. All films were cured after exposure to 100 ° C in the oven for a period of 1 h. The films could be easily released from the glass plate after curing by hand.
  • the pot life of the mixture was too low at 1 minute to use the mixture in a roll-to-roll process. Also, the one-component operation is unsuitable, since the mixture is solidified after application in the roll-to-roll process in the commissioned work after a few minutes and so a continuous coating is not possible. Also, the drying time was much too long with one hour.
  • a glass plate is an inflexible carrier that is not suitable as a release film in a roll-to-roll process.
  • the raw materials used were not degassed separately. 29.412 g of Desmodur® XP 2599 and 50.0 g of Desmophen® C 2200 were mixed with 0.045 g of Desmorapid® SO and 0.05 g of Irganox® 1 076 in a polypropylene beaker in the Speedmixer at 3000 rpm for the duration of 1 minute mixed. From the still liquid reaction mixture were placed on glass plates of 1 and 1 films of a wet film thickness of 1 mm geräkelt. All films were dried after production at 80 ° C in a drying oven overnight and then post-annealed at 120 ° C for 5 min. The films could be easily released from the glass plate after tempering by hand.
  • the pot life of the mixture was too low at 1 minute to use the mixture in a roll-to-roll process. Also, the one-component operation is unsuitable, since the mixture is solidified after application in the role-to-Roile process in the commissioned work after a few minutes and so a continuous coating is not possible.
  • a glass plate is an inflexible carrier that is not suitable as a release film in a roll-to-roll process. The electrical resistance is too low.
  • the raw materials used were not degassed separately. 50.0 g Desmophen® C 1200 was mixed with 0.05 g Irganox® 1076, 9.188 g Desmodur® N100 and 0.013 g DBTDL in a polypropylene beaker in the Speedmixer at 3000 revolutions per minute for 1 minute. From the still liquid reaction mixture, films of a wet layer thickness of 1 mm were laced by hand on glass plates. All films were dried after production at 80 ° C in a drying oven overnight and then post-annealed at 120 ° C for 5 min. The films could be easily released from the glass plate after tempering by hand.
  • a glass plate is an inflexible carrier that is not suitable as a release film in a roll-to-roll process.
  • the raw materials used were not degassed separately.
  • 309.5 g of the prepolymer from Example 1 was preheated to 60 ° C, with 10.0 g of TMP, 0.2 g of DBTDL and 0.01 g Irganox ® was weighed into a polypropylene beaker 1076 and in the Speedmixer at 3000 revolutions per minute mixed for a period of 1 minute
  • films of a wet film thickness of 1 mm were lapped on glass plates from Iand. All films were cured after production at 100 ° C in the oven for a period of 1 h. The films could be easily released from the glass plate after curing by hand.
  • the pot life of the mixture was too low at 1 minute to use the mixture in a roll-to-roll process. Also, the one-component operation is unsuitable, since the mixture is solidified after application in a roll-to-roll process in the commissioned work after a few minutes and so a continuous coating is not possible. Also, the drying time was much too long with one hour.
  • a glass plate is an inflexible carrier that is not suitable as a release film in a roll-to-roll process.
  • the electrical resistance is too low.
  • reaction paste was poured onto a glass plate and pulled out with a squeegee of wet film thickness 500 ⁇ to form a homogeneous film of solids content 2%.
  • the film was then annealed at 80 ° C for 16 h.
  • the breakdown field strength was determined to 5 V / ⁇ and the resistance to 2.00E03 ohm m. Both values are below the requirements.
  • the breakdown field strength was determined to 30 V / ⁇ and the resistance to 1, 67E08 ohm m. Both values are below the requirements.
  • Viscosity (viscometer, 23 ° C): 4600 mPas
  • each polymer layer was not degassed separately.
  • the required amount of 100 g of the solution was weighed into a polypropylene beaker (PP cup).
  • PP cup polypropylene beaker
  • 1 mm layers of the wet film thickness of 1 mm were lapped on glass plates. All layers were dried after production at 30 ° C in a drying oven overnight and then post-annealed at 120 ° C for 5 min. The layers could be easily released as films after annealing by hand from the glass plate.
  • the creep was determined to be 42.5%. This is far beyond the requirements of ⁇ 10%.
  • the creep was determined to be 13.5%, the electrical resistance to 3.54 HO 8 ohm m and the fürbruchfeidStore to 20.4 V / ⁇ . This is outside the requirements.
  • Breakdown field strength to 21.3 V / ⁇ . This is outside the requirements.
  • the creep was determined to be 30.3%, the electrical resistance to 4.77E08 ohm m and the breakdown field strength to 25 V / ⁇ . This is outside the requirements.
  • the electrical resistance was determined to 5.08E08 ohm m and the breakdown field strength to 25.4 V / ⁇ . This is outside the requirements.
  • the electrical resistance was determined to 1 .501: 09 ohm m and the breakdown field strength to 33.4 V / ⁇ . This is outside the requirements.
  • films of a wet layer thickness of 1 mm were laced by hand on glass plates. All films were dried after production at 80 ° C in a drying oven overnight and then post-annealed at 120 ° C for 5 min. The films could be easily released from the glass plate after tempering by hand.
  • the creep was determined to 21, 3%, the electrical resistance to 1 .74F09 ohm m and the breakdown field strength to 24.6 V / ⁇ . This is outside the requirements.
  • films of a wet layer thickness of 1 mm were laced by hand on glass plates. All films were dried after the preparation at 80 ° C in a drying oven overnight and then postcured for 5 min at 120 ° C. The films could be easily released from the glass plate after tempering by hand.
  • the creep was determined to 24.4%, the electrical resistance to 1, 421: 09 ohm m and the breakdown field strength to 18.2 V / ⁇ . This is outside the requirements.
  • This mixture was then treated with 66.16 g of a polyfunctional polypropylene glycol-polyethylene glycol polyether having a number average molecular weight of 4000 g / mol and a content of ethylene oxide units of 20 wt .-%, based on the polyether, in an amount of 0.322 g of DBTDL was mixed in a polypropylene blender at 3000 rpm for 3 minutes in the Speedmixer films of a wet film thickness of 1 mm were stripped from the still liquid reaction mixture on glass plates of all countries Production was dried overnight at 80 ° C. in the drying oven and then post-baked for 5 minutes at 120 ° C. The films could be easily detached from the glass plate after tempering by hand.
  • the raw materials used were not degassed separately. 9.0 g of the prepolymer described above were weighed with 1.0 g of Desmodur N 3300 in a polypropylene beaker and mixed together in the Speedmixer at 3000 revolutions per minute for 1 minute. This mixture was then mixed with 24.22 g of a difunctional polypropylene glycol polyethyleneglycol polyether having a number average molecular weight of 4000 g / mol and a content of ethylene oxide units of 20% by weight, based on the polyether, in an amount of 0.048 g DB DL mixed in a polypropylene beaker in Speedmixer at 3000 rpm for 3 minutes.
  • Viscosity 1300 mPas
  • the required amount of 100 g of the dispersion was weighed in a PP beaker. From the still liquid reaction mixture, films of the wet film thickness 1 mm were hand-rolled onto glass plates by hand. All films were dried after production at 30 ° C in a drying oven overnight and then post-annealed at 120 ° C for 5 min. The films could be easily released from the glass plate after tempering by hand.
  • the creep was determined to 48.3% fürbruchfeidGood to 21 V / ⁇ and are thus outside the required requirements.
  • Viscosity 1000 mPas The required amount of 100 g of the dispersion was weighed in a PP beaker. From the still liquid reaction mixture, films of the wet film thickness 1 mm were hand-rolled onto glass plates by hand. All films were dried after production at 30 ° C in a drying oven overnight and then post-annealed at 120 ° C for 5 min. The films could be easily released from the glass plate after tempering by hand. The creep was determined to 48.3%, the breakdown field strength to 23 V / ⁇ and are thus outside the required requirements.
  • the films according to the invention offer distinct advantages over those of the prior art. Also, the films of the present invention were produced on an industrial scale in a roll-to-roll coating process. The comparative examples are laboratory approaches. Particularly advantageous in the films of the invention, the combination of very high electrical resistance and high breakdown field strength. The films of the invention can be used in particular for the production of electromechanical transducers with particularly good efficiencies.

Abstract

La présente invention concerne un procédé de fabrication d'un film de polyuréthane diélectrique, dans lequel on effectue en continu au moins les étapes suivantes : I) on prépare un mélange comprenant : a) un composé contenant des groupes isocyanate à une teneur > 10 % en poids et ≤ 50 % en poids, b) un composé contenant des groupes réagissant avec les isocyanates ayant un indice d'OH ≥ 20 et ≤ 150, au moins un solvant ayant une pression de vapeur > 0,1 mbar et < 200 mbar à 20 °C, au moins un additif mouillant, la somme des fonctionnalités moyennes en nombre en groupes isocyanate et en groupes réagissant avec les isocyanates des composés a) et b) étant ≥ 2,6 et ≤ 6 ; II) on dépose le mélange immédiatement après sa préparation sous la forme d'un film humide sur un substrat ; III) on durcit le film humide afin de former le film de polyuréthane ; et IV) on sépare le film de polyuréthane du substrat. L'invention concerne en outre un film de polyuréthane diélectrique qui peut être obtenu par le procédé de l'invention, un procédé de fabrication d'un convertisseur électrochimique, ainsi qu'un convertisseur électrochimique qui peut être obtenu par ce procédé.
EP13734687.0A 2012-06-27 2013-06-24 Film de polyuréthane diélectrique Withdrawn EP2867281A1 (fr)

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EP12173770 2012-06-27
PCT/EP2013/063170 WO2014001272A1 (fr) 2012-06-27 2013-06-24 Film de polyuréthane diélectrique
EP13734687.0A EP2867281A1 (fr) 2012-06-27 2013-06-24 Film de polyuréthane diélectrique

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EP (1) EP2867281A1 (fr)
JP (1) JP2015524359A (fr)
KR (1) KR20150023462A (fr)
CN (1) CN104379643A (fr)
TW (1) TW201418305A (fr)
WO (1) WO2014001272A1 (fr)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104379643A (zh) * 2012-06-27 2015-02-25 拜耳材料科技股份有限公司 介电聚氨酯薄膜
KR20150035799A (ko) * 2012-07-03 2015-04-07 바이엘 머티리얼사이언스 아게 다층 유전성 폴리우레탄 필름 시스템의 제조 방법
EP3143061A1 (fr) 2014-05-12 2017-03-22 Covestro Deutschland AG Films diélectriques eap à bas point de transition vitreuse et à base de polyester-polyols
EP3037449A1 (fr) 2014-12-22 2016-06-29 Covestro Deutschland AG Polyuréthane modifié dipolaire, son procédé de fabrication et utilisation destiné à fabrication de feuilles élastomères de coulée à base de polyuréthane électroactif
FR3034256B1 (fr) * 2015-03-24 2017-04-14 Commissariat Energie Atomique Dispositif piezoelectrique
FR3034248B1 (fr) 2015-03-27 2017-04-14 Commissariat Energie Atomique Dispositif a resistance thermosensible
EP3098248A1 (fr) 2015-05-29 2016-11-30 Covestro Deutschland AG Additif polymère non lié destiné à l'augmentation de la constante diélectrique dans des polymères de polyuréthane électroactif
KR102042302B1 (ko) * 2015-09-25 2019-11-07 주식회사 엘지화학 디스플레이용 폴리우레탄 필름 및 이의 제조방법
KR102042873B1 (ko) * 2015-09-25 2019-11-08 주식회사 엘지화학 디스플레이용 pdms-폴리우레탄 필름 및 이의 제조방법
CN105949745A (zh) * 2016-05-24 2016-09-21 无锡市长安曙光手套厂 一种透明tpu薄膜及其制备方法和应用
AT518804B1 (de) * 2016-06-21 2018-07-15 Mock Herbert Verfahren und Vorrichtung zum Aufbringen von dekorativen Darstellungen auf einer mehrschichtigen Oberfläche von Kaffee
US11104571B2 (en) 2016-06-24 2021-08-31 Knowles Electronics, Llc Microphone with integrated gas sensor
WO2018148755A1 (fr) * 2017-02-13 2018-08-16 Tactus Technology, Inc. Procédé pour former un élastomère coulé
WO2018182289A2 (fr) * 2017-03-27 2018-10-04 주식회사 엘지화학 Film de polyuréthane thermoplastique et procédé de préparation associé
CN107488254B (zh) * 2017-08-29 2019-12-20 北京石油化工学院 介电弹性体材料及其制备方法
WO2019182862A1 (fr) * 2018-03-22 2019-09-26 Aleo Bme, Inc. Compositions et procédés de fabrication des applications à couche mince
CN108912661B (zh) * 2018-08-14 2021-04-20 南京大学射阳高新技术研究院 一种介电薄膜及其制备方法
US11633881B1 (en) 2018-12-20 2023-04-25 General Nano Llc Heated composite tool and method for building and use
CN112175161B (zh) * 2019-07-03 2022-05-20 北京化工大学 一种生物基热塑性介电弹性体材料及其制备方法
CN111403080A (zh) * 2020-03-24 2020-07-10 东莞讯滔电子有限公司 电缆及其制造方法
CN112239552B (zh) * 2020-09-18 2021-09-17 东莞市雄林新材料科技股份有限公司 一种汽车座椅悬膜用tpu薄膜及其制备方法
CN112625267B (zh) * 2020-12-17 2023-04-11 郑州轻工业大学 氰乙基纤维素-聚氯乙烯复合凝胶电致动器及其制备方法和应用

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1111996A (fr) * 1978-09-20 1981-11-03 Som N. Khanna Mousse de polyurethane amortisseuse semi-souple
JPS60260615A (ja) * 1985-04-17 1985-12-23 Toray Ind Inc ポリウレタン樹脂の製造方法
US5158922A (en) 1992-02-04 1992-10-27 Arco Chemical Technology, L.P. Process for preparing metal cyanide complex catalyst
US5470813A (en) 1993-11-23 1995-11-28 Arco Chemical Technology, L.P. Double metal cyanide complex catalysts
CN1149327A (zh) * 1994-05-06 1997-05-07 W·L·戈尔及同仁股份有限公司 三维、无缝、防水、透气、柔性的复合制品
US7034432B1 (en) 1997-02-07 2006-04-25 Sri International Electroactive polymer generators
JP2000336137A (ja) * 1999-06-01 2000-12-05 Nisshinbo Ind Inc 透明ポリウレタン回転成形体用樹脂組成物
JP4873831B2 (ja) * 2003-10-31 2012-02-08 スリーエム イノベイティブ プロパティズ カンパニー ポリウレタン組成物及びウレタン樹脂フィルム
JP4378624B2 (ja) * 2004-02-10 2009-12-09 株式会社イノアックコーポレーション シール部材の製造方法
US7338983B2 (en) * 2004-02-10 2008-03-04 World Properties, Inc. Low density polyurethane foam, method of producing, and articles comprising the same
DE602006008007D1 (de) * 2005-08-03 2009-09-03 Dow Global Technologies Inc Aus fettsäureamiden mit hydroxyl hergestellte polyurethane
CN1911979B (zh) * 2005-08-11 2011-04-20 环球产权公司 低密度聚氨酯泡沫、生产方法和产品组成
EP1919071B1 (fr) 2006-11-03 2011-04-27 Danfoss A/S Composite diélectrique et procédé de fabriation d'un composite diélectrique
DE102007005960A1 (de) * 2007-02-07 2008-08-14 Bayer Materialscience Ag Ruß-gefüllte Polyurethane mit hoher Dielektrizitätskonstante und Durchschlagsfestigkeit
JP5118898B2 (ja) * 2007-06-22 2013-01-16 大日精化工業株式会社 プラスチック用塗料
DE102007059858A1 (de) 2007-12-12 2009-06-18 Bayer Materialscience Ag Energiewandler hergestellt aus filmbildenden wässrigen Polymer-Dispersionen, insbesondere Polyurethan-Dispersionen
DE102008010705A1 (de) * 2008-02-22 2009-08-27 Byk-Chemie Gmbh Netz- und Dispergiermittel, deren Herstellung und Verwendung
EP2154167A1 (fr) 2008-07-30 2010-02-17 Bayer MaterialScience AG Convertisseur électromécanique doté d'un élément polymère à base de polyisocyanate
EP2182559A1 (fr) * 2008-10-30 2010-05-05 Bayer MaterialScience AG Convertisseur d'énergie à base de solutions de polyuréthane
EP2280034A1 (fr) * 2009-07-31 2011-02-02 Bayer MaterialScience AG Convertisseur électromécanique doté d'un élément polymère basé sur un mélange en polyisocyanate et de pré-polymères fonctionnels avec de l'isocyanate et sur une liaison dotée d'au moins deux groupes hydroxy réactifs à isocyanate
EP2330649A1 (fr) * 2009-12-04 2011-06-08 Bayer MaterialScience AG Convertisseur électromécanique comprenant un polymère de polyuréthane doté d'unités d'éther de poly-tétra-méthylène-glycol
US8257889B2 (en) * 2010-07-28 2012-09-04 Xerox Corporation Imaging members comprising capped structured organic film compositions
CN104379643A (zh) * 2012-06-27 2015-02-25 拜耳材料科技股份有限公司 介电聚氨酯薄膜

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2014001272A1 *

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Publication number Publication date
KR20150023462A (ko) 2015-03-05
JP2015524359A (ja) 2015-08-24
US9643840B2 (en) 2017-05-09
US20150321908A1 (en) 2015-11-12
WO2014001272A1 (fr) 2014-01-03
TW201418305A (zh) 2014-05-16
CN104379643A (zh) 2015-02-25

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